Low-temperature Spectra Research Articles

An investigation of exciton behavior in type-II self-assembled GaSb/GaAs quantum dots

We report the investigation of exciton dynamics in type-II self-assembled GaSb/GaAs quantum dots. The GaSb/GaAs quantum dots (QDs) were grown using a modified liquid phase epitaxy technique. Statistical size distributions of the uncapped QDs were investigated experimentally by field-emission scanning electron microscopy (SEM) and atomic force microscopy (AFM), and theoretically by an eight-band k · p calculation, which demonstrated a dissolution effect. Furthermore, the low-temperature luminescence spectra of type-II GaSb/GaAs QDs with a thick capping layer exhibit well-resolved emission bands and LO-phonon-assisted transitions in the GaSb wetting layer. However, the luminescence lines quench at temperatures above 250 K, which is attributed to the weak quantum confinement of electrons participating in indirect exciton recombination. It was demonstrated that the room temperature stability of the excitons in type-II GaSb/GaAs QDs could be achieved by growing thin a capping layer, which provides strong quantum confinement in the conduction band and enhances the electron–hole Coulomb interaction, stabilizing the excitons.

Interaction of sphalerite with potassium n-butyl xanthate and copper sulfate solutions studied by XPS of fast-frozen samples and zeta-potential measurement

We acquired low-temperature X-ray photoelectron spectra of fast-frozen wet pastes prepared by centrifugation of the natural sphalerite slurries containing potassium n-butyl xanthate (KBX), without washing or any additional treatment, before and after the mineral activation in 0.1 mM CuSO4 solution. Zeta potentials of the slurry particles were also measured. The method allowed characterizing the mineral surfaces and adsorbates, volatile substances and hydrated species within the interfacial layers under more realistic flotation-related conditions. The uptake of xanthate by unactivated mineral was low even in 10 mM KBX, while the surface became metal-deficient (enriched in sulfur), more hydrophobic and contaminated with carbonaceous matter. Dibutyl dixanthogen was the major interfacial product of the interaction of Cu-activated sphalerite having the surface atomic Zn/Cu ratio of 3 and excess of sulfur with the KBX solutions. The spectra revealed only minor quantities of Zn and Cu xanthates and oxyhydroxides at all the samples; some hydrated K+ counter-ions were detected at the negatively charged surfaces after the xanthate treatment. The dixanthogen was concluded to form via oxidation of xanthate at the interface, probably catalyzed by surface cuprous species but not direct interaction with cupric ions.

Multiparticle states and the factors that complicate an experimental observation of the quantum coherence in the exciton gas of SiGe/Si quantum wells

The measured stationary and time-resolved photoluminescence is used to study the properties of the exciton gas in a second-order 5-nm-thick Si0.905Ge0.095/Si quantum well. It is shown that, despite the presence of an electron barrier in the Si0.905Ge0.095 layer, a spatially indirect biexciton is the most favorable energy state of the electron–hole system at low temperatures. This biexciton is characterized by a lifetime of 1100 ns and a binding energy of 2.0–2.5 meV and consists of two holes localized in the SiGe layer and two electrons mainly localized in silicon. The formation of biexcitons is shown to cause low-temperature (5 K) luminescence spectra over a wide excitation density range and to suppress the formation of an exciton gas, in which quantum statistics effects are significant. The Bose statistics can only be experimentally observed for a biexciton gas at a temperature of 1 K or below because of the high degree of degeneracy of biexciton states (28) and a comparatively large effective mass (about 1.3m e ). The heat energy at such temperatures is much lower than the measured energy of localization at potential fluctuations (about 1 meV). This feature leads to biexciton localization and fundamentally limits the possibility of observation of quantum coherence in the biexciton gas.

Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission.

We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine, and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ∼1.7 eV, values that are lower than the RCB of the uncomplexed PtCl6 (2-) dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl6 (2-) ⋅ thymine and PtCl6 (2-) ⋅ adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)4 (2-) ⋅ nucleobase complexes [A. Sen et al., J. Phys. Chem. B 119, 11626 (2015)]. The observation of delayed electron emission bands in the PtCl6 (2-) ⋅ nucleobase spectra obtained in this work, as for the previously studied Pt(CN)4 (2-) ⋅ nucleobase complexes, is attributed to one-photon excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. This strongly supports our previous suggestion that the dianion within these clusters can be viewed as a "dynamic tag" which has the propensity to emit electrons when the attached nucleobase decays over a time scale long enough to allow autodetachment.

Unified analysis of ensemble and single-complex optical spectral data from light-harvesting complex-2 chromoproteins for gaining deeper insight into bacterial photosynthesis.

Bacterial light-harvesting pigment-protein complexes are very efficient at converting photons into excitons and transferring them to reaction centers, where the energy is stored in a chemical form. Optical properties of the complexes are known to change significantly in time and also vary from one complex to another; therefore, a detailed understanding of the variations on the level of single complexes and how they accumulate into effects that can be seen on the macroscopic scale is required. While experimental and theoretical methods exist to study the spectral properties of light-harvesting complexes on both individual complex and bulk ensemble levels, they have been developed largely independently of each other. To fill this gap, we simultaneously analyze experimental low-temperature single-complex and bulk ensemble optical spectra of the light-harvesting complex-2 (LH2) chromoproteins from the photosynthetic bacterium Rhodopseudomonas acidophila in order to find a unique theoretical model consistent with both experimental situations. The model, which satisfies most of the observations, combines strong exciton-phonon coupling with significant disorder, characteristic of the proteins. We establish a detailed disorder model that, in addition to containing a C_{2}-symmetrical modulation of the site energies, distinguishes between static intercomplex and slow conformational intracomplex disorders. The model evaluations also verify that, despite best efforts, the single-LH2-complex measurements performed so far may be biased toward complexes with higher Huang-Rhys factors.

Magnetic excitations in the spin-1/2 triangular-lattice antiferromagnet Cs2CuBr4

We report on high-field electron spin resonance (ESR) studies of magnetic excitations in the spin-1/2 triangular-lattice antiferromagnet Cs2CuBr4. Frequency-field diagrams of ESR excitations are measured for different orientations of magnetic fields up to 25 T. We show that the substantial zero-field energy gap, K, observed in the low-temperature excitation spectrum of Cs2CuBr4, (Zvyagin et al 2014 Phys. Rev. Lett.112 077206) is present well above TN. Noticeably, the transition into the long-range magnetically ordered phase does not significantly affect the size of the gap, suggesting that even below TN the high-energy spin dynamics in Cs2CuBr4 is determined by short-range-order spin correlations. The experimental data are compared with results of model spin-wave-theory calculations for spin-1/2 triangular-lattice antiferromagnet.

Effects of AlN buffer on the physical properties of GaN films grown on 6H-SiC substrates

In this study, 1.5-μm-thick GaN films with AlN buffer were prepared on 6H-SiC substrates by metal-organic chemical vapor deposition. To determine the effects of growth conditions of AlN buffer on crystalline quality and stress state of GaN films, two series of experiments were carried out. By optimizing growth conditions of AlN buffer, the full width at half maximum values of (0002) and \((10\bar{1}2)\) rocking curves of GaN films were improved to 136 and 225 arcsec, respectively. A smooth surface was obtained with a small root-mean-squared roughness of 0.332 nm and the excellent optical property was observed. Simultaneously, threading dislocation density and tensile stress in GaN films were reduced by increasing AlN buffer growth temperature and its thickness in some extent. Besides, stress values in GaN films were confirmed by Raman and low-temperature photoluminescence spectra, which indicated that the lower tensile stress in GaN film, the higher the film crystallinity.

Light-induced metal-insulator transition inSrTiO3by photoresistance spectroscopy

Photoresistivity and its spectral response has been systematically studied in oxygen-deficient ${\mathrm{SrTiO}}_{3}$ single crystals for a wide range of resistivities $\ensuremath{\rho}$ and carrier densities $n$. At room temperature we found a persistent photoresistance that gradually decreases as $\ensuremath{\rho}$ is diminished or $n$ is increased, in addition to relaxation times of seconds to a few minutes, suggesting that trapping of carriers is playing a major role. An analysis of the photoresistance excitation spectra showed two distinctive features that are related to the indirect gap of ${\mathrm{SrTiO}}_{3}$ at $(3.25\ifmmode\pm\else\textpm\fi{}0.04)\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$ and to a direct transition at $(3.40\ifmmode\pm\else\textpm\fi{}0.03)\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$. The photoresistive crystals present a temperature-dependent resistivity under illumination that experiences a metal-insulator transition below $T\ensuremath{\sim}85\phantom{\rule{0.28em}{0ex}}\mathrm{K}$. The low-temperature photoresistance spectrum reveals a suitable technique to understand the origin of this transition, pointing to an enhanced efficiency of the $\ensuremath{\sim}3.25\phantom{\rule{0.28em}{0ex}}\mathrm{eV}$ gap to promote electrons to the bottom of the conduction band.

Research on superconductivity of epitaxial FeSe films

The newly discovered iron-based superconductors in 2008 have become the second class of high temperature superconductor besides the cuprates. Among all these iron-based compounds, β-FeSe has the simplest chemical structure and can be an archetype system for unraveling the mechanism of superconductivity. By using state-of-the-art molecular beam epitaxy (MBE) technique, high-quality superconducting FeSe single crystalline films with finely controllable topography and composition have been successfully prepared, with their superconducting properties extensively investigated. The low-temperature scanning tunneling spectra reveal that the superconducting gap in the quasiparticle density of states is visible down to two unit cells of FeSe films, and evidence for a gap function with nodal lines. Electron pairing with two-fold symmetry has also been demonstrated by direct imaging of quasiparticle excitations in the vicinity of magnetic vortex cores, Fe adatoms and Se vacancies. The two-fold pairing symmetry is supported by our observation of striped electronic nanostructures in the slightly Se-doped samples, primarily due to the orbital ordering. Twin boundaries run at approximately 45° to the Fe-Fe bond directions, and noticeably suppress the superconducting gap and pin magnetic vortices. This is likely caused by the increased Se height in the vicinity of twin boundaries, providing the first local evidence for the importance of this height to the mechanism of superconductivity. Furthermore, we reveal signatures of a bosonic mode in the local quasiparticle density of states of superconducting FeSe films, whose energy reduces with decreasing gap magnitude Ω . Recently, the growth recipe has been further extended to grow FeSe film on SrTiO3(001) substrate, leading to the high- T c superconductivity in the very FeSe/SrTiO3 interface. A superconducting gap as large as 20 meV and the magnetic field induced vortex state revealed by in situ scanning tunneling microscopy suggest that the superconductivity of single-unit-cell FeSe films could occur around 77 K. Our subsequent transport and measurements of the one-unit-cell thick FeSe films on insulating SrTiO3 substrates with non-superconducting FeTe protection layers provide definitive evidence for high temperature superconductivity with an onset T c above 40 K which are much higher than T c~9.4 K for bulk FeSe, respectively. The finding provides a completely new avenue and method to reveal the pairing mechanism of high- T c superconductors, and to further enhance T c, stirring up worldwide increasing attention in the field of high- T c superconductors and material sciences.

MBE growth and optical properties of GaAs nanowires grown on Si(111) substrate using two-temperature steps regime

We report on the growth and optical properties of pencil-like GaAs nanowires (NWs) grown using an original two-temperature growth mode on Si substrate. Optically, the NWs array is active up to the room temperature. The low-temperature PL spectra is composed by the narrow bands corresponding to the direct, bound to surface states and bound to impurity excitons. After toluene treatment, the fine structure is disappeared in the spectra.

Strong Optical Absorption and Photocarrier Relaxation in 2-D Semiconductors

Strongly bound excitons in the 2-D crystals of transition metal dichalcogenides give rise to characteristic optical absorption and emission features. Here, we review and provide additional experimental evidence on the unusually strong optical absorption features of monolayer molybdenum disulfide (MoS2) arising from band nesting and corresponding divergence of joint density of states, which is a distinct signature of 2-D systems. We study low-temperature photoluminescence excitation spectra of suspended MoS2 and discuss spontaneous formation of indirect excitons for excitation at the band nesting point.

Cubic silicon carbide as a potential photovoltaic material

In this work we present a significant advancement in cubic silicon carbide (3C-SiC) growth in terms of crystal quality and domain size, and indicate its potential use in photovoltaics. To date, the use of 3C-SiC for photovoltaics has not been considered due to the band gap of 2.3eV being too large for conventional solar cells. Doping of 3C-SiC with boron introduces an energy level of 0.7eV above the valence band. Such energy level may form an intermediate band (IB) in the band gap. This IB concept has been presented in the literature to act as an energy ladder that allows absorption of sub-bandgap photons to generate extra electron–hole pairs and increase the efficiency of a solar cell. The main challenge with this concept is to find a materials system that could realize such efficient photovoltaic behavior. The 3C-SiC bandgap and boron energy level fits nicely into the concept, but has not been explored for an IB behavior.For a long time crystalline 3C-SiC has been challenging to grow due to its metastable nature. The material mainly consists of a large number of small domains if the 3C polytype is maintained. In our work a crystal growth process was realized by a new approach that is a combination of initial nucleation and step-flow growth. In the process, the domains that form initially extend laterally to make larger 3C-SiC domains, thus leading to a pronounced improvement in crystalline quality of 3C-SiC. In order to explore the feasibility of IB in 3C-SiC using boron, we have explored two routes of introducing boron impurities; ion implantation on un-doped samples and epitaxial growth on un-doped samples using pre-doped source material. The results show that 3C-SiC doped with boron is an optically active material, and thus is interesting to be further studied for IB behavior.For the ion implanted samples the crystal quality was maintained even after high implantation doses and subsequent annealing. The same was true for the samples grown with pre-doped source material, even with a high concentration of boron impurities.We present optical emission and absorption properties of as-grown and boron implanted 3C-SiC. The low-temperature photoluminescence spectra indicate the formation of optically active deep boron centers, which may be utilized for achieving an IB behavior at sufficiently high dopant concentrations. We also discuss the potential of boron doped 3C-SiC base material in a broader range of applications, such as in photovoltaics, biomarkers and hydrogen generation by splitting water.

Vibronic coupling in molecular crystals: A Franck-Condon Herzberg-Teller model of H-aggregate fluorescence based on quantum chemical cluster calculations.

Here, we present a general approach to treating vibronic coupling in molecular crystals based on atomistic simulations of large clusters. Such clusters comprise model aggregates treated at the quantum chemical level embedded within a realistic environment treated at the molecular mechanics level. As we calculate ground and excited state equilibrium geometries and vibrational modes of model aggregates, our approach is able to capture effects arising from coupling to intermolecular degrees of freedom, absent from existing models relying on geometries and normal modes of single molecules. Using the geometries and vibrational modes of clusters, we are able to simulate the fluorescence spectra of aggregates for which the lowest excited state bears negligible oscillator strength (as is the case, e.g., ideal H-aggregates) by including both Franck-Condon (FC) and Herzberg-Teller (HT) vibronic transitions. The latter terms allow the adiabatic excited state of the cluster to couple with vibrations in a perturbative fashion via derivatives of the transition dipole moment along nuclear coordinates. While vibronic coupling simulations employing FC and HT terms are well established for single-molecules, to our knowledge this is the first time they are applied to molecular aggregates. Here, we apply this approach to the simulation of the low-temperature fluorescence spectrum of para-distyrylbenzene single-crystal H-aggregates and draw comparisons with coarse-grained Frenkel-Holstein approaches previously extensively applied to such systems.

Symmetric minimally entangled typical thermal states

We extend White's minimally entangled typically thermal states approach (METTS) to allow Abelian and non-Ablian symmetries to be exploited when computing finite-temperature response functions in one-dimensional (1D) quantum systems. Our approach, called SYMETTS, starts from a METTS sample of states that are not symmetry eigenstates, and generates from each a symmetry eigenstate. These symmetry states are then used to calculate dynamic response functions. SYMETTS is ideally suited to determine the low-temperature spectra of 1D quantum systems with high resolution. We employ this method to study a generalized diamond chain model for the natural mineral azurite Cu${}_3$(CO${}_3)_2$(OH$)_2$, which features a plateau at $\frac{1}{3}$ in the magnetization curve at low temperatures. Our calculations provide new insight into the effects of temperature on magnetization and excitation spectra in the plateau phase, which can be fully understood in terms of the microscopic model.

Optical properties and Zeeman spectroscopy of niobium in silicon carbide

The optical signature of niobium in the low-temperature photoluminescence spectra of three common polytypes of SiC (4H, 6H, and 15R) is observed and confirms the previously suggested concept that Nb occupies preferably the Si-C divacancy with both Si and C at hexagonal sites. Using this concept we propose a model considering a Nb-bound exciton, the recombination of which is responsible for the observed luminescence. The exciton energy is estimated using first-principles calculation and the result is in very good agreement with the experimentally observed photon energy in 4H SiC at low temperature. The appearance of six Nb-related lines in the spectra of the hexagonal 4H and 6H polytypes at higher temperatures is tentatively explained on the grounds of the proposed model and the concept that the Nb center can exist in both ${\mathrm{C}}_{1h}$ and ${\mathrm{C}}_{3v}$ symmetries. The Zeeman splitting of the photoluminescence lines is also recorded in two different experimental geometries and the results are compared with theory based on phenomenological Hamiltonians. Our results show that Nb occupying the divacancy at the hexagonal site in the studied SiC polytypes behaves like a deep acceptor.

Electron Detachment as a Probe of Intrinsic Nucleobase Dynamics in Dianion-Nucleobase Clusters: Photoelectron Spectroscopy of the Platinum II Cyanide Dianion Bound to Uracil, Thymine, Cytosine, and Adenine.

We report the first low-temperature photoelectron spectra of isolated gas-phase complexes of the platinum II cyanide dianion bound to nucleobases. These systems are models for understanding platinum-complex photodynamic therapies, and a knowledge of the intrinsic photodetachment properties is crucial for characterizing their broader photophysical properties. Well-resolved, distinct peaks are observed in the spectra, consistent with complexes where the Pt(CN)4(2-) moiety is largely intact. Adiabatic electron detachment energies for the dianion-nucleobase complexes are measured to be 2.39-2.46 eV. The magnitudes of the repulsive Coulomb barriers of the complexes are estimated to be between 1.9 and 2.1 eV, values that are lower than for the bare Pt(CN)4(2-) dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four dianion-nucleobase complexes and also in the 266 nm spectra of the Pt(CN)4(2-)·thymine and Pt(CN)4(2-)·adenine complexes. The selective excitation of these features in the 266 nm spectra is attributed to one-photon excitation of [Pt(CN)4(2-)·thymine]* and [Pt(CN)4(2-)·adenine]* long-lived excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment signals. We attribute the delayed electron detachment bands observed here for Pt(CN)4(2-)·thymine and Pt(CN)4(2-)·adenine but not for Pt(CN)4(2-)·uracil and Pt(CN)4(2-)·cytosine to fundamental differences in the individual nucleobase photophysics following 266 nm excitation. This indicates that the Pt(CN)4(2-) dianion in the clusters can be viewed as a "dynamic tag" which has the propensity to emit electrons when the attached nucleobase displays a long-lived excited state.

Formation of definite GaN p–n junction by Mg-ion implantation to n−-GaN epitaxial layers grown on a high-quality free-standing GaN substrate

P-type conversion of n−-GaN by Mg-ion implantation was successfully performed using high quality GaN epitaxial layers grown on free-standing low-dislocation-density GaN substrates. These samples showed low-temperature PL spectra quite similar to those observed from Mg-doped MOVPE-grown p-type GaN, consisting of Mg related donor–acceptor pair (DAP) and acceptor bound exciton (ABE) emission. P–n diodes fabricated by the Mg-ion implantation showed clear rectifying I–V characteristics and UV and blue light emissions were observed at forward biased conditions for the first time.

Low-temperature spectrum of correlation lengths of the XXZ chain in the antiferromagnetic massive regime**Dedicated to Professor Baxter on the occasion of his 75th birthday.

We consider the spectrum of correlation lengths of the spin− XXZ chain in the antiferromagnetic massive regime. These are given as ratios of eigenvalues of the quantum transfer matrix of the model. The eigenvalues are determined by integrals over certain auxiliary functions and by their zeros. The auxiliary functions satisfy nonlinear integral equations. We analyse these nonlinear integral equations in the low-temperature limit. In this limit we can determine the auxiliary functions and the expressions for the eigenvalues as functions of a finite number of parameters which satisfy finite sets of algebraic equations, the so-called higher-level Bethe ansatz equations. The behaviour of these equations, if we send the temperature T to zero, is different for zero and non-zero magnetic field h. If h is zero the situation is much like in the case of the usual transfer matrix. Non-trivial higher-level Bethe ansatz equations remain which determine certain complex excitation parameters as functions of hole parameters which are free on a line segment in the complex plane. If h is non-zero, on the other hand, a remarkable restructuring occurs, and all parameters which enter the description of the quantum transfer matrix eigenvalues can be interpreted entirely in terms of particles and holes which are freely located on two curves when T goes to zero.

Transient electrically detected magnetic resonance spectroscopy applied to organic solar cells

The influence of light-induced paramagnetic states on the photocurrent generated by polymer:fullerene solar cells is studied using spin-sensitive techniques in combination with laser-flash excitation. For this purpose, we developed a setup that allows for simultaneous detection of transient electron paramagnetic resonance as well as transient electrically detected magnetic resonance (trEDMR) signals from fully processed and encapsulated solar cells. Combining both techniques provides a direct link between photoinduced triplet excitons, charge transfer states, and free charge carriers as well as their influence on the photocurrent generated by organic photovoltaic devices. Our results obtained from solar cells based on poly(3-hexylthiophene) as electron donor and a fullerene-based electron acceptor show that the resonant signals observed in low-temperature (T = 80 K) trEDMR spectra can be attributed to positive polarons in the polymer as well as negative polarons in the fullerene phase, indicating that both centers are involved in spin-dependent processes that directly influence the photocurrent.

Exploration of Yb^3+:ScBO_3- a novel laser crystal in the rare-earth ion doped orthoborate system

Growth of optical-quality crystals with a borate anionic group and small-diameter cations is challenging. By compensating for the volatilization of boracic acid, an optical-quality Yb3+:ScBO3 laser crystal suitable for laser applications has been grown by the Czochralski method. The thermal and spectral properties of Yb3+:ScBO3 were experimentally and theoretically studied, including the thermal expansion, thermal diffusivity, specific heat, thermal conductivity, and the absorption and low-temperature emission spectra. The results indicate that this crystal exhibits a thermal conductivity that increases with temperature, and large energy storage properties that indicate promise for utilization in moderate power lasers. A continuous-wave Yb3+:ScBO3 crystal laser has, to the best of our knowledge, been demonstrated for the first time, with a maximum output power of 106 mW. All the results are indicative of a novel promising laser medium for applications in low and even moderate power lasers.