Electronic Optical Transitions Research Articles

In English

In mini-review, theoretical studies of some optical properties of heteronanosystems of the second type are considered. These nanosystems are germanium/silicon with germanium quantum dots (QDs). The influence of the interfaces on the radiation intensity of optical transitions and lifetimes of electronic excitations in germanium/silicon nanosystems with germanium in the germanium/silicon nanosystems with germanium QDs is studied. Dipole-allowed optical transitions between quasi-stationary and stationary states, which occur over the spherical surface of a single germanium QD embedded in a silicon matrix, are theoretically investigated. A mechanism is proposed for a significant increase (four times) in the intensities of optical interband and intraband transitions between quasi-stationary and stationary SIE-states arising above a spherical surface of a single germanium QD placed in a silicon matrix. These optical electronic transitions occur in the real space of the silicon matrix. Such a mechanism, apparently, will apparently solve the problem of a significant increase in the radiative intensity in germanium/silicon heterostructures with germanium QDs. This will provide an opportunity to develop fundamental and applied foundations, allowing to create a new generation of effective light-emitting and photodetector devices based on germanium/silicon heterostructures with germanium quantum dots. The theoretically predicted long-lived SIE-states, apparently, will make it possible to realize high-temperature quantum Bose-gases SIE-states in the nanosystem under study.

Shallow donor states and interlevel transitions in gapped graphene bilayers

Abstract A variational calculation for the energies of the ground and first excited states of a shallow donor impurity in bilayer graphene (BLG) with an open energy gap is presented in this study. It is shown that the binding energies of the lowest states and the distance between them can be tuned in the region of few tens of meV by changing the gap and tight binding parameter γ 1 , which is responsible for the nearest neighboring interlayer coupling. Based on the results obtained, the optical transition of an impurity electron from the ground to the first excited state in BLG is investigated. We find that the oscillator strength of the transition between the lowest energy states 1 S → 2 P x of a shallow donor also depends on the gap and tight binding parameter γ 1 , but is not sensitive to the value of the cutting parameter of the soft Coulomb potential that is proposed. The transitions between shallow impurity levels in BLG can serve as an alternative tunable source of terahertz radiation. The possibility to tune the energy levels of hydrogenic-like impurities can open new ways for either the creation of coherent superpositions of the energy states or the coherent population transfer between them by applying laser pulses.

Optical and photoelectric properties of nanostructured SnS films obtained by spraying ink using a nanoparticle suspension

Abstract In this work, SnS films were prepared using spraying ink with a nanoparticle suspension. The average size of the synthesized nanoparticles was (18-20) nm. The structural, optical and photoelectric properties of SnS films were investigated using different characterization techniques. XRD and EDX results show that the investigated films exhibited an orthorhombic SnS phase with a composition close to the stoichiometry (CS/CSn = 0.99) and low level of microdeformation (ε = 1.8×10-3). In addition, the hexagonal SnS2 and tetragonal SnO2 phases were also observed. The presence of SnS and SnS2 phases is confirmed by Raman characteristics. The band gap of the SnS, SnS2, and SnO2 phases was determined using the novel ACFD method based on the analysis of the spectra of the first derivative of the absorption coefficient, which directly determines the energy of both band-to-band optical transitions and transitions involving defect`s levels. These results correlate very well with data obtained using photoconductivity spectra. The nature of the electronic optical transitions as well as the type and energy position of various defect levels were established. It was shown that the energy of direct and indirect band-to-band optical transitions of SnS compound correspond to 1.72 eV and 1.16 eV, respectively. At the same time, the band gap of SnS2 phase equal to 2.05 eV. The ionization energy of the acceptor (233 meV) and donor (100 meV) levels that determine the p- and n-type conductivity of SnS and SnS2 compounds, respectively were defined. Due to its properties, SnS films may be suitable for the development of novel effective solar cells with SnS absorber layers.

Asymmetrically Fused Nanographene‐Porphyrin Architectures

AbstractA strategy to combine three standalone aromatic building blocks in one coherent, fully conjugated molecule is presented. Namely, benzene, pyrene, and hexa‐peri‐hexabenzocoronene (HBC) are assembled around a central porphyrin core in an ABAC type of geometry and interconnected under oxidative Scholl conditions to achieve merging of the individual π‐systems. The three asymmetric porphyrin conjugates obtained this way exhibit intriguing absorption features, namely strongly red‐shifted and broadened spectra. The presented series of molecules demonstrates the ability to control and influence these optical properties with high precision by altering the size of the aromatic system in a controlled manner. Density functional theory calculations gave more profound insights into the electronic structure and optical transitions of the investigated fused architectures.

The effect of annealing on the structural, optical, electrical and photoelectric properties of ZnO/NiO heterostructures

In this study, n-ZnO/p-NiO heterostructures on glass substrates with an indium tin oxide (ITO) covering were obtained by using the spray pyrolysis methodology. In order to act on the structural and local compositional defects, the samples were annealed under vacuum in the temperature range of Ta = (300 – 500)°C in steps of ΔT = 50°C. X-ray diffraction results indicate the presence of only the hexagonal ZnO and cubic NiO phases in the studied samples, which was confirmed by Raman spectroscopy. Low-temperature photoluminescence (PL), as well as absorption and photoconductivity, were studied to establish the optical properties, the nature of electronic optical transitions, the energy level position of the different defects present in the samples, and the effect of temperature annealing on these properties The band gap of the compounds was determined using the Tauc approximation and the first derivative of the absorption coefficient. Likewise, the current-voltage characteristics of the n-ZnO/p-NiO heterostructures and their diode character, were analyzed.

Investigations on structural and opto-electrical characterization of Ag-TCNQ (metal-organic frameworks) as complex thin films for potential device applications

The silver- (7, 7, 8, 8-tetracyanoquinodimethane (Ag-TCNQ) organometallic complex was synthesized chemically as a nano-powder and thereafter deposited as a thin film by thermal evaporation. The monoclinic, needle-like, polycrystalline structure of the Ag-TCNQ complex was analyzed employing x-ray diffraction (XRD) and a scanning electron microscope (SEM). Whereas their chemical structure and stability were explored using Fourier transformation infrared (FTIR) techniques. The findings imply a charge transfer of degree −0.5 between TCNQ° and TCNQ−, as revealed by the shift of the bands of the C≡N stretching and the (C═C-H) bond positioned at 2198 and 824 cm−1, respectively. As well as the optical properties of Ag-TCNQ thin film were studied using spectrophotometric measuring in the wavelength ranging 200 to 2500 nm. The measurement of transmittance and reflectance spectra were employed to calculate the refractive index (n), dielectric constant, absorption index (k), surface and volume energy loss functions, and optical conductivity. In the normal dispersion zone, optical characteristics such free charge carrier concentration, infinity dielectric constant (ε ∞), lattice dielectric constant (ε L), oscillator energy (Eo), and dispersion energy (Ed) were estimated. Furthermore, the optoelectronic nonlinear optical features and electronic transitions for the Ag-TCNQ thin film were assessed. Finally, these findings are promising milestones on the path to providing convincing evidence for the synthesis of stoichiometric thermally stable Ag-TCNQ thin film by conventional thermal evaporation technique that is potential to be utilized in optoelectronic devices applications.

Molten flux growth of single crystals of quasi-1D hexagonal chalcogenide BaTiS3

BaTiS3, a quasi-1D complex chalcogenide, has gathered considerable scientific and technological interest due to its giant optical anisotropy and electronic phase transitions. However, the synthesis of high-quality BaTiS3 crystals, particularly those featuring crystal sizes of millimeters or larger, remains a challenge. Here, we investigate the growth of BaTiS3 crystals utilizing a molten salt flux of either potassium iodide, or a mixture of barium chloride and barium iodide. The crystals obtained through this method exhibit a substantial increase in volume compared to those synthesized via the chemical vapor transport method, while preserving their intrinsic optical and electronic properties. Our flux growth method provides a promising route toward the production of high-quality, large-scale single crystals of BaTiS3, which will greatly facilitate advanced characterizations of BaTiS3 and its practical applications that require large crystal dimensions. Additionally, our approach offers an alternative synthetic route for other emerging complex chalcogenides.Graphical

Modification of transition pathways in polarized resonance Raman spectroscopy for carbon nanotubes by highly confined near-field light

We observed a modification of transition pathways in polarized resonance Raman spectroscopy during tip-enhanced Raman spectroscopy (TERS) analysis of metallic carbon nanotubes (CNTs). At a spatial resolution reaching up to the sub-nanometer regime, the signal intensity of the typical D-band is observed to be even higher than the intensity of the G-band all over the probed CNTs in TERS imaging. The measured D-band is attributed to the non-vertical transitions of electrons in k-space that are facilitated by highly confined near-field light at the tip–sample junction of our scanning tunneling microscope based TERS system. The D-band signal was observed even when the CNTs were excited by light polarized perpendicular to the tube axis that corresponds to electronic excitations between different cutting line numbers of a CNT. By combining the electron pathways brought about by both the near-field light and its polarization, we found a unique optical transition of electrons of CNTs in near-field Raman spectroscopy.

Impact of annealing temperature on optical, morphological, and surface characteristics of PC/PBT blend exposed to alpha particles

The induced modifications of the optical and surface characteristics in the annealed α-irradiated polycarbonate/polybutylene terephthalate (PC/PBT) blend have been studied in the temperature annealing range from 100 to 200 °C for 15 min. Several techniques have been used to study the changes in chemical composition, optical-electronic transitions, photoemission, contact angle, surface roughness, and hardness of annealed samples comparable to the pristine one. The FTIR spectra exhibit aggregate changes in the band intensities after annealing, indicating the scission and cross-linking of the polymer chains. The intensity of the peaks reduced with α-irradiation but began to increase with increasing annealing temperature. The trend of the function groups found in the annealed samples with the rise in annealing temperature supports the crosslinking mechanism. The UV/Vis spectra revealed that the absorption edges of annealed samples were shifted toward lower photon energy (red shift), reflecting the decrease of optical energy gap from 4 eV to 3.6 eV for direct transition and from 3.8 eV to 3.5 eV for indirect transition at the highest temperature. Further, the number of carbon atoms and the number of carbon clusters increases with the increase in the annealing temperature. The refractive index of the samples decreases from 1.5479 for the pristine sample to 1.4008 for the sample at the highest temperature. Moreover, the dielectric parameters and optical conductivity of the annealed samples were modified after thermal annealing. The PL emission yields are decreased with the increase in annealing temperatures that indicating an enhancement in the non-radiative recombination rate relative to the radiative recombination, which may be due to the increasing in the surface density states. The α-irradiated samples showed a notable increase in contact angle and a notable decrease in surface tension values with increasing the annealing temperatures. The side chain induction, which readily bundles and recombines the annealed parts by raising temperatures, also causes the surface roughness of annealed samples to decrease from 1.099 μm for the pristine sample to 0.696 μm for the annealed sample at the highest temperature. It is noteworthy that there is an increase in the hardness from 10.49 ΜPa for the pristine sample to 41.98 ΜPa for the annealed sample at the highest temperature. This is related to the results of changes in the polymer chains due to the active sites or branching points created by scission, which can lead to cross-linking.

Photoluminescence features of nickel-nitrogen complexes in Ib HPHT diamond matrix

The multiple color centers based on nickel-nitrogen complexes in synthetic Ib HPHT diamond matrices were optically characterized with an accent on a comparative analysis of temperature dependencies of photoluminescence spectra of two different Ni-N complexes with the phononless electronic transitions at 1.56 eV and 1.66 eV. The comparison shows that the intensities, widths, and energies of the bands of electronic and vibronic optical transitions, as well as temperature dependences of these parameters, measured in temperature range of 77–300 K, are essentially differ due to distinction in electron-vibrational interaction in the complexes.

Density functional theory study of Al, Ga and in impurities in diamond

As a consequence of its high atomic number density, diamond can incorporate a relatively limited range of impurities as distributed point-defects, chiefly N, B and H. A few other species can be grown-in, and other impurity species incorporated via implantation and annealing. For applications including electronic, electrical and quantum devices, the presence of states deep within the wide band-gap is of importance, and the list of potential colour centres available for exploitation continues to grow. Although B can be grown into diamond at high concentration, study of other group-13 elements is rather limited. In this paper we present the results of modelling of Al, Ga and In. We find all species readily form complexes with vacancies, and exhibit electronic structures that parallel those of the SiV complex. We report electronic structures, electrical levels, optical transitions and hyperfine interactions of the colour centres, as well as reflect upon the thermodynamics of the complexes. We suggest that co-implanting group-13 elements with nitrogen would give rise to the defect charge states with potential for quantum applications.

Design Rules, Accurate Enthalpy Prediction, and Synthesis of Stoichiometric Eu3+ Quantum Memory Candidates.

Stoichiometric Eu3+ compounds have recently shown promise for building dense, optically addressable quantum memory as the cations' long nuclear spin coherence times and shielded 4f electron optical transitions provide reliable memory platforms. Implementing such a system, though, requires ultranarrow, inhomogeneous linewidth compounds. Finding this rare linewidth behavior within a wide range of potential chemical spaces remains difficult, and while exploratory synthesis is often guided by density functional theory (DFT) calculations, lanthanides' 4f electrons pose unique challenges for stability predictions. Here, we report DFT procedures that reliably reproduce known phase diagrams and correctly predict two experimentally realized quantum memory candidates. We are the first to synthesize the double perovskite halide Cs2NaEuF6. It is an air-stable compound with a calculated band gap of 5.0 eV that surrounds Eu3+ with mononuclidic elements, which are desirable for avoiding inhomogeneous linewidth broadening. We also analyze computational database entries to identify phosphates and iodates as the next generation of chemical spaces for stoichiometric quantum memory system studies. This work identifies new candidate platforms for exploring chemical effects on quantum memory candidates' inhomogeneous linewidth while also providing a framework for screening Eu3+ compound stability with DFT.

Deciphering the structural heterogeneity behaviors of (K, Na)NbO[formula omitted]-based piezoelectric ceramics with multi-scale analyses

Inducing local structural heterogeneity is one of the most attractive strategies to enhance the piezoelectricity in lead-free piezoceramics, while the underlying mechanisms have not been well clarified, such as phase coexistence and domain boundary. Here, we mainly focus on analyzing the structure evolution mechanism of 0.96(K0.48Na0.52)(Nb1−xSbx)O3-0.04(Bi0.5Ag0.5)ZrO3 (0≤x≤0.1) (KNN) lead-free piezoelectric ceramics to study the intrinsic structural contributions from chemical modifying and/or alloy replacement. We explore the relation between structural characteristics and physical functionality by combining macro-spectral and micro-heterogeneity characterizations. It was found that Raman- and infrared-active phonon evolutions with respect to the motion of oxygen octahedron reveal the enhanced lattice symmetry when x increases to 0.06, along with the upswing optical electronic transitions. Moreover, we clarify the local heterogeneous structure of ceramics in terms of the spatial distribution of phonon traits on the micron scale accompanied with the atom-resolution polar vector state. The detected nanoscale atomic displacement clusters are directly related to the excellent polarization properties. Additionally, the phonon thermodynamics evolution was investigated in a wide temperature range of 80-720 K with unpolarized and polarized geometries. The detailed phase transition evolution and rhombohedral–orthorhombic–tetragonal multi-phase coexistence have been confirmed with Sb incorporation. The present work boosts the understanding of the compound-structure-functionality relation of KNN-based heterophase coexistent system, which could promote the development of the promising high-performance piezoelectric materials.

Dangerous Bonds Individual of Hydrogenated Amorphous Silicon and Defect Absorption Spectra

In this work, defect absorption spectra for defects characteristic of hydrogenated amorphous silicon are theoretically studied. It is shown that in order to determine defect absorption spectra using the Kubo-Greenwood formula, the indefinite integral in this formula must be written in a certain form. It was discovered that electronic transitions involving defect states are divided into two parts depending on the energy of absorbed photons. The values of the partial defect absorption spectrum at low energies of absorbed photons have almost no effect on the overall defect absorption spectrum. It has been established that the main role in determining the defect absorption spectrum is played by partial spectra determined by optical transitions of electrons between allowed bands and defects. It is shown that with a power-law distribution of the density of electronic states in allowed bands, the spectra of optical transitions between them and defects do not depend on the value of this power.

Molecular heteroassociation in films of thiochrome and tryptophan

Optical absorption spectra were studied for films of tryptophan, thiochrome and their layer-by-layer composites. It was shown that the absorption spectra were rearranged in the composites. Quantum-chemical modeling of the electronic structure and optical transitions of the specified molecules, and their complexes, indicate that the reason for the rearrangement of the optical spectra is the heteroassociation between the molecules of thiochrome and tryptophan, which is accompanied by significant changes in the electronic states of the formed complexes.

[formula omitted] Mössbauer, optical and structural properties with ligand field effects of borosilicate glass doped with iron oxide

Here, an investigation of borosilicate glass doped with iron oxide and prepared by classical melt-quenching method. The internal macrostructure, optical absorbance, ligand field parameters, and Mössbauer spectra were studied. The density increased with increasing SiO2 content, while Fourier-transform infrared (FTIR) analysis reported that BO4 and SiO4 content increase with a decrease in NBO content. Optical electronic transitions through wavelength (402–948 nm) confirmed the existence of Fe3+ state, while the Fe2+ is not observed in optical absorbance because of its inane electronic transition at 2222 nm. The electronic transitions at (402, 452, 513, 602, and 701 nm) are assigned to Fe3+ in tetrahedral coordination (FeO4), while the electronic transitions at (795 and 948 nm) are related to Fe3+ in octahedral coordination (FeO6). Astonishingly, the ligand field parameters of Fe ions were studied. The crystal field splitting exhibits increasing values, while Racah parameters exhibit decreasing values. Moreover, nephelauxetic parameters reflect the propensity of the bonding nature between the Fe cations and their ligands towards a higher covalent nature with SiO2 additives. Further, a scant decrease in the optical band gap was explained based on the mixed former effect. Moreover, non-linear refractive indices augment with SiO2 addition. The decrease in the optical gap energy justified such a trend. Bewitchingly, Mössbauer spectra reported the existence ofFe3+ ions with isomer shift (0.285–0.314) mm s−1 in tetrahedral sites, while Fe3+ ions with isomer shift (0.339–0.425) mm s−1 in octahedral sites, agreeing with optical data. Surprisingly, Fe2+ ions with isomer shift at about 0.905 mm s−1 in tetrahedral sites was observed. The observed decrease in isomer shift of all phases is due to the decrease in electronegativity of formers. Furthermore, the decrease in quadrable splitting is attributed to the decline in the polarization power of the glass former cations with SiO2 addition.

Radiation intensity of optical transitions in the germanium/silicon nanosystems with germanium quantum dots

Dipole-allowed optical transitions between quasi-stationary and stationary states, which occur over the spherical surface of a single germanium quantum dot (QD) embedded in a silicon matrix, are theoretically investigated. These optical electron transitions, which occur in the real space of the silicon matrix, allow for solving the problem of a significant increase in the radiation intensity in germanium/silicon heterostructures with germanium QDs. Long-lived quasistationary and stationary states will make it possible to realize high-temperature quantum Bose-gases states in the nanosystem under study.

Quantum-dimensional near-surface recombination of photocarriers in CdTe microcrystals

The low-temperature (T = 2 K) photoluminescence spectra of a p-CdTe/n-CdS film heterostructure containing CdTe microcrystals have been studied. In the spectral region above the intrinsic absorption edge of bulk CdTe, a dominant “superhot” radiation band was found. The band arises because of optical transitions of electrons from near-surface levels of the spatial quantization of a microcrystal to the valence band states.

Zeolite-Encaged Luminescent Silver Nanoclusters.

Silver nanoclusters (Ag NCs) are nanoscale aggregates that possess molecular-like discrete energy levels, resulting in electronic configuration-dependent tunable luminescence spanning the entire visible range. Benefiting from the efficient ion exchange capacity, nanometer dimensional cages, and high thermal and chemical stabilities, zeolites have been employed as desirable inorganic matrices to disperse and stabilize Ag NCs. This paper reviewed the recent research progresses on the luminescence properties, spectral manipulation, as well as the theoretical modelling of electronic structure and optical transition of Ag NCs confined inside various zeolites with different topology structures. Furthermore, potential applications of the zeolite-encaged luminescent Ag NCs in lighting, gas monitoring and sensing were presented. This review concludes with a brief comment on the possible future directions in the study of zeolite-encaged luminescent Ag NCs.

Band Structure and Exciton Dynamics in Quasi‐2D Dodecylammonium Halide Perovskites

AbstractFemtosecond transient absorption spectroscopy (FTAS) is an important tool to investigate the physics of halide perovskites having different dimensionality, morphology, and architectures, giving insights into the electronic and excitonic optical transitions. Here, FTAS on monolayer (n = 1) and multilayer (n = 2, 3) quasi‐2D perovskites in the Ruddlesden–Popper phase: DA2MAn‐1PbnI3n+1 (DAMAPI) is presented, with the dodecylammonium (DA = CH3‐(CH2)11‐NH3+) as the spacer and methylammonium (MA = CH3NH3+) as the organic cation for samples with n > 1. The measurements, performed at 77 K and room temperature using several pump energies and excitation densities, allow the observation of different absorption bleaching energies. Those energies are compared with the results of first‐principles theoretical simulations based on density functional theory, the GW method, and the Bethe–Salpeter equation and assigned to transitions involving excitons with principal quantum numbers 1s and 2s. The temporal analysis of the absorption bleaching indicates the exciton–exciton annihilation as the main relaxation mechanism in the first picoseconds after excitation, while exciton radiative recombination is observed at longer time delays (>100 ps). Therefore, FTAS allows the study of the carrier dynamics and, given its high sensitivity to carrier density changes, the observation of spectral features not observable with steady‐state measurements.