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Controlled insertion of electronic states within the band gap of semiconductor nanocrystals (NCs) is a powerful tool for tuning their physical properties. One compelling example is II-VI NCs incorporating heterovalent coinage metals in which hole capture produces acceptor-bound excitons. To date, the opposite donor-bound exciton scheme has not been realized because of the unavailability of suitable donor dopants. Here, we produce a model system for donor-bound excitons in CdSeS NCs engineered with sulfur vacancies (VS) that introduce a donor state below the conduction band (CB), resulting in long-lived intragap luminescence. VS-localized electrons are almost unaffected by trapping, and suppression of thermal quenching boosts the emission efficiency to 85%. Magneto-optical measurements indicate that the VS are not magnetically coupled to the NC bands and that the polarization properties are determined by the spin of the valence-band photohole, whose spin flip is massively slowed down due to suppressed exchange interaction with the donor-localized electron.

The in-plane anisotropy of monolayer InSe plays a critical role in the application of photodetectors. In this work, through nonequilibrium Green's function density functional theory (NEGF-DFT) and time-dependent density functional theory (TD-DFT) calculations, we investigated the anisotropic quantum transport in darkness and under linearly polarized light, and explored the role of surface-bound excitons in the anisotropic photocurrent. The anisotropic dark quantum transport is attributed to different potential barriers in the zigzag and armchair orientations (Id-zig/Id-arm = 1.2 × 102). Linearly polarized photocurrent calculations show that the extinction ratio reaches a maximum value of 105.67. Moreover, surface-bound exciton calculations via TD-DFT revealed that the strong anisotropic photocurrent derives from surface-bound excitons generated in the In 5pz, Se 4pz, and Se 4dz2 orbitals. InSe shows tremendous potential for use in field-effect transistors, flexible nano- and optoelectronics, and polarized light devices.

The monolayer transition metal dichalcogenides are an emergent semiconductor platform exhibiting rich excitonic physics with coupled spin-valley degree of freedom and optical addressability. Here, we report a new series of low energy excitonic emission lines in the photoluminescence spectrum of ultraclean monolayer WSe2. These excitonic satellites are composed of three major peaks with energy separations matching known phonons, and appear only with electron doping. They possess homogenous spatial and spectral distribution, strong power saturation, and anomalously long population (> 6 $��$s) and polarization lifetimes (> 100 ns). Resonant excitation of the free inter- and intra-valley bright trions leads to opposite optical orientation of the satellites, while excitation of the free dark trion resonance suppresses the satellites photoluminescence. Defect-controlled crystal synthesis and scanning tunneling microscopy measurements provide corroboration that these features are dark excitons bound to dilute donors, along with associated phonon replicas. Our work opens opportunities to engineer homogenous single emitters and explore collective quantum optical phenomena using intrinsic donor-bound excitons in ultraclean 2D semiconductors., to be appear in Nature Communications

Lead-free halide double perovskites have emerged as a nontoxic alternative to the heavily researched lead-based halide perovskites. However, their optical properties and the initial charge carrier relaxation processes are under debate. In this study, we apply time-resolved photoluminescence and differential transmission spectroscopy to investigate the photoexcited charge carrier dynamics within the indirect band structure of Cs2AgBiBr6 nanocrystals. Interestingly, we observe a high energetic emission stemming from the direct band gap, besides the previously reported emission from the indirect band gap transition. We attribute this emission to the radiative recombination of direct bound excitons. This emission maximum redshifts nearly 1 eV within 10 ps due to electron intervalley scattering, which leads to a transfer of direct to indirect bound excitons. We conclude that these direct bound excitons possess a giant oscillator strength causing not only a pronounced absorption peak at the optical band gap energy but also luminescence to occur at the direct band gap transition in spite of the prevailing intervalley scattering process. These results expand the understanding of the optical properties and the charge carrier relaxation in double perovskites, thus, facilitating the further development of optoelectronic devices harnessing lead-free perovskites.

The successful synthesis of Janus transition metal dichalcogenides offers new opportunities in two-dimensional materials due to its novel properties induced by structural mirror asymmetry. Herein, by using the first-principle calculations, the thermodynamical stability for monolayers MoSSe and WSSe is demonstrated by phonon dispersion with no imaginary frequencies. No longitudinal optical-transverse optical (LO-TO) splitting exists at the Γ point and phonon frequencies are red-shifted, since the 2D Coulomb screening effect is introduced to eliminate the spurious interaction between adjacent layers. An indirect-direct-indirect transition in band gaps for both MoSSe and WSSe is observed, and tunable mobilities can be realized by uniaxial strain, reaching up to 10

We study photoluminescence (PL) spectra and exciton dynamics of the MoS2 monolayer (ML) grown by the chemical vapor deposition technique. In addition to the usual direct A-exciton line, we observe a low-energy line of bound excitons dominating the PL spectra at low temperatures. This line shows unusually strong redshift with an increase in the temperature and submicrosecond time dynamics suggesting indirect nature of the corresponding transition. By monitoring the temporal dynamics of exciton PL distribution in the ML plane, we observe diffusive transport of A-excitons and measure the diffusion coefficient up to 40 cm2/s at elevated excitation powers. The bound exciton spatial distribution spreads over tens of micrometers in ∼1 μs. However, this spread is subdiffusive, characterized by a significant slowing down with time. The experimental findings are interpreted as a result of the interplay between the diffusion and Auger recombination of excitons.

Monolayer and few-layer phosphorene are anisotropic quasi-two-dimensional (quasi-2D) van der Waals (vdW) semiconductors with the linear-dichroic light-matter interaction and the widely tunable direct band gap in the infrared frequency range. Despite recent theoretical predictions of strongly bound excitons with unique properties, it remains experimentally challenging to probe excitonic quasiparticles due to the severe oxidation that occurs during device fabrication. In this study, we report the observation of strongly bound excitons and trions with highly anisotropic optical properties in intrinsic bilayer phosphorene, which are protected from oxidation by encapsulation with hexagonal boron nitride (hBN) in a field-effect transistor (FET) geometry. Reflection contrast and photoluminescence spectroscopy clearly reveal the linear-dichroic optical spectra from anisotropic excitons and trions in the hBN-encapsulated bilayer phosphorene. The optical resonances from the exciton Rydberg series indicate that the neutral exciton binding energy is over 100 meV even with the dielectric screening from hBN. The electrostatic injection of free holes enables an additional optical resonance from a positive trion (charged exciton) \ensuremath{\sim}30 meV below the optical band gap of the charge-neutral system. Our work shows exciting possibilities for monolayer and few-layer phosphorene as a platform to explore many-body physics and photonics and optoelectronics based on strongly bound excitons with twofold anisotropy.

Illuminating the charge transport at photoanode-electrolyte interface is pivotal for optimizing photoelectrochemical (PEC) water oxidation performance of BiVO4. Our study demonstrates a preferentially photogenerated electrons trapping process at BiVO4 surface, followed by the formation of surface-bound excitons. A facile LSV treatment method is described, which remarkably changes the surface termination of BiVO4 photoanode. The surface electron trapping states could be passivated by LSV treatment and “free” the photogenerated holes from the surface-bound excitons. As a result, more photogenerated holes transfer to BiVO4 surface and the PEC performance is enhanced.

First-principles studies of electronic structures, excitons, and defects in Li2B12H12 reveal unique photophysical properties of Li2B12H12 and its potential as a neutron scintillator material. We identify the electronic shell structure in (B12H12)2−, which gives rise to strong chemical stability of (B12H12)2− and a large band gap of Li2B12H12. Based on hybrid functional calculations, we show that excitons in Li2B12H12 are strongly self-trapped and predict that the exciton excitation and emission are both in the UV range and are not related to the bright blue emission observed in the experiment. The experimentally observed blue emission in Li2B12H12 is likely due to the emission of excitons bound to hydrogen vacancies. The calculated strong localization and large exciton trapping energy at hydrogen vacancies indicate enhanced radiative recombination, while the calculated large Stokes shift suggests that the self-absorption and the resonance transfer of the excitation energy may be suppressed. These properties should promote efficient defect emission at room temperature. The efficient defect emission, combined with the large thermal neutron capture cross-section by Li and B and the efficient energy transfer between fast neutrons and H, suggests potential applications of Li2B12H12 as a thermal or fast neutron scintillator. Optical characterization of VH may also be used to monitor H and Li concentrations in Li2B12H12-based hydrogen storage materials and solid-state electrolytes in Li batteries.

Lasers and light emitting diodes are found in numerous applications in our daily lives. The performance and applications of these diodes are very dependent on the choice of light emitting material. Ideally, these materials should be brightly emitting, solution-processible, low cost, and tunable. Among the vast variety of light emitting materials, three dimensional organic-inorganic halide perovskites are found to inherit these characteristics. As such, their light emitting and optical gain properties have been in the limelight over the past few years. On the contrary, not much attention was given to their low dimensional counterparts, which exhibit bright excitonic emission. In these low dimensional systems, the role of bound excitons cannot be neglected as they are an important species that influences light emitting and optical gain properties. In particular, this work explores the role of bound excitons in these perovskites for optical gain and white emission, which could be attractive for electrically pumped gated laser and white LEDs respectively. Bound excitons, in particular defect-bound excitons, were found to be one of the problems in limiting low temperature biexcitonic optical gain in (C6H5C2H4NH3)2PbI4 two dimensional perovskites. In this material, biexcitonic states were found to be populated through free-to-bound excitonic relaxation followed by bound-to-biexcitonic relaxation. Through these relaxation pathways, both free and bound excitonic recombinations can take place, which effectively compete withbiexcitonic population inversion build up. Theoretical modelling revealed a high biexcitonic optical gain threshold, which is consistent with the presence of strongly competing relaxation channels. Low optical damage threshold is another problem that is inherent in this material. This threshold, which is ∼1 order of magnitude lower than the theoretical biexcitonic optical gain threshold, could impede the path to achieving optical gain. On the other hand, bound excitons, in the form of self-trapped excitons, are responsible for white emission from low dimensional perovskites, such as (C6H5C2H4NH3)2PbCl4 and (NH3CH2C6H4CH2NH3)PbBr6. Notably, white emission is only observed in the latter thin films fabricated with excess PbBr2. Importantly, these excitons were found to undergo self-trapping at different locations in the two materials, with exciton self-trapping at the organic framework for the former and at the inorganic framework for the latter. Nonetheless, large exciton-phonon coupling strength, which is indicative of self-trapped excitons, was measured from both materials. Self-trapping phenomenon at the organic framework provide a new perspective on the origin of white emission in these systems, which deviates from conventional understanding of self-trapping in inorganic semiconductor systems. These two findings suggest that judicious selection of both organic and inorganic precursors are crucial for developing high efficiency white emitting perovskites. In retrospect, the presence of bound excitons in low dimensional perovskites serves as a double-edged sword, which either limits optical gain or gives rise to white emission. Doctor of Philosophy (IGS)

International audience; This study aims at a quantitative understanding of the optical spectra taken from bound excitons weakly coupled to phonons in indirect semiconductors, which had been missing for decades. Insights on the properties of excitons bound at neutral acceptor impurities are obtained by analyzing the spectra reported for diamond with appropriate boron doping [Y. Kubo, Appl. Phys. Lett. 114, 132104 (2019)APPLAB0003-695110.1063/1.5089894]. We focus on the mirror symmetry holding between phonon-assisted absorption and luminescence simultaneously regarding energies, linewidths, and intensities. New analytic expressions are proposed to reproduce the spectra of phonon-assisted recombination lines. The detailed analysis reveals the contribution from excited bound-exciton states whose origin is discussed and modeled. Taking them into account improves simulation of the bound-exciton optical spectra in indirect band-gap semiconductors up to a quantitative level.

The present work reports on the tunable optical emission from oxygen vacancies in ZnO nanorods. The common green luminescence at room temperature originated from oxygen vacancy defects can be mediated by simply controlling pH values of alkaline solutions without the introduction of any intentional dopants. The peak energies of the green band are found to be monotonously tuned in the range from 2.17 to 2.47 eV, which could promote the applications of tunable wavelength ZnO optoelectronic devices. The temperature dependent behavior of exciton transitions and oxygen vacancy recombinations in ZnO nanorods is investigated in detail. It is suggested that the localized bound exciton (LBX) attached near the lateral facets of ZnO nanorods could survive up to nearly room temperature due to the large binding energy.

Anatase TiO2 is among the most studied materials for light-energy conversion applications, but the nature of its fundamental charge excitations is still unknown. Yet it is crucial to establish whether light absorption creates uncorrelated electron-hole pairs or bound excitons and, in the latter case, to determine their character. Here, by combining steady-state angle-resolved photoemission spectroscopy and spectroscopic ellipsometry with state-of-the-art ab initio calculations, we demonstrate that the direct optical gap of single crystals is dominated by a strongly bound exciton rising over the continuum of indirect interband transitions. This exciton possesses an intermediate character between the Wannier-Mott and Frenkel regimes and displays a peculiar two-dimensional wavefunction in the three-dimensional lattice. The nature of the higher-energy excitations is also identified. The universal validity of our results is confirmed up to room temperature by observing the same elementary excitations in defect-rich samples (doped single crystals and nanoparticles) via ultrafast two-dimensional deep-ultraviolet spectroscopy.Here the authors combine steady-state angle-resolved photoemission spectroscopy, ellipsometry and ultrafast two-dimensional ultraviolet spectroscopy to examine the role of many-body correlations in anatase TiO2, revealing the existence of strongly bound excitons in single crystals and nanoparticles.

We report the ultraviolet absorption of boron-bound excitons at low temperature in a single crystal of diamond grown by chemical vapor deposition. The no-phonon (NP) and phonon-assisted lines are identified by comparison with cathodoluminescence. The oscillator strength of the NP lines was found to be 3.0 × 10−5 based on the measured absorption cross-section. This value is discussed in terms of the scaling law known for doped silicon, where the oscillator strength varies proportionally to E loc 2.5, with Eloc being the localization energy of excitons on acceptors. More importantly, we also could assess the oscillator strength of the dominant transverse optical phonon-assisted transition, which is found to be equal to 1.2 × 10 − 3. The associated radiative lifetime for the boron-bound exciton is 1.8 μs, which is much longer than the non-radiative Auger lifetime that governs its decay.We report the ultraviolet absorption of boron-bound excitons at low temperature in a single crystal of diamond grown by chemical vapor deposition. The no-phonon (NP) and phonon-assisted lines are identified by comparison with cathodoluminescence. The oscillator strength of the NP lines was found to be 3.0 × 10−5 based on the measured absorption cross-section. This value is discussed in terms of the scaling law known for doped silicon, where the oscillator strength varies proportionally to E loc 2.5, with Eloc being the localization energy of excitons on acceptors. More importantly, we also could assess the oscillator strength of the dominant transverse optical phonon-assisted transition, which is found to be equal to 1.2 × 10 − 3. The associated radiative lifetime for the boron-bound exciton is 1.8 μs, which is much longer than the non-radiative Auger lifetime that governs its decay.

The steady-state and time-resolved photoluminescence (PL) of excitons bound on intercalated iodine molecules was studied for the first time in MoSe2:I2 layered single crystals. Along with narrow exciton spectral lines located near the energy of the MoSe2 indirect bandgap in the region of 0.98–1.06 eV, an IR broadband radiation centered at 0.78 eV and caused by the recombination of photoexcited carriers through the intrinsic lattice defects were found. To describe the temperature dependences of the intensity of steady-state PL, as well as its temporal characteristics, a kinetic model was proposed that takes into account the radiative and non-radiative recombination channels present in this quasi-two-dimensional semiconductor.

The excitonic effects in two-dimensional transition metal dichalcogenides and their heterostructures have been extensively investigated. Significantly, the moire excitons, induced by a moire superlattice in a twisted heterostructure, have triggered tremendous attention, demonstrating the practicability of artificial excitonic crystals. Besides, recent works have shown that the excitonic states in homostructures also exhibit novel properties worthy of further development. Here, we present a tear-and-stack technique for fabricating a regular or a twisted homostructure. Such a strategy was utilized to reassemble a monolayer WSe2 into a twisted homostructure, and various excitons from this structure have been identified in the photoluminescence spectra. Interestingly, the unusual equidistant splitting was first observed in the defect-bound excitons. It is believed that this phenomenon is attributed to the various defect states and the local stacking patterns. This interpretation is supported by theoretical calculations, which show the dependence of the energy band structure on different defect states and local stacking patterns. These unconventional defect-bound excitons are key building blocks in the research of homostructures that highlight the feasibility of artificially manipulating local excitons for practical applications.

CH3NH3PbCl3 (MAPbCl3) perovskite single crystal is attractive for the ultra-violet detector due to its wide bandgap and comparative stability over iodine or bromine systems. Single crystals of MAPbCl3 perovskite are also intriguing owing to its generic type of materials for fundamental photophysical properties and excitonic behaviors for its use in devices. Furthermore, recent progress using crystal-based device fabrication will shed light on semiconducting devices like III–V compounds. In this study, a structurally well-defined crystal is grown and examined to reveal free and bound excitonic behaviors depending on the structural phase transition. We classified the free and bound excitonic behaviors by temperature- and power density-dependent photoluminescence and optical transmission spectra. The single emission peak located at 3.1 eV and blueshift depending on decreasing the temperature is attributed to the radiative recombination of the free exciton at the cubic and the tetragonal phases, whereas the several peaks from the bound excitonic transition are just revealed under 120 K of the orthorhombic phase. We also determined the work function distribution and band structures with excitonic bound states via Kelvin probe force microscopy. The optoelectronic properties resulted in the excitonic behaviors can be a fundamental approach for the construction of perovskite-based optoelectronic and photonic applications.

In atomically thin two-dimensional semiconductors such as transition metal dichalcogenides (TMDs), controlling the density and type of defects promises to be an effective approach for engineering light-matter interactions. We demonstrate that electron-beam irradiation is a simple tool for selectively introducing defect-bound exciton states associated with chalcogen vacancies in TMDs. Our first-principles calculations and time-resolved spectroscopy measurements of monolayer ${\mathrm{WSe}}_{2}$ reveal that these defect-bound excitons exhibit exceptional optical properties including a recombination lifetime approaching 200 ns and a valley lifetime longer than $1\text{ }\text{ }\ensuremath{\mu}\mathrm{s}$. The ability to engineer the crystal lattice through electron irradiation provides a new approach for tailoring the optical response of TMDs for photonics, quantum optics, and valleytronics applications.

When two sheets of graphene stack in a twisted bilayer graphene (tBLG) configuration, the resulting constrained overlap between interplanar 2p orbitals produce angle-tunable electronic absorption resonances. By applying a novel combination of multiphoton transient absorption (TA) microscopy and TEM, we resolve the electronic structure and ensuing relaxation by probing resonant excitations of single tBLG domains. Strikingly, we find that the transient electronic population in resonantly excited tBLG domains is enhanced many fold, forming a major electronic relaxation bottleneck. Two-photon TA microscopy shows this bottleneck effect originates from a strongly bound, dark exciton state lying ∼0.37 eV below the 1-photon absorption resonance. This stable coexistence of strongly bound excitons alongside free-electron continuum states has not been previously observed in a metallic, 2D material.

Bound exciton is a signature of sulfur vacancies, and thus, it can be used to investigate defects in atomically thin materials., Defects play a significant role in tailoring the optical properties of two-dimensional materials. Optical signatures of defect-bound excitons are important tools to probe defective regions and thus interrogate the optical quality of as-grown semiconducting monolayer materials. We have performed a systematic study of defect-bound excitons using photoluminescence (PL) spectroscopy combined with atomically resolved scanning electron microscopy and first-principles calculations. Spatially resolved PL spectroscopy at low temperatures revealed bound excitons that were present only on the edges of monolayer tungsten disulfide and not in the interior. Optical pumping of the bound excitons was sublinear, confirming their bound nature. Atomic-resolution images reveal that the areal density of monosulfur vacancies is much larger near the edges (0.92 ± 0.45 nm−2) than in the interior (0.33 ± 0.11 nm−2). Temperature-dependent PL measurements found a thermal activation energy of ~36 meV; surprisingly, this is much smaller than the bound-exciton binding energy of ~300 meV. We show that this apparent inconsistency is related to a thermal dissociation of the bound exciton that liberates the neutral excitons from negatively charged point defects. First-principles calculations confirm that sulfur monovacancies introduce midgap states that host optical transitions with finite matrix elements, with emission energies ranging from 200 to 400 meV below the neutral-exciton emission line. These results demonstrate that bound-exciton emission induced by monosulfur vacancies is concentrated near the edges of as-grown monolayer tungsten disulfide.

Stacking and twisting 2D van der Walls (vdW) materials can create unique electronic properties that are not accessible in a single sheet of material. When two sheets of van der Waals material such as graphene are stacked in an off-axis angle, in a twisted bilayer graphene (tBLG) configuration, electronic properties are modified from interlayer orbital hybridization effects. For instance, in tBLG we can access both massless and massive chiral quasiparticles characteristics of graphene and bilayer graphene, as well as angle tunable optical resonances that are not present in graphene or bilayer graphene. In addition, first principle simulation predicts that upon optical resonant excitation of tBLG, bound exciton formation is a possibility due to cancelation of exciton-continuum coupling from anti-symmetric superposition of degenerate resonant transitions. In order to study possible bound exciton formation, we map out the electronic structure of single grain tBLG using multi-photon transient absorption microscopy. Surprisingly, upon resonant optical excitations, tBLG shows enhanced transient response with longer carrier compared to AB stacked bilayer graphene. Further, we find that the origin of this unexpected optical response can be best explained by the presence of a lower lying bound exciton state predicted by recent theoretical simulations. This suggests that tBLG is a novel 2D hybrid material that enables the creation of both strongly-bound excitons along-side highly-conductive continuum states. Recently, the family of 2D vdW materials has grown appreciably. As such, there are countless possibilities for stacking and twisting 2D vDw materials to produce similar interlayer electronic states for next generation optoelectronics.

International audience; The dynamics of the free-exciton capture by boron acceptors and phosphorus donors in diamond is observed in the picosecond range by time-resolved photoluminescence experiments at low temperature. The formation of boron-bound excitons is observed with a delay of 410 ps after the formation of free excitons. For phosphorus, this delay is 120 ps. This is the result of the free-exciton capture by B0 and P0 impurities. The lifetimes of boron- and phosphorus-bound excitons are measured and found to be equal to 270 and 70 ps, respectively. These values are about four orders of magnitude shorter than for the same impurities in silicon. Ei being the ionization energy of dopants, these results scale well with the E4i dependence of the Auger recombination rate expected for bound excitons in indirect band-gap semiconductors.

We have investigated the detailed features of photoluminescence (PL) in vertically aligned ZnO nanotube (NT) arrays as a function of temperature, pumping power, and experimental geometries. In samples with different wall thickness (15 or 60 nm), the temperature-dependent PL energy followed the Varshni's formula whose fitting parameters were found to be rather close to zero-dimensional case in the 15 nm-thick NTs with much larger intensity. In reflective geometry with circular excitation beam shape, the emission gradually evolved from spontaneous to stimulated regime, inferred from amplitude and line-width variation. On the other hand, in the edge-emission geometry with needle-like excitation shape, the interaction length dependence was directly traced by using an adjustable slit.

We present Auger-electron-detected magnetic resonance (AEDMR) experiments on phosphorus donors in silicon, where the selective optical generation of donor-bound excitons is used for the electrical detection of the electron spin state. Because of the long dephasing times of the electron spins in isotopically purified $^{28}$Si, weak microwave fields are sufficient, which allow to realize broadband AEDMR in a commercial ESR resonator. Implementing Auger-electron-detected ENDOR, we further demonstrate the optically-assisted control of the nuclear spin under conditions where the hyperfine splitting is not resolved in the optical spectrum. Compared to previous studies, this significantly relaxes the requirements on the sample and the experimental setup, e.g. with respect to strain, isotopic purity and temperature. We show AEDMR of phosphorus donors in silicon with natural isotope composition, and discuss the feasibility of ENDOR measurements also in this system., 5 pages, 5 figures

Solar cells incorporating organic-inorganic perovskite, which may be fabricated using low-cost solution-based processing, have witnessed a dramatic rise in efficiencies yet their fundamental photophysical properties are not well understood. The exciton binding energy, central to the charge collection process, has been the subject of considerable controversy due to subtleties in extracting it from conventional linear spectroscopy techniques due to strong broadening tied to disorder. Here we report the simultaneous observation of free and defect-bound excitons in CH3NH3PbI3 films using four-wave mixing (FWM) spectroscopy. Due to the high sensitivity of FWM to excitons, tied to their longer coherence decay times than unbound electron- hole pairs, we show that the exciton resonance energies can be directly observed from the nonlinear optical spectra. Our results indicate low-temperature binding energies of 13 meV (29 meV) for the free (defect-bound) exciton, with the 16 meV localization energy for excitons attributed to binding to point defects. Our findings shed light on the wide range of binding energies (2–55 meV) reported in recent years.

This paper reports on the results of investigations into the cathodoluminescence spectra of ZnSe crystals grown from a vapor phase and annealed in a bismuth melt [ZnSe(Bi) crystals], as well as in a bismuth melt containing aluminum [ZnSe(Bi,Al) crystals], at a temperature of 1200 K for 120 h. The longitudinal optical (LO) phonon replicas of the emission lines of free excitons are dominant in the cathodoluminescence spectra of the samples subjected to annealing in the bismuth melt with subsequent quenching. The emission spectra of all the samples studied, including the initial crystals, contain series of I1s,d-nLO lines of bound excitons. It is revealed that plasmon replicas are characteristic not only of the I1s-nLO lines. A weak exciton-plasmon interaction manifests itself in the form of single-plasmon Stokes satellites of the I1d-nLO spectral lines. A theory describing the multiphoton optical transitions of bound excitons with the participation of mixed plasmonphonon vibrational modes is proposed. This theory makes it possible to calculate the shape function of an emission spectrum without recourse to model concepts. The results of the theoretical calculations are in agreement with the experimental data.

The spectra and relaxation kinetics of the anomalous (τ < 10 ns) luminescence of Li 6GdB 3O 9:Ce 3+ crystals have been experimentally detected. The time-resolved vacuum ultraviolet spectroscopy study has shown that optical transitions at 6.2 eV, caused by the transfer of an electron from the 4f 1 ground state of Ce 3+ to autoionizing states near the conduction band bottom of a crystal, lead to the formation of an impurity-bound exciton with the hole component localized on the 4f state of Ce 3+ and the electron localized on states of the conduction band bottom. It has been found that the decay of such an exciton in Li 6GdB 3O 9:Ce 3+ occurs through radiative recombination, leading to fast luminescence at 4.25 eV. The energy threshold for the formation of the impurity-bound exciton has been determined. The distribution functions of elementary relaxations over the reaction rate constants H(k), which determine the relaxation kinetics and luminescence quenching processes, have been calculated. © 2012 Pleiades Publishing, Ltd.

We report new data on the transient photoluminescence behaviour of free and donor bound excitons in high quality bulk GaN material grown by HVPE. With 266 nm photoexcitation the no-phonon free exci ...

The effect of microwave radiation on the transformation of impurity-based structural complexes in CdTe:Cl single crystals is studied using low-temperature photoluminescence measurements. It is shown that microwave radiation activates ClTe centers, resulting in an increase in the intensity of photoluminescence line of excitons bound at the corresponding ClTe donor centers. A nonmonotonic dependence of the integrated photoluminescence intensity on the duration of microwave irradiation is observed. At the initial stage of microwave irradiation (t = 30 s), an increase in the integrated excitonic photoluminescence intensity is observed; as the duration of microwave irradiation is increased, the photoluminescence intensity decreases. The experimentally observed variations in the photoluminescence intensity are athermal in nature. The hypothetical mechanism of transformation of impurity-based structural complexes is described.

Based on first-principles calculations, the structural, electronic, and optical properties of monolayers PtS2 and PtSe2 are investigated. The bond stiffnesses and elastic moduli are determined by means of the spring constants and strain-energy relations, respectively. Dynamic stability is confirmed by calculating the phonon spectra, which shows excellent agreement with experimental reports for the frequencies of the Raman-active modes. The Heyd-Scuseria-Ernzerhof functional results in electronic bandgaps of 2.66 eV for monolayer PtS2 and 1.74 eV for monolayer PtSe2. G0W0 calculations combined with the Bethe-Salpeter equation are used to predict the optical spectra and exciton binding energies (0.78 eV for monolayer PtS2 and 0.60 eV for monolayer PtSe2). It turns out that the excitons are strongly bound and therefore very stable against external perturbations.

Time-resolved as well as time-integrated photoluminescence measurements at 4.2 K have been performed on compensated high-resistivity CdTe single crystals doped with a low indium concentration (less than 1×1016 cm−3). Three kinds of bound excitons, a neutral donor and a neutral acceptor bound excitons, and a defect related bound exciton, were observed with a Lorentzian line shape in the near-band edge region. The radiative recombination lifetimes of these bound excitons are 400, 1460 and 2560 ps, respectively. These values agree well with theoretical values, which are estimated by using Rashba and Gurgenishvili theory. Full time evolutions of these bound excitons were also analyzed by a set of rate equations.

Properties of the bound excitons associated to the 3838A line in 4H-SiC and the 4182A line in 6H-SiC

We present a study of excitons bound to sulphur- and copper-related isoelectronic centres in highly enriched 28Si. The S-related centre, which has been shown to have two configurations, SA and SB, was believed to consist of a substitutional sulphur atom paired with an interstitial copper atom. High resolution photoluminescence (PL) emissions from the no-phonon S B 0 transition reveal fine structure not observable in natural silicon. In both 28Si:natS and 28Si:34S, low temperature PL reveals at least 18 distinct components of the S B 0 system, including a triplet splitting seen in natSi:natS by optical detection of magnetic resonance. Investigation of the effect of copper isotopic composition on the S B 0 system shows that the centre contains at least three copper atoms. We also present results of the copper isotope effect on the 943.7 meV *Cu00 system in 28Si and show that three Cu atoms contribute to the Cu isotope shift of *Cu00.

We study x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers (SAMs), investigating excitations from the nitrogen K edge. Azobenzene with H-termination and functionalized with CF3 groups is considered. The Bethe-Salpeter equation is employed to compute the spectra, including excitonic effects, and to determine the character of the near-edge resonances. Our results indicate that core-edge excitations are intense and strongly bound: Their binding energies range from about 6 to 4 eV, going from isolated molecules to densely-packed SAMs. Electron-hole correlation rules these excitations, while the exchange interaction plays a negligible role.

Homoepitaxial GaN layers grown by MOVPE on a pre-treated GaN single crystal are almost strain-free, have very low defect densities and low impurity levels. These layers show strong, extraordinarily sharp photoluminescence spectra. Especially, the donor-(D0, X) and acceptor-(A0, X) bound excitons at ≈3.471 eV and 3.465 eV, respectively, exhibit line widths of ≈100 μeV, and ample fine structures can be resolved. For the (D0, X), complicated spectra are observed in the spectral region of two-electron-transitions and in the excited bound exciton state. For both (D0, X) and (A0, X), the respective bound exciton states belonging to all three valence bands are found. By variation of the sample temperature and excitation density, we separate the spectral features contributed by different impurities and reassign several lines in the band gap region.

The luminescence characteristics of M3+: Al2O3 crystals, where M3+ stands for an isoelectronic cation impurity with a filled electron shell, namely, Sc3+, Y3+, or La3+, were studied. The luminescence of excitons bound (BE) to these impurities was detected. The position of the BE energy states at the long-wavelength absorption edge as a function of the M3+ ionic radius was established. The energies of the long-wavelength BE creation threshold and of the maximum of the BE luminescence band were approximated empirically by third-order polynomials of the Toyozawa polynomial type, which describes electron-phonon interaction. The energy and spatial structure of the BE was found to be similar to that of a self-trapped exciton (STE). The BE and STE states are separated by an energy barrier, and energy transfer from the STE to BE is frozen at low temperatures.

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In this paper recent results of optical studies of bound excitons in wide-gap II‐VI and nitride semiconductors are surveyed. In the first part latest results about self-compensation mechanisms will be presented. Then, the dynamical characteristics of excitonic transitions are evaluated for various impurities, dopants, and dopant concentrations, and for excitation via particular resonant excitation channels. Relaxation and conversion channels between excitonic systems are analyzed, especially in strained heteroepitaxial systems which show splitting effects of the bands from which the carriers stem. The dynamical behavior of excitons in wide-gap material gives evidence of nonradiative decay channels. Calorimetric spectroscopy at mK temperatures was used to investigate the nonradiative processes and to determine quantum efficiencies. Recent results of transient fourwave mixing experiments at bound-exciton complexes will be shown to demonstrate that shallow defects influence the dephasing in the investigated systems which gives information about the homogeneous and inhomogeneous broadening mechanisms. In the last part negatively charged excitons (trions) were observed in unintentionally donor doped Zn0.90Mg0.10Se/ZnSe single quantum wells by magneto-luminescence experiments. The binding energy of the trion singlet ground state is about 2.7 meV.

Nanoparticles of Titanium dioxide [Formula: see text] with its unique optical and electronic characteristics is an important material for photochemical catalysis. The efficiency of catalytic activity of [Formula: see text] anatase nanostructures is greatly influenced by the photo-generated bound excitons. It is found that the interaction of bound excitons generated in [Formula: see text] enhances the cubic nonlinearity of the system due to strong oscillation of photo-generated bound excitons. The trapped electron hole pair concentration is directly proportional to the photocatalytic efficiency of the [Formula: see text] anatase nanostructures. In our report, we show how these photo-generated bound excitons play a significant role in origin of third-order optical nonlinearities. In particular, we have measured large phase shift and seen two photon absorption process through closed and open aperture Z-scan, respectively, using femtosecond pulses at 532[Formula: see text]nm.

We investigate the origin of the fast recombination dynamics of bound and free excitons in GaN nanowire ensembles by temperature-dependent photoluminescence spectroscopy using both continuous-wave and pulsed excitation. The exciton recombination in the present GaN nanowires is dominated by a nonradiative channel between 10 and 300 K. Furthermore, bound and free excitons in GaN NWs are strongly coupled even at low temperatures resulting in a common lifetime of these states. By solving the rate equations for a coupled two-level system, we show that one cannot, in practice, distinguish whether the nonradiative decay occurs directly via the bound or indirectly via the free state. The nanowire surface and coalescence-induced dislocations appear to be the most obvious candidates for nonradiative defects, and we thus compare the exciton decay times measured for a variety of GaN nanowire ensembles with different surface-to-volume ratio and coalescence degrees. The data are found to exhibit no correlation with either of these parameters, i.e., the dominating nonradiative channel in the GaN nanowires under investigation is neither related to the nanowire surface, nor to coalescence-induced defects. Hence we conclude that nonradiative point defects are the origin of the fast recombination dynamics of excitons in GaN nanowires.

Exciton binding energy and excited states in monolayers of tungsten diselenide (WSe2) are investigated using the combined linear absorption and two-photon photoluminescence excitation spectroscopy. The exciton binding energy is determined to be 0.37eV, which is about an order of magnitude larger than that in III-V semiconductor quantum wells and renders the exciton excited states observable even at room temperature. The exciton excitation spectrum with both experimentally determined one- and two-photon active states is distinct from the simple two-dimensional (2D) hydrogenic model. This result reveals significantly reduced and nonlocal dielectric screening of Coulomb interactions in 2D semiconductors. The observed large exciton binding energy will also have a significant impact on next-generation photonics and optoelectronics applications based on 2D atomic crystals., 19 pages, 4 figures, to appear in PRL

A set of new excitonic recombinations is observed in arsenic-implanted diamond. It is composed of two groups of emissions at 5.355/5.361 eV and at 5.215/5.220/5.227 eV. They are respectively attributed to the no-phonon and transverse-optical phonon-assisted recombinations of excitons bound to neutral arsenic donors. From the Haynes rule, an ionization energy of 0.41 eV is deduced for arsenic in diamond, which shows that arsenic is a shallower donor than phosphorus (0.6 eV), in agreement with theory.

Here we summarize the advantages of excitons bound to isolated fluorine donor in ZnSe/ZnMgSe quantum well nano-structures. Devices based on these semiconductors, are particularly suited to implement concepts of the optical manipulation of quantum states in solid-state material. The fluorine donor in ZnSe provides a physical qubit with potential advantages over previously researched qubits. In this context we show several initial demonstrations of devices, such as a low-threshold microdisk laser and an indistinguishable single photon source. Additionally we demonstrate the realization of a controllable three-level-system qubit consisting of a single Fluorine donor in a ZnSe nano-pillar, which provides an optical accessible single electon spin qubit.

A study is reported of the reflectance and low-temperature photoluminescence (PL) spectra of ZnTe films grown by molecular-beam epitaxy (MBE) on GaAs substrates [(100) orientation, 3° deflection toward 〈110〉]. It is shown that the strain-induced splitting of the free-exciton energy level (ΔEex) does not depend on ZnTe film thickness within the 1–5.7 µm range and is due to biaxial in-plane film tension. The stresses are primarily determined by the difference between the thermal expansion coefficients of the film and the substrate. It is also shown that the residual stresses originating from incomplete relaxation of the film lattice parameter to its equilibrium value at the growth temperature likewise provide a certain contribution. The position of the spectral line of an exciton bound to a neutral acceptor (As) is well approximated in terms of the present models, taking into account the stresses calculated using the value of ΔEex.

ZnO single crystals, epilayers, and nanostructures often exhibit a variety of narrow emission lines in the spectral range between 3.33 and 3.35 eV which are commonly attributed to deeply bound excitons (Y lines). In this work, we present a comprehensive study of the properties of the deeply bound excitons with particular focus on the Y0 transition at 3.333 eV. The electronic and optical properties of these centers are compared to those of the shallow impurity related exciton binding centers (I lines). In contrast to the shallow donors in ZnO, the deeply bound exciton complexes exhibit a large discrepancy between the thermal activation energy and localization energy of the excitons and cannot be described by an effective mass approach. The different properties between the shallow and deeply bound excitons are also reflected by an exceptionally small coupling of the deep centers to the lattice phonons and a small splitting between their two electron satellite transitions. Based on a multitude of different experimental results including magnetophotoluminescence, magnetoabsorption, excitation spectroscopy (PLE), time resolved photoluminescence (TRPL), and uniaxial pressure measurements, a qualitative defect model is developed which explains all Y lines as radiative recombinations of excitons bound to extended structural defect complexes. These defect complexes introduce additional donor states in ZnO. Furthermore, the spatially localized character of the defect centers is visualized in contrast to the homogeneous distribution of shallow impurity centers by monochromatic cathodoluminescence imaging. A possible relation between the defect bound excitons and the green luminescence band in ZnO is discussed. The optical properties of the defect transitions are compared to similar luminescence lines related to defect and dislocation bound excitons in other II-VI and III-V semiconductors. © 2011 American Physical Society.

We report luminescence from spin triplet states of excitons bound to interstitial carbon-interstitial oxygen defects in silicon. The peak, which we call CT-line, has an energy 2.64 meV lower than 790 meV (C-line), and splits into three peaks by application of magnetic field. Moreover, its peak position does not depend on the angle between the magnetic field direction and crystallographic orientation indicating the quenching of orbital angular momentum of the hole bound to the defect. These observations lead us to conclude that the CT-line is the photoluminescence from a triplet state.