Excitonic Structure Research Articles

Positively versus negatively charged excitons: A high magnetic field study of CdTe/Cd1−xMgxTe quantum wells

A magneto-optical study of the energy and spin structure of charged excitons in a 20-nm-thick CdTe/Cd${}_{0.65}$Mg${}_{0.35}$Te quantum well is performed in strong magnetic fields up to 51 T. The type of resident carriers (holes or electrons) in the quantum well is controlled optically by above-barrier illumination, permitting a direct comparison of positively (T${}^{+}$) versus negatively (T${}^{\ensuremath{-}}$) charged excitons. The binding energies of the singlet states of these complexes behave qualitatively differently with increasing magnetic field $B$; namely, the binding energy decreases for ${\mathrm{T}}^{+}$ and increases for ${\mathrm{T}}^{\ensuremath{-}}$ with $B$. The triplet state of ${\mathrm{T}}^{+}$ is identified in strong fields with a binding energy smaller than that of the ${\mathrm{T}}^{\ensuremath{-}}$ triplet state.

Modulational instability and solitons in excitonic semiconductor waveguides

Nonlinear light propagation in a single-mode micron-size waveguide made of semiconducting excitonic material has been theoretically studied in terms of exciton-polaritons by using an analysis based on macroscopic fields. When a light pulse is spectrally centered in the vicinity of the ground-state Wannier exciton resonance, it interacts with the medium nonlinearly. This optical cubic nonlinearity is caused by the repulsive exciton-exciton interactions in the semiconductor, and at resonance it is orders of magnitude larger than the Kerr nonlinearity (e.g., in silica). We demonstrate that a very strong and unconventional modulational instability takes place, which has not been previously reported. After reducing the problem to a single nonlinear Schr\"odinger-like equation, we also explore the formation of solitary waves both inside and outside the polaritonic gap and find evidence of spectral broadening. A realistic physical model of the excitonic waveguide structure is proposed.

Excitonic Energy Level Structure and Pigment−Protein Interactions in the Recombinant Water-Soluble Chlorophyll Protein. II. Spectral Hole-Burning Experiments

Persistent spectral hole burning at 4.5 K has been used to investigate the excitonic energy level structure and the excited state dynamics of the recombinant class-IIa water-soluble chlorophyll-binding protein (WSCP) from cauliflower. The hole-burned spectra are composed of four main features: (i) a narrow zero-phonon hole (ZPH) at the burn wavelength, (ii) a number of vibrational ZPHs, (iii) a broad low-energy hole at ~665 and ~683 nm for chlorophyll b- and chlorophyll a-WSCP, respectively, and (iv) a second satellite hole at ~658 and ~673 nm for chlorophyll b- and chlorophyll a-WSCP, respectively. The doublet of broad satellite holes is assigned to an excitonically coupled chlorophyll dimer. The lower-energy holes at ~665 and ~683 nm for chlorophyll b- and chlorophyll a-WSCP, respectively, represent the lower exciton states. Taking into account the parameters of electron-phonon coupling, the lower exciton state can be assigned as the fluorescence origin. The lower exciton state is populated by two processes: (i) exciton relaxation from the higher exciton state and (ii) vibrational relaxation within the lower exciton state. Assuming identical site energies for the two excitonically coupled chlorophyll molecules, the dipole-dipole interaction energy J is directly determined to be 85 and 100 cm(-1) for chlorophyll b- and chlorophyll a-WSCP, respectively, based on the positions of the satellite holes. The Gaussian low-energy absorption band identified by constant fluence hole burning at 4.5 K has a width of ~150 cm(-1) and peaks at 664.9 and 682.7 nm for chlorophyll b- and chlorophyll a-WSCP, respectively. The action spectrum is broader and blue-shifted compared to the fluorescent lower exciton state. This finding can be explained by a slow protein relaxation between energetically inequivalent conformational substates within the lowest exciton state in agreement with the results of Schmitt et al. (J. Phys. Chem. B2008, 112, 13951).

Correlation between structural and luminescent properties of Eu3+-doped ZnO epitaxial layers

We have studied the epitaxial growth and photoluminescent (PL) properties of Eu3+-doped ZnO layers in correlation with structural analyses. Incorporation of Eu3+ ions into a ZnO host resulted in deterioration in crystal quality and lattice distortion. The spectral structure of Eu3+ emission revealed that Eu3+ ions were located at site symmetries lower than the original C3v of the Zn2+ ion sites in a hexagonal wurtzite structure of ZnO, which allowed for efficient red luminescence based on the electric dipole transitions. Moreover, we have found an anticorrelation of PL intensity between the excitonic and Eu3+ emissions, related to energy transfer from the ZnO host to the Eu3+ ions. The excitonic structure at the band edge was obscured upon doping with Eu3+ ions due to the formation of a band tail around 3.2 eV. This correlated with a reduction in excitonic emissions, leading to enhancement of Eu3+ emission. Strong PL emission from Eu3+ ions was only observed at low temperatures, and was remarkably suppressed with increasing temperature due to two types of nonradiative energy transfer paths. For the energy transfer process to Eu3+ ions, we suggest that the recombination energy of an electron–hole pair at the band tail near the band edge is close to that of high-lying excited levels in the Eu3+ 4f shell, providing an efficient energy pathway for the excitation of Eu3+ ions in the ZnO system.

(Invited) Energy Structures of Excitons and Trions in Single-Walled Carbon Nanotubes

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Davydov Splitting of Excitons in Cyclic Bacteriochlorophyll a Nanoaggregates of Bacterial Light‐Harvesting Complexes between 4.5 and 263 K

The nature of electronic excitations created by photon absorption in the cyclic B850 aggregates of 18 bacteriochlorophyll molecules of LH2 antenna complexes of photosynthetic bacteria is studied over a broad temperature range using absorption, fluorescence, and fluorescence anisotropy spectra. The latter technique has been proved to be suitable for revealing the hidden structure of excitons in inhomogeneously broadened spectra of cyclic aggregates. A theoretical model that accounts for differences of absorbing excitons in undeformed and emitting exciton polarons in deformed antenna lattices is also developed. Only a slight decrease of the exciton bandwidth and exciton coupling energy with temperature is observed. Survival of excitons in the whole temperature span from cryogenic to nearly ambient temperatures strongly suggests that collective, coherent electronic excitations might play a role in the functional light-harvesting process taking place at physiological temperatures.

Excitons in semiconducting carbon nanotubes: diameter-dependent photoluminescence spectra

Semiconducting single-walled carbon nanotubes are one-dimensional (1D) quantum nanostructures and their unique optical responses arise from stable 1D excitons with huge binding energies. Here we review recent studies on optical properties of semiconducting carbon nanotubes. The diameter dependence of luminescence spectra and dynamics are revealed by single-nanotube spectroscopy and time-resolved optical spectroscopy. Short-range Coulomb interactions play a crucial role in energy structures of dark, triplet, and charged excitons. Enhanced exciton-exciton interactions in 1D semiconductor nanostructures determine nonlinear optical responses. We present generic configurations of neutral and charged excitons and discuss exciton optics of single-walled carbon nanotubes.

Fine structure and size dependence of exciton and biexciton optical spectra in CdSe nanocrystals

Theory of electronic and optical properties of exciton and bi-exciton complexes confined in CdSe spherical nanocrystals is presented. The electron and hole states are computed using atomistic $sp^3d^5s^*$ tight binding Hamiltonian including an effective crystal field splitting, spin-orbit interactions, and model surface passivation. The optically excited states are expanded in electron-hole configurations and the many-body spectrum is computed in the configuration-interaction approach. Results demonstrate that the low-energy electron spectrum is organized in shells ($s$, $p$, ...), whilst the valence hole spectrum is composed of four low-lying, doubly degenerate states separated from the rest by a gap. As a result, the bi-exciton and exciton spectrum is composed of a manifold of closely lying states, resulting in a fine structure of exciton and bi-exciton spectra. The quasi-degenerate nature of the hole spectrum results in a correlated bi-exciton state, which makes it slowly convergent with basis size. We carry out a systematic study of the exciton and bi-exciton emission spectra as a function of the nanocrystal diameter and find that the interplay of repulsion between constituent excitons and correlation effects results in a change of the sign of bi-exciton binding energy from negative to positive at a critical nanocrystal size.

Band-edge excitons in PbSe nanocrystals and nanorods

We investigate the fine structure of band-edge excitons in PbSe nanocrystals and nanorods using circularly polarized magnetophotoluminescence and optically detected magnetic resonance and, based on the results, propose a singlet-triplet model of exciton photoluminescence from nondegenerate conduction and valence bands. From the data and model we extract $g$-factors for electrons and holes of $+1.2$ and $+0.8$, respectively. The splitting of the triplet ground state, which is responsible for the low-temperature photoluminescence, is $88\text{ }\ensuremath{\mu}\text{eV}$ for nanorods, and less than $20\text{ }\ensuremath{\mu}\text{eV}$ for nanocrystals. The intervalley splitting of the electron and hole levels in the nanocrystals is much larger than the electron-hole exchange interaction.

Unraveling the Structure and Dynamics of Excitons in Semiconductor Quantum Dots

The quantum dot, one of the central materials in nanoscience, is a semiconductor crystal with a physical size on the nanometer length scale. It is often called an "artificial atom" because researchers can create nanostructures which yield properties similar to those of real atoms. By virtue of having a size in between molecules and solids, the quantum dot offers a rich palette for exploring new science and developing novel technologies. Although the physical structure of quantum dots is well known, a clear understanding of the resultant electronic structure and dynamics has remained elusive. However, because the electronic structure and dynamics of the dot, the "excitonics", confer its function in devices such as solar cells, lasers, LEDs, and nonclassical photon sources, a more complete understanding of these properties is critical for device development. In this Account, we use colloidal CdSe dots as a test bed upon which to explore four select issues in excitonic processes in quantum dots. We have developed a state-resolved spectroscopic approach which has yielded precise measurements of the electronic structural dynamics of quantum dots and has made inroads toward creating a unified picture of many of the key dynamic processes in these materials. We focus on four main topics of longstanding interest and controversy: (i) hot exciton relaxation dynamics, (ii) multiexcitons, (iii) optical gain, and (iv) exciton-phonon coupling. Using this state-resolved approach, we reconcile long standing controversies related to phenomena such as exciton cooling and exciton-phonon coupling and make surprising new observations related to optical gain and multiexcitons.

Field-modulation spectroscopy of pentacene thin films using field-effect devices: Reconsideration of the excitonic structure

Field-modulation spectroscopy of pentacene thin films using field-effect devices: Reconsideration of the excitonic structure

Reduction of nonradiative recombination center for ZnO films grown under Zn-rich conditions by metal organic chemical vapor deposition

ZnO films were grown by metalorganic chemical vapor deposition using the repeated temperature modulation in an H2 ambient. The crystalline quality, as defined by the full-width at half-maximum of the ω (101¯1) reflection, was found to be correlated with the photoluminescence (PL) lifetime at 300 K. The fine structure of the PL spectra for the samples grown under Zn-rich condition at 8 K indicated the higher order (n=2) structure of free exciton A, two electron satellites and phonon-replicas. The internal quantum efficiency and the PL lifetime at 300 K were 5.5% and 2.6 ns, respectively, indicating a reduction in Zn vacancies in the ZnO films.

Yb 2 + -doped SrCl2: Electronic structure of impurity states and impurity-trapped excitons

First-principles electronic structure calculations of the excited states of Yb(2+)-doped SrCl(2) crystals up to 65,000 cm(-1) reveal the existence of unexpected excited states with double-well potential energy surfaces and dual electronic structure lying above and very close in energy to the 4f(13)5d manifold, with which they interact strongly through spin-orbit coupling. The double-well energy curves result from avoided crossings between Yb-trapped exciton states (more stable at short Yb-Cl distances) and 4f(13)6s impurity states (more stable at long Yb-Cl distances); the former are found to be preionization states in which the impurity holds the excited electron in close lying empty interstitials located outside the YbCl(8) moiety. Spin-orbit coupling between the double-well states and the lower lying 4f(13)5d impurity states spreads the dual electronic structure character to lower energies and, hence, the instability of the divalent oxidation state is also spread. To some extent, the dual electronic structure (impurity-trapped exciton-impurity state) of some excited states expresses and gives support to hypotheses of interaction between Yb(2+) and Yb(3+) pairs proposed to understand the complex spectroscopy of the material and conciliates these hypotheses with interpretations in terms of the existence of only one type of Yb(2+) defect. The results presented confirm the presence of impurity states of the 4f(13)6s configuration among the 4f(13)5d manifolds, as proposed in literature, but their energies are very different from those assumed. The Yb-trapped excitons found in this chloride host can be seen as precursors of the luminescent Yb-trapped excitons characterized experimentally in the isomorphous SrF(2) crystals.

Quantum entanglement in lateral GaAs/AlGaAs quantum dot molecules

We calculate the excitonic structure of pairs of GaAs/AlGaAs quantum dots forming lateral molecules and obtain the entanglement of exciton states. The following advantages of the lateral geometry over the vertical one are found: (1) The energy structures of the dots forming a molecule can be in principle identical. (2) Comparable tunneling of electrons and holes ensures a high entanglement of antisymmetric excitons. A drawback of existing structures are very low tunneling energies, which make the entanglement vulnerable against differences in the sizes and shapes of both dots.

Lowest Electronic States of the CP47 Antenna Protein Complex of Photosystem II: Simulation of Optical Spectra and Revised Structural Assignments

In this work, we present simulated steady-state absorption, emission, and nonresonant hole burning (HB) spectra for the CP47 antenna complex of photosystem II (PS II) based on fits to recently refined experimental data (Neupane et al. J. Am. Chem. Soc. 2010, 132, 4214). Excitonic simulations are based on the 2.9 Å resolution structure of the PS II core from cyanobacteria (Guskov et al. Nat. Struct. Mol. Biol. 2009, 16, 334), and allow for preliminary assignment of the chlorophylls (Chls) contributing to the lowest excitonic states. The search for realistic site energies was guided by experimental constraints and aided by simple fitting algorithms. The following experimental constraints were used: (i) the oscillator strength of the lowest-energy state should be approximately ≤0.5 Chl equivalents; (ii) the excitonic structure must explain the experimentally observed red-shifted (∼695 nm) emission maximum; and (iii) the excitonic interactions of all states must properly describe the broad (non-line-narrowed, NLN) HB spectrum (including its antihole) whose shape is extremely sensitive to the excitonic structure of the complex, especially the lowest excitonic states. Importantly, our assignments differ significantly from those previously reported by Raszewski and Renger (J. Am. Chem. Soc. 2008, 130, 4431), due primarily to differences in the experimental data simulated. In particular, we find that the lowest state localized on Chl 526 possesses too high of an oscillator strength to fit low-temperature experimental data. Instead, we suggest that Chl 523 most strongly contributes to the lowest excitonic state, with Chl 526 contributing to the second excitonic state. Since the fits of nonresonant holes are more restrictive (in terms of possible site energies) than those of absorption and emission spectra, we suggest that fits of linear optical spectra along with HB spectra provide more realistic site energies.

Effects of symmetry-breaking perturbations on excitonic states bound to systems of reduced symmetry

Using an invariant expansion, we build an Hamiltonian describing the influence of the crystal-field, the electron-hole exchange interaction, and any symmetry-breaking perturbations on the fine structure of excitons bound to systems of reduced symmetry: D2d, C3v, and C2v. Several perturbations are considered, including, but not limited to, an electric field, a magnetic field, a strain field, and their combinations. For each symmetry system considered, symmetrized excitonic wave functions, build from heavy- and light-holes states, are used to expand the Hamiltonian in the form of matrices, whose eigenvalues directly provide the energy of the excitonic states and whose eigenstates can be used to determine oscillator strengths of optical transitions. Using this model, we satisfactorily reproduce the excitonic emission observed from nitrogen dyads in GaAs and tellurium dyads in strained ZnSe. We also present Hamiltonians for independent heavy- and light-hole subsystems. Comparing the two models, we demonstrate that the splitting observed in strained quantum dots of C2v symmetry does not necessarily imply a significant anisotropic exchange interaction. This splitting can be produced by a weak coupling between heavy- and light-hole bands.

A density matrix based approach for studying excitons in organic crystals

A theoretical analysis of molecular excitons in crystalline p-Nitro-Aniline (PNA) is presented. The approach is general and can be straightforwardly extended to the calculation of the exciton structure of other molecular crystals or aggregates. Based on the evaluation of transition density matrices (TDM), the method allows to easily classify the excited states of interacting molecules on the basis of those of the constituent molecules. Exciton couplings of selected dimers within the PNA crystal have been evaluated and the exciton dispersion has been determined. The experimental absorption spectrum of PNA powders can be analysed in details based on the exciton density of states.

Many particle approach to excitons in crystals: Electron–electron and electron–phonon interactions

A many particle system of electrons interacting one with another and also with the crystal lattice vibrations was studied theoretically. The particular diagonalization of the Hamiltonian was fulfilled and it was shown that the structure of bands (exciton structure) in the absorption spectra of the crystal is really the set of electron–phonon maxima. Numerical calculations showed also that full electron bands, valence and conductivity, are responsible for the formation of exciton maxima and even states located far from the edge of zones have significant effect on the occurrence of exciton peaks – which is in disagreement with the effective mass approximation (EMA). The results are compared with known experimental data for wide band ZnO and CdS crystals.

Revisiting the optical properties of the FMO protein

We review the optical properties of the FMO complex as found by spectroscopic studies of the Q y band over the last two decades. This article emphasizes the different methods used, both experimental and theoretical, to elucidate the excitonic structure and dynamics of this pigment–protein complex.Electronic supplementary materialThe online version of this article (doi:10.1007/s11120-010-9540-1) contains supplementary material, which is available to authorized users.

Insight into the Electronic Structure of the CP47 Antenna Protein Complex of Photosystem II: Hole Burning and Fluorescence Study

We report low temperature (T) optical spectra of the isolated CP47 antenna complex from Photosystem II (PSII) with a low-T fluorescence emission maximum near 695 nm and not, as previously reported, at 690-693 nm. The latter emission is suggested to result from three distinct bands: a lowest-state emission band near 695 nm (labeled F1) originating from the lowest-energy excitonic state A1 of intact complexes (located near 693 nm and characterized by very weak oscillator strength) as well as emission peaks near 691 nm (FT1) and 685 nm (FT2) originating from subpopulations of partly destabilized complexes. The observation of the F1 emission is in excellent agreement with the 695 nm emission observed in intact PSII cores and thylakoid membranes. We argue that the band near 684 nm previously observed in singlet-minus-triplet spectra originates from a subpopulation of partially destabilized complexes with lowest-energy traps located near 684 nm in absorption (referred to as AT2) giving rise to FT2 emission. It is demonstrated that varying contributions from the F1, FT1, and FT2 emission bands led to different maxima of fluorescence spectra reported in the literature. The fluorescence spectra are consistent with the zero-phonon hole action spectra obtained in absorption mode, the profiles of the nonresonantly burned holes as a function of fluence, as well as the fluorescence line-narrowed spectra obtained for the Q(y) band. The lowest Q(y) state in absorption band (A1) is characterized by an electron-phonon coupling with the Huang-Rhys factor S of approximately 1 and an inhomogeneous width of approximately 180 cm(-1). The mean phonon frequency of the A1 band is 20 cm(-1). In contrast to previous observations, intact isolated CP47 reveals negligible contribution from the triplet-bottleneck hole, i.e., the AT2 trap. It has been shown that Chls in intact CP47 are connected via efficient excitation energy transfer to the A1 trap near 693 nm and that the position of the fluorescence maximum depends on the burn fluence. That is, the 695 nm fluorescence maximum shifts blue with increasing fluence, in agreement with nonresonant hole burned spectra. The above findings provide important constraints and parameters for future excitonic calculations, which in turn should offer new insight into the excitonic structure and composition of low-energy absorption traps.