We numerically investigate the odd parity states of the green exciton series in cuprous oxide. Taking into account the coupling to the yellow series and especially to the yellow continuum, the green excitons are quasi-bound resonances with a finite lifetime which cannot be described with Hermitian operators. To calculate their positions and linewidths, we use the method of complex-coordinate rotation, leading to a non-Hermitian complex eigenvalue problem. We find that the behavior of the dominant P states is very well approximated by a modified Rydberg formula using a negative quantum defect. The corresponding linewidths induced by the coupling to the yellow continuum decrease with the third power of the principal quantum number.
The recent observation of dipole-allowed $P$-excitons up to principal quantum numbers of $n=25$ in cuprous oxide has given insight into exciton states with unprecedented spectral resolution. While so far the exciton description as a hydrogen-like complex has been sufficient for cubic crystals, we demonstrate here distinct deviations: The breaking of rotational symmetry leads to mixing of high angular momentum $F$- and $H$-excitons with the $P$-excitons so that they can be observed in absorption. The $F$-excitons show a three-fold splitting that depends systematically on $n$, in agreement with …
In this study we analyze the transmission spectrum of a thin plate of Cuprous Oxide in the range of the absorption of the yellow exciton states with the coherent transfer matrix method. We demonstrate that, in contrast to the usual analysis using Beer's law, which turns out to be a rather good approximation only in the spectral region of high principal quantum numbers, a consistent quantitative description over the whole spectral range under consideration is possible. This leads to new and more accurate parameters not only for the Rydberg exciton states, but also for the strengths of indirect …
We experimentally and numerically investigate the exchange interaction of the yellow excitons in cuprous oxide. By varying the material parameters in the numerical calculations, we can interpret experimental findings and understand their origin in the complex band structure and central-cell corrections. In particular, we experimentally observe the reversal of the ortho- and paraexciton for the $2S$ yellow exciton, and explain this phenomenon by an avoided crossing with the green $1S$ orthoexciton in a detailed numerical analysis. Furthermore, we discuss the exchange splitting as a function of …
Excitons with a radius of a few lattice constants can be affected by strong central-cell corrections, leading to significant deviations of the optical spectrum from the hydrogen-like Rydberg series, and also to an enhancement of the exciton mass. We present an approach to this situation based on a lattice model that incorporates the effects of a non-parabolic band structure, short distance corrections to the Coulomb interaction between electrons and holes, spin-orbit and exchange coupling. The lattice model allows for observation of the crossover from large radius Wannier to small radius Frenk…
The various decay mechanisms of excitons in cuprous oxide (Cu2O) are highly sensitive to defects which can relax selection rules. Here we report cryogenic hyperspectral imaging of exciton luminescence from cuprous oxide crystals grown via the floating zone method showing the samples have few defects. Some locations, however, show strain splitting of the 1s orthoexciton triplet polariton luminescence. Strain is reduced by annealing. In addition, annealing causes annihilation of oxygen and copper vacancies, which leads to a negative correlation between luminescence of unlike vacancies.
We present a theoretical calculation of the absorption spectrum of cuprous oxide $\left(\mathrm{Cu_{2}O}\right)$ based on the general theory developed by Y. Toyozawa. An inclusion not only of acoustic phonons but also of optical phonons and of specific properties of the excitons in $\mathrm{Cu_{2}O}$ like the central-cell corrections for the $1S$-exciton allows us to calculate the experimentally observed line widths in experiments by T. Kazimierczuk et al [Nature 514, 343, (2014)] within the same order of magnitude, which demonstrates a clear improvement in comparison to earlier work on this t…
Present paper reports the effect of ZnO additives on humidity and temperature sensing properties of cuprous oxide. The cuprous oxide powder was mixed with 10% and 25% ZnO by weight and these samples were pelletized by using hydraulic pressing machine. The sensing materials were also investigated by Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD). SEM images show morphology and porosity of material. The average particles size of cuprous oxide was found to be 1.2 micron. The sheet like structures of ZnO is evident in micrographs. From XRD all peaks are well identified and crystall…
For an ultra-dense exciton gas in cuprous oxide (Cu$_2$O), exciton-exciton interactions are the dominant cause of exciton decay. This study demonstrates that the accepted Auger recombination model overestimates the exciton decay rate following intense two photon excitation. Two exciton decay is relevant to the search for collective quantum behavior of excitons in bulk systems. These results suggest the existence of a new high density regime of exciton behavior.
Experimental and theoretical investigations of excitons in cuprous oxide have revealed a significant fine-structure splitting of the excitonic Rydberg states caused by a strong impact of the valence band structure. We provide a semiclassical interpretation of that splitting by investigating the classical dynamics of the excitonic electron-hole pair beyond the hydrogen-like model. Considering the slow motion of Rydberg excitons in coordinate space compared to the fast dynamics of quasispin and hole spin we use an adiabatic approach and energy surfaces in momentum space for the computation of th…
We demonstrate that the optical linewidth of Rydberg excitons in Cu2O can be completely explained by scattering with acoustical and optical phonons, whereby the dominant contributions stems from the non-polar optical modes. The consequences for the observation of polariton effects are discussed. We find that an anti-crossing of photon and exciton dispersions exists only for states with main quantum numbers n>28, so polariton effects do not play any role in the experiments reported up to now.
As a potential solution for low-cost efficient solar cells, radial junctions consisting of ZnO nanowires arrays embedded in Cu2O thin films have been theoretically modeled. Calculations have been performed to explore the geometric dependence of performance of such wire-based solar cells. By properly setting material properties and cell dimensions, a reasonable power conversion efficiency of 19.7% can be expected in a material with 2 μm minority carrier diffusion length. The detrimental effects of bulk, interface and contact-related states on solar cell performance have also been studied, from …
Highly excited atoms with an electron moved into a level with large principal quantum number are fascinating hydrogen-like objects. The giant extension of these Rydberg atoms leads to huge interaction effects. Monitoring these interactions has provided novel insights into molecular and condensed matter physics problems on a single quantum level. Excitons, the fundamental optical excitations in semiconductors consisting of a negatively charged electron and a positively charged hole, are the condensed matter analogues of hydrogen. Highly excited excitons with extensions similar to Rydberg atoms …
We investigate and compare experimental and numerical excitonic spectra of the yellow series in cuprous oxide Cu$_2$O in the Voigt configuration and thus partially extend the results from Schweiner et al. [Phys. Rev. B 95, 035202 (2017)], who only considered the Faraday configuration. The main difference between the configurations is given by an additional effective electric field in the Voigt configuration, caused by the motion of the exciton through the magnetic field. This Magneto-Stark effect was already postulated by Gross et al. and Thomas et al. in 1961 [Sov. Phys. Solid State 3, 221 (1…
We theoretically demonstrate the formation of multiple bi-stability regions in the temperature pattern on the interface between a cuprous oxide quantum well and DCM2:CA:PS organic compound. The Frenkel molecular exciton of the DCM2 is brought into resonance with the $1S$ quadrupole Wannier-Mott exciton in the cuprous oxide by "solvatochromism" with CA. The resulting hybrid is thermalized with surrounding helium bath. This leads to strongly non-linear temperature dependence of the laser field detuning from the quadrupole exciton energy band which is associated with the temperature induced red s…
We study the absorption spectra of the yellow excitons in Cu$_2$O in high magnetic fields using polarization-resolved optical absorption measurements with a high frequency resolution. We show that the symmetry of the yellow exciton results in unusual selection rules for the optical absorption of polarized light and that the mixing of ortho- and para- excitons in magnetic field is important. Our calculation of the energies of the yellow exciton series in an arbitrary magnetic field gives an excellent fit to experimental data and allows us to understand the complex structure of excitonic levels …
Phonons are produced when an excited vacancy in cuprous oxide (Cu$_2$O) relaxes. Time resolved luminescence was used to find the excited copper vacancy (acceptor) and oxygen vacancy (donor) trap levels and lifetimes. It was also used to determine the typical energy and number of phonons in the phonon pulses emitted by vacancies. The vacancy properties of cuprous oxide are controlled by several synthesis parameters and by the temperature. We directly demonstrate the absorption of light by oxygen vacancies with transient absorption. Copper and oxygen vacancies behave differently, in part because…
Two of the most striking experimental findings when investigating exciton spectra in cuprous oxide using high-resolution spectroscopy are the observability and the fine structure splitting of $F$ excitons reported by J. Thewes et al. [Phys. Rev. Lett. 115, 027402 (2015)]. These findings show that it is indispensable to account for the complex valence band structure and the cubic symmetry of the solid in the theory of excitons. This is all the more important for magnetoexcitons, where the external magnetic field reduces the symmetry of the system even further. We present the theory of excitons …
The efficiency of third harmonic generation in cuprous oxide was measured. Intensities followed a non-cubic power law which indicates nonperturbative behavior. Polarization anisotropy of the harmonic generation was demonstrated and related to the third order susceptibility. The results will influence the understanding of harmonic generation in centrosymmetric materials and are potentially relevant to device design and the interpretation of exciton behavior.
The electronic transport through Au-(Cu$_{2}$O)$_n$-Au junctions is investigated using first-principles calculations and the nonequilibrium Green's function method. The effect of varying the thickness (i.e., $n$) is studied as well as that of point defects and anion substitution. For all Cu$_{2}$O thicknesses the conductance is more enhanced by bulk-like (in contrast to near-interface) defects, with the exception of O vacancies and Cl substitutional defects. A similar transmission behavior results from Cu deficiency and N substitution, as well as from Cl substitution and N interstitials for th…
Cuprous (I) oxide (Cu_{2}O) based solar cells were fabricated with the use of the electrodeposition technique at nanometre scale, and the structural, morphological and electrical properties were investigated. The Cu_{2}O layers were electrodeposited on crystalline and polycrystalline copper substrates. To complete the Cu_{2}O/Cu(100) and Cu_{2}O/Cu interfaces as the solar cells the top electrodes of silver paste were painted on the rear of Cu_{2}O. The theoretical analysis of the current voltage curve was provided to determine the values of electrical parameters of the most efficient solar cel…
High-lying Rydberg states of Mott-Wannier excitons are receiving considerable interest due to the possibility of adding long-range interactions to the physics of exciton-polaritons. Here, we study Rydberg excitation in bulk synthetic cuprous oxide grown by the optical float zone technique and compare the result with natural samples. X-ray characterization confirms both materials are mostly single crystal, and mid-infrared transmission spectroscopy revealed little difference between synthetic and natural material. The synthetic samples show principal quantum numbers up to $n=10$, exhibit additi…
The observation of giant Rydberg excitons in cuprous oxide $\left(\mathrm{Cu_{2}O}\right)$ up to a principal quantum number of $n=25$ by T.~Kazimierczuk \emph{et al.} [Nature \textbf{514}, 343, (2014)] inevitably raises the question whether these quasi-particles must be described within a multi-polariton framework since excitons and photons are always coupled in the solid. In this paper we present the theory of exciton-polaritons in $\mathrm{Cu_{2}O}$. To this end we extend the Hamiltonian which includes the complete valence band structure, the exchange interaction, and the central-cell correc…
We present a comparative analysis of a 'conventional' phonoriton (coherent superposition of exciton-photon-phonon) and a polariton (coherent exciton-photon superposition) 'weakly' coupled to the LA-phonons bath. Depending on duration of the pumping laser field the phonon-induced decoherence results in two distinct types of excitation. Long ($ms$) laser pumping pulses form an 'equilibrium' polariton. The generic feature here is a pronounced photo-thermal bi-stability. i.e. formation of four distinct branches. Transitions between branches can be achieved by excitation energy fluctuations as smal…
Crystallization of thin film materials by exploiting laser induced crystallization has been advancing for the past four decades. This unique thin film technique has been predominantly used in processing thin film materials made of a single chemical element; however, harnessing this technique to extend its use for thin film materials containing multiple chemical elements (e.g., metal oxides) unlocks applications currently not accessible. In this study, laser crystallization of a Cu2O strip was demonstrated. A continuous-wave laser diode with a micrometer-scale chevron-shaped beam profile (micro…
We report calculated substantial enhancement of the second harmonic generation (SHG) in cuprous oxide crystals resonantly hybridized with an appropriate organic material (DCM2:CA:PS 'solid-state solvent'). The quadrupole origin of the inorganic part of the quadrupole-dipole hybrid provides inversion symmetry breaking and the organic part contributes to the oscillator strength of the hybrid. We show that the enhancement of the SHG, compared to bulk cuprous oxide crystal, is proportional to the ratio of the DCM2 dipole moment and the effective dipole moment of the quadrupole transitions in the c…
We report measurements of the attenuation of a beam of orthoexciton-polaritons by a photoionizing optical probe. Excitons were prepared in a narrow resonance by two photon absorption of a 1.016 eV, 54 ps pulsed light source in cuprous oxide (Cu2O) at 1.4 K. A collinear, 1.165 eV, 54 ps probe delayed by 119 ps was used to measure the photoionization cross section of the excitons. Two photon absorption is quadratic with respect to the intensity of the pump and leads to polariton formation. Ionization is linear with respect to the intensity of the probe. Subsequent carrier recombination is quadra…
Nanostructured metal oxides, such as Cu2O, CeO2, α-Fe2O3, and TiO2 can efficiently mediate photocatalysis for solar-to-chemical energy conversion and pollution remediation. In this contribution, we report a novel approach, dielectric Mie resonance-enhanced photocatalysis, to enhance the catalytic activity of metal oxide photocatalysts. Specifically, we demonstrate that Cu2O nanostructures exhibiting dielectric Mie resonances can exhibit up to an order of magnitude higher photocatalytic rate as compared to Cu2O nanostructures not exhibiting dielectric Mie resonances. Our finite-difference time-…
The complete theoretical description of experimentally observed magnetoexcitons in cuprous oxide has been achieved by F. Schweiner et al [Phys. Rev. B 95, 035202 (2017)], using a complete basis set and taking into account the valence band structure and the cubic symmetry of the solid. Here, we extend these calculations by investigating numerically the autoionising resonances of cuprous oxide in electric fields and in parallel electric and magnetic fields oriented in [001] direction. To this aim we apply the complex-coordinate-rotation method. Complex resonance energies are computed by solving …
We report an experimental investigation on the irradiation of copper thin films with high repetition rate femtosecond laser pulses (1040 nm, 50 MHz), in ambient air and liquid water. We observe a novel, striking phenomenon of chromatic copper oxides (cupric oxide and cuprous oxide) annuli generation. The characteristic features of the chromatic copper oxide annuli are studied by exploiting micro-Raman Spectroscopy, Optical and Scanning Electron Microscopies. In the case of irradiation in water, the seldom investigated effects of the immersion time, after irradiation with a fixed number of puls…
In the work we demonstrate the formation of new type of polariton on the interface between a cuprous oxide slab and a polystyrene micro-sphere placed on the slab. The evanescent field of the resonant whispering gallery mode (WGM) has a substantial gradient, and therefore effectively couples with the quadrupole $1S$ excitons in cuprous oxide. This evanescent polariton has a long life-time ($1.7 ns$), which is determined only by its excitonic component. The polariton lower branch has a well pronounced minimum. This suggests that this excitation can be utilized for BEC. The spatial coherence of t…
Highly-excited states of excitons in cuprous oxide have recently been observed at a record quantum number of up to $n=25$. Here, we evaluate the long-range interactions between pairs of Rydberg excitons in Cu$_2$O, which are due to direct Coulomb forces rather than short-range collisions typically considered for ground state excitons. A full numerical analysis is supplemented by the van der Waals asymptotics at large exciton separations, including the angular dependence of the potential surfaces.
Tuning exciton emission via ferroelectric polarization at a heterogeneous interface between a monolayer transition metal dichalcogenide and a perovskite oxide membrane
Excitation of ionic solids with extreme ultraviolet pulses creates localized core-excitons, which in some cases couple strongly to the lattice. Here, core-excitonic states of magnesium oxide are studied in the time domain at the Mg $\text{L}_{2,3}$ edge with attosecond transient reflectivity spectroscopy. Attosecond pulses trigger the excitation of these short-lived quasiparticles, whose decay is perturbed by time-delayed near infrared optical pulses. Combined with a few-state theoretical model, this reveals that the optical pulse shifts the energy of bright core-exciton states as well as indu…
Cuprous oxide (Cu$_2$O) is a semiconductor with large exciton binding energy and significant technological importance in applications such as photovoltaics and solar water splitting. It is also a superior material system for quantum optics that enabled the observation of two intriguing phenomena, i.e. Rydberg excitons as solid-state analogue to highly-excited atomic states and dense exciton gases showing quantum degeneracy when approaching the phase transition to Bose-Einstein condensation. Previous experiments focused on natural bulk crystals due to major difficulties in growing high-quality …
The Auger recombination in bulk semiconductors can depopulate the charge carriers in a non-radiative way, which, fortunately, only has detrimental impact on optoelectronic device performance under the condition of high carrier density because the restriction arising from concurrent momentum and energy conservation limits the Auger rate. Here, we surprisingly found that the Auger recombination in bulk Fe2O3 films was more efficient than narrow-bandgap high-mobility semiconductors that were supposed to have much higher Auger rate constants than metal oxides. The Auger process in Fe2O3 was ascrib…
Many linked processes occur concurrently in strongly excited semiconductors, such as interband and intraband absorption, scattering of electrons and holes by the heated lattice, Pauli blocking, bandgap renormalization and the formation of Mahan excitons. In this work, we disentangle their dynamics and contributions to the optical response of a ZnO thin film. Using broadband pump-probe ellipsometry, we can directly and unambiguously obtain the real and imaginary part of the transient dielectric function which we compare with first-principles simulations. We find interband and excitonic absorpti…
In correlated oxides the coupling of quasiparticles to other degrees of freedom such as spin and lattice plays critical roles in the emergence of symmetry-breaking quantum ordered states such as high temperature superconductivity. We report a strong lattice coupling of photon induced Hubbard excitonic quasiparticles in spin-orbital coupling Mott insulator Sr2IrO4. Combining time-resolved optical spectroscopy techniques, we further reconstructed spatiotemporal map of the diffusion of quasiparticles via time-dependent coherence analysis of the x-ray Bragg diffraction peak. Due to the unique elec…
Exciton polaritons in atomically-thin transition metal dichalcogenide crystals (monolayer TMDCs) have emerged as a promising candidate to enable topological transport, ultra-efficient laser technologies, and collective quantum phenomena such as polariton condensation and superfluidity at room temperature. However, integrating monolayer TMDCs into high-quality planar microcavities to achieve the required strong coupling between the cavity photons and the TMDC excitons (bound electron-hole pairs) has proven challenging. Previous approaches to integration had to compromise between various adverse…
The Ruddlesden-Popper (RP) homologous series Sr$_{n+1}$Ti$_{n}$O$_{3n+1}$ provides a useful template for the study and control of the effects of dimensionality and quantum confinement on the excited state properties of the complex oxide SrTiO$_3$. We use ab initio many-body perturbation theory within the $GW$ approximation and the Bethe-Salpeter equation approach to calculate quasiparticle energies and absorption spectrum of Sr$_{n+1}$Ti$_{n}$O$_{3n+1}$ for $n=1-5$ and $\infty$. Our computed direct and indirect optical gaps are in excellent agreement with spectroscopic measurements. The calcul…
