Donor-bound Exciton Research Articles

Electrical properties of lightly Ga-doped ZnO nanowires

We investigated the growth, crystal structure, elemental composition and electrical transport characteristics of ZnO nanowires, a promising candidate for optoelectronic applications in the UV-range. Nominally-undoped and Ga-doped ZnO nanowires were grown by metal-organic chemical vapor deposition. Photoluminescence measurements confirmed the incorporation of Ga via donor-bound exciton emission. With atom-probe tomography we estimated an upper limit of the Ga impurity concentration (). We studied the electrical transport characteristics of these nanowires with a W-nanoprobe technique inside a scanning electron microscope and with lithographically-defined contacts allowing back-gated measurements. An increase in apparent resistivity by two orders of magnitude with decreasing radius was measured with both techniques with a much larger distribution width for the nanoprobe method. A drop in the effective carrier concentration and mobility was found with decreasing radius which can be attributed to carrier depletion and enhanced scattering due to surface states. Little evidence of a change in resistivity was observed with Ga doping, which indicates that the concentration of native or background dopants is higher than the Ga doping concentration.

Defect-induced excitonic recombination in TixZn1−xO thin films grown by DC-unbalanced magnetron sputtering

We study the effects of Ti doping on the near-band-edge emission (NBE) and defect-related deep-level emission (DLE) of ZnO thin films grown by DC unbalanced magnetron sputtering. DLE in pure ZnO is contributed by zinc and oxygen vacancies (VZn+VO), as revealed by photoluminescence (PL) spectroscopy, current–voltage (I–V) characteristic measurement, and spectroscopic ellipsometry. The reduction in the number of VZn states is clearly observed upon Ti doping, resulting in the enhancement of green emission from VO. Interestingly, the thin film with a Ti concentration of 1 at. % shows a higher excitonic emission. Furthermore, the temperature dependence of PL spectra shows that the enhanced excitonic emission originates from the donor-bound exciton promoted by the Ti dopant and native VO. This study shows an important role of the defects in controlling the optical and electronic properties of ZnO films for future optoelectronic applications.

Damping of Rabi oscillations in intensity-dependent photon echoes from exciton complexes in a CdTe/(Cd,Mg)Te single quantum well

We study Rabi oscillations detected in the coherent optical response from various exciton complexes in a 20~nm-thick CdTe/(Cd,Mg)Te quantum well using time-resolved photon echoes. In order to evaluate the role of exciton localization and inhomogeneous broadening we use selective excitation with spectrally narrow ps-pulses. We demonstrate that the transient profile of the photon echo from the localized trion (X$^-$) and the donor-bound exciton (D$^0$X) transitions strongly depends on the strength of the first pulse. It acquires a non-Gaussian shape and experiences significant advancement for pulse areas larger than $\pi$ due to non-negligible inhomogeneity-induced dephasing of the oscillators during the optical excitation. Next, we observe that an increase of the area of either the first (excitation) or the second (rephasing) pulse leads to a significant damping of the photon echo signal, which is strongest for the neutral excitons and less pronounced for the donor-bound exciton complex (D$^0$X). The measurements are analyzed using a theoretical model based on the optical Bloch equations which accounts for the inhomogeneity of optical transitions in order to reproduce the complex shape of the photon echo transients. In addition, the spreading of Rabi frequencies within the ensemble due to the spatial variation of the intensity of the focused Gaussian beams and excitation-induced dephasing are required to explain the fading and damping of Rabi oscillations. By analyzing the results of the simulation for the X$^-$ and the D$^0$X complexes we are able to establish a correlation between the degree of localization and the transition dipole moments determined as $\mu($X$^-$)=73~D and $\mu($D$^0$X)=58~D.

High-Resolution Two-Dimensional Optical Spectroscopy of Electron Spins

Multidimensional coherent optical spectroscopy is one of the most powerful tools for investigating complex quantum mechanical systems. While it was conceived decades ago in magnetic resonance spectroscopy using micro- and radio-waves, it has recently been extended into the visible and UV spectral range. However, resolving MHz energy splittings with ultrashort laser pulses has still remained a challenge. Here, we analyze two-dimensional Fourier spectra for resonant optical excitation of resident electrons to localized trions or donor-bound excitons in semiconductor nanostructures subject to a transverse magnetic field. Particular attention is devoted to Raman coherence spectra which allow one to accurately evaluate tiny splittings of the electron ground state and to determine the relaxation times in the electron spin ensemble. A stimulated step-like Raman process induced by a sequence of two laser pulses creates a coherent superposition of the ground state doublet which can be retrieved only optically due to selective excitation of the same sub-ensemble with a third pulse. This provides the unique opportunity to distinguish between different complexes that are closely spaced in energy in an ensemble. The related experimental demonstration is based on photon echo measurements in an n-type CdTe/(Cd,Mg)Te quantum well structure detected by a heterodyne technique. The difference in the sub-$\mu$eV range between the Zeeman splittings of donor-bound electrons and electrons localized at potential fluctuations can be resolved even though the homogeneous linewidth of the optical transitions is larger by two orders of magnitude.

Time-resolved photon echoes from donor-bound excitons in ZnO epitaxial layers

The coherent optical response from 140~nm and 65~nm thick ZnO epitaxial layers is studied using transient four-wave-mixing spectroscopy with picosecond temporal resolution. Resonant excitation of neutral donor-bound excitons results in two-pulse and three-pulse photon echoes. For the donor-bound A exciton (D$^0$X$_\text{A}$) at temperature of 1.8~K we evaluate optical coherence times $T_2=33-50$~ps corresponding to homogeneous linewidths of $13-19~\mu$eV, about two orders of magnitude smaller as compared with the inhomogeneous broadening of the optical transitions. The coherent dynamics is determined mainly by the population decay with time $T_1=30-40$~ps, while pure dephasing is negligible in the studied high quality samples even for strong optical excitation. Temperature increase leads to a significant shortening of $T_2$ due to interaction with acoustic phonons. In contrast, the loss of coherence of the donor-bound B exciton (D$^0$X$_\text{B}$) is significantly faster ($T_2=3.6$~ps) and governed by pure dephasing processes.

Fabrication, Structural Characterization and Optical Properties of Oversized ZnO Microwires

In this paper, large-sized ZnO microwires (MWs) were successfully synthesized without using any catalyst, following a simple chemical vapor deposition (CVD) method. Highly crystalline ZnO MWs of several hundred micrometers length having diameter in the range of 10–40[Formula: see text][Formula: see text]m were obtained. The synthesized MWs showed a hexagonal cross-sectional morphology and the longest MW was found to be 1[Formula: see text]mm long. The structural and optical properties of an individual large sized ZnO MWs were studied. Temperature-dependent photoluminescence (PL) spectra showed emissions for free excitons (FX) and donor-bound excitons (D0X) and decomposition of the D0X into FX was observed beyond 140[Formula: see text]K. The whispering gallery mode (WGM) lasing in an individual ZnO MW was achieved and also confirmed by two-dimensional finite difference time domain (2D-FDTD) method. These oversized ZnO MWs may find potential applications as WGM resonant cavities and optical waveguides.

Thermodynamic behaviors of excitonic emission in ZnO nanorods grown by pulsed laser deposition

We investigated the thermodynamic behaviors of the exciton emission in ZnO nanorods that had been grown by laser ablation. The ZnO nanorods exhibited a clear luminescence peak from the neutral donor-bound exciton (D0X), which persisted near room temperature. Through analyzing temperature-dependences of photoluminescence properties, we found out insignificant thermal-quenching of D0X, arising from the large donor binding energy (i.e., EbD(NR) ~ 51.1 ± 7.3meV). A small discrepancy of EbD(NR) from ZnO bulks’ values (i.e., EbD(Bulk) = 53 – 72meV) is associated with inhomogeneous thermal-broadening factors such as defect-scattering at the surface of the nanorod. Despite of inhomogeneous thermal-broadening, the ZnO nanorods still have a high luminescence efficiency because of the weak homogeneous thermal-broadening effect (i.e., low exciton-phonon coupling).

Nature of the 550 nm emission and d0 ferromagnetism in ZnO nanocrystals revealed by H2O2 etching

Clarifying the origin of green photoluminescence and the room temperature ferromagnetism in ZnO is crucial for its potential application. In this work, we show that the characteristic 368 nm donor-bound exciton and the g = 1.96 electron spin resonance (ESR) signal in ZnO nanocrystals were eliminated after H2O2 oxidation, along with the appearance of 550 nm photoluminescence, unambiguously evidencing the creation of acceptor defects. Meanwhile, the d0 ferromagnetism was significantly enhanced. In combination with the fact that ambient O2 exposure also resulted in a significant boost of ferromagnetism in ZnO particles with different grain sizes, we surmise that adsorbed oxygen facilitates the d0 ferromagnetism in ZnO while VZn causes the 550 nm green emission. This work illustrates that oxygen exposure is an efficient way to tune the physics in metal oxides through engineering defects.

Electron nuclear double resonance with donor-bound excitons in silicon

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.

High-Fidelity and Ultrafast Initialization of a Hole Spin Bound to a Te Isoelectronic Center in ZnSe.

We demonstrate the optical initialization of a hole-spin qubit bound to an isoelectronic center (IC) formed by a pair of Te impurities in ZnSe, an impurity-host system providing high optical homogeneity, large electric dipole moments, and potentially advantageous coherence times. The initialization scheme is based on the spin-preserving tunneling of a resonantly excited donor-bound exciton to a positively charged Te IC, thus forming a positive trion. The radiative decay of the trion within less than 50ps leaves a heavy hole in a well-defined polarization-controlled spin state. The initialization fidelity exceeds 98.5% for an initialization time of less than 150ps.

Selective area growth of high-density GaN nanowire arrays on Si(111) using thin AlN seeding layers

Selective area growth (SAG) of high-density (2.5×109cm−2) GaN nanowires (NWs) on Si(111) substrate by plasma-assisted molecular beam epitaxy is presented. The effects of morphology and thickness of the AlN seeding layer on the quality of SAG GaN NWs are investigated. A thin AlN seeding layer of 30nm thick with a surface roughness of less than 0.5nm is suitable for high quality SAG GaN NWs growth. High-density AlN nanopedestal arrays used as seeds for SAG GaN NWs are fabricated from thin AlN seeding layers using soft nanoimprint lithography. By adjusting the growth temperature and Ga/N flux ratio, hexagonal shaped SAG GaN NWs are realized. The quality of SAG GaN NWs is evaluated by low temperature photoluminescence (PL) measurements. Three major groups of PL peaks at 3.47, 3.45, and 3.41eV are identified. The peak at 3.471eV is related to the neutral donor-bound exciton emission, and the 3.41eV broadband emission is attributed to stacking faults or structural defects. The 3.45eV peak is identified as the emission due to exciton recombination at polar inversion domain boundaries of NWs.

Bright green emission and temperature dependent localized bound exciton transitions from undoped ZnO films

Bright green luminescence is achieved from undoped ZnO films prepared by the reaction of oxygen and zinc powder. The green emission band is considered to be mainly due to the singly ionized oxygen vacancies. Temperature dependence of exciton transitions in the undoped ZnO films has been investigated in the range from 10 to 270K. The PL spectrum at 10K is dominated by neutral donor-bound exciton (D°X) emissions. The dominant emission centered at about 3.303eV at above 45K can be attributed to the localized bound exciton (LBX) transitions related to basal plane stacking faults. LBX transitions can survive up to near room temperature due to the LBX binding energy of 68meV.

The hydride vapor phase epitaxy of GaN on silicon covered by nanostructures

GaN several tens of μm thick has been deposited on a silicon substrate using a two-step hydride vapor phase epitaxy (HVPE) process. The substrates were covered by AlN layers and GaN nanostructures grown by plasma-assisted molecular-beam epitaxy. During the first low-temperature (low-T) HVPE step, stacking faults (SF) form, which show distinct luminescence lines and stripe-like features in the cathodoluminescence images of the cross-section of the layers. These cathodoluminescence features provide an insight into the growth process. During a second high-temperature (high-T) step, the SFs disappear, and the luminescence of this part of the GaN layer is dominated by the donor-bound exciton. For templates consisting of both a thin AlN buffer and GaN nanostructures, the incorporation of silicon into the GaN grown by HVPE is not observed. Moreover, the growth mode of the (high-T) HVPE step depends on the specific structure of the AlN/GaN template, where in the first case, epitaxy is dominated by the formation of slowly growing facets, while in the second case, epitaxy proceeds directly along the c-axis. For templates without GaN nanostructures, cathodoluminescence spectra excited close to the Si/GaN interface show a broadening toward higher energies, indicating the incorporation of silicon at a high dopant level.

Annealing effects on Cd0.96Zn0.04Te crystals with Te inclusions probed by photoluminescence spectroscopy

With effectively improved spectral resolution and signal-to-noise ratio, PL features are well resolved in the Te- and Cd-rich CdZnTe crystals and ascribed to the neutral donor-bound exciton (DX), acceptor-bound exciton (AX), A-center, and deep donor–acceptor pair. A detailed analysis indicates that (i) Cd pressure annealing drives the Te inclusions to the surface region of the crystal, destroys the inclusions by excess Cd atoms, and releases abundant donor-like and acceptor-like impurities; (ii) the PL features of the deep energy levels at 1.30–1.55 eV originate in the A-center consisting Cd vacancy and one type shallow donor, and the PL feature at 1.474 eV is the so-called SA luminescence of a donor–acceptor transition between an A-center and another shallow donor. A quantitative description of the recombination scheme is established, and by which the effects of the annealing are clarified.

High-resolution photoluminescence spectroscopy of Sn-doped ZnO single crystals

Group IV donors in ZnO are poorly understood, despite evidence that they are effective n-type dopants. Here we present high-resolution photoluminescence (PL) spectroscopy studies of unintentionally doped and Sn-doped ZnO single crystals grown by the chemical vapor transport method. Doped samples showed greatly increased emission from the I10 bound exciton transition that was recently proven to be related to the incorporation of Sn impurities based on radio-isotope studies. The PL linewidths are exceptionally sharp for these samples, enabling a clear identification of several donor species. Temperature-dependent PL measurements of the I10 line emission energy and intensity dependence reveal a behavior that is similar to other shallow donors in ZnO. Ionized donor bound-exciton and two-electron satellite transitions of the I10 transition are unambiguously identified and yield a donor binding energy of 71meV. In contrast to recent reports of Ge-related donors in ZnO, the spectroscopic binding energy for the Sn-related donor bound exciton follows a linear relationship with donor binding energy (Haynes rule) similar to recently observed carbon related donors, and confirming the shallow nature of this defect center, which was recently attributed to a SnZn double donor compensated by an unknown single acceptor.

The quadratic Zeeman effect used for state-radius determination in neutral donors and donor bound excitons in Si:P

We have measured the near-infrared photoluminescence spectrum of phosphorus doped silicon (Si:P) and extracted the donor-bound exciton (D0X) energy at magnetic fields up to 28 T. At high field the Zeeman effect is strongly nonlinear because of the diamagnetic shift, also known as the quadratic Zeeman effect (QZE). The magnitude of the QZE is determined by the spatial extent of the wave-function. High field data allows us to extract values for the radius of the neutral donor (D0) ground state, and the light and heavy hole D0X states, all with more than an order of magnitude better precision than previous work. Good agreement was found between the experimental state radius and an effective mass model for D0. The D0X results are much more surprising, and the radius of the mJ = ±3/2 heavy hole is found to be larger than that of the mJ = ±1/2 light hole.

Inhomogeneous nuclear spin polarization induced by helicity-modulated optical excitation of fluorine-bound electron spins in ZnSe

Optically-induced nuclear spin polarization in a fluorine-doped ZnSe epilayer is studied by time-resolved Kerr rotation using resonant excitation of donor-bound excitons. Excitation with helicity-modulated laser pulses results in a transverse nuclear spin polarization, which is detected as a change of the Larmor precession frequency of the donor-bound electron spins. The frequency shift in dependence on the transverse magnetic field exhibits a pronounced dispersion-like shape with resonances at the fields of nuclear magnetic resonance of the constituent zinc and selenium isotopes. It is studied as a function of external parameters, particularly of constant and radio frequency external magnetic fields. The width of the resonance and its shape indicate a strong spatial inhomogeneity of the nuclear spin polarization in the vicinity of a fluorine donor. A mechanism of optically-induced nuclear spin polarization is suggested based on the concept of resonant nuclear spin cooling driven by the inhomogeneous Knight field of the donor-bound electron.

PREPARATION AND PHOTOLUMINESCENCE PROPERTIES OF RF-SPUTTERED ZnO FILMS

<p class="TRANSAffiliation"><span>ZnO/Si films were prepared by radio frequency (RF) magnetron sputtering at room temperature. By optimizing the heat treatment conditions, we obtained a good quality film annealed at 700 ºC for longer 60 minutes. This process was monitored carefully by Raman scattering spectroscopy, and X-ray diffraction. The photoluminescence study on this film revealed that only ultraviolet emissions due to donor-acceptor pair (DAP), neutral acceptor-bound exciton (AºX) and donor-bound exciton (DºX) were observed. The intensity and peak position of these emissions depend on the measurement temperature and excitation power density.</span></p>

Kinetics of self-induced nucleation and optical properties of GaN nanowires grown by plasma-assisted molecular beam epitaxy on amorphous AlxOy

Nucleation kinetics of GaN nanowires (NWs) by molecular beam epitaxy on amorphous AlxOy buffers deposited at low temperature by atomic layer deposition is analyzed. We found that the growth processes on a-AlxOy are very similar to those observed on standard Si(111) substrates, although the presence of the buffer significantly enhances nucleation rate of GaN NWs, which we attribute to a microstructure of the buffer. The nucleation rate was studied vs. the growth temperature in the range of 720–790 °C, which allowed determination of nucleation energy of the NWs on a-AlxOy equal to 6 eV. This value is smaller than 10.2 eV we found under the same conditions on nitridized Si(111) substrates. Optical properties of GaN NWs on a-AlxOy are analyzed as a function of the growth temperature and compared with those on Si(111) substrates. A significant increase of photoluminescence intensity and much longer PL decay times, close to those on silicon substrates, are found for NWs grown at the highest temperature proving their high quality. The samples grown at high temperature have very narrow PL lines. This allowed observation that positions of donor-bound exciton PL line in the NWs grown on a-AlxOy are regularly lower than in samples grown directly on silicon suggesting that oxygen, instead of silicon, is the dominant donor. Moreover, PL spectra suggest that total concentration of donors in GaN NWs grown on a-AlxOy is lower than in those grown under similar conditions on bare Si. This shows that the a-AlxOy buffer efficiently acts as a barrier preventing uptake of silicon from the substrate to GaN.

Interplay of Electron and Nuclear Spin Noise in n-Type GaAs.

We present spin-noise spectroscopy measurements on an ensemble of donor-bound electrons in ultrapure GaAs:Si covering temporal dynamics over 6 orders of magnitude from milliseconds to nanoseconds. The spin-noise spectra detected at the donor-bound exciton transition show the multifaceted dynamical regime of the ubiquitous mutual electron and nuclear spin interaction typical for III-V-based semiconductor systems. The experiment distinctly reveals the finite Overhauser shift of an electron spin precession at zero external magnetic field and a second contribution around zero frequency stemming from the electron spin components parallel to the nuclear spin fluctuations. Moreover, at very low frequencies, features related with time-dependent nuclear spin fluctuations are clearly resolved making it possible to study the intricate nuclear spin dynamics at zero and low magnetic fields. The findings are in agreement with the developed model of electron and nuclear spin noise.