Free Exciton Emission Research Articles

Structure and composition evaluation of heavily Ge-doped ZnO nanocrystal films

A series of high quality zinc oxide (ZnO) nanocrystal films doped with Ge at different Ge/Zn molar ratios were synthesized by the sol-gel method, and structural and compositional changes induced by Ge doping in the ZnO films were analyzed by x-ray diffraction, x-ray photoelectron spectroscopy and cathodoluminescence spectroscopy. Heavy Ge doping in ZnO was found to effectively reduce intrinsic defects in the films and suppress free exciton emission and defect-related emissions in the visible green-red region, by the substitution of Ge at Zn sites and the formation of non-radiative deep-level traps (GeZn)+. The generation of such non-radiative traps was found to be suppressed with respect to the dopant increase, because of a reduction in carrier concentration along with a formation of stable defect complex GeZn–VZn at high doping content. The clarification of defect alterations in Ge-doped ZnO lays the foundation of quantitative evaluation of defect effects on the electrical and optical properties for improving the quality of GeZnO devices.

Effect of optical waveguide on photoluminescence polarization in layered material GaSe with millimeter scale

We investigate the photoluminescence (PL) polarization of millimeter-scale GaSe films with 100 nm and 150 µm thicknesses by excitation with linearly and circularly polarized light. Although free exciton emission predominates at 140 K, multiple peaks appear at 30 K owing to the recombination with impurity and/or localized states. Despite the circularly and linearly polarized excitations, the 100-nm-thick GaSe film constantly shows linear polarization in both band-edge and impurity/localized PLs. By rotating the sample geometry, the observed linear polarization is also rotated. This indicates that linear polarization is sensitive to the sample geometry and originates from the optical waveguide effect.

Effects of deposition temperature and ammonia flow on metal-organic chemical vapor deposition of hexagonal boron nitride

The use of metal-organic chemical vapor deposition at high temperature is investigated as a means to produce epitaxial hexagonal boron nitride (hBN) at the wafer scale. Several categories of hBN films were found to exist based upon precursor flows and deposition temperature. Low, intermediate, and high NH3 flow regimes were found to lead to fundamentally different deposition behaviors. The low NH3 flow regimes yielded discolored films of boron sub-nitride. The intermediate NH3 flow regime yielded stoichiometric films that could be deposited as thick films. The high NH3 flow regime yielded self-limited deposition with thicknesses limited to a few mono-layers. A Langmuir-Hinshelwood mechanism is proposed to explain the onset of self-limited behavior for the high NH3 flow regime. Photoluminescence characterization determined that the intermediate and high NH3 flow regimes could be further divided into low and high temperature behaviors with a boundary at 1500 °C. Films deposited with both high NH3 flow and high temperature exhibited room temperature free exciton emission at 210 nm and 215.9 nm.

Two-Dimensional Lead Halide Perovskites Templated by a Conjugated Asymmetric Diammonium.

We report novel two-dimensional lead halide perovskite structures templated by a unique conjugated aromatic dication, N,N-dimethylphenylene-p-diammonium (DPDA). The asymmetrically substituted primary and tertiary ammoniums in DPDA facilitate the formation of two-dimensional network (2DN) perovskite structures incorporating a conjugated dication between the PbX42- (X = Br, I) layers. These 2DN structures of (DPDA)PbI4 and (DPDA)PbBr4 were characterized by single-crystal X-ray diffraction, showing uniquely low distortions in the Pb-X-Pb bond angle for 2D perovskites. The Pb-I-Pb bond angle is very close to ideal (180°) for a 2DN lead iodide perovskite, which can be attributed to the ability of the rigid diammonium DPDA to insert into the PbX62- octahedral pockets. Optical characterization of (DPDA)PbI4 shows an excitonic absorption peak at 2.29 eV (541 nm), which is red-shifted in comparison to similar 2DN lead iodide structures. Temperature-dependent photoluminescence of both compounds reveals both a self-trapped exciton and free exciton emission feature. The reduced exciton absorption energy and emission properties are attributed to the dication-induced structural order of the inorganic PbX42- layers. DFT calculation results suggest mixing of the conjugated organic orbital component in the valence band of these 2DN perovskites. These results demonstrate a rational new strategy to incorporate conjugated organic dications into hybrid perovskites and will spur spectroscopic investigations of these compounds as well as optoelectronic applications.

Time-resolved photoluminescence and photoreflectance spectroscopy of GaN layers grown on SiN-treated sapphire substrate: Optical properties evolution at different growth stages

In this paper, we present a systematic study of the optical properties evolution of GaN films during the complete growth process on SiN-treated sapphire substrates by atmospheric pressure metalorganic vapor phase epitaxy. The growth process was monitored using in-situ laser reflectometry and was interrupted at different stages to obtain the studied samples. The obtained samples were ex-situ characterized by means of photoluminescence (PL), photoreflectance (PR) and time-resolved PL (TRPL) spectroscopies. The PL emission from the samples of the initial growth stages originates from nano-crystallite and defect states due to the 3D growth mode. However, with increasing layer thickness, the 2D growth mode is established, and the PL spectrum is dominated by free-exciton emission. The electric field extracted by applying the Franz-Keldysh oscillation (FKO) theory on the PR spectra shows a trend to decrease as the GaN layer thickness is increased. For fully coalesced layers, the FKO totally disappears, and the PR spectrum is dominated by free-exciton transitions. TRPL measurements demonstrate the contribution of two processes to the PL decay, i.e., fast and slow components. While the slow decay time reveals the same sensitivity to different types of dislocations (twist and tilt mosaics), the fast decay time is more affected by the twist mosaic than by the tilt one.

Calibration on wide-ranging aluminum doping concentrations by photoluminescence in high-quality uncompensated p-type 4H-SiC

Previous work has shown that the concentration of shallow dopants in a semiconductor can be estimated from the photoluminescence (PL) spectrum by comparing the intensity of the bound-to-the-dopant exciton emission to that of the free exciton. In this work, we study the low-temperature PL of high-quality uncompensated Al-doped p-type 4H-SiC and propose algorithms for determining the Al-doping concentration using the ratio of the Al-bound to free-exciton emission. We use three different cryogenic temperatures (2, 41, and 79 K) in order to cover the Al-doping range from mid 1014 cm−3 up to 1018 cm−3. The Al-bound exciton no-phonon lines and the strongest free-exciton replica are used as a measure of the bound- and free-exciton emissions at a given temperature, and clear linear relationships are obtained between their ratio and the Al-concentration at 2, 41, and 79 K. Since nitrogen is a common unintentional donor dopant in SiC, we also discuss the criteria allowing one to determine from the PL spectra whether a sample can be considered as uncompensated or not. Thus, the low-temperature PL provides a convenient non-destructive tool for the evaluation of the Al concentration in 4H-SiC, which probes the concentration locally and, therefore, can also be used for mapping the doping homogeneity.

Impact of Thermal Treatments in Crystalline Reconstruction and Electrical Properties of Diamond Ohmic Contacts Created by Boron Ion Implantation

To obtain p‐type doping of diamond through B ion implantation, thermal treatments are necessary to reconstruct the diamond lattice and to locate B atoms in substitutional lattice positions. The present contribution evaluates by STEM‐EELS and CL spectroscopy the amorphisation of diamond lattice under the B+ bombardment and its subsequent reconstruction after the thermal treatment. In addition, TEM observations allowed localizing the boron spatial distribution. Carbon‐related peaks of EELS spectroscopy shows a nearly complete recovery of the diamond lattice after thermal treatment. Indeed, at 1600 °C, sp2/sp3 ratio in implanted regions changes from 0.56 to 0.18 (0.15 value was measured before implantation). On the other hand, CL spectroscopy reveals how A‐Band and free exciton emission peaks, which are quenched by B+ implantation, recover after annealing. Boron ion implantation was used to create ohmic contacts in two different diamond samples, treated with different annealing velocities. Crystalline reconstruction, evidenced by TEM data explains the related electric behaviour. Nanoscale evidences of amorphisation, lattice reconstruction and dopant activation are presented and discussed in this work.

Substrate engineering for high-quality emission of free and localized excitons from atomic monolayers in hybrid architectures

Atomic monolayers represent a novel class of materials to study localized and free excitons in two dimensions and to engineer optoelectronic devices based on their significant optical response. Here, we investigate the role of the substrate on the photoluminescense response of MoSe$_2$ and WSe$_2$ monolayers exfoliated either on SiO$_2$ or epitaxially grown InGaP substrates. In the case of MoSe$_2$, we observe a significant qualitative modification of the emission spectrum, which is widely dominated by the trion resonance on InGaP substrates. However, the effects of inhomogeneous broadening of the emission features are strongly reduced. Even more strikingly, in sheets of WSe$_2$, we could routinely observe emission lines from localized excitons with linewidths down to the resolution limit of 70\,$\mu$ eV. This is in stark contrast to reference samples featuring WSe$_2$ monolayers on SiO$_2$ surfaces, where the emission spectra from localized defects are widely dominated by spectral diffusion and blinking behaviour. Our experiment outlines the enormous potential of III-V-monolayer hybrid architectures to obtain high quality emission signals from atomic monolayers, which are straight forward to integrate into nanophotonic and integrated optoelectronic devices.

Excitonic Properties of 3D Hybrid Organic-Perovskites

A renewed interest in hybrid organic perovskites (HOPs) has emerged since 2012 following the increase of HOP solar cell efficiency. Despite the impressive performances of the devices, there is still lot of room for improvement. In particular, the development of applications will benefit of a better understanding of the photophysics of HOPs. In this talk, we will discuss about the excitonic properties of CH3NH3PbI3 (MAPI) single crystals at low temperature, and compare them to those of thin polycrystalline films. The main feature is the appearance of a sharp emission line (FWHM ~ 5 meV) at high energy that is attributed to the free exciton signature, and which is completely absent in thin-films. The observation of the free excitonic emission in the low temperature phase allow to monitor the huge thermal broadening due to electron-LO-phonon coupling [1].

Room temperature photoluminescence of mixed titanium-manganese oxides

Titanium-manganese mixed oxides TiO2/MnOx (TMO) were prepared by chemical precipitation of manganese hydroxide on pure nanocrystalline rutile TiO2 particles with subsequent thermal treatment at different temperatures. The morphology, structural and optical properties of TMO samples were investigated using standard XRD, SEM, EDS, XRF, TGA, FT-Raman and UV–vis absorption spectroscopic techniques. The photoluminescence (PL) in TMO was excited by the UV laser pulses (337.1nm). All measurements were carried out at room temperature. Examination of PL spectra revealed that they are strongly dependent on the phase composition and Mn concentration in TMO compounds. The quenching of the PL is connected with the oxygen vacancies in the TMO structure, in particular, the intensity lowering for the near band edge emission at 3.06eV (405nm) and the free exciton emission at 2.92eV (424nm) is interpreted by the non-radiative Auger recombination. The relative increase and decrease in the ratio of PL intensities for UV and visible bands with increasing Mn content (from 9 to 16at%) is explained by the concentration effects.

Sub-bandgap Voltage Electroluminescence and Magneto-oscillations in a WSe2 Light-Emitting van der Waals Heterostructure.

We report on experimental investigations of an electrically driven WSe2 based light-emitting van der Waals heterostructure. We observe a threshold voltage for electroluminescence significantly lower than the corresponding single particle band gap of monolayer WSe2. This observation can be interpreted by considering the Coulomb interaction and a tunneling process involving excitons, well beyond the picture of independent charge carriers. An applied magnetic field reveals pronounced magneto-oscillations in the electroluminescence of the free exciton emission intensity with a 1/B periodicity. This effect is ascribed to a modulation of the tunneling probability resulting from the Landau quantization in the graphene electrodes. A sharp feature in the differential conductance indicates that the Fermi level is pinned and allows for an estimation of the acceptor binding energy.

Strain Gradient Modulated Exciton Evolution and Emission in ZnO Fibers

One-dimensional semiconductor can undergo large deformation including stretching and bending. This homogeneous strain and strain gradient are an easy and effective way to tune the light emission properties and the performance of piezo-phototronic devices. Here, we report that with large strain gradients from 2.1–3.5% μm−1, free-exciton emission was intensified, and the free-exciton interaction (FXI) emission became a prominent FXI-band at the tensile side of the ZnO fiber. These led to an asymmetric variation in energy and intensity along the cross-section as well as a redshift of the total near-band-edge (NBE) emission. This evolution of the exciton emission was directly demonstrated using spatially resolved CL spectrometry combined with an in situ tensile-bending approach at liquid nitrogen temperature for individual fibers and nanowires. A distinctive mechanism of the evolution of exciton emission is proposed: the enhancement of the free-exciton-related emission is attributed to the aggregated free excitons and their interaction in the narrow bandgap in the presence of high bandgap gradients and a transverse piezoelectric field. These results might facilitate new approaches for energy conversion and sensing applications via strained nanowires and fibers.

Bose–Einstein oscillators and the excitation mechanism of free excitons in 2D layered organic–inorganic perovskites

Bose–Einstein oscillators contribute to the anomalous temperature variation of the free-exciton emission energy in 2D layered CH3(CH2)3NH3PbI4perovskite, in which coherent two-photon absorption results in the two-photon photoluminescence.

Narrow Linewidth Excitonic Emission in Organic-Inorganic Lead Iodide Perovskite Single Crystals.

Hybrid perovskite thin films have demonstrated impressive performance for solar energy conversion and optoelectronic applications. However, further progress will benefit from a better knowledge of the intrinsic photophysics of materials. Here, the temperature-dependent emission properties of CH3NH3PbI3 single crystals are investigated and compared to those of thin polycrystalline films by means of steady-state and time-resolved photoluminescence spectroscopy. Single crystals photoluminescence present a sharp excitonic emission at high energy, with full width at half maximum of only 5 meV, assigned to free excitonic recombination. We highlight a strong thermal broadening of the free excitonic emission, due to exciton-LO-phonon coupling. The emission turned to be very short-lived with a subnanosecond dynamics, mainly induced by the fast trapping of the excitons. The free excitonic emission is completely absent of the thin film spectra, which are dominated by trap state bands.

Photoluminescence properties of zinc white: an insight into its emission mechanisms through the study of historical artist materials

While the photophysical properties of ZnO nanostructures have been widely explored, less research has focused on the bulk material present in artist pigments. This study is based on the analysis of historical pastels, representative of artist materials available at the turn of the twentieth century, and of the pure powder pigment as the control sample. The study of the intensity of the photoluminescence emission as a function of the fluence and of the nanosecond and microsecond emission decay kinetic properties allows the elucidation of the emission mechanisms in control ZnO and historical samples containing ZnO. Data suggest that in historical samples the near-band-edge free-exciton photoluminescence emission, typically occurring in the pure semiconductor, is influenced by the interaction of the pigment with surrounding organic binding material. Conversely, crystal defects, typically expected in historical samples following the imperfect synthesis process available at the beginning of the twentieth century, introduce minor modifications to the photoluminescence emission. The study further suggests that zinc carboxylates, detected in all historical samples and known to introduce characteristic groups on the surface of ZnO, could be responsible for changes in emission mechanisms. Research demonstrates how photoluminescence decay kinetics and the study of the dependence of the emission intensity on the fluence are powerful methods for elucidating the nature of the mechanism processes in luminescent semiconductor pigments.

Photoluminescence of transparent glass-ceramics based on ZnO nanocrystals and co-doped with Eu3+, Yb3+ ions

Glasses of the K2OZnOAl2O3SiO2 system co-doped with Eu2O3 and Yb2O3 were prepared by the melt-quenching technique. Transparent zincite (ZnO) glass–ceramics were obtained by secondary heat-treatments at 680–860 °C. At 860 °C, traces of Eu oxyapatite appeared in addition to ZnO nanocrystals. The average crystal size obtained from the X-ray diffraction data was found to range between 14 and 35 nm. Absorption spectra of the initial glasses are composed of an absorption edge and absorption bands due to electronic transitions of Eu3+ ions. With heat-treatment, the absorption edge pronouncedly shifts to the visible spectral range. The luminescence properties of the glass and glass-ceramics were studied by measuring their excitation and emission spectra at 300, 78, and 4.2 K. Strong red emission of Eu3+ ions dominated by the 5D0–7F2 (612 nm) electric dipole transition was detected. Changes in the luminescence properties of the Eu3+-related excitation and emission bands were observed after heat-treatments at 680 °C and 860 °C. The ZnO nanocrystals showed both broad luminescence (400–850 nm) and free-exciton emission near 3.3 eV at room temperature. The upconversion luminescence spectrum of the initial glass was obtained under excitation of the 976 nm laser source.

Review—Hexagonal Boron Nitride Epilayers: Growth, Optical Properties and Device Applications

This paper provides a brief overview on recent advances made in authors’ laboratory in epitaxial growth and optical studies of hexagonal boron nitride (h-BN) epilayers and heterostructures. Photoluminescence spectroscopy has been employed to probe the optical properties of h-BN. It was observed that the near band edge emission of h-BN is unusually high and is more than two orders of magnitude higher than that of high quality AlN epilayers. It was shown that the unique quasi-2D nature induced by the layered structure of h-BN results in high optical absorption and emission. The impurity related and near band-edge transitions in h-BN epilayers were probed for materials synthesized under varying ammonia flow rates. Our results have identified that the most dominant impurities and deep level defects in h-BN epilayers are related to nitrogen vacancies. By growing h-BN under high ammonia flow rates, nitrogen vacancy related defects can be eliminated and epilayers exhibiting pure free exciton emission have been obtained. Deep UV and thermal neutron detectors based on h-BN epilayers were shown to possess unique features. It is our belief that h-BN will lead to many potential applications from deep UV emitters and detectors, radiation detectors, to novel 2D photonic and electronic devices.

Optical and Electric Properties of Cu-Doped ZnO Films Grown on MgO (100) Substrate

This work studied the luminescent and electric properties of Cu-doped ZnO films grown on MgO (100) substrate by plasma-assisted molecular beam epitaxy. The doping quantity was controlled by regulating Cu Kundsen cell temperature. The crystallinity and surface morphology of the Cu-doped ZnO films were characterized by high resolution X-ray diffraction, atomic force microscopy, and scanning electron microscopy. The chemical state and elemental compositions was analyzed by X-ray photoelectron spectroscopy (XPS). The near-band-edge emission (NBE) and defect-related emission (DLE) were analyzed by photoluminescence spectroscopy. The electric properties were determined by Hall measurement and four-point probe measurement. The experimental results revealed that ZnO films grown epitaxially on MgO substrate with (10-10)ZnO//(100)MgO. X-ray rocking curve measurements showed that the (10-10)ZnO reflection exhibits a full width at half maximum value of about 0.7o-1.0o. The XPS analysis showed that the doped copper atoms have a monovalent state in the ZnO films grown at Cu Kundsen cell temperatures lower than 900oC. The amount of Cu incorporation was estimated to be in the range of 1x1019 to 1x1021 atoms/cm3. The NBE peak of the Cu-doped ZnO films can be deconvoluted into three sub-peaks: a free exciton emission at 3.29 eV, a basal-plane stacking fault emission at 3.19 eV, and a third peak at 3.25 eV. The third peak might be related to an acceptor-bound excitons due to the doping of copper, since it disappeared after annealing. Hall measurement indicated that both pure and Cu-doped ZnO films are n-type semiconductor. The electron concentration of undoped ZnO film is 1x1018 cm-3, whereas that of the Cu-doped ZnO films are in the range of 5x1015~5x1016 cm-3. Obviously, the electron concentration of ZnO is compensated by the substitution of Cu+ to Zn2+ which generates acceptor levels. However, the electron concentration of the Cu-doped ZnO films rose back to the order of magnitudes 1018 cm-3 after annealed in oxygen or hygrogen, indicating the acceptor states were eliminated. Moreover, in this study, the incorporation of copper in ZnO does not result in an increase of the yellow-green luminescence.

Effects of MgO buffer annealing on optical and electrical quality of P-MBE grown ZnO films on c-sapphire

Zinc oxide (ZnO) has been attracting much attention because of its potential applications in photonic and optoelectronic devices. In this present study, we investigated the effect of MgO buffer annealing on the optical and electrical quality of P-MBE grown ZnO films on c-sapphire with MgO buffer layer. The optical quality was observed by low-temperature PL (photoluminescence) measurement in the near band edge emission region measured at 10K and at 77K. The emission line located at 3.368eV dominates the spectrum in both samples (ZnO with and without MgO buffer annealing) at 10K and 77K. This emission can be divided into two peaks, 3.367eV and 3.363eV and assigned as I2 (ionized donor bound excitons emission) and I4 (Hydrogen donor related emission), respectively. The relative intensity of these donor bound exactions to free exaction emission of the sample without MgO buffer annealing is greater than that of the sample with MgO buffer annealing. Comparison of the PL spectra of ZnO with and without annealing revealed that the intensity of free exciton emission from the sample with MgO buffer annealing is twice of that from the sample without annealing. We also found that the intensity of deep-level broad emission is reduced by about 1/3 by MgO-buffer annealing. Hence, the decrease of deep level emission intensity and the increase of free exciton emission intensity by annealing of MgO buffer corresponds to the reduction of defects of the ZnO film. The PL properties also suggest that there are fewer nonradiative recombination centers in ZnO layers with MgO buffer annealing than those in ZnO layers grown without MgO buffer annealing. The electrical quality was measured by room temperature Hall measurements. We found that the samples have a background n-type carrier concentration. The ZnO samples with MgO buffer annealing has a carrier concentration of 1.17×1017 cm-3 and Hall mobility of 120 cm2/V.s, while the ZnO sample without MgO buffer annealing has a carrier concentration of 2.63 × 1016 cm-3 and Hall mobility of 105 cm2/V.s. The improvement of electron mobility of ZnO films by MgO buffer annealing is due to a decrease in dislocation density. We conclude that annealing of MgO buffer layer increases the optical and electrical quality of the ZnO films. These results agree with the structural quality as observed by HRXRD.

High-performance diamond radiation detectors produced by lift-off method

For stable semiconductor detector operation under harsh environments, an ideal single-crystal diamond without a charge trapping centre is required. For this study, a self-standing single-crystal CVD diamond was fabricated using a lift-off method. The reduction of charge trapping factors such as structural defects, point defects, and nitrogen impurities, was attempted using 0.2% of low-methane concentration growth and using a full metal seal chamber. A high-quality self-standing diamond with strong free-exciton recombination emission was obtained. Charge collection efficiencies were 100.1% for holes and 99.8% for electrons, provided that and . Energy resolutions were 0.38% for both holes and electrons. We produced a high-performance diamond radiation detector using the productive lift-off method.