Low-temperature Photoluminescence Research Articles

Morphological and optical characterizations of different ZnO nanostructures grown by mist-CVD

In this study, the effects of growth temperatures, post-growth treatment, and substrate cleaning recipes on structural, morphological, luminescence, and growth kinetics of ZnO nanostructures grown by mist Chemical Vapor Deposition method (mist-CVD) on SiO2/Si substrates are investigated. The grown ZnO nanostructures have polycrystalline wurtzite (wz) hexagonal crystal structure according to X-ray Diffraction (XRD) measurements. However, the lower growth temperature is found to lead to the formation of ZnO nanostructures oriented in the [0002] direction. From Atomic Force Microscope (AFM) measurements, it is seen that the Root Mean Square (RMS) values decrease with decreasing growth temperature. In addition, it is shown that the surface covering is tightly dependent on decreasing growth temperature of the ZnO nanostructures. The hexagonal and triangular pyramid-like ZnO nanostructures are grown on the surface according to the Scanning Electron Microscope (SEM) measurements. The wurtzite type of crystallization is also demonstrated by confocal Raman measurements. The characteristic vibration modes related to Zn and O motion in the lattice are found to be ∼435 cm−1 and ∼100 cm−1, respectively. The luminescence properties are studied by low-temperature (10 K) Photoluminescence (PL) measurements. The spectra are dominated by the transition related to the donor-bound exciton (DBE) with a peak position typically observed at ∼369 nm (3.362 eV) in hexagonal ZnO structures. Defect-related transitions are observed to be strongly correlated with growth temperature and post-growth treatment.

Investigation of Modulation Bandwidth of InGaN Green Micro-LEDs by Varying Quantum Barrier Thickness

InGaN-based micro light-emitting diodes (micro-LEDs) with 5, 10, and 13 nm quantum barrier (QB) thickness were fabricated by metal-organic chemical vapor deposition (MOCVD) to investigate the influence of quantum-confined Stark effect (QCSE) on modulation bandwidth and luminous performance of devices. The room-temperature photoluminescence (PL), low-temperature time-resolved PL (TRPL), and electroluminescence (EL) results show that the decrease of QB thickness is beneficial to reduce QCSE of the device. The thinner QB thickness is good for improving the modulation bandwidth because the thinner QB is more beneficial to increase the total carrier recombination rate, but it is not conducive to the improvement of external quantum efficiency (EQE) due to degraded crystal quality. In addition, the modulation bandwidth of the device was calculated by using ABC model in combination with simulation. The calculation is in good agreement with the measured value. What is more, an optical link using an orthogonal-frequency division multiplexing (OFDM) modulation scheme was demonstrated. The transmission data rate increases with the increase of QB thickness from 1.309 to 1.773 Gbps, even though the modulation bandwidth decreases from 245 to 169 MHz. This work provides a way to balance the quantum efficiency and communication performance of green micro-LEDs.

Low‐Temperature Photoluminescence Investigation of Light‐Induced Degradation in Boron‐Doped CZ Silicon

Light‐induced degradation (LID) in boron‐doped Czochralski grown (CZ) silicon is a severe problem for silicon devices such as solar cells or radiation detectors. Herein, boron‐doped CZ silicon is investigated by low‐temperature photoluminescence (LTPL) spectroscopy. An LID‐related photoluminescence peak is already found while analyzing indium‐doped p‐type silicon samples and is associated with the ASi–Sii defect model. Herein, it is investigated whether a similar peak is present in the spectra of boron‐doped p‐type CZ silicon samples. The presence of change in the photoluminescence signal intensity due to activation of the boron defect is investigated as well. Numerous measurements on boron‐doped samples are made. For this purpose, samples with four different boron doping concentrations are analyzed. The treatments for activation of the boron defect are based on the LID cycle. During an LID cycle, an additional peak or shoulder neither in the areas of the boron‐bound exciton transverse acoustic and nonphonon‐assisted peaks (BTA, BNP) nor in the area of the boron‐bound exciton transverse optical phonon‐assisted peak (BTO) is found. The defect formation also does not lead to a lower photoluminescence (PL) intensity ratio BTO(BE)/ITO(FE).

Indium incorporation at InxGa1-xN relaxed self-assembled nanostructures on Si substrates

In this work, we report on self-assembling of InxGa1-xN nanostructures under strong nitrogen-rich conditions on Si (111) substrates by molecular beam epitaxy. In-situ analysis of the reflection high-energy electron diffraction patterns allowed to follow the strain evolution of the films as well as to monitor the morphological changes related to the In incorporation. Scanning electron microscopy and atomic force microscopy images of the samples evidenced the growth of different nanostructures such as nanocolumns and nanowalls depending on the In content. X-ray diffraction (XRD) measurements allowed to determine the indium concentration while Rutherford backscattering spectrometry (RBS) was used to obtain the composition and thickness of the films and to explore the way in which In and Ga atoms are incorporated in the InxGa1-xN ternary alloy. XRD and RBS complementary analysis suggests that phase separation, occurring at the higher indium concentration, induces both the In and Ga rich phases segregation towards the external surface of the growths. Therefore, the columnar surface arrangement observed on the extreme binary compounds is transformed into separated nanowalls as the indium content increases. The probable origin of this morphology change is discussed. A shift towards lower energies of the low temperature photoluminescence spectra was observed for increased In concentration and a value of the bowing band gap parameter of about 3 was estimated using the extrema binary compounds and the intermediated indium concentration samples.

Unveiling the phonon effect on the narrow-band deep-red emission from solution-combustion synthesized Mn4+ doped CaYAlO4 microcrystals

In this study, we report a unique solution-combustion synthesis of Mn4+ doped CaYAlO4 microcrystals and demonstrate a narrow-band deep-red emission. Through the simulation of low-temperature photoluminescence (PL) spectroscopy and theoretical fitting on temperature-dependent PL intensity at T < 400 K, we obtained a dominant phonon mode with energy of 40 meV during the vibronic coupling process, with a small Huang-Rhys factor of S= 0.68. From the analysis of the measured PL lifetime evolution of Mn4 + doped CaYAlO4, it is found that luminescence thermal quenching effect was mainly attributed to four-dominant phonon interaction with Mn4+ electronic states. More interestingly, the deviation of luminescence decay curve from the single-exponential mode at T > 400 K suggests that the occurrence of two radiative transitions is a consequence of ionically thermal excitation to the second excited state of 4T2. These findings provide not only a general approach to identify the predominant phonon vibration, but also deep insights into the effect of weak electron-phonon coupling on PL properties of solid-state luminescent.

Selective Area Epitaxy of GaN Nanowires on Si Substrates Using Microsphere Lithography: Experiment and Theory.

GaN nanowires were grown using selective area plasma-assisted molecular beam epitaxy on SiOx/Si(111) substrates patterned with microsphere lithography. For the first time, the temperature–Ga/N2 flux ratio map was established for selective area epitaxy of GaN nanowires. It is shown that the growth selectivity for GaN nanowires without any parasitic growth on a silica mask can be obtained in a relatively narrow range of substrate temperatures and Ga/N2 flux ratios. A model was developed that explains the selective growth range, which appeared to be highly sensitive to the growth temperature and Ga flux, as well as to the radius and pitch of the patterned pinholes. High crystal quality in the GaN nanowires was confirmed through low-temperature photoluminescence measurements.

Selectively Strong Coupling of MoS2 Excitons to a Metamaterial at Room Temperature

Light emitters in the vicinity of a hyperbolic metamaterial (HMM) show a range of quantum optical phenomena from spontaneous decay-rate enhancement to strong coupling. In this study, we integrate a monolayer molybdenum disulfide (${\mathrm{Mo}\mathrm{S}}_{2}$) emitter in the near-field region of the HMM. The ${\mathrm{Mo}\mathrm{S}}_{2}$ monolayer has $A$ and $B$ excitons, which emit in the red region of the visible spectrum. We find that the $B$ excitons couple to the HMM differently compared to $A$ excitons. The fabricated HMM transforms to a hyperbolic dispersive medium at 2.14 eV, from an elliptical dispersive medium. The selective coupling of $B$ excitons to the HMM modes is attributed to the inbuilt field gradient of the transition. The $B$ exciton energy lies close to the transition point of the HMM, relative to the $A$ exciton. So, the HMM modes couple more to the $B$ excitons and the metamaterial functions as a selective coupler. The coupling strength calculations show that coupling is 2.5 times stronger for $B$ excitons relative to $A$ excitons. High near field of HMM, large magnitude, and the in-plane transition dipole moment of ${\mathrm{Mo}\mathrm{S}}_{2}$ excitons, result in strong coupling of $B$ excitons and formation of hybrid light-matter states. The measured differential reflection and photoluminescence spectra indicate the presence of hybrid light-matter states, i.e., exciton polaritons. Rabi splitting of $143.5\phantom{\rule{0.2em}{0ex}}\mathrm{meV}\ifmmode\pm\else\textpm\fi{}14.4$ meV at room temperature is observed. The low-temperature photoluminescence measurement shows mode anticrossing, which is a characteristic feature of hybrid states. Our results show that the HMM works as an energy-selective coupler for multiexcitonic systems as ${\mathrm{Mo}\mathrm{S}}_{2}$.

Yellow to green excitonic emission of nearly lattice-matched Zn1−zCdzSe/Zn1−xCdxSe/Zn1−yMgySe (z > x) quantum wells grown on GaAs(0 0 1)

We report the results obtained from the design, epitaxial elaboration, and characterization of nearly lattice matched ZnCdSe quantum wells (QWs) with ZnMgSe barriers, specifically designed with emission in selected wavelengths in the yellow-green spectral range. The quantum wells were deposited on ZnSe/GaAs(0 0 1); ZnSe and ZnMgSe materials were grown by molecular beam epitaxy and ZnCdSe by submonolayer pulsed beam epitaxy in a sequential layer-by-layer mode. The three ZnCdSe layers of the QWs consist of a central region with i monolayers, 3 ≤ i ≤ 7, of Zn1−zCdzSe and at each side are 8 monolayers of Zn1−xCdxSe with Cd contents such that x < z in order to obtain a staggered potential. The barriers are made of Zn1−yMgySe adjusting the composition for lattice matching to the lateral regions of Zn1−xCdxSe, then, only the central quantum well region is lattice mismatched. The low temperature photoluminescence spectra of the QW heterostructures with 3, 4, 6 and 7 MLs central regions of Zn1−zCdzSe (z ∼ 0.77 ± 0.02) surrounded at each side by 8 MLs thick Zn1−xCdxSe layers (x = 0.25) presented excitonic emission at 14 K around 2.337, 2.292, 2.197 and 2.176 eV, respectively, that are in very good agreement with the model calculations. The only modification of the heterostructures was the layer thickness of the central region, indicating the feasibility of these QWs with minimized strain for excitonic emission in the yellow-green spectral region.

Evaluation of crystalline quality of traveling heater method (THM) grown Cd0.9Zn0.1Te0.98Se0.02 crystals

Because of its excellent opto-electronic properties, CdZnTe (CZT) has been the material of choice for x- and gamma-ray detectors operable at room temperature. CZT is the leading commercially available room-temperature radiation detector material today. Although much progress has been made over the past three decades, today's CZT crystals still face certain challenges, especially the presence of the performance-limiting materials defects and the associated relatively high production cost. In this regard, CdxZn1−xTeySe1−y (CZTS) is emerging as a next-generation compound semiconductor, which overcomes some of the limitations of CZT technology for the stated applications. Here, we conducted a study to evaluate the crystalline quality of the traveling heater method grown CZTS with an optimized alloy composition, i.e., Cd0.9Zn0.1Te0.98Se0.02. The as-grown samples were evaluated by low-temperature photoluminescence (PL) spectroscopy and high-resolution x-ray diffraction using the synchrotron light source at Brookhaven National Laboratory. The full width at half maximum of both the PL and x-ray rocking curves was observed to be broadened due to the lattice disorder of the quaternary compound, eventually degrading the crystalline quality. This was consistent with density functional theory calculations.

Low-temperature recombination luminescence of La-doped Ca2SnO4

Low-temperature ultraviolet-excited photoluminescence (PL) and recombination luminescence (RL) properties of La-doped Ca2SnO4 have been investigated by luminescence, electron paramagnetic resonance (EPR) and optically-detected magnetic resonance (ODMR) techniques. Two PL and RL bands at 340 nm and 450 nm have been observed. PL excitation spectra measurements with a synchrotron source showed a significant difference between the 450 nm and the 340 nm PL bands. The 450 nm band has a long-lasting hyperbolic decay, while the 350 nm band shows a fast decay. Assuming an excitonic nature of the 340 nm band, the band gap of the Ca2SnO4:La has been estimated to be approximately 5.5 eV. ODMR measurements suggest that the low-temperature RL band at 450 nm is caused by tunnelling recombination of electron trap and hole trap centres, and the recombination energy is transferred to Sn2+ luminescence centres.

Carrier localization effect in the photoluminescence of In composition engineered InAlAs random alloy

Detailed spectral structures in the low-temperature photoluminescence (3.5 K) of an InAlAs random alloy grown by molecular beam epitaxy on an InP substrate were studied, with three clearly distinguished emission peaks. Based on the temperature-dependent photoluminescence measurements, the two peaks at 1.5404 and 1.5229 eV are localized state emissions, and the one at 1.4916 eV is likely caused by longitudinal optical (LO) phonon replica. The peak assignments are also supported by excitation intensity-dependent photoluminescence spectrum and Raman spectrum measurements. The peak at 1.5229 eV shows a strongly localized behavior evidenced by the typical inverted S-shaped variation of the peak position with respect to increased temperatures which can be well described by the localized-state ensemble (LSE) model. A localization energy of around 19.8 meV is determined for the 1.5229 eV emission at 3.5 K. The temporal behaviors of these emissions at 3.5 K were also discussed based on the time-resolved photoluminescence spectra. The findings here unveil the characteristics of the localized states in the InAlAs alloy and may be useful for developing optoelectronic devices in the near IR region.

TiO2-X mesoporous nanospheres/BiOI nanosheets S-scheme heterostructure for high efficiency, stable and unbiased photocatalytic hydrogen production

The efficiency of hydrogen production via semiconductor photocatalysts is currently limited by poorly light adsorption, rapid recombination of photogenerated carriers, ineffective surface catalytic behavior, and field-instability. Herein, a hierarchical S-scheme photocatalyst composite of BiOI nanosheets (NS) with Ti3+ self-doped black TiO2-X mesoporous nanospheres (MS) was prepared, from which we observed an improve light utilization, as well as the accelerated separation and migration of photogenerated carriers. Furthermore, the optimized TiO2-X/BiOI heterostructure exhibited a robust H2 evolution rate of 794.28 μmol g−1h−1, which was approximately 9.2 and 3 times that of pure BiOI NS and TiO2 MS, respectively. The photocatalytic mechanism of S-scheme heterostructure between black TiO2-X and BiOI was proposed by combining upconversion spectrum, low temperature photoluminescence spectrum and theoretical calculations. This work provides not only a facile synthetic method to prepare the heterojunction structures with high catalytic activity, but also establishes a platform for future materials-by-design with S-scheme energy band structures.

Revealing the vertical structure of in-situ fabricated perovskite nanocrystals films toward efficient pure red light-emitting diodes

The development of efficient perovskite light-emitting diodes (PeLEDs) relies strongly on the fabrication of perovskite films with rationally designed structures (grain size, composition, surface, etc.). Therefore, an understanding of structure-performance relationships is of vital importance for developing high-performance perovskite devices, particularly for devices with in-situ fabricated perovskite nanocrystal films. In this study, we reveal the vertical structure of an in-situ fabricated quasi-two-dimensional perovskite film. By combining time-of-flight secondary ion mass spectrometry, energy dispersive spectroscopy, grazing incidence wide-angle X-ray scattering (GIWAXS), and low-temperature photoluminescence spectra, we illustrate that the resulting in-situ fabricated DPPA2Csn-1Pbn(Br0.3I0.7)3n+1 (DPPA+: 3,3-diphenylpropylammonium) film has a gradient structure with a very thin layer of ligands on the surface, predominantly small-n domains at the top, and predominantly large-n domains at the bottom owing to the solubility difference of the precursors. In addition, GIWAXS measurements show that the domain of n = 2 on the top layer has an ordered in-plane alignment. Based on the understanding of the film structure, we developed an in-situ fabrication process with ligand exchange to achieve efficient pure red PeLEDs at 638 nm with an average external quantum efficiency (EQE) of 7.4%. The optimized device had a maximum luminance of 623 cd/m2 with a peak EQE of 9.7%.

Optically pumped low-threshold microdisk lasers on a GeSn-on-insulator substrate with reduced defect density

Despite the recent success of GeSn infrared lasers, the high lasing threshold currently limits their integration into practical applications. While structural defects in epitaxial GeSn layers have been identified as one of the major bottlenecks towards low-threshold GeSn lasers, the effect of defects on the lasing threshold has not been well studied yet. Herein, we experimentally demonstrate that the reduced defect density in a GeSn-on-insulator substrate improves the lasing threshold significantly. We first present a method of obtaining high-quality GeSn-on-insulator layers using low-temperature direct bonding and chemical–mechanical polishing. Low-temperature photoluminescence measurements reveal that the reduced defect density in GeSn-on-insulator leads to enhanced spontaneous emission and a reduced lasing threshold by ∼ 10 times and ∼ 6 times, respectively. Our result presents a new path towards pushing the performance of GeSn lasers to the limit.

Passivation efficacy study of Al2O3 dielectric on self-catalyzed molecular beam epitaxially grown GaAs1-x Sb x nanowires

This work evaluates the passivation efficacy of thermal atomic layer deposited (ALD) Al2O3 dielectric layer on self-catalyzed GaAs1-x Sb x nanowires (NWs) grown using molecular beam epitaxy. A detailed assessment of surface chemical composition and optical properties of Al2O3 passivated NWs with and without prior sulfur treatment were studied and compared to as-grown samples using x-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and low-temperature photoluminescence (PL) spectroscopy. The XPS measurements reveal that prior sulfur treatment followed by Al2O3 ALD deposition abates III–V native oxides from the NW surface. However, the degradation in 4K-PL intensity by an order of magnitude observed for NWs with Al2O3 shell layer compared to the as-grown NWs, irrespective of prior sulfur treatment, suggests the formation of defect states at the NW/dielectric interface contributing to non-radiative recombination centers. This is corroborated by the Raman spectral broadening of LO and TO Raman modes, increased background scattering, and redshift observed for Al2O3 deposited NWs relative to the as-grown. Thus, our work seems to indicate the unsuitability of ALD deposited Al2O3 as a passivation layer for GaAsSb NWs.

Photoluminescence Induced by Substitutional Nitrogen in Single-Layer Tungsten Disulfide.

The electronic and optical properties of two-dimensional materials can be strongly influenced by defects, some of which can find significant implementations, such as controllable doping, prolonged valley lifetime, and single-photon emissions. In this work, we demonstrate that defects created by remote N2 plasma exposure in single-layer WS2 can induce a distinct low-energy photoluminescence (PL) peak at 1.59 eV, which is in sharp contrast to that caused by remote Ar plasma. This PL peak has a critical requirement on the N2 plasma exposure dose, which is strongest for WS2 with about 2.0% sulfur deficiencies (including substitutions and vacancies) and vanishes at 5.6% or higher sulfur deficiencies. Both experiments and first-principles calculations suggest that this 1.59 eV PL peak is caused by defects related to the sulfur substitutions by nitrogen, even though low-temperature PL measurements also reveal that not all the sulfur vacancies are remedied by the substitutional nitrogen. The distinct low-energy PL peak suggests that the substitutional nitrogen defect in single-layer WS2 can potentially serve as an isolated artificial atom for creating single-photon emitters, and its intensity can also be used to monitor the doping concentrations of substitutional nitrogen.

100 Mev Ag and 25 Kev He Induced Defects in 4H-SiC

We demonstrate the formation of radiative defects, known as color centres, in 100 MeV Ag and 25 keV He irradiated semi-insulating 4H-SiC using low-temperature (~77 K) photoluminescence (PL). In PL, the luminescence resulting from radiative recombination of photo-excited carriers (electrons and holes) is studied. In our work, a 266 nm deep UV excitation source is utilized for performing PL measurements. In the range, 850-1150 nm, the photoluminescent peaks ascribed to silicon vacancies (V Si) and unknown defect-related bands (UD3 and UD4) are observed after both ion irradiations. It has also been observed that till an optimum irradiation fluence there is an enhancement of photoluminescence from the ion irradiation-induced defects but further increase in irradiation fluence results in accumulation of photo-absorbing defects, providing pathways for non-radiative processes. In addition, ion irradiation has been shown to suppress the undesirable luminescence in the range 300-600 nm caused by the intrinsic defects in as-grown 4H-SiC.

Reduced Recombination and Improved Performance of CdSe/CdTe Solar Cells due to Cu Migration Induced by Light Soaking.

The performance of CdTe solar cells has advanced impressively in recent years with the incorporation of Se. Instabilities associated with light soaking and copper reorganization have been extensively examined for the previous generation of CdS/CdTe solar cells, but instabilities in Cu-doped Se-alloyed CdTe devices remain relatively unexplored. In this work, we fabricated a range of CdSe/CdTe solar cells by sputtering CdSe layers with thicknesses of 100, 120, 150, 180, and 200 nm on transparent oxide-coated glass and then depositing CdTe by close-spaced sublimation. After CdCl2 annealing, Cu-doping, and back metal deposition, a variety of analyses were performed both before and after light soaking to understand the changes in device performance. The device efficiency was degraded with light soaking in most cases, but devices fabricated with a CdSe layer thickness of 120 nm showed reasonably good efficiency initially (13.5%) and a dramatic improvement with light soaking (16.5%). The efficiency improvement is examined within the context of Cu ion reorganization that is well known for CdS/CdTe devices. Low-temperature photoluminescence data and Voc versus temperature measurements indicate a reduction in nonradiative recombination due to the passivation of defects and defect complexes in the graded CdSexTe1-x layer.

UV-Activated NO2 Gas Sensing by Nanocrystalline ZnO: Mechanistic Insights from Mass Spectrometry Investigations

In this work, the photostimulated processes of O2 and NO2 molecules with the surface of ZnO under UV radiation were studied by in situ mass spectrometry in the temperature range of 30–100 ∘C. Nanocrystalline needle-like ZnO was synthesized by decomposition of basic zinc carbonate at 300 ∘C, and the surface concentration of oxygen vacancies in it were controlled by reductive post-annealing in an inert gas at 170 ∘C. The synthesized materials were characterized by XRD, SEM, low-temperature nitrogen adsorption (BET), XPS, Raman spectroscopy, and PL spectroscopy. Irradiation of samples with UV light causes the photoabsorption of both O2 and NO2. The photoadsorption properties of ZnO are compared with its defective structure and gas-sensitive properties to NO2. A model of the sensor response of ZnO to NO2 under UV photoactivation is proposed.

Magnon-Coupled Intralayer Moiré Trion in Monolayer Semiconductor-Antiferromagnet Heterostructures.

Moiré fringe patterns created by stacking different 2D layered materials as artificial van der Waals (vdW) heterostructures have become a novel platform to study and engineer optically generated excitonic properties. The moiré patterns contribute to the formation of spatially ordered excitonic states (excitons and trions), which can be used in the quantum simulation of many-body systems and ensembles of coherent quantum light emitters. The intriguing moiré excitonic properties are affected by and controlled via the interaction with magnetic elements. Here, a moiré excitonic system interacting with the magnetic elementary excitation of antiferromagnetic orders in MoSe2 /MnPS3 vdW heterostructures is reported. The low-temperature photoluminescence spectra with additional fine spectral structures on the low-energy side, which are coupled magnon-trion peaks below the Néel temperature of MnPS3 , are carefully investigated. The fine spectral structures with long lifetime and coherence time are assigned to intralayer trion-magnon complexes trapped in the moiré potentials (moiré trion-magnon complexes). These findings highlight the emergence of moiré trion-magnon complexes and provide a new way to explore novel quantum phenomena in moiré excitonic systems with magnetic functionalities.