Photoreflectance Measurements Research Articles

Raman scattering study on dilute nitride-bismide GaNAsBi alloys: behavior of photo-excited LO phonon-plasmon coupled mode

We present a Raman scattering study of as-grown and annealed GaAsBi, GaNAs, and GaNAsBi epilayers grown by plasma-assisted molecular beam epitaxy. In particular, photo-excited longitudinal optical phonon-plasmon-coupled (LOPC) modes were investigated using excitation power-dependent measurements. The optical properties of the samples were characterized by photoluminescence and photoreflectance measurements. From Raman scattering, local vibrational modes and disordered activated modes originating from N- and Bi-alloying were confirmed. The strong photo-excited LOPC modes observed in GaAsBi can be attributed to hole trapping caused by the Bi-induced shallow localized states. The weak photo-excited LOPC modes observed in the as-grown GaNAs and GaNAsBi indicate rapid carrier trapping owing to the high defect density in these dilute nitride alloys. After thermal annealing of GaNAs and GaNAsBi, the heavily damped photo-excited LOPC modes were observed, which can be explained by the low electron mobilities related to the N-induced shallow localized states.

Band-gap and strain engineering in GeSn alloys using post-growth pulsed laser melting

The pseudomorphic growth of Ge1−x Sn x on Ge causes in-plane compressive strain, which degrades the superior properties of the Ge1−x Sn x alloys. Therefore, efficient strain engineering is required. In this article, we present strain and band-gap engineering in Ge1−x Sn x alloys grown on Ge a virtual substrate using post-growth nanosecond pulsed laser melting (PLM). Micro-Raman and x-ray diffraction (XRD) show that the initial in-plane compressive strain is removed. Moreover, for PLM energy densities higher than 0.5 J cm−2, the Ge0.89Sn0.11 layer becomes tensile strained. Simultaneously, as revealed by Rutherford Backscattering spectrometry, cross-sectional transmission electron microscopy investigations and XRD the crystalline quality and Sn-distribution in PLM-treated Ge0.89Sn0.11 layers are only slightly affected. Additionally, the change of the band structure after PLM is confirmed by low-temperature photoreflectance measurements. The presented results prove that post-growth ns-range PLM is an effective way for band-gap and strain engineering in highly-mismatched alloys.

Photoreflectance system based on vacuum ultraviolet laser at 177.3 nm

Photoreflectance (PR) spectroscopy is a powerful and non-destructive experimental technique to explore interband transitions of semiconductors. In most PR systems, the photon energy of the pumping beam is usually chosen to be higher than the bandgap energy of the sample. To the best of our knowledge, the highest energy of pumping laser in reported PR systems is 5.08 eV (244 nm), not yet in the vacuum ultraviolet (VUV) region. In this work, we report the design and construction of a PR system pumped by VUV laser of 7.0 eV (177.3 nm). At the same time, dual-modulated technique is applied and a dual channel lock-in-amplifier is integrated into the system for efficient PR measurement. The system’s performance is verified by the PR spectroscopy measurement of well-studied semiconductors, which testifies its ability to probe critical-point energies of the electronic band in semiconductors from ultraviolet to near-infrared spectral region.

Influence of interface states on built-in electric field and diamagnetic-Landau energy shifts in asymmetric modulation-doped InGaAs/GaAs QWs

The impact of interface defect states on the recombination and transport properties of charges in asymmetric modulation-doped InGaAs/GaAs quantum wells (QWs) is investigated. Three sets of high-mobility InGaAs QW structures are systematically designed and grown by the metal-organic vapor phase epitaxy technique to probe the effect of carrier localization on the electro-optical processes. In these structures, a built-in electric field drifts electrons and holes towards the opposite hetero-junctions of the QW, where their capture/recapture processes are assessed by temperature-dependent photoreflectance, photoluminescence, and photoconductivity measurements. The strength of the electric field in the structures is estimated from the Franz Keldysh oscillations observed in the photoreflectance spectra. The effects of the charge carrier localization at the interfaces lead to a reduction of the net electric field at a low temperature. Given this, the magnetic field is used to re-distribute the charge carriers and help in suppressing the effect of interface defect states, which results in a simultaneous increase in luminescence and photoconductivity signals. The in-plane confinement of charge carriers in QW by the applied magnetic field is therefore used to compensate the localization effects caused due to the built-in electric field. Subsequently, it is proposed that under the presence of large interface defect states, a magnetic field-driven diamagnetic-Landau shift can be used to estimate the fundamental parameters of charge carriers from the magneto-photoconductivity spectra instead of magneto-photoluminescence spectra. The present investigation would be beneficial for the development of high mobility optoelectronic and spin photonic devices in the field of nano-technology.

Electronic and optical properties of SixGe1−x−ySny alloys lattice-matched to Ge

We present a combined experimental and theoretical analysis of the evolution of the near-band gap electronic and optical properties of Si$_{x}$Ge$_{1-x-y}$Sn$_{y}$ alloys lattice-matched to Ge and GaAs substrates. We perform photoreflectance (PR) and photoluminescence (PL) measurements on Si$_{x}$Ge$_{1-x-y}$Sn$_{y}$ epitaxial layers grown via chemical vapour deposition, for Si (Sn) compositions up to $x =$ 9.6% ($y =$ 2.5%). Our measurements indicate the presence of an indirect fundamental band gap, with PL observed $\approx$ 200-250 meV lower in energy than the direct $E_0$ transition identified by PR measurements. The measured PL is Ge-like, suggesting that the alloy conduction band (CB) edge is primarily derived from the Ge L-point CB minimum. Interpretation of the PR and PL measurements is supported by atomistic electronic structure calculations. Effective alloy band structures calculated via density functional theory confirm the presence of an indirect fundamental band gap, and reveal the origin of the observed inhomogeneous broadening of the measured optical spectra as being alloy-induced band hybridisation occurring close in energy to the CB edge. To analyze the evolution of the band gap, semi-empirical tight-binding (TB) calculations are employed to enable calculations for large supercell sizes. TB calculations reveal that the alloy CB edge is hybridized in nature, consisting at low Si and Sn compositions of an admixture of Ge L-, $\Gamma$- and X-point CB edge states, and confirm that the alloy CB edge retains primarily Ge L-point CB edge character. Our experimental measurements and theoretical calculations confirm a direct transition energy close to 1 eV in magnitude for Si and Sn compositions $x =$ 6.8 - 9.6% and $y =$ 1.6 - 2.2%.

Design and growth of InAsP metamorphic buffers for InGaAs thermophotovoltaic cells

The structural and optical properties of InAsxP1-x metamorphic buffers grown by metal–organic chemical vapor deposition on InP (100) substrates have been investigated. High-resolution X-ray reciprocal space mapping around the (115) InP lattice point reveals that the strain relaxations of the InAsxP1-x with x = 0.5, 0.55, and 0.7 are 98%, 92%, and 96%, while the lateral correlation lengths are 17, 62, and 28 nm, respectively. The optical bandgap energy of the InAsP derived from photoreflectance (PR) measurements decreases from 0.819 to 0.621 eV at 300 K when increasing As composition from x = 0.5 to 0.7. The bowing parameter for the optical bandgap of the InAsP is increased with increasing As composition, which is attributable to the increased spontaneous CuPt-type ordering in InAsP. It is found from the excitation power-dependent PR measurement that the InAsxP1-x layers have different degrees of the bandgap redshift due to the reduced thermal conductivity caused by crystal imperfections generated during the strain relaxation process.

Correlation of structural and optical properties of AlGaN films grown on SiN-treated sapphire by MOVPE

We investigated the structural and optical properties of AlGaN films grown on SiN-treated sapphire substrates, without and with GaN-template, by atmospheric pressure metal organic vapor phase epitaxy. The samples were characterized using high-resolution X-ray diffraction (HR-XRD), time-resolved photoluminescence (TR-PL), and photoreflectance (PR) spectroscopies. Furthermore, the carrier mobility was determined from Hall-effect measurements. When the AlGaN (GaN-template) layer thickness increases up to 0.6 µm (1.3 µm), an increase in the PL decay times is observed and correlated with the transition from 3D to 2D growth mode resulting in a decrease in the dislocations density as obtained from the HR-XRD measurements. Beyond the aforementioned layer thicknesses, we observed a deterioration in the PL transient corresponds to an increase in the density of VAl-related complexes during the relaxation process, which act as non-radiative recombination centers. Our observations strongly suggest that this type of defects influences the carrier transport and carrier recombination process in the AlGaN layers. Furthermore, our results reveal a phenomenological linear relationship between the internal electric field, obtained from the PR measurements, and the dislocations density. This finding predicts an increase in the GaN internal electric field by about 147 KV/cm when the Al content is increased to 7% in the AlGaN layers. We attribute this increase to a rise in the polarization-induced electric field due to Al incorporation in the AlGaN layer. Based on the obtained correlation between the internal electric field and the dislocation density, we propose an experimental approach that can be utilized to determine the internal electric field, at zero dislocation density, which is very important for designing high-efficient electronic and optoelectronic devices.

Temperature-dependent study of GaAs1−x−yNxBiy alloys for band-gap engineering: photoreflectance and k · p modeling

Photoreflectance measurements were performed for GaAs1−x−yNxBiy layers in the temperature range of 20–300 K. For each sample a transition related to the band-gap was observed, which red-shifts with increasing nitrogen and bismuth content. The temperature dependencies of the band-gap were fitted by the Varshni and Bose–Einstein formulas and simulated within the band anticrossing model of the interaction between the extended band states of the GaAs and the localized states associated with nitrogen and bismuth atoms. The reduction of the band-gap was found to be ∼80–100 meV.

Valley polarization investigation of GeS under high pressure

GeS and its analog compounds exhibit unique properties that combine some of the most desired features of other two-dimensional compounds, such as transition-metal dichalcogenides and graphene. These include high electron mobilities or valley physics that result in strong optical and electronic anisotropy. Here, we present an experimental and theoretical study of the electronic band structure of GeS at high hydrostatic pressures. Polarization-resolved high-pressure photoreflectance measurements allow us to extract the energies, optical dichroic ratios, and pressure coefficients of the direct optical transitions. These findings are discussed in view of first-principles calculations, which predict that nondegenerate states in different valleys can be individually selected through linearly polarized light. Based on this, an assignation of the direct optical transitions to the electronic band structure is provided. Finally, the effect of pressure on the electronic band structure is discussed in terms of orbital composition. These results provide evidence that GeS is a strong candidate for valleytronic applications in nondegenerate systems.

Structural Optimization and Temperature-Dependent Electrical Characterization of GaAs Single-Junction Solar Cells

This paper reports the structural optimization and the temperature-dependent electrical characterization of GaAs single-junction solar cells (SJSCs) based on the p+-n-n+ junction structure. First, the effects of the p+-Al0.9Ga0.1As window layer were investigated using illuminated current density-voltage (LJ−V) and photoreflectance measurements to determine the optimal structure of the SJSC. In addition, the thickness and the doping concentration of different layers, such as the p+-GaAs emitter and the n-GaAs base layers, were optimized, leading to the maximum efficiency (η = 21.53%). These results show that the device performance can be improved further when compared to the world record (η = 28.8%). Second, the capacitance-voltage (C−V) and the dark J−V characteristics of a GaAs SJSC with the optimal structure were investigated over the temperature range from 100 to 300 K. As the temperature was increased, both the junction capacitance at zero voltage (Cj0) and the carrier concentration in the active region (Nd) increased while the depletion width (W) and the built-in potential (Vbi) decreased due to purely thermal effects. Among the SC parameters obtained from the dark J−V curves, the ideality factor (n) decreased from 4.38 to 1.70 and the reverse saturation current density (J0) increased from 6.05 × 10 −12 to 4.26 × 10 −10 A/cm2 with increasing temperature. These values at 300 K were similar to those simulated theoretically and reported previously for high-quality GaAs junction diodes.

Optical spectroscopy studies of atom intermixing in the core versus growth temperature of the claddings in MOCVD-grown quantum cascade lasers

Here we present optical spectroscopy studies to examine structural and optical properties of active region of quantum cascade lasers grown fully by MOCVD technique. The active part is InGaAs/AlInAs based multilayer structure nominally lattice matched to InP substrate. In this communication we study a set of structures with different growth temperature of the cladding layers and its influence on the properties of active core. The x-ray spectroscopy (XRD) allowed to determine the widths of constituent layers and compare obtained values with nominal ones. Fourier-transformed photoluminescence (FTPL) and photoreflectance (PR) measurements provided high signal to noise spectra, proving good optical and structural properties of investigated samples. A model of atoms interdiffusion processes was presented to explain observed small energy shifts of the transitions energies within the investigated multilayer structures.

Ge/SiGe parabolic quantum wells

Quantum wells with parabolic confining potentials allow the realization of semiconductor heterostructures mimicking the physical properties of a quantum harmonic oscillator. Here we report the attempt of attaining such parabolic quantum wells (PQWs) within the Ge/SiGe material platform. Multiple PQWs featuring different widths and composition have been epitaxially grown and characterized by means of high-resolution x-ray diffraction and scanning transmission electron microscopy. The compositional profile is seen to deviate slightly from an ideal parabola, but the quantum confined states are almost equally spaced within the valence and conduction band as indicated by photoreflectance measurements and modelling.

Supercontinuum source as a probing beam in photoreflectance and photoacoustic spectroscopy

In this paper we show a proof of concept for the application of the supercontinuum light source as a probing beam in photoreflectance (PR) and photoacoustic (PA) spectroscopies. We have observed that the signal-to-noise ratio in PR measurements is about one order of magnitude worse when the supercontinuum is applied as the probing beam instead of the quartz tungsten halogen (QTH) lamp, which is a typical light source for PR measurements. When the PR signal is relatively strong (ΔR/R ≥ 10−4) measurements with no significant loss in spectral details can be obtained. It means that the supercontinuum light source has promising perspectives in the application in PR spectroscopy especially that with this light source it is easy: i) to eliminate the unwanted photoluminescence signal, ii) to increase the distance between the sample and the optical elements of the experimental setup, and iii) to improve the spatial resolution in PR measurements. Moreover, it is shown that the supercontinuum can be applied in PA spectroscopy. In this case we did not observe any significant differences in the signal-to-noise ratio for measurements with supercontinuum and QTH lamp.

Effect of exciton transfer on recombination dynamics in vertically nonuniform GaAsSb epilayers

Low-temperature photoluminescence (PL), photoreflectance (PR), and temperature dependent time-resolved PL spectroscopies are employed to investigate optical emission processes and exciton dynamics in graded GaAsSb epilayers. The nonuniformity in the Sb composition along the growth direction is disclosed by low-temperature PL and PR measurements. Furthermore, significant differences in PL dynamics are found at low temperatures for the PL emissions originating from spatial regions with the low and high Sb compositions, with a fast decay and a slow rise at the early stage of the PL transient, respectively. This finding is attributed to exciton transfer from the low Sb region to the high Sb region. The obtained results are important for a general understanding of optical transitions and exciton/carrier dynamics in material systems with a graded alloy composition.

Type I GaSb1-xBix/GaSb quantum wells dedicated for mid infrared laser applications: Photoreflectance studies of bandgap alignment

To determine the band alignment at the GaSb1-xBix/GaSb interface, a set of GaSb1-xBix/GaSb quantum wells (QWs) of various widths (7, 11, and 15 nm) and contents (Bi ≤ 12%) were grown by molecular beam epitaxy and investigated by photoreflectance (PR) spectroscopy. In PR spectra, the optical transitions related to both the ground and the excited states in the QW were clearly observed. It is a direct experimental evidence that the GaSb1-xBix/GaSb QW is a type-I QW with a deep quantum confinement in both the conduction and valence bands. From the comparison of PR data with calculations of energies of QW transitions performed for the varying valence band offset (VBO), the best agreement between experimental data and theoretical calculations has been found for the VBO ∼50 ± 5%. A very similar VBO was obtained from ab initio calculations. These calculations show that the incorporation of Bi atoms into a GaSb host modifies both the conduction and valence band: the conduction-band position changes linearly at a rate of ∼15–16 meV per % Bi and the valence band position changes at a rate of ∼15–16 meV per % Bi. The calculated shifts of valence and conduction bands give the variation of VBO between GaSb1-xBix and GaSb in the range of ∼48%–52%, which is in good agreement with conclusions derived from PR measurements. In addition, it has been found that the electron effective mass reduces linearly with the increase in Bi concentration (x): meffGaSbBi=meffGaSb−0.2x, where meffGaSb is the electron effective mass of GaSb. Moreover, a strong photoluminescence (PL) was observed and a negligible Stokes shift (less than a few meV) between the PL peak and the fundamental transition in the PR spectrum was detected for all QWs at low temperatures. It means that the investigated QWs are very homogeneous, and the carrier localization for this alloy is very weak in contrast to other dilute bismides.

Pressure dependence of direct optical transitions in ReS2 and ReSe2

The ReX2 system (X = S, Se) exhibits unique properties that differ from other transition metal dichalcogenides. Remarkably, its reduced crystal symmetry results in a complex electronic band structure that confers this material in-plane anisotropic properties. In addition, multilayered ReX2 presents a strong 2D character even in its bulk form. To fully understand the interlayer interaction in this system, it is necessary to obtain an accurate picture of the electronic band structure. Here, we present an experimental and theoretical study of the electronic band structure of ReS2 and ReSe2 at high-hydrostatic pressures. The experiments are performed by photoreflectance spectroscopy and are analyzed in terms of ab initio calculations within the density functional theory. Experimental pressure coefficients for the two most dominant excitonic transitions are obtained and compared with those predicted by the calculations. We assign the transitions to the Z k-point of the Brillouin zone and other k-points located away from high-symmetry points. The origin of the pressure coefficients of the measured direct transitions is discussed in terms of orbital analysis of the electronic structure and van der Waals interlayer interaction. The anisotropic optical properties are studied at high pressure by means of polarization-resolved photoreflectance measurements.

Strain related relaxation of the GaAs-like Raman mode selection rules in hydrogenated GaAs1−xNx layers

The GaAs-like longitudinal-optical (LO) phonon frequency in hydrogenated GaAs1−xNx (x = 0.01) layers—with different H doses and similar low-energy irradiation conditions—was investigated by micro-Raman measurements in different scattering geometries and compared with those of epitaxial GaAs and as-grown GaAs1−xNx reference samples. A relaxation of the GaAs selection rules was observed, to be explained mainly on the basis of the biaxial strain affecting the layers. The evolution of the LO phonon frequency with increasing hydrogen dose was found to heavily depend on light polarization, thus suggesting that a linear relation between strain and the frequency of the GaAs-like LO phonon mode should be applied with some caution. Moreover, photoreflectance measurements in fully passivated samples of identical N concentration show that the blueshift of the GaAs-like LO frequency, characteristic of the hydrogenated structures, is dose-dependent and strictly related to the strain induced by the specific type of the dominant N-H complexes. A comparison of photoreflectance results with the finite element method calculations confirms that this dependence on the H dose is due to the gradual replacement of the N-2H complexes responsible for the electronic passivation of N with N-3H complexes, which are well known to induce an additional and sizeable lattice expansion.

Combined photo- and electroreflectance of multijunction solar cells enabled by subcell electric coupling

Electric coupling between subcells of a monolithically grown multijunction solar cell in short circuit allows their simultaneous and independent characterization by means of photo- and electro-reflectance. The photovoltage generated by selective absorption of the pump beam in a given subcell during photoreflectance measurements results in reverse biasing the complementary subunits at the modulation frequency set on the pump illumination. Such voltage bias modulation then acts as external perturbation on the complementary subcells. The spectral separation of different subcell absorption ranges permits the probe beam to record in a single spectrum the response of the complete device as a combination of photo- and electro-reflectance, thereby providing access for the diagnosis of subcells on an individual basis. This form of modulation spectroscopy is demonstrated on a GaInP/GaAs tandem solar cell.

Effect of V/III ratio on the optical properties of (3 1 1)A and (3 1 1) B oriented InAlAs/InP heterostructures

Abstract InAlAs alloy were grown on a InP (3 1 1) substrate with different polarity, by metalorganic chemical vapor deposition (MOCVD) growth. Photoluminescence (PL) and Photoreflectance (PR) measurements have been carried out, in our samples, in order to study the V/III flux ratio effect in type-II heterostructures. It is found that, with increasing excitation power density, the PL line was shifted at higher energy side and no saturation of its associated PL intensity was observed. It is a fingerprint of type II transition emission. Yet, the type II interface recombination has shown a strong dependence on AsH3 overpressure and substrate polarity. Therefore, the arsenic overpressures (V/III) affect the piezoelectric (PZ) field and the As/P exchange in our investigated structures. Indeed, we have observed an opposite behavior of type II energy transition shift from A (Indium In face) to B (Phosphorus P face) polarity substrate in respect to V/III flow ratio variation. This fact has been explained as an atomic terminated surface (In or P) in InP substrate. In the other side, PR signals corresponding to Franz-Keldysh Oscillation (FKO) have been observed, in InAlAs/InP (3 1 1). The analysis of their period has allowed one to determine the value of the PZ field in the samples. This result enables us to extract the V/III ratio and the substrate polarity effect on the type II transition shift, in such heterostructures.

(Invited) Electrochemical Formation and Application of Porous Gallium Nitride

Gallium nitride (GaN), which is a III-V compound semiconductor, has wide direct bandgap (3.4 eV), high breakdown electric field (3.3x106 V/cm) and high saturation electron velocity (2.7 x107 cm/sec). On the basis of excellent optical and electrical properties, significant progress has been achieved in the GaN-based devices, such as ultraviolet laser diodes, white light-emitting diodes, high electron mobility transistors (HEMTs), and high-power FETs. In addition, GaN and its alloys are getting much attention as building block materials for electrochemical (EC) energy conversion systems such as chemical sensors, water splitting, and artificial photosynthesis due to their superior chemical stability, direct transition, and widely tunable bandgap by alloying. Among the various techniques for improving their conversion efficiency, porosification utilizing EC reactions is one of the most powerful because a high-density array of pores exhibits high specific surface area, low reflectance, and high absorptance properties. In addition, this technique is performed at room temperature and does not require any complicated process such as lithography, indicating lower damage and higher productivity than other nanostructure fabrication techniques such as reactive ion etching and selective-area growth. In this presentation, we review our recent work on the fabrication of porous GaN utilizing various EC techniques and their applications [1-3]. One example is the two-step process combining EC etching process with conventional chemical etching process. EC etching was first performed in the dark condition using an aqueous electrolyte consisting of H2SO4 and H3PO4. Wet chemical etching was subsequently conducted in 25 % tetramethylammonium hydroxide (TMAH) at 90°C. The porous structure formed by the first EC etching has straight pores oriented perpendicular to the top surface. Pore depth linearly increased with EC etching time, indicating that superior depth control was achieved. This behavior can be explained as resulting from anisotropy of the EC etching. Namely, the etching reaction proceeded only to the direction belong to the high-electric field induced by the anodic voltage. On the other hand, the pore diameter kept a constant value throughout the EC etching and could not be controlled by the EC etching time. However, the pore diameter could be changed by wet chemical etching utilizing TMAH as subsequent treatment after the EC etching. By applying TMAH etching, pore shape changed from a round to a hexagonal shape surrounded with 6 facets of {1−100}. In addition, the pore diameter estimated from SEM observation increased linearly with the TMAH etching time, whereas the pore depth was unchanged. These results indicate that TMAH etching proceeds anisotropically in the horizontal direction, but not in the vertical direction of the substrate. The optical and photoelectrochemical properties of porous GaN were very sensitive to the structural properties. From the photoluminescence (PL) measurements, the intensity of yellow luminescence (YL) related to high-density point defects was drastically decreased by the formation of porous structures, suggesting that gallium vacancy (V Ga) related defects were preferentially removed by EC etching. Photoreflectance measurement revealed that porous sample had an effective refractive index that could be controlled by TMAH etching time. In photoelectrochemical measurement, the incident-photon-to-current conversion efficiency (IPCE) was dramatically enhanced by the formation of porous structures. A series of experimental results were consistently explained by the change of thickness of pore wall with a width of space charge region. These results suggest that precise structural controlling is crucially important to obtain superior capability for EC energy conversion systems, and the two-step process utilizing anisotropic EC etching and TMAH etching is very promising as a nanostructure fabrication technique. Acknowledgement: This work was supported by JSPS KAKENHI - JP15K13937，JP16H06421，JP17H03224. A. Watanabe et al., ECS Electrochem. Lett., 4, H11 (2015).Y. Kumazaki et al., J. Electrochem. Soc., 164, H477 (2017).M. Toguchi et al., 233rd ECS Meeting, Z01-2550, Seattle, WA, 15 May (2018).