Search Results (12)

We investigate how grain growth, strain relaxation, and vacancy chemistry shape the near-edge optical response of nanocrystalline Ce${\mathrm{O}}_{2-\delta }$ prepared by a chymosin-assisted Pechini route from nitrate–citrate precursors. Rietveld line-profile analysis shows that phase-pure Ce${\mathrm{O}}_{2-\delta }$ forms after calcination between 400 and 1000 °C. Over this range, the average crystallite size increases from ≈3.4 to ≈57 nm, while the microstrain decreases from 0.79% to 0.05%, with size–strain scaling consistent with interface-controlled grain growth that follows a normal growth law with exponent $m=2$ and activation energy $Q\approx 155$ kJ ${\mathrm{mol}}^{-1}$. Raman spectroscopy tracks the sharpening of the $F_{2g}$ mode and the fading of defect-related bands, X-ray photoelectron spectroscopy reveals a nonmonotonic evolution of the surface ${\mathrm{Ce}}^{3+}$ fraction and separates lattice from adsorbed oxygen species, and electron paramagnetic resonance detects vacancy-bound ${\mathrm{Ce}}^{3+}$ polarons that weaken at high temperature. Diffuse-reflectance UV–Vis spectra show a modest blue shift of the apparent band gap from $E_g\approx 2.78$ to 2.95 eV as crystallites coarsen, while the Urbach energy $E_u$ follows the ${\mathrm{Ce}}^{3+}$ content and sub-gap tailing. The structural, spectroscopic, and optical results together map out a quantitative connection between grain growth, vacancy populations, and near-edge optical properties in ${\mathrm{CeO}}_{2-\delta }$ nanoparticles. Full article

Kapton-H type is an optical plastic with a UV-Vis-NIR spectrum characterized by abrupt absorbance change at a wavelength of ca. 550 nm. Such sharp optical discontinuity, known as the fundamental absorption edge, has been investigated using the Tauc plot method, and a band gap energy (E_g) of (2.22 ± 0.05) eV for an indirect allowed electron transition model has been found. The Cody plot has also been applied, and a slightly lower band gap energy value (i.e., E_g = 2.33 ± 0.05 eV) has been found. The Urbach rule applied to the spectrum tail has provided an Urbach energy value (E_U) of ca. (185 ± 2) meV, which is quite a high value that is fully compatible with the highly disordered structure of this sterically rigid semi-crystalline polymer. The cut-on wavelength (550 nm), visible transparency (T% of ca. 80), and other relevant optical characteristics of the Kapton-H type have been also evaluated and compared with corresponding values of polyetherimide. Full article

We have studied the variations in the temperature-dependent absorption edge of a bulk InSe-layered semiconductor using photoconductivity (PC) measurements. From both the X-ray diffraction (XRD) and Raman experimental results, the structural phase of the as-prepared InSe sample was confirmed to be γ-polytype. Upon heating from 15 K to 300 K, the absorption edge of PC spectra was found to shift significantly toward lower energy, and the absorption edge as a function of temperature was further analyzed by the Varshni’s relationship and Bose–Einstein empirical equation. The Urbach energy as a function of temperature was obtained by fitting the absorption tail below the absorption coefficient of the PC spectrum, and the effective phonon energy can be derived from the temperature-dependent steepness parameter associated with Urbach energy. Our study indicates that the broadening of the absorption edge in the as-synthesized bulk γ-InSe is caused by a combination of electron/exciton–phonon interactions and thermal/structural disorder. Full article

An approach to derive the below-bandgap absorption in GaSb/GaAs self-assembled quantum dot devices using room-temperature external quantum efficiency measurement results is presented. Devices with five layers of delta-doped quantum dots placed in the intrinsic, n- and p-regions of a GaAs solar cell are studied. The importance of incorporating an extended Urbach tail absorption in analyzing the absorption strength of quantum dots and the transition states is demonstrated. The theoretically integrated absorbance via quantum dot ground states is calculated as 1.04 × 10¹⁵ cm⁻¹s⁻¹, which is in reasonable agreement with the experimentally derived value 8.1 × 10¹⁵ cm⁻¹s⁻¹. The wetting layer and quantum dot absorption contributions are separated from the tail absorption and their transition energies are calculated. Using these transition energies and the GaAs energy gap of 1.42 eV, the heavy hole confinement energies for the quantum dots (320 meV) and for the wetting layer (120 meV) are estimated. Full article

Materials engineering based on metal oxides for manipulating the solar spectrum and producing solar energy have been under intense investigation over the last years. In this work, we present NiO thin films double doped with niobium (Nb) and nitrogen (N) as cation and anion dopants (NiO:(Nb,N)) to be used as p-type layers in all oxide transparent solar cells. The films were grown by sputtering a composite Ni-Nb target on room-temperature substrates in plasma containing 50% Ar, 25% O₂, and 25% N₂gases. The existence of Nb and N dopants in the NiO structure was confirmed by the Energy Dispersive X-Ray and X-Ray Photoelectron Spectroscopy techniques. The nominally undoped NiO film, which was deposited by sputtering a Ni target and used as the reference film, was oxygen-rich, single-phase cubic NiO, having a visible transmittance of less than 20%. Upon double doping with Nb and N the visible transmittance of NiO:(Nb,N) film increased to 60%, which was further improved after thermal treatment to around 85%. The respective values of the direct band gap in the undoped and double-doped films were 3.28 eV and 3.73 eV just after deposition, and 3.67 eV and 3.76 eV after thermal treatment. The changes in the properties of the films such as structural disorder, direct and indirect energy band gaps, Urbach tail states, and resistivity were correlated with the incorporation of Nb and N in their structure. The thermally treated NiO:(Nb,N) film was used to form a diode with a spin-coated two-layer, mesoporous on top of a compact, TiO₂ film. The NiO:(Nb,N)/TiO₂heterojunction exhibited visible transparency of around 80%, showed rectifying characteristics and the diode’s parameters were deduced using the I-V method. The diode revealed photovoltaic behavior upon illumination with UV light exhibiting a short circuit current density of 0.2 mA/cm² and open-circuit voltage of 500 mV. Improvements of the output characteristics of the NiO:(Nb,N)/TiO₂ UV-photovoltaic by proper engineering of the individual layers and device processing procedures are addressed. Transparent NiO:(Nb,N) films can be potential candidates in all-oxide ultraviolet photovoltaics for tandem solar cells, smart windows, and other optoelectronic devices. Full article

In this study, we delved into the influence of Ir nanofilm coating thickness on the optical and optoelectronic behavior of ultrathin MoO₃ wafer-scale devices. Notably, the 4 nm Ir coating showed a negative Hall voltage and high carrier concentration of 1.524 × 10¹⁹ cm⁻³ with 0.19 nm roughness. Using the Kubelka–Munk model, we found that the bandgap decreased with increasing Ir thickness, consistent with Urbach tail energy suggesting a lower level of disorder. Regarding transient photocurrent behavior, all samples exhibited high stability under both dark and UV conditions. We also observed a positive photoconductivity at bias voltages of >0.5 V, while at 0 V bias voltage, the samples displayed a negative photoconductivity behavior. This unique aspect allowed us to explore self-powered negative photodetectors, showcasing fast response and recovery times of 0.36/0.42 s at 0 V. The intriguing negative photoresponse that we observed is linked to hole self-trapping/charge exciton and Joule heating effects. Full article

Highly transparent thin films with the chemical formula BaSrMgWO₆ were deposited by spin coating using a solution of nitrates of Ba, Sr, and Mg and ammonium paratungstate in dimethylformamide with a Ba:Sr:Mg:W ratio = 1:1:1:1. XRD, SEM, EDX, and XPS investigations evidenced that annealing at 800 °C for 1 h results in an amorphous structure having a precipitate on its surface, and that supplementary annealing at 850 °C for 45 min forms a nanocrystalline structure and dissolves a portion of the precipitates. A textured double perovskite cubic structure (61.9%) was found, decorated with tetragonal and cubic impurity phases (12.7%), such as BaO₂, SrO₂, and MgO, and an under-stoichiometric phase (24.4%) with the chemical formula Ba_2−(x+y) Sr_xMg_yWO₅. From transmittance measurements, the values of the optical band gap were estimated for the amorphous (E_gdir = 5.21 eV, E_gind = 3.85 eV) and nanocrystalline (E_gdir = 4.69 eV, E_gind = 3.77 eV) phases. The presence of a lattice disorder was indicated by the high Urbach energy values and weak absorption tail energies. A decrease in their values was observed and attributed to the crystallization process, lattice strain diminution, and cation redistribution. Full article

Several, nearly-1-µ$\mathrm{m}$-thick, pure, unhydrogenated amorphous-silicon (a-Si) thin layers were grown at high rates by non-equilibrium rf-magnetron Ar-plasma sputtering (RFMS) onto room-temperature low-cost glass substrates. A new approach is employed for the optical characterization of the thin-layer samples, which is based on some new formulae for the normal-incidence transmission of such a samples and on the adoption of the inverse-synthesis method, by using a devised Matlab GUI environment. The so-far existing limiting value of the thickness-non-uniformity parameter, $\Delta d$, when optically characterizing wedge-shaped layers, has been suppressed with the introduction of the appropriate corrections in the expression of transmittance. The optical responses of the H-free RFMS-a-Si thin films investigated, were successfully parameterized using a single, Kramers–Krönig (KK)-consistent, Tauc–Lorentz oscillator model, with the inclusion in the model of the Urbach tail (TLUC), in the present case of non-hydrogenated a-Si films. We have also employed the Wemple–DiDomenico (WDD) single-oscillator model to calculate the two WDD dispersion parameters, dispersion energy, $E_{\mathrm{d}}$, and oscillator energy, $E_{\mathrm{so}}$. The amorphous-to-crystalline mass-density ratio in the expression for $E_{\mathrm{d}}$ suggested by Wemple and DiDomenico is the key factor in understanding the refractive index behavior of the a-Si layers under study. The value of the porosity for the specific rf-magnetron sputtering deposition conditions employed in this work, with an Ar-pressure of ~4.4 Pa, is found to be approximately 21%. Additionally, it must be concluded that the adopted TLUC parameterization is highly accurate for the evaluation of the UV/visible/NIR transmittance measurements, on the H-free a-Si investigated. Finally, the performed experiments are needed to have more confidence of quick and accurate optical-characterizations techniques, in order to find new applications of a-Si layers in optics and optoelectronics. Full article

We are reporting an esoteric method to determine the optical bandgap of direct gap materials by employing Urbach’s rule. The latter, which describes the slope of the band tail absorption in semiconductors, in its original version, cannot be employed to pinpoint the optical bandgap. Herein, however, we show that a modified form of Urbach’s rule defines the optical bandgap, and therefore, enables the accurate determination of the optical bandgap energy, which turns out to be identical with the threshold energy for the band tail absorption. The model further produces an explicit expression for the absorption coefficient at the optical bandgap energy. Full article

The current work examines the effects of cesium lead bromide (CsPbBr₃) perovskite quantum dots (PQDs) on the structural and optical properties of conjugated polymer blends of poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylene vinylene] (MEH–PPV) and poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO). MEH–PPV/PFO composite thin-films containing PQDs with weight ratios between 0.5 wt.% and 10 wt.% were prepared via a solution-blending method prior to spin-coating on glass substrates. The MEH–PPV/PFO composites’ crystallinity was improved, and the roughness was dramatically increased with higher PQDs content, as confirmed by X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. Conversely, a higher PQDs content resulted in a gradual reduction of the Urbach tail and an increase in the steepness parameter, thereby reducing the localized density of the electronic states within the forbidden bandgap of the hybrids. Moreover, a slight reduction in the direct and indirect bandgaps was found in PQDs/(MEH–PPV/PFO) composite films containing a higher PQDs content and provided evidence of the low concentration of the localized states. The incorporation of the PQDs resulted in enhanced non-radiative energy transfer processes in the MEH–PPV/PFO hybrids, which are very important for the development of optimized optoelectronic devices. Full article

The influence of O₂ flow rate on the compositional, optical and electrical characteristics of silicon oxide (SiO_x) thin films (x < 2) were studied in this work. The SiO_x thin films were obtained by pulsed direct current (DC) magnetron sputtering (PMS) onto n-type Si wafers (and also on glass substrates) at a vacuum of 3 × 10⁻³ Pa. Rutherford backscattering spectrometry (RBS) was used to check the compositional elements of deposited films and its oxidized states were analysed via Fourier-transform infrared (FTIR) spectroscopy. The optical properties of as-deposited SiO_x thin films were investigated from transmittance measurements at room temperature in the wavelength range of 250–800 nm. The obtained data reveal that the Urbach energy (a measure of the band tail extension, E_u) decreased from about 523 to 172 meV as the rate of oxygen gas flow increased. On the contrary, the optical energy band-gap (E_g) increased from 3.9 to 4.2 eV. Conduction and valance band positions (relative to the normal hydrogen electrode) were also evaluated. The observed behavior is probably associated with the degree of disorder and defects presented in the as-deposited SiO_x thin films, probably due to the presence of newly inserted oxidized O_nSiH_y species resulting from some contamination with water vapor desorbed from the walls of the deposition vacuum chamber. After deposition of a gold top electrode, the electrical characteristics of the fabricated Au/SiO_x/n-Si system (i.e., a metal/insulator/semiconductor structure—MIS) were studied via characteristic I-V curves and their dependence upon the O₂ flow rate are reported. It was observed that the Au/SiO_x/n-Si structure behaves like a Schottky-diode exhibiting a very good diode rectifying performance with a rectification ratio of at least 300 and up to 10⁴, which refers to the samples produced with the lower and higher O₂ flow rates, respectively. It was also found that the O₂ flow rate influences the rectifying performance of the SiO_x/n-structures since both the diode ideality factor, n, and the diode series-resistance, R_S decreases with the increase of O₂ content, possibly reflecting a closer approximation to a full stoichiometric condition. Full article

In this paper, the sample preparation of polymer nanocomposites based on methyl cellulose (MC) with small optical bandgaps has been discussed. Copper monosulfide (CuS) nanoparticles have been synthesized from the sodium sulphide (Na₂S) and copper chloride (CuCl₂) salts. Distinguishable localized surface resonance plasmon (LSRP) absorption peaks for CuS nanoparticles within the 680–1090 nm scanned wavelength range were observed for the samples. An absorption edge (E_d) was found to be widely shifted to a lower photon energy region. A linear relationship between the refractive index of the samples and the CuS fraction was utilized to describe the distribution of the particle. The optical bandgap of MC was reduced from 6.2 to 2.3 eV upon the incorporation of 0.08 M of CuS nanoparticles. The optical dielectric loss, as an alternative method, was used successfully to estimate the optical bandgap. Moreover, the electronic transition type was identified by using Tauc’s extrapolation method. The plots of the optical dielectric constant and energy bandgap as a function of the CuS concentration were utilized to examine the validity of the Penn model. For the nanocomposite samples, the Urbach energy was found to be increased, which can be evidence for a large possible number of bands-to-tail and tail-to-tail transitions. However, from the X-ray diffraction (XRD) analysis, it was also found that the synthesized CuS nanoparticles disrupted the crystallinity phase of the MC polymer. Finally, fourier transform infrared (FTIR) spectroscopy for the samples was also performed. Significant decreases of transmittance intensity as well as band shifting in the FTIR spectra were observed for the doped samples. Full article