Fe-doped Crystals Research Articles

Growth and characteristics of bicolor Fe-doped MgAl2O4 crystals

Bicolor Fe-doped MgAl2O4 crystals were successfully grown using the floating zone technique. These bicolor crystals were grown with composition ratios of MgO to Al2O3 (x) ranging from 0.3 to 1.0 and Fe2O3 concentrations of 0.1 mol%–2.0 mol%. Their growth process involved changing the O2 concentrations in the growth atmospheres: 0 vol% O2–100 vol% Ar, 50 vol% O2–50 vol% Ar, and 100 vol% O2–0 vol% Ar. The color of the resultant crystals changes with the growth conditions employed. Crystals manifested in six colors: pink, green, purple, violet, blue, yellow, and brown, based on the combination of Fe2O3 concentrations, O2 concentrations, and x. Additionally, bicolor crystals could be grown by suddenly changing the O2 concentration in the growth atmosphere, while tri-color crystals could be achieved through gradual alterations in the O2 concentration in the growth atmosphere. The color change of the bicolor crystals is considered to be caused by the change in the optical absorption ratio at λ = 455 (blue light) and λ = 550 nm (green light) due to the change in the concentration ratio of Fe2+ and Fe3+ in the crystal.

Red Photoluminescence from Fe-Doped MgAl2O4 Crystals

The influence of variations in composition (x = MgO/Al2O3 = 0.3–1.0), Fe2O3 concentrations (0.05 mol%–2.0 mol%), and O2 concentrations (100 vol% and 0 vol%) in the atmosphere on the PL characteristics of Fe-doped MgAl2O4 crystals were investigated using single phase spinel crystals grown by FZ technique. The peak wavelength shift of photoluminescence at around 730 nm are observed depending on the Fe2O3 concentration and composition. Concentration quenching of red PL occurred at Fe2O3 concentration above 0.1 mol%. PL intensity was higher in samples grown in 100 vol% O2 compared to those grown in 100 vol% Ar. PL intensity from Fe-doped MgAl2O4 increased with increasing compositions x from 0.3 to 1.0. MgAl2O4 doped with 0.1 mol% Fe2O3, and a stoichiometric composition (x = 1.0) grown in 100 vol% O2, demonstrated strong red PL with ultraviolet-C (UVC) lights excitation.

Polarized photoluminescence from Sn, Fe, and unintentionally doped β-Ga2O3

In this work, we demonstrate that β-Ga2O3 shows orientation-dependent polarized photoluminescence (PL) emission and give a comprehensive insight into gallium oxide's PL spectral properties. We characterized the polarization and spectral dependencies of both the incident and emitted light for (−201) unintentionally doped (UID) as well as (−201) and (010) Sn-doped and Fe-doped crystals. We observed for UID and Sn-doped samples that the electron to self-trapped hole and native defect-related emission bands are linearly polarized with polarized emission intensities ordered as E || c (and c*) > E || a (and a*) > E || b. Furthermore, the spectral shape of emission does not change between the UID and Sn-doped samples; instead, the Sn-doping quenches the total PL spectral intensity. For Fe-doped samples, polarized red emission caused by unintentional Cr3+ doping generates emission intensities ordered E || b > E || c (and c*) > E || a (and a*). It is also observed that in some circumstances, for some doped crystals, the PL spectra can show variations not only in intensity but also in spectral shape along different polarization directions. As an example, the PL emission band for emission along c is blueshifted relative to that along a in Sn-doped β-Ga2O3.

Impact of electron irradiation on semi-insulating and conductive β-Ga2O3 single crystals.

The damage behavior and defect evolution in Si-doped and Fe-doped β-Ga2O3 crystals were investigated using an electron irradiation of 1 MeV at a dose of 1 × 1016 cm-2 in conjunction with structural and optoelectronic characterizations. Distinct decline in electron spin resonance (ESR) signal with g = 1.96 and a UV luminesce of 375 nm were observed in Si-doped β-Ga2O3 due to the capture of free carriers by irradiation defects. As for the Fe-doped sample, both defect-related blue emission and Cr3+ impurity-related red luminescence underwent prominent suppression after electron irradiation, which can be correlated to the creation of VO and VGa defects and the formation of non-radiative recombination. Noticeably, neither VO- nor VGa-related ESR signals were detected in Fe-doped and Si-doped β-Ga2O3 irrespective of irradiation; g = 2.003 resonance was observed in Mg-doped β-Ga2O3 and it experienced remarkable augmentation after electron irradiation. We assigned the g = 2.003 peak to the VGa acceptor. Besides, although the Raman mode of 258 cm-1 in Si-doped β-Ga2O3 has been suggested to be electron concentration dependent, no obvious change in peak intensity was observed before and after electron irradiation.

Role of Native Defects in Fe-Doped β-Ga2O3.

Iron impurities are believed to act as deep acceptors that can compensate for the n-type conductivity in as-grown Ga2O3, but several scientific issues, such as the site occupation of the Fe heteroatom and the complexes of Fe-doped β-Ga2O3 with native defects, are still lacking. In this paper, based on first-principle density functional theory calculations with the generalized gradient approximation approach, the controversy regarding the preferential Fe incorporation on the Ga site in the β-Ga2O3 crystal has been addressed, and our result demonstrates that Fe dopant is energetically favored on the octahedrally coordinated Ga site. The structural stabilities are confirmed by the formation energy calculations, the phonon dispersion relationships, and the strain-dependent analyses. The thermodynamic transition level Fe3+/Fe2+ is located at 0.52 eV below the conduction band minimum, which is consistent with Ingebrigtsen's theoretical conclusion, but slightly smaller than some experimental values between 0.78 eV and 1.2 eV. In order to provide direct guidance for material synthesis and property design in Fe-doped β-Ga2O3, the defect formation energies, charge transitional levels, and optical properties of the defective complexes with different kinds of native defects are investigated. Our results show that VGa and Oi can be easily formed for the Fe-doped β-Ga2O3 crystals under O-rich conditions, where the +3 charge state FeGaGai and -2 charge state FeGaOi are energetically favorable when the Fermi level approaches the valence and conduction band edges, respectively. Optical absorption shows that the complexes of FeGaGai and FeGaVGa can significantly enhance the optical absorption in the visible-infrared region, while the energy-loss function in the β-Ga2O3 material is almost negligible after the extra introduction of various intrinsic defects.

Defect pairing in Fe-doped SnS van der Waals crystals: a photoemission and scanning tunneling microscopy study.

We investigate the effect of low concentrations of iron on the physical properties of SnS van der Waals crystals grown from the melt. By means of scanning tunneling microscopy (STM) and photoemission spectroscopy we study Fe-induced defects and observe an electron doping effect in the band structure of the native p-type SnS semiconductor. Atomically resolved and bias dependent STM data of characteristic defects are compared to ab initio density functional theory simulations of vacancy (VS and VSn), Fe substitutional (FeSn), and Fe interstitial (Feint) defects. While native SnS is dominated by acceptor-like VSn vacancies, our results show that Fe preferentially occupies donor-like interstitial Feint sites in close proximity to VSn defects along the high-symmetry c-axis of SnS. The formation of such well-defined coupled (VSn, Feint) defect pairs leads to local compensation of the acceptor-like character of VSn, which is in line with a reduction of p-type carrier concentrations observed in our Hall transport measurements.

Synthesis and Characterization of Fe-Doped CaTiO3 Polyhedra Prepared by Molten NaCl Salt

CaTiO3 as one of the perovskite-based photocatalysts has a band gap energy of 3.5 eV (~354 nm), thus will work at the ultraviolet light region. One of the strategies to decrease the band gap energy is doping metal. In this research, CaTiO3 was doped by Fe element as purposes to decreasing its band gap energy. Fe doped CaTiO3 compounds were synthesized using molten NaCl salt method. The diffractogram samples showed that the Fe-doped CaTiO3 crystal was successfully prepared. Meanwhile, the SEM images showed that the particle shape was regular polyhedral morphology, and doping Fe3+ caused the particle size to decrease and agglomerated. The UV-Vis DRS spectra showed that the Fe-dopant revealed the absorption light at visible range wavelength.

Controllable growth of Fe-doped NiS2 on NiFe-carbon nanofibers for boosting oxygen evolution reaction

The construction of high-efficiency and low-cost electrocatalysts toward oxygen evolution reaction (OER) to improve the overall water decomposition performance is a fascinating route to deal with the clean energy application. Herein, Fe-doped NiS2 crystals grown on the surface of carbon nanofibers (CNFs) encapsulated with NiFe alloy nanoparticles ((Ni,Fe)S2/NiFe-CNFs) are fabricated through an electrospinning-calcination-vulcanization process, which has been used as a splendid electrocatalyst for OER. Benefitting from the abundant electrochemical active sites from the incorporation of Fe element in NiS2 and the synergistic effect between NiFe-CNFs and surface sulfides, the obtained (Ni,Fe)S2/NiFe-CNFs catalyst exhibits highly electrochemical activities and satisfactory durability toward OER in an alkaline medium with a low overpotential of only 287 mV at a high current density of 30 mA cm−2, and with a little decline in the current retention after 48 h, suggesting its superior OER performance even compared with some noble metal-based electrocatalysts. Additionally, a two-electrode system conducted by using the (Ni,Fe)S2/NiFe-CNFs and commercial Pt/C as electrodes, only needs a cell voltage of 1.54 V to afford 10 mA cm−2 for overall water splitting, which is even much better than the RuO2||Pt/C electrolyzer. This study offers a promising approach to prepare high-efficiency OER catalysts toward overall water splitting.

Three-photon absorption and Kerr nonlinearity in pristine and doped β-Ga2O3 single crystals

We report the spectral dependence of the three-photon absorption coefficient γ and third-order nonlinear refractive index n2 in pristine, Sn-doped and Fe-doped β-Ga2O3 crystals using 190 fs pulses in the range of 540–750 nm, i.e., photon energy between half and one-third of the bandgap Eg. The nonlinear coefficient n2 is found to be independent of Sn or Fe doping, and the maximum value of n2 is about 4 × 10−19 m2/W when the photon energy is near Eg/2. However, we observe that Fe doping can significantly enhance the γ value in the range of 540–600 nm (near Eg/2) while doping has negligible impact on γ for wavelength larger than 620 nm. Femtosecond pump-probe measurements show that Fe doping induced a fast (∼50 ps) carrier decay process after photo excitation, which could be attributed to the Fe induced deep trap states. We obtain three-photon figures of merit that allow operational intensities up to 100 GW/cm2. Our results indicate that β-Ga2O3 has great potential for all-optical switching applications in red and near IR regimes.

Fe-related optical transitions in floating zone and Czochralski grown β-Ga2O3 crystals

Gallium oxide (Ga2O3), a promising candidate for high-power electronics, may be doped with Fe to control the native n-type conductivity and produce semi-insulating single-crystalline substrates. Here, intentionally as well as unintentionally Fe-doped β-Ga2O3 crystals grown by the Czochralski (Cz) and the floating zone (FZ) methods are studied. While the Cz samples contain Ir on the order of 1017 cm−3 due to the Ir crucible, the FZ samples are free of this contaminant. Photoinduced electron paramagnetic resonance (EPR) is performed by illuminating the samples with light emitting diodes from 0.7 to 4.7 eV while monitoring the intensity of the EPR signal. The following optical transitions associated with Fe are observed: one between 1 and 2 eV occurs in both Cz and FZ samples, another near 2.5 eV is unique to Cz Ga2O3, and a third near 3 eV appears in FZ material. The transition below 2 eV is the well-studied Fe2+-to-Fe3+ transition, intrinsic to Fe. Near 2.5 and 3 eV, the amount of Fe3+ decreases by capturing electrons excited from other defects present near or below the middle of the bandgap. By comparing Cz and Ir-free FZ crystals, we show that the 2.5 eV transition is primarily caused by Ir in Fe-doped Cz samples, whereas the ∼3 eV transition observed in FZ samples could be caused by isolated or complex intrinsic defects. By differentiating transitions between Cz and FZ material, the results will be relevant to epitaxial films, which do not contain the Ir present in the commonly studied Cz material.

Tuning the flat bands of the kagome metal CoSn with Fe, In, or Ni doping

CoSn is a Pauli paramagnet with relatively flat d-bands centered about 100 meV below the Fermi energy Ef. Single crystals of CoSn lightly doped with Fe, In, or Ni are investigated using x-ray and neutron scattering, magnetic susceptibility and magnetization, ac susceptibility, specific heat and resistivity measurements. Within the rigid band approximation, hole doping with a few percent of Fe or In should move the flat bands closer to Ef, whereas electron doping with Ni should move the flat bands further away from Ef. We provide evidence that this indeed occurs. Fe and In doping drive CoSn toward magnetism, while Ni doping suppresses CoSn's already weak magnetic response. The resulting ground state is different for Fe versus In doping. For Fe-doped crystals, Co1-xFexSn, with 0.02 < x < 0.27, the magnetic and specific heat data are consistent with the formation of a spin glass, with a glass transition temperature, Tg, ranging from 1 K for x=0.02 to 10 K for x= 0.27. Powder and single crystal neutron diffraction found no evidence of long-range magnetic order below Tg with x = 0.17. For In-doped crystals, CoSn1-yIny, both the magnetic susceptibility and the Sommerfeld coefficient, gamma, increase substantially relative to pure CoSn, but with no clear indication of a magnetic transition for 0.05 < y < 0.2. CoSn crystals doped with Ni (Co0.93Ni0.07Sn) have a significantly smaller magnetic susceptibility and gamma than pure CoSn, consistent with the flat bands further from Ef.

Deep donor behavior of iron in β-Ga2O3 crystals: Establishing the Fe4+/3+ level

The Fe4+/3+ donor level is experimentally determined to be 0.70 eV (±0.05 eV) above the valence band maximum in β-Ga2O3. Electron paramagnetic resonance (EPR) is used to monitor Fe3+ ions that are unintentionally present in an Mg-doped β-Ga2O3 crystal (with a low Fermi level). For temperatures near 255 K, exposure to 325 nm laser light converts a portion of the Fe3+ ions to Fe4+ and Fe2+ ions and, at the same time, forms neutral magnesium acceptors (MgGa0) and neutral Ir donors (Ir3+). After removing the light, the intensity of the Fe3+ EPR spectrum has a significant additional decrease as holes thermally released to the valence band from rapidly decaying neutral Mg acceptors are trapped at Fe3+ ions and form even more Fe4+ ions. This demonstrates that the Mg0/− acceptor level, near 0.65 eV, is closer to the valence band than the Fe4+/3+ level. Following the fast initial post-light decrease, the Fe3+ spectrum then slowly recovers as Fe4+ ions are destroyed by electrons thermally excited from the valence band. An activation energy for the thermal decay of the Fe4+ donors, and thus a value for the Fe4+/3+ level, is obtained from the analysis of five Fe3+ isothermal recovery curves taken from the Mg-doped crystal between 250 and 270 K. A first-order kinetics model is used, as minimal retrapping is observed. In separate experiments, EPR shows that Fe4+ ions are also produced in an Fe-doped β-Ga2O3 crystal (without Mg acceptors) during exposures to laser light at temperatures near 255 K.

Single-Iron Site Catalysts with Self-Assembled Dual-size Architecture and Hierarchical Porosity for Proton-Exchange Membrane Fuel Cells

Atomically dispersed and nitrogen coordinated single iron site (i.e., FeN4) catalysts (Fe-N-C) are the most promising platinum group metal (PGM)-free cathode for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). However, current Fe-N-C catalysts are limited by the inferior exposure of active FeN4 sites due to the inevitable agglomeration of particles in cathodes. Herein, we report a self-assembled strategy to synthesize the atomically dispersed FeN4 site catalysts with a hierarchically porous matrix derived from dual-size Fe-doped ZIF-8 crystal precursors by using large particles to support small particles. The tailored structure is effective in mitigating the particle migration, agglomeration, and spatial overlap, thereby exposing increased accessible active sites and facilitating mass transport. The best performing catalyst composed of 100 nm “nucleated seed” assembled by 30 nm “satellite” demonstrates exceptional ORR activity in acidic electrolyte and membrane electrode assembly. This work provides new concepts for designing hierarchically porous catalysts with single metal atom dispersion via self-assembly of ZIF-8 crystal precursors with tunable particle sizes and nanostructures.

Deep donors and acceptors in β-Ga2O3 crystals: Determination of the Fe2+/3+ level by a noncontact method

Electron paramagnetic resonance (EPR), infrared absorption, and thermoluminescence (TL) are used to determine the Fe2+/3+ level in Fe-doped β-Ga2O3 crystals. With these noncontact spectroscopy methods, a value of 0.84 ± 0.05 eV below the conduction band is obtained for this level. Our results clearly establish that the E2 level observed in deep level transient spectroscopy (DLTS) experiments is due to the thermal release of electrons from Fe2+ ions. The crystals used in this investigation were grown by the Czochralski method and contained large concentrations of Fe acceptors and Ir donors, and trace amounts of Cr donors. Exposing a crystal at room temperature to 325, 375, or 405 nm laser light converts neutral Fe3+ acceptors to their singly ionized Fe2+ charge state and, at the same time, converts a similar number of neutral Ir3+ donors to the Ir4+ charge state. The Fe3+ EPR spectrum slowly recovers after the light is removed, as electrons are thermally released from Fe2+ ions to the conduction band. Most of these released electrons recombine nonradiatively with holes at the deep Ir4+ donors. Using a general-order kinetics model, the analysis of isothermal recovery curves for the Fe3+ EPR signal taken between 296 and 310 K gives the activation energy for the decay of the photoinduced Fe2+ ions. A TL peak, with emitted light having wavelengths longer than 500 nm, occurs near 349 K when a few of the electrons released from Fe2+ ions recombine radiatively with holes at Ir4+ and Cr4+ donors. Photoluminescence and EPR verify the presence of Cr3+ ions.

Ir4+ ions in β-Ga2O3 crystals: An unintentional deep donor

Electron paramagnetic resonance (EPR) and infrared absorption are used to detect Ir4+ ions in β-Ga2O3 crystals. Mg and Fe doped crystals are investigated, and concentrations of Ir4+ ions greater than 1 × 1018 cm−3 are observed. The source of the unintentional deep iridium donors is the crucible used to grow the crystal. In the Mg-doped crystals, the Ir4+ ions provide compensation for the singly ionized Mg acceptors and thus contribute to the difficulties in producing p-type behavior. The Ir4+ ions replace Ga3+ ions at the Ga(2) sites, with the six oxygen neighbors forming a distorted octahedron. A large spin-orbit coupling causes these Ir4+ ions to have a low-spin (5d5, S = 1/2) ground state. The EPR spectrum consists of one broad line with a significant angular dependence. Principal values of the g matrix are 2.662, 1.815, and 0.541 (with principal axes near the crystal a, b, and c directions, respectively). Ionizing radiation at 77 K decreases the Ir4+ EPR signal in Mg-doped crystals and increases the signal in Fe-doped crystals. In addition to the EPR spectrum, the Ir4+ ions have an infrared absorption band representing a d-d transition within the t2g orbitals. At room temperature, this band peaks near 5153 cm−1 (1.94 μm) and has a width of 17 cm−1. The band is highly polarized: its intensity is maximum when the electric field E is parallel to the b direction in the crystal and is nearly zero when E is along the c direction.

Spectral and Kinetic Characteristics of the Luminescence of Ga2O3 Crystals Excited by Nano- and Subnanosecond Electron Beams

The spectral and kinetic characteristics of the emission of Sn- and Fe-doped Ga2O3 crystals excited by a nanosecond electron beam are studied. A new cathodoluminescence band of the Fe-doped crystal is revealed with a maximum at λm = 315 nm. Comparison with the data obtained with a subnanosecond duration of the beam current pulse is performed. It is shown that, with increasing duration of the beam current pulse, the main contribution is made by cathodoluminescence in the range of 300–450 nm.

Photogalvanic/pyroelectric power conversion and self-pulsing of electro-wetting of LC droplet on lithium niobate (LN)-crystal

Photogalvanic current and voltage photoinduced by CW laser illumination of Fe-doped LN reveals quasi-periodic pulsing due to microplasmas discharges. This transformation of constant external influence into periodic response is interesting as example of self-excited systems, resembling pulsations of biological systems. Microplasmas discharges are also interesting for applications in various fields, such as surface treatment, sterilization, water splitting. We analyze self-pulsing of photogalvanic current visualized by dynamic electrowetting in a simple LC-cell, formed by a nematic LC droplet placed on Fe-doped LN crystal. In modeling contributions from both photogalvanic (bulk photovoltaic) and pyroelectric (charging by heating-cooling) effect are included. The analysis of dynamic regime reveals that a current pulse (in microsecond range) has asymmetric shape with extremely sharp rise with longer decay time. Reflected interference patterned was modulated by the dynamic electro-wetting effect. For high light intensity power conversion efficiency is enhanced due to nonlinear photogalvanic effect and microplasmas discharges.

Luminescence of Ga2O3 Crystals Excited with a Runaway Electron Beam

The spectra and amplitude–time characteristics of the radiation of studied Sn and Fe-doped Ga2O3 crystals excited with a runaway electron beam and an excilamp with a wavelength of 222 nm were investigated. The main contribution to the luminescence of samples in the region of 280–900 nm under excitation with a beam was shown to be made by cathodoluminescence. In the Fe-doped crystal, a new cathodeand photoluminescence band was detected within a wavelength range of 650–850 nm. In the Sn-doped crystal, Vavilov–Cherenkov radiation was detected in the region of 280–300 nm using a monochromator and a photomultiplier.

Two-photon photoluminescence and second-harmonic generation from unintentionally doped and semi-insulating GaN crystals

Unintentionally doped and semi-insulating Fe-doped GaN crystals grown by hydride vapor phase epitaxy have been investigated with two-photon photoluminescence and second-harmonic generation spectroscopy to reveal doping effects on the nonlinear optical properties and thus indirectly on crystal properties. Like for linear luminescence, it is found that Fe doping strongly reduces nonlinear luminescence. Recording of second-harmonic generation spectra in transmission probing bulk properties shows no significant difference between doped and un-doped crystals. Reflected second-harmonic generation probing 50–100 nm at the surface, on the other hand, shows significantly lower signal from the doped sample. Secondary ion mass spectroscopy shows that the Fe concentration is higher at the surface than in the bulk of the doped crystal. It is suggested that this causes higher defect density and degraded order in the surface region, thus reducing the second-harmonic signal.

Photogalvanic self-pulsing of electro-wetting of LC droplet on LN-crystal

Photogalvanic current photoinduced by CW laser illumination of Fe-doped LN reveals quasi-periodic pulsing due to microplasmas discharges. This transformation of constant external influence into periodic response is interesting as example of self-excited systems, resembling pulsations of biological systems (including heart beats). Microplasmas is also interesting for potential applications in various fields, such as surface treatment, sterilization, water splitting, light sources, micro jets. Self-pulsing regime of microplasmas discharges in microhollow cathode discharges was observed and modeled in plasmas physics. In this paper, we analyze self-pulsing of photogalvanic current visualized by dynamic electrowetting in a simple LC-cell, formed by a nematic LC droplet placed on Fe-doped LN crystal. We have developed model of self-pulsing regime based on nonlinear discharge resistance. Experimental phase-space plot may be used to find parameters of the nonlinear discharge resistance. In the dynamic modeling contributions from both photogalvanic and pyroelectric effect are included. The analysis of dynamic regime reveals that a current pulse (in microsecond range) have asymmetric shape with extremely sharp rise with longer decay time. These self-pulsations are visualized by reflection of laser light from a LC droplet placed on LN-crystal. Reflected interference patterned was modulated by the dynamic electro-wetting effect.