skip to main content

Title: Ir 6 In 32 S 21 , a polar, metal-rich semiconducting subchalcogenide
Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal–metal and metal–chalcogenide interactions. Herein, we present Ir 6 In 32 S 21 , a novel semiconducting subchalcogenide compound that crystallizes in a new structure type in the polar P 31 m space group, with unit cell parameters a = 13.9378(12) Å, c = 8.2316(8) Å, α = β = 90°, γ = 120°. The compound has a large band gap of 1.48(2) eV, and photoemission and Kelvin probe measurements corroborate this semiconducting behavior with a valence band maximum (VBM) of −4.95(5) eV, conduction band minimum of −3.47(5) eV, and a photoresponse shift of the Fermi level by ∼0.2 eV in the presence of white light. X-ray absorption spectroscopy shows absorption edges for In and Ir do not indicate clear oxidation states, suggesting that the numerous coordination environments of Ir 6 In 32 S 21 make such assignments ambiguous. Electronic structure calculations confirm the semiconducting character with a nearly direct band gap, and electron localization function (ELF) analysis suggests that the origin of the gap is the result of electron transfer from the In atoms to the S 3p and Ir 5d orbitals. DFT calculations indicate that the more » average hole effective masses near the VBM (1.19 m e ) are substantially smaller than the average electron masses near the CBM (2.51 m e ), an unusual feature for most semiconductors. The crystal and electronic structure of Ir 6 In 32 S 21 , along with spectroscopic data, suggest that it is neither a true intermetallic nor a classical semiconductor, but somewhere in between those two extremes. « less
; ; ; ; ; ; ; ; ;
Award ID(s):
Publication Date:
Journal Name:
Chemical Science
Page Range or eLocation-ID:
870 to 878
Sponsoring Org:
National Science Foundation
More Like this
  1. Resonant tunneling diodes (RTDs) have come full-circle in the past 10 years after their demonstration in the early 1990s as the fastest room-temperature semiconductor oscillator, displaying experimental results up to 712 GHz and fmax values exceeding 1.0 THz [1]. Now the RTD is once again the preeminent electronic oscillator above 1.0 THz and is being implemented as a coherent source [2] and a self-oscillating mixer [3], amongst other applications. This paper concerns RTD electroluminescence – an effect that has been studied very little in the past 30+ years of RTD development, and not at room temperature. We present experiments and modeling of an n-type In0.53Ga0.47As/AlAs double-barrier RTD operating as a cross-gap light emitter at ~300K. The MBE-growth stack is shown in Fig. 1(a). A 15-μm-diam-mesa device was defined by standard planar processing including a top annular ohmic contact with a 5-μm-diam pinhole in the center to couple out enough of the internal emission for accurate free-space power measurements [4]. The emission spectra have the behavior displayed in Fig. 1(b), parameterized by bias voltage (VB). The long wavelength emission edge is at  = 1684 nm - close to the In0.53Ga0.47As bandgap energy of Ug ≈ 0.75 eV at 300 K.more »The spectral peaks for VB = 2.8 and 3.0 V both occur around  = 1550 nm (h = 0.75 eV), so blue-shifted relative to the peak of the “ideal”, bulk InGaAs emission spectrum shown in Fig. 1(b) [5]. These results are consistent with the model displayed in Fig. 1(c), whereby the broad emission peak is attributed to the radiative recombination between electrons accumulated on the emitter side, and holes generated on the emitter side by interband tunneling with current density Jinter. The blue-shifted main peak is attributed to the quantum-size effect on the emitter side, which creates a radiative recombination rate RN,2 comparable to the band-edge cross-gap rate RN,1. Further support for this model is provided by the shorter wavelength and weaker emission peak shown in Fig. 1(b) around = 1148 nm. Our quantum mechanical calculations attribute this to radiative recombination RR,3 in the RTD quantum well between the electron ground-state level E1,e, and the hole level E1,h. To further test the model and estimate quantum efficiencies, we conducted optical power measurements using a large-area Ge photodiode located ≈3 mm away from the RTD pinhole, and having spectral response between 800 and 1800 nm with a peak responsivity of ≈0.85 A/W at  =1550 nm. Simultaneous I-V and L-V plots were obtained and are plotted in Fig. 2(a) with positive bias on the top contact (emitter on the bottom). The I-V curve displays a pronounced NDR region having a current peak-to-valley current ratio of 10.7 (typical for In0.53Ga0.47As RTDs). The external quantum efficiency (EQE) was calculated from EQE = e∙IP/(∙IE∙h) where IP is the photodiode dc current and IE the RTD current. The plot of EQE is shown in Fig. 2(b) where we see a very rapid rise with VB, but a maximum value (at VB= 3.0 V) of only ≈2×10-5. To extract the internal quantum efficiency (IQE), we use the expression EQE= c ∙i ∙r ≡ c∙IQE where ci, and r are the optical-coupling, electrical-injection, and radiative recombination efficiencies, respectively [6]. Our separate optical calculations yield c≈3.4×10-4 (limited primarily by the small pinhole) from which we obtain the curve of IQE plotted in Fig. 2(b) (right-hand scale). The maximum value of IQE (again at VB = 3.0 V) is 6.0%. From the implicit definition of IQE in terms of i and r given above, and the fact that the recombination efficiency in In0.53Ga0.47As is likely limited by Auger scattering, this result for IQE suggests that i might be significantly high. To estimate i, we have used the experimental total current of Fig. 2(a), the Kane two-band model of interband tunneling [7] computed in conjunction with a solution to Poisson’s equation across the entire structure, and a rate-equation model of Auger recombination on the emitter side [6] assuming a free-electron density of 2×1018 cm3. We focus on the high-bias regime above VB = 2.5 V of Fig. 2(a) where most of the interband tunneling should occur in the depletion region on the collector side [Jinter,2 in Fig. 1(c)]. And because of the high-quality of the InGaAs/AlAs heterostructure (very few traps or deep levels), most of the holes should reach the emitter side by some combination of drift, diffusion, and tunneling through the valence-band double barriers (Type-I offset) between InGaAs and AlAs. The computed interband current density Jinter is shown in Fig. 3(a) along with the total current density Jtot. At the maximum Jinter (at VB=3.0 V) of 7.4×102 A/cm2, we get i = Jinter/Jtot = 0.18, which is surprisingly high considering there is no p-type doping in the device. When combined with the Auger-limited r of 0.41 and c ≈ 3.4×10-4, we find a model value of IQE = 7.4% in good agreement with experiment. This leads to the model values for EQE plotted in Fig. 2(b) - also in good agreement with experiment. Finally, we address the high Jinter and consider a possible universal nature of the light-emission mechanism. Fig. 3(b) shows the tunneling probability T according to the Kane two-band model in the three materials, In0.53Ga0.47As, GaAs, and GaN, following our observation of a similar electroluminescence mechanism in GaN/AlN RTDs (due to strong polarization field of wurtzite structures) [8]. The expression is Tinter = (2/9)∙exp[(-2 ∙Ug 2 ∙me)/(2h∙P∙E)], where Ug is the bandgap energy, P is the valence-to-conduction-band momentum matrix element, and E is the electric field. Values for the highest calculated internal E fields for the InGaAs and GaN are also shown, indicating that Tinter in those structures approaches values of ~10-5. As shown, a GaAs RTD would require an internal field of ~6×105 V/cm, which is rarely realized in standard GaAs RTDs, perhaps explaining why there have been few if any reports of room-temperature electroluminescence in the GaAs devices. [1] E.R. Brown,et al., Appl. Phys. Lett., vol. 58, 2291, 1991. [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [2] M. Feiginov et al., Appl. Phys. Lett., 99, 233506, 2011. [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [3] Y. Nishida et al., Nature Sci. Reports, 9, 18125, 2019. [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [4] P. Fakhimi, et al., 2019 DRC Conference Digest. [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018). [5] S. Sze, Physics of Semiconductor Devices, 2nd Ed. 12.2.1 (Wiley, 1981). [6] L. Coldren, Diode Lasers and Photonic Integrated Circuits, (Wiley, 1995). [7] E.O. Kane, J. of Appl. Phy 32, 83 (1961). [8] T. Growden, et al., Nature Light: Science & Applications 7, 17150 (2018).« less
  2. In this paper, the photoluminescent properties of a lead-free double perovskite Cs 2 NaInCl 6 doped with Sb 3+ are explored. The host crystal structure is a cubic double perovskite with Fm 3̄ m symmetry, a = 10.53344(4) Å, and rock salt ordering of Na + and In 3+ . It is a wide bandgap compound ( E g ≈ 5.1 eV), and substitution with Sb 3+ leads to strong absorption in the UV due to localized 5s 2 → 5s 1 5p 1 transitions on Sb 3+ centers. Radiative relaxation back to the 5s 2 ground state, via a 3 P 1 → 1 S 0 transition, leads to intense blue luminescence, centered at 445 nm, with a photoluminescent quantum yield of 79%. The Stokes shift of 0.94 eV is roughly 33% smaller than it is in the related vacancy ordered double perovskite Cs 2 SnCl 6 . The reduction in Stokes shift is likely due to a change in coordination number of Sb 3+ from 6-coordinate in Cs 2 NaInCl 6 to 5-coordinate in Cs 2 SnCl 6 . In addition to the high quantum yield, Cs 2 NaInCl 6 :Sb 3+ exhibits excellent air/moisture stability and canmore »be prepared from solution; these characteristics make it a promising blue phosphor for applications involving near-UV excitation.« less
  3. Achieving a molecular-level understanding of how the structures and compositions of metal–organic frameworks (MOFs) influence their charge carrier concentration and charge transport mechanism—the two key parameters of electrical conductivity—is essential for the successful development of electrically conducting MOFs, which have recently emerged as one of the most coveted functional materials due to their diverse potential applications in advanced electronics and energy technologies. Herein, we have constructed four new alkali metal (Na, K, Rb, and Cs) frameworks based on an electron-rich tetrathiafulvalene tetracarboxylate (TTFTC) ligand, which formed continuous π-stacks, albeit with different π–π-stacking and S⋯S distances ( d π–π and d S⋯S ). These MOFs also contained different amounts of aerobically oxidized TTFTC˙ + radical cations that were quantified by electron spin resonance (ESR) spectroscopy. Density functional theory calculations and diffuse reflectance spectroscopy demonstrated that depending on the π–π-interaction and TTFTC˙ + population, these MOFs enjoyed varying degrees of TTFTC/TTFTC˙ + intervalence charge transfer (IVCT) interactions, which commensurately affected their electronic and optical band gaps and electrical conductivity. Having the shortest d π–π (3.39 Å) and the largest initial TTFTC˙ + population (∼23%), the oxidized Na-MOF 1-ox displayed the narrowest band gap (1.33 eV) and the highest room temperature electrical conductivitymore »(3.6 × 10 −5 S cm −1 ), whereas owing to its longest d π–π (3.68 Å) and a negligible TTFTC˙ + population, neutral Cs-MOF 4 exhibited the widest band gap (2.15 eV) and the lowest electrical conductivity (1.8 × 10 −7 S cm −1 ). The freshly prepared but not optimally oxidized K-MOF 2 and Rb-MOF 3 initially displayed intermediate band gaps and conductivity, however, upon prolonged aerobic oxidation, which raised the TTFTC˙ + population to saturation levels (∼25 and 10%, respectively), the resulting 2-ox and 3-ox displayed much narrower band gaps (∼1.35 eV) and higher electrical conductivity (6.6 × 10 −5 and 4.7 × 10 −5 S cm −1 , respectively). The computational studies indicated that charge movement in these MOFs occurred predominantly through the π-stacked ligands, while the experimental results displayed the combined effects of π–π-interactions, TTFTC˙ + population, and TTFTC/TTFTC˙ + IVCT interaction on their electronic and optical properties, demonstrating that IVCT interactions between the mixed-valent ligands could be exploited as an effective design strategy to develop electrically conducting MOFs.« less
  4. Rocksalt structure nitrides emerge as a promising class of semiconductors for high-temperature thermoelectric and plasmonic applications. Controlling the bandgap and strain is essential for the development of a wide variety of electronic devices. Here we use (Ti 0.5 Mg 0.5 ) 1−x Al x N as a model system to explore and demonstrate the tunability of both the bandgap and the strain state in rocksalt structure nitrides, employing a combined experimental and computational approach. (Ti 0.5 Mg 0.5 ) 1−x Al x N layers with x ≤ 0.44 deposited on MgO(001) substrates by reactive co-sputtering at 700 °C are epitaxial single crystals with a solid-solution B1 rocksalt structure. The lattice mismatch with the substrate decreases with increasing x , leading to a transition in the strain-state from partially relaxed (74% and 38% for x = 0 and 0.09) to fully strained for x ≥ 0.22. First-principles calculations employing 64-atom Special Quasirandom Structures (SQS) indicate that the lattice constant decreases linearly with x according to a = (4.308 − 0.234 x ) Å for 0 ≤ x ≤ 1. In contrast, the measured relaxed lattice parameter a o = (4.269 − 0.131 x ) Å is linear only for x ≤more »0.33, its composition dependence is less pronounced, and x > 0.44 leads to the nucleation of secondary phases. The fundamental (indirect) bandgap predicted using the same SQS supercells and the HSE06 functional increases from 1.0 to 2.6 eV for x = 0–0.75. In contrast, the onset of the measured optical absorption due to interband transitions increases only from 2.3 to 2.6 eV for x = 0–0.44, suggesting that the addition of Al in the solid solution relaxes the electron momentum conservation and causes a shift from direct to indirect gap transitions. The resistivity increases from 9.0 to 708 μΩ m at 77 K and from 6.8 to 89 μΩ m at 295 K with increasing x = 0–0.44, indicating an increasing carrier localization associated with a randomization of cation site occupation and the increasing bandgap which also causes a 33% reduction in the optical carrier concentration. The overall results demonstrate bandgap and strain engineering in rocksalt nitride semiconductors and show that, in contrast to conventional covalent semiconductors, the random cation site occupation strongly affects optical transitions.« less
  5. Orthorhombic BaZrS 3 is a potential optoelectronic material with prospective applications in photovoltaic and thermoelectric devices. While efforts exist on understanding the effects of elemental substitution and material stability, fundamental knowledge on the electronic transport properties are sparse. We employ first principles calculations to examine the electronic band structure and optical band gap and interrogate the effect of electron transport on electrical and thermal conductivities, and Seebeck coefficient, as a function of temperature and chemical potential. Our results reveal that BaZrS 3 has a band gap of 1.79 eV in proximity of the optimal 1.35 eV recommended for single junction photovoltaics. An absorption coefficient of 3 × 10 5 cm −1 at photon energies of 3 eV is coupled with an early onset to optical absorption at 0.5 eV, significantly below the optical band gap. The carrier effective mass being lower for electrons than holes, we find the Seebeck coefficient to be higher for holes than electrons. A notable (≈1.0 at 300 K) upper limit to the thermoelectric figure of merit, obtained due to high Seebeck coefficient (3000 μV K −1 ) and ultra-low electron thermal conductivity, builds promise for BaZrS 3 as a thermoelectric.