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1. Ferromagnetism in 2D organic iron hemoglobin crystals based on nitrogenated conjugated micropore materials

   https://doi.org/10.1039/c9cp04509k  

   Pimachev, Artem ; Nielsen, Robert D. ; Karanovich, Anri ; Dahnovsky, Yuri ( November 2019 , Physical Chemistry Chemical Physics)

   In this work we study a low-cost two-dimensional ferromagnetic semiconductor with possible applications in biomedicine, solar cells, spintronics, and energy and hydrogen storage. From first principle calculations we describe the unique electronic, transport, optical, and magnetic properties of a π-conjugated micropore polymer (CMP) with three iron atoms placed in the middle of an isolated pore locally resembling heme complexes. This material exhibits strong Fe-localized d z2 bands. The bandgap is direct and equal to 0.28 eV. The valence band is doubly degenerate at the Γ -point and for larger k -wavevectors the HOMO band becomes flat with low contribution to charge mobility. The absorption coefficient is roughly isotropic. The conductivity is also isotropic with the nonzero contribution in the energy range 0.3–8 eV. The xy -component of the imaginary part of the dielectric tensor determines the magneto-optical Faraday and Kerr rotation. Nonvanishing rotation is observed in the interval of 0.5–5.0 eV. This material is found to be a ferromagnet of an Ising type with long-range exchange interactions with a very high magnetic moment per unit cell, m = 6 μ B . The exchange integral is calculated by two independent methods: (a) from the energy difference between ferromagnetic and antiferromagneticmore »states and (b) from a magnon dispersion curve. In the former case J nn = 27 μeV. In the latter case the magnon dispersion is fitted by the Ising model with the nearest and next-nearest neighbor spin interactions. From these estimations we find that J nn = 19.5 μeV and J nnn = −3 μeV. Despite the different nature of the calculations, the exchange integrals are only within 28% difference.« less
2. RTD Light Emission around 1550 nm with IQE up to 6% at 300 K

   https://doi.org/10.1109/DRC50226.2020.9135175  

   Brown, E. R. ; Zhang, W-D. ; Fakhimi, P. ; Growden, T. A. ; Berger, P.R. ( June 2020 , IEEE Device Research Conference (DRC), Columbus, OH (June 22-24, 2020))

   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
3. Modular Design of Multifunctionality in TCNQ-Based Fe(II) Spin Crossover Complexes

   Üngör, Ö. ; Choi, E. S. ; Shatruk, M. ( April 2021 , National Meeting of the Anerican Chemical Society)

   Fe(II) coordination complexes with ligands of an intermediate field strength often show witching between the high-spin (HS) and low-spin (LS) electronic configurations, known as spin crossover (SCO). This spin-state conversion is achieved by changes in temperature, pressure, or photoexcitation, which make SCO complexes promising materials for various applications that rely on bistable systems. Multifunctional materials that exhibit both spin-state switching and conductivity can be created by combining Fe(II) SCO complexes with organic TCNQ-type electron acceptors. In such complexes, TCNQ●d– radical anions are typically arranged in layers of one-dimensional stacks that provide conducting pathways (Fig. 1). The stacking distance can be affected by structural changes induced by the alteration in the electronic configuration and, thus, bond lengths at the Fe(II) center, resulting in synergy between SCO and conductivity. The synthesis of such materials can be approached in two ways: (1) by coordinating TCNQ●d– ligands directly to the Fe(II) center, which is partially protected by blocking ligands that limit the growth of extended structures or (2) by co-crystallizing completely blocked Fe(II) centers with free TCNQ●d– radicals. We will discuss several examples of the second approach, in which homoleptic Fe(II) cationic SCO complexes with tridentate 2,6-bispyrazolyl-pyridine (bpp) type ligands have been co-crystallized withmore »fractionally-charged TCNQ●d– radical anions. The temperature- and solvent-dependent magnetic behavior and transport properties of these materials will be discussed. We will also present new pathways to improve the design of such molecule-based conductors with spin-state switching properties. To the best of out knowledge, we report the first examples of Fe(II) based conducting molecular materials with abrupt temperature-driven spin transitions.« less
4. Spectroscopic Properties of the Astrochemical Molecules [Al, O, Si] ^x (x = 0, +1)

   https://doi.org/10.3847/1538-4357/ac92fb  

   Friskey, Jacqueline M. ; Esposito, Vincent J. ; Trabelsi, Tarek ; Francisco, Joseph S. ( October 2022 , The Astrophysical Journal)

   Aluminum and silicon are present in large quantities in the interstellar medium, making the triatomic species consisting of both elements intriguing with regard to the foundations of astrochemistry. Spectroscopic parameters have been calculated via high-level ab initio methods to assist with laboratory and observational detection of [Al, O, Si]^x(x= 0,+1). All [Al, O, Si]^x(x= 0,+1) isomers exist in the linear geometry, with linear AlOSi (X²Π) and linear AlOSi⁺(X¹Δ) being the most stable neutral and cationic species, respectively. Formation of the neutral species most likely occurs via reaction of AlO/SiO on an Si/Al dust grain surface, respectively. The cation molecules may form via ion–neutral reaction or as a consequence of photoionization. The rotational frequencies of linear AlOSi (X²Π) have been calculated using vibrationally corrected rotational constants and centrifugal distortion to lead experimental and observational radio detection. The rotational frequencies are discussed for three temperatures indicative of various astronomical environments: the central circumstellar envelope (CSE) (100 K), outer CSE (30 K), and the interstellar medium (3 K). At 100 K, the lines originating fromJ′ > 30 are the best candidates for detection via ground-based telescope. Anharmonic vibrational analysis revealed various Fermi resonances that may complicate the vibrational spectrum of linear AlOSimore »(X²Π). Finally, electronic spectroscopy may be the best means for laboratory detection of linear AlOSi (X²Π), due to the presence of two overlapping electronic transitions with large oscillator strengths occurring at approximately 250 nm.

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5. Elucidating the Role of B-Site Cations toward CO ₂ Reduction in Perovskite-Based Solid Oxide Electrolysis Cells

   https://doi.org/10.1149/1945-7111/ac5e9b  

   Tezel, Elif ; Guo, Dezhou ; Whitten, Ariel ; Yarema, Genevieve ; Freire, Maikon ; Denecke, Reinhard ; McEwen, Jean-Sabin ; Nikolla, Eranda ( March 2022 , Journal of The Electrochemical Society)

   Solid oxide electrolysis cells (SOECs) are promising for the selective electrochemical conversion of CO 2 , or mixed streams of CO 2 and H 2 O, into high energy products such as CO and H 2 . However, these systems are limited by the poor redox stability of the state-of-the-art Ni-based cathode electrocatalysts. Due to their favorable redox properties, mixed ionic-electronic conducting (MIEC) oxides have been considered as promising alternatives. However, improvement of the electrochemical performance of MIEC-based SOEC electrocatalysts is needed and requires an understanding of the factors that govern their activity. Herein, we investigate the effect of B-site 3 d metal cations (Cr, Fe, Co, Ni) of LaBO 3 perovskites on their CO 2 electrochemical reduction activity in SOECs. We find that their electrochemical performance is highly dependent on the nature of the B-site cation and trends as LaFeO 3 > LaCoO 3 > LaNiO 3 > LaCrO 3 . Among these perovskites, LaNiO 3 is the least stable and decomposes under electrochemical conditions. In situ characterization and ab initio theoretical calculations suggest that both the nature of the B-site cation and the presence of oxygen surface vacancies impact the energetics of CO 2 adsorption and reduction. Thesemore »studies provide fundamental insights critical toward devising ways to improve the performance of MIEC-based SOEC cathodes for CO 2 electroreduction.« less