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1. Bandgap and strain engineering in epitaxial rocksalt structure (Ti _0.5 Mg _0.5 ) _1−x Al _x N(001) semiconductors

   https://doi.org/10.1039/d0tc03598j  

   Wang, Baiwei ; Zhang, Minghua ; Adhikari, Vijaya ; Fang, Peijiao ; Khare, Sanjay V. ; Gall, Daniel ( September 2020 , Journal of Materials Chemistry C)

   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
2. The impact of site selectivity and disorder on the thermoelectric properties of Yb ₂₁ Mn ₄ Sb ₁₈ solid solutions: Yb ₂₁ Mn _4−x Cd _x Sb ₁₈ and Yb _21−y Ca _y Mn ₄ Sb ₁₈

   https://doi.org/10.1039/d1ma00497b  

   He, Allan ; Cerretti, Giacomo ; Kauzlarich, Susan M. ( August 2021 , Materials Advances)

   Thermoelectric materials can convert heat into electricity. They are used to generate electricity when other power sources are not available or to increase energy efficiency by recycling waste heat. The Yb 21 Mn 4 Sb 18 phase was previously shown to have good thermoelectric performance due to its large Seebeck coefficient (∼290 μV K −1 ) and low thermal conductivity (0.4 W m −1 K −1 ). These characteristics stem respectively from the unique [Mn 4 Sb 10 ] 22− subunit and the large unit cell/site disorder inherent in this phase. The solid solutions, Yb 21 Mn 4− x Cd x Sb 18 ( x = 0, 0.5, 1.0, 1.5) and Yb 21− y Ca y Mn 4 Sb 18 ( y = 3, 6, 9, 10.5) have been prepared, their structures characterized and thermoelectric properties from room temperature to 800 K measured. A detailed look into the structural disorder for the Cd and Ca solid solutions was performed using synchrotron powder X-ray diffraction and pair distribution function methods and shows that these are highly disordered structures. The substitution of Cd gives rise to more metallic behavior whereas Ca substitution results in high resistivity. As both Cd and Ca aremore »isoelectronic substitutions, the changes in properties are attributed to changes in the electronic structure. Both solid solutions show that the thermal conductivities remain extremely low (∼0.4 W m −1 K −1 ) and that the Seebeck coefficients remain high (>200 μV K −1 ). The temperature dependence of the carrier mobility with increased Ca substitution, changing from approximately T −1 to T −0.5 , suggests that another scattering mechanism is being introduced. As the bonding changes from polar covalent with Yb to ionic for Ca, polar optical phonon scattering becomes the dominant mechanism. Experimental studies of the Cd solid solutions result in a max zT of ∼1 at 800 K and, more importantly for application purposes, a ZT avg ∼ 0.6 from 300 K to 800 K.« less
3. Facile Processing and Properties of P-Type SnOx and Oxide-based p-n Heterojunction Application with n-InGaZnO

   Lee, Dong Hun ; Song, Han Wook ; Rothschild, Molly ; Choi, Joonsoo ; Lee, Sunghwan ( June 2022 , 64th Electronic Materials Conference)

   In recent years, oxide electronics has emerged as one of the most promising new technologies for a variety of electrical and optoelectronic applications, including next-generation displays, solar cells, batteries, and photodetectors. Oxide electronics have a lot of potential because of their high carrier mobilities and ability to be manufactured at low temperatures. However, the preponderance of oxide semiconductors is n-type oxides, limiting present applications to unipolar devices and stifling the development of oxide-based bipolar devices like p-n diodes and complementary metal-oxide–semiconductors. We have contributed to oxide electronics, particularly on transition metal oxide semiconductors of which the cations include In, Zn, Sn and Ga. We have integrated these oxide semiconductors into thin film transistors (TFTs) as active channel layer in light of the unique combination of electronic and optical properties such as high carrier mobility (5-10 cm2/Vs), optical transparency in the visible regime (>~90%) and mild thermal budget processing (200-400°C). In this study, we achieved four different results. The first result is that unlike several previous reports on oxide p-n junctions fabricated exploiting a thin film epitaxial growth technique (known as molecular beam epitaxy, MBE) or a high-powered laser beam process (known as pulsed laser deposition, PLD) that requires ultra-high vacuummore »conditions, a large amount of power, and is limited for large-area processing, we demonstrate oxide-based heterojunction p-n diodes that consist of sputter-synthesized p-SnOx and n-IGZO of which the manufacturing routes are in-line with current manufacturing requirements. The second result is that the synthesized p-SnOx films are devoid of metallic Sn phases (i.e., Sn0 state) with carrier density tuneability and high carrier mobility (> 2 cm2/Vs). The third result is that the charge blocking performance of the metallurgical junction is significantly enhanced by the engineering of trap/defect density of n-IGZO, which is identified using photoelectron microscopy and valence band measurements. The last result is that the resulting oxide-based p-n heterojunction exhibits a high rectification ratio greater than 103 at ±3 V (highest among the sputter-processed oxide junctions), a low saturation current of ~2×10-10 A, and a small turn-on voltage of ~0.5 V. The outcomes of the current study are expected to contribute to the development of p-type oxides and their industrial device applications such as p-n diodes of which the manufacturing routes are in-line with the current processing requirements.« less
4. Effect of R-site element on crystalline phase and thermal stability of Fe substituted Mn mullite-type oxides: R ₂ (Mn _1−x Fe _x ) ₄ O _10−δ (R = Y, Sm or Bi; x = 0, 0.5, 1)

   https://doi.org/10.1039/C7RA09699B  

   Thampy, Sampreetha ; Ashburn, Nickolas ; Martin, Thomas J. ; Li, Chenzhe ; Zheng, Yongping ; Chan, Julia Y. ; Cho, Kyeongjae ; Hsu, Julia W. ( January 2018 , RSC Advances)

   Combining experimental and theoretical studies, we investigate the role of R-site (R = Y, Sm, Bi) element on the phase formation and thermal stability of R 2 (Mn 1−x Fe x ) 4 O 10−δ ( x = 0, 0.5, 1) mullite-type oxides. Our results show a distinct R-site dependent phase behavior for mullite-type oxides as Fe is substituted for Mn: 100% mullite-type phase was formed in (Y, Sm, Bi) 2 Mn 4 O 10 ; 55% and 18% of (Y, Sm) 2 Mn 2 Fe 2 O 10−δ was found when R = Y and Sm, respectively, for equal Fe and Mn molar concentrations in the reactants, whereas Bi formed 54% O10- and 42% O9-mixed mullite-type phases. Furthermore, when the reactants contain 100% Fe, no mullite-type phase was formed for R = Y and Sm, but a sub-group transition to Bi 2 Fe 4 O 9 O9-phase was found for R = Bi. Thermogravimetric analysis and density functional theory (DFT) calculation results show a decreasing thermal stability in O10-type structure with increasing Fe incorporation; for example, the decomposition temperature is 1142 K for Bi 2 Mn 2 Fe 2 O 10−δ vs. 1217 K for Bi 2 Mn 4more »O 10 . On the other hand, Bi 2 Fe 4 O 9 O9-type structure is found to be thermally stable up to 1227 K. These findings are explained by electronic structure calculations: (1) as Fe concentration increases, Jahn–Teller distortion results in mid band-gap empty states from unstable Fe 4+ occupied octahedra, which is responsible for the decrease in O10 structure stability; (2) the directional sp orbital hybridization unique to Bi effectively stabilizes the mullite-type structure as Fe replaces Mn.« less
5. Laser-induced atmospheric Cu _x O formation on copper surface with enhanced electrochemical performance for non-enzymatic glucose sensing

   https://doi.org/10.1039/d1tc01289d  

   Sedaghat, Sotoudeh ; Nejati, Sina ; Bermejo, Luis Helena ; He, Zihao ; Alcaraz, Alejandro M. ; Roth, Alexander ; Li, Zheng ; Pol, Vilas G. ; Wang, Haiyan ; Rahimi, Rahim ( November 2021 , Journal of Materials Chemistry C)

   Copper oxide nanostructures are widely used for various applications due to their unique optical and electrical properties. In this work, we demonstrate an atmospheric laser-induced oxidation technique for the fabrication of highly electrochemically active copper oxide hierarchical micro/nano structures on copper surfaces to achieve highly sensitive non-enzymatic glucose sensing performance. The effect of laser processing power on the composition, crystallinity, microstructure, wettability, and color of the laser-induced oxide on copper (LIO-Cu) surface was systematically studied using scanning electron microscopy (SEM), grazing incidence X-ray diffraction (GI-XRD), Raman spectroscopy, energy dispersive X-ray spectroscopy (EDX), EDX-mapping, water contact angle measurements, and optical microscopy. Results of these investigations showed a remarkable increase in copper oxide composition by increasing the laser processing power. The pore size distribution and surface area of the pristine and LIO-Cu sample estimated by N 2 adsorption–desorption data showed a developed mesoporous LIO-Cu structure. The size of the generated nano-oxides, crystallinity, and electroactivity of the LIO-Cu were observed to be adjustable by the laser processing power. The electrocatalytic activity of LIO-Cu surfaces was studied by means of cyclic voltammetry (CV) within a potential window of −0.8 to +0.8 V and chronoamperometry in an applied optimized potential of +0.6 V, in 0.1more »M NaOH solution and phosphate buffer solution (PBS), respectively. LIO-Cu surfaces with optimized laser processing powers exhibited a sensitivity of 6950 μA mM −1 cm −2 within a wide linear range from 0.01 to 5 mM, with exceptional specificity and response time (<3 seconds). The sensors also showed excellent response stability over a course of 50 days that was originated from the binder-free robust electroactive film fabricated directly onto the copper surface. The demonstrated one-step LIO processing onto commercial metal films, can potentially be applied for tuneable and scalable roll-to-roll fabrication of a wide range of high surface area metal oxide micro/nano structures for non-enzymatic biosensing and electrochemical applications.« less