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1. Towards Horizontal Heterojunctions for Tunnel Field Effect Transistors with Template Assisted Selective Epitaxy via MOCVD

   Brunelli, Simone ; Markman, B ; Wu, J ; Tseng, HY ; Goswami, A ; Rodwell, M ; Palmstrøm, P ; Klamkin, K ( June 2018 , International conference on MOVPE)

   Tunneling field effect transistors (TFETs) have gained much interest in the previous decade for use in low power CMOS electronics due to their sub-thermal switching [1]. To date, all TFETs are fabricated as vertical nanowires or fins with long, difficult processes resulting in long learning cycle and incompatibility with modern CMOS processing. Because most TFETs are heterojunction TFETs (HJ-TFETs), the geometry of the device is inherently vertically because dictated by the orientation of the tunneling HJ, achieved by typical epitaxy. Template assisted selective epitaxy was demonstrated for vertical nanowires [2] and horizontally arranged nanorods [3] for III-V on Si integration. In this work, we report results on the area selective and template assisted epitaxial growth of InP, utilizing SiO2 based confined structures on InP substrates, which enables horizontal HJs, that can find application in the next generation of TFET devices. The geometries of the confined structures used are so that only a small area of the InP substrate, dubbed seed, is visible to the growth atmosphere. Growth is initiated selectively only at the seed and then proceeds in the hollow channel towards the source hole. As a result, growth resembles epitaxial lateral overgrowth from a single nucleation point [4], reapingmore »the benefits of defect confinement and, contrary to spontaneous nanowire growth, allows orientation in an arbitrary, template defined direction. Indium phosphide 2-inch (110) wafers are used as the starting substrate. The process flow (Fig.1) consists of two plasma enhanced chemical vapor deposition (PECVD) steps of SiO2, appropriately patterned with electron beam lithography (EBL), around a PECVD amorphous silicon sacrificial layer. The sacrificial layer is ultimately wet etched with XeF2 to form the final, channel like template. Not shown in the schematic in Fig.1 is an additional, ALD deposited, 3 nm thick, alumina layer which prevents plasma damage to the starting substrate and is removed via a final tetramethylammonium hydroxide (TMAH) based wet etch. As-processed wafers were then diced and loaded in a Thomas Swan Horizontal reactor. Successful growth conditions found were 600°C with 4E6 mol/min of group III precursor, a V/III ratio of 400 and 8 lpm of hydrogen as carrier gas. Trimethylindium (TMIn) and tertiarybutylphosphine (TBP) were used as In and P precursors respectively. Top view SEM (Fig.2) confirms growth in the template thanks to sufficient Z-contrast despite the top oxide layer, not removed before imaging. TEM imaging shows a cross section of the confined structure taken at the seed hole (Fig.3). The initial growth interface suggests growth was initiated at the seed hole and atomic order of the InP conforms to the SiO2 template both at the seed and at the growth front. A sharp vertical facet is an encouraging result for the future development of vertical HJ based III-V semiconductor devices.« less
2. Improvements in Gold Nanorod Biocompatibility with Sodium Dodecyl Sulfate Stabilization

   https://doi.org/10.3390/jnt2030010  

   Terracciano, Rossana ; Zhang, Aobo ; Simeral, Mathieu L. ; Demarchi, Danilo ; Hafner, Jason H. ; Filgueira, Carly S. ( September 2021 , Journal of Nanotheranostics)

   Due to their well-defined plasmonic properties, gold nanorods (GNRs) can be fabricated with optimal light absorption in the near-infrared region of the electromagnetic spectrum, which make them suitable for cancer-related theranostic applications. However, their controversial safety profile, as a result of surfactant stabilization during synthesis, limits their clinical translation. We report a facile method to improve GNR biocompatibility through the presence of sodium dodecyl sulfate (SDS). GNRs (120 × 40 nm) were synthesized through a seed-mediated approach, using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant to direct the growth of nanorods and stabilize the particles. Post-synthesis, SDS was used as an exchange ligand to modify the net surface charge of the particles from positive to negative while maintaining rod stability in an aqueous environment. GNR cytotoxic effects, as well as the mechanisms of their cellular uptake, were examined in two different cancer cell lines, Lewis lung carcinoma (LLC) and HeLa cells. We not only found a significant dose-dependent effect of GNR treatment on cell viability but also a time-dependent effect of GNR surfactant charge on cytotoxicity over the two cell lines. Our results promote a better understanding of how we can mediate the undesired consequences of GNR synthesis byproducts whenmore »exposed to a living organism, which so far has limited GNR use in cancer theranostics.« less
3. Catalytic oxidation of propane over palladium alloyed with gold: an assessment of the chemical and intermediate species

   https://doi.org/10.1039/c8cy01704b  

   Kareem, Haval ; Shan, Shiyao ; Wu, Zhi-Peng ; Velasco, Leslie ; Moseman, Kelli ; O'Brien, Casey P. ; Tran, Dat T. ; Lee, Ivan C. ; Maswadeh, Yazan ; Yang, Lefu ; et al ( November 2018 , Catalysis Science & Technology)

   Understanding the catalytic oxidation of propane is important for developing catalysts not only for catalytic oxidation of hydrocarbons in emission systems but also for selective oxidation in the chemical processing industry. For palladium-based catalysts, little is known about the identification of the chemical or intermediate species involved in propane oxidation. We describe herein findings of an investigation of the catalytic oxidation of propane over supported palladium nanoalloys with different compositions of gold (Pd n Au 100−n ), focusing on probing the chemical or intermediate species on the catalysts in correlation with the bimetallic composition and the alloying phase structure. In addition to an enhanced catalytic activity, a strong dependence of the catalytic activity on the bimetallic composition was revealed, displaying an activity maximum at a Pd : Au ratio of 50 : 50 in terms of reaction temperature. This dependence is also reflected by its dependence on the thermochemical treatment conditions. While the activity for nanoalloys with n ∼ 50 showed little change after the thermochemical treatment under oxygen, the activities for nanoalloys with n < 50 and n > 50 showed opposite trends. Importantly, this catalytic synergy is linked to the subtle differences of chemical and intermediate species which have been identified formore »the catalysts with different bimetallic compositions by in situ measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). For the catalytic oxidation of propane over the highly-active catalyst with a Pd : Au ratio of 50 : 50, the major species identified include acetate and bicarbonate, showing subtle differences in comparison with the identification of bicarbonate and formate for the catalyst with <50% Au (with a lower activity) and the absence of apparent species for the catalyst with >50% Au (activity is largely absent). The alloying of 50% Au in Pd is believed to increase the oxophilicity of Pd, which facilitates the first carbon–carbon bond cleavage and oxygenation of propane. The implications of the findings on the catalytic synergy of Pd alloyed with Au and the design of active Pd alloy catalysts are also discussed.« less
4. Thermophoresis of gold nanorods from surface enhanced Raman scattering and real-time Rayleigh scattering in solution

   https://doi.org/10.1039/c9ay00104b  

   Makihara, Takuma ; Demers, Steven M. ; Cole, Louis E. ; Zhang, Aobo ; Hafner, Jason H. ( May 2019 , Analytical Methods)

   Surface-enhanced Raman scattering (SERS) from gold and silver nanoparticles suspended in solution enables a more quantitative level of analysis relative to SERS from aggregated nanoparticles and roughened metal substrates. This is due to the more predictable and consistent near field enhancement regions created by isolated nanoparticles, and to averaging over the many nanoparticles that diffuse through the excitation beam during the measurement. However, we find that localized heating of the solution by the focused excitation leads to thermophoresis which alters the nanorod concentration in the focal volume and therefore impacts quantitative analysis. Since many phenomena may impact the Raman signal, we record both the Rayleigh and Raman scattering from gold nanoparticle solutions. This allows us to distinguish molecular processes from depletion of nanoparticles in the excitation beam. We observe that the concentration of nanorods can deplete to less than 50% of its original value over 100 second timescale, which are consistent with a thermophoretic effect driving nanoparticles from the beam spot. We also find that the particle motion drives convection within the sample cell that further contributes to signal instabilities.
5. Electrochemical investigations of metal nanostructure growth with single crystals

   https://doi.org/10.1039/c9nr05782j  

   Kim, Myung Jun ; Brown, Micah ; Wiley, Benjamin J. ( November 2019 , Nanoscale)

   Control over the nanoscopic structure of a material allows one to tune its properties for a wide variety of applications. Colloidal synthesis has become a convenient way to produce anisotropic metal nanostructures with a desired set of properties, but in most syntheses, the facet-selective surface chemistry causing anisotropic growth is not well-understood. This review highlights the recent use of electrochemical methods and single-crystal electrodes to investigate the roles of organic and inorganic additives in modulating the rate of atomic addition to different crystal facets. Differential capacitance and chronocoulometric techniques can be used to extract thermodynamic data on how additives selectively adsorb, while mixed potential theory can be used to observe the effect of additives on the rate of atomic addition to a specific facet. Results to date indicate that these experimental methods can provide new insights into the role capping agents and halides play in controlling anisotropic growth.