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Wang, Cai; Zheng, Chunfang; Zhao, Huaping; Fu, Qun; Lei, Yong
TiO2 thickness-dependent charge transfer effect in p-aminothiophenol molecules chemisorbed on TiO2/Ni substrates. - In: Applied surface science, Bd. 610 (2023), 155573

Semiconductors have been modulated in thickness to optimize their surface-enhanced Raman scattering (SERS) activity in noble metal/semiconductor SERS substrates. However, the charge transfer (CT) resonance mechanism caused by the change of the semiconductor thickness has not been fully clarified yet, due to the influence of the strong surface plasmon resonance (SPR) effect from the noble metals. Here, systems of p-aminothiophenol (PATP) molecules chemisorbed on TiO2/Ni nanopillar array films with precisely controlled TiO2 thicknesses (PATP/TiO2/Ni) were developed to systematically evaluate the TiO2 thickness-dependent CT mechanism on the premise of minimizing the SPR influence. Ultraviolet-visible, photoluminescence and X-ray photoelectron spectroscopy results demonstrated that four parts that ascribed to the SERS enhancement, photo-induced CT from Ni to TiO2, resonance excitation of TiO2, CT from TiO2 surface states to PATP molecules, and the molecular resonance of PATP molecules, are highly TiO2-thickness dependent. Hence the whole system exhibits a strong TiO2-thickness-dependent CT effect (at the two interfaces of Ni-TiO2 and TiO2-PATP) and SERS activity with a maximum SERS intensity at a TiO2 thickness of 40 nm. This work shall be valuable for future developing an optimal metal/semiconductor SERS substrates and obtaining an in-depth understanding of the semiconductor-thickness-dependent charge transfer mechanism for SERS applications.
Link, Steffen; Dimitrova, Anna; Krischok, Stefan; Ivanov, Svetlozar
Electrochemical deposition of silicon in organic electrolytes. - In: Reference module in chemistry, molecular sciences and chemical engineering, (2023)

Electrodeposition is a versatile instrumental technique, already applied in many industrial fields. However, the deposition of silicon and other reactive elements is still challenging and requires further research and improvement. Accomplishing an efficient electrodeposition of silicon at room temperature is very attractive due to the high number of manufacturing technologies that would benefit from this approach. This work provides an overview of the electrochemical approaches for silicon deposition performed in organic electrolytes. The main factors that impact this process are individually discussed and exemplified with appropriately updated literature sources. Furthermore, the previously available research on characterization of electrodeposited silicon containing layers is provided. These studies are presented in the context of better understanding the structure, composition, and functional properties of the deposited silicon material, which may attract the attention of young academic scientists and process engineers.
Borkenhagen, Benjamin; Paszuk, Agnieszka; Knoop, Franz Niklas; Supplie, Oliver; Nandy, Manali; Lilienkamp, Gerhard; Kleinschmidt, Peter; Hannappel, Thomas; Daum, Winfried
Structure and origin of antiphase domains and related defects in thin GaP epilayers on As-modified Si(100). - In: Crystal growth & design, ISSN 1528-7505, Bd. 22 (2022), 12, S. 7040-7049

We study the origin and formation of antiphase domains (APDs) and related defects in 7 nm thin, lattice-matched GaP buffer layers deposited by metal-organic chemical vapor deposition (MOCVD) on well-defined, nearly single-domain, double-layer stepped, low-miscut Si(100) substrates obtained by specific treatment with arsenic. Using dark-field imaging modes in low-energy electron microscopy (LEEM), the minority reconstruction domains of Si(100):As and the APDs of the deposited GaP epilayer are identified, quantified, and compared. We show that residual (2x1)-reconstructed terraces of the minority domain on the Si substrate cause the formation of APDs and that the fraction of the minority domain of the substrate (≅0.07) entails a comparable fraction of APDs in thin GaP epilayers. The topographies of APDs are revealed by atomic force microscopy (AFM) and by scanning tunneling microscopy (STM). We observe two very different APD-related defects in the GaP epilayer, both pinned to residual monolayer steps of the substrate. GaP growth on minority domain terraces with widths in the range of 40-100 nm gives rise to APDs of comparable lateral dimensions. Minority domain terraces of the substrate with widths <20 nm cause the formation of 7-20 nm wide trenches in the GaP layer with rampart-like mounds along their rims. Using nanoscale Auger electron spectroscopy (AES), we provide evidence that these trenches extend through the GaP layer down to the exposed, uncovered Si substrate. We conclude that nucleation of GaP on small minority domain terraces is largely inhibited as most Ga and P atoms deposited on these terraces diffuse across the domain boundary and side walls of emerging trenches to adjacent majority domain terraces where they form the observed mounds. Nucleation of GaP does take place on minority domain terraces with widths ≥40 nm and leads to the growth of APDs.
Qiao, Yu; Zhao, Huaping; Rao, Zhonghao; Lei, Yong
High adsorption graphene oxide prepared by graphite anode from spent lithium-ion batteries for methylene blue removal. - In: Batteries, ISSN 2313-0105, Bd. 8 (2022), 249, 249, S. 1-13

Limited by the service life, a large amount of spent lithium-ion batteries (LIBs) have been produced in recent years. Without proper disposal, spent LIBs can cause environmental pollution and waste of resources. In this paper, we focus on the recycling of the graphite anode (GA) in spent LIBs. GAs from spent LIBs were converted to graphene oxide (GO) through a modified Hummers method. Then the prepared GO was applied to absorb methylene blue in dyeing wastewater under different reaction conditions. The experimental results indicate that GO can quickly and effectively adsorb methylene blue, which also exhibits thermal stability. The maximum adsorption capacity and removal rate are about 833.11 mg/g and 99.95%, respectively. The adsorption kinetics and isotherms were investigated; the adsorption process of GO is more consistent with the pseudo-second-order adsorption kinetic model while the isotherm is close to the Langmuir isotherm. This study is of great significance for the economy and environment. The reaction can turn waste into wealth and is a win-win approach for both spent LIBs recycling and dyeing wastewater cleaning.
Gizatullin, Bulat; Mattea, Carlos; Stapf, Siegfried
Three mechanisms of room temperature dynamic nuclear polarization occur simultaneously in an ionic liquid. - In: Physical chemistry, chemical physics, ISSN 1463-9084, Bd. 24 (2022), 44, S. 27004-27008

Dynamic nuclear polarization is a versatile approach to increasing the sensitivity of NMR measurements and is achieved by any of four different mechanisms which dominate for either liquids or solids, depending on temperature and radical density. In this work, we unequivocally demonstrate for the first time the coexistence, at a comparable magnitude, of several mechanisms, namely the Overhauser effect, solid effect, and cross-effect/thermal mixing in a viscous ionic liquid at ambient temperatures.
Glahn, Luis Joel; Ruiz Alvarado, Isaac Azahel; Neufeld, Sergej; Zare Pour, Mohammad Amin; Paszuk, Agnieszka; Ostheimer, David; Shekarabi, Sahar; Romanyuk, Oleksandr; Moritz, Dominik Christian; Hofmann, Jan Philipp; Jaegermann, Wolfram; Hannappel, Thomas; Schmidt, W. Gero
Clean and hydrogen-adsorbed AlInP(001) surfaces: structures and electronic properties. - In: Physica status solidi, ISSN 1521-3951, Bd. 259 (2022), 11, 2200308, S. 1-6

Total energy and electronic structure calculations based on density functional theory are performed in order to determine the atomic structure and electronic properties of clean and hydrogen-adsorbed Al0.5In0.5P(001) surfaces. It is found that most of the stable surfaces obey the electron-counting rule and are characterized by surface atom dimerization. The dimer-related surface states are predicted to occur in the vicinity of the bulk band edges. For a very narrow range of preparation conditions, ab initio thermodynamics predicts metal atomic wires formed by surface cations. A surface covered with a monolayer of buckled phosphorus dimers, where half of the phosphorus atoms are hydrogen saturated, is found to be stable for metal-organic vapor-phase epitaxy growth conditions. The occurrence of this structure is confirmed by low-energy electron diffraction and X-ray photoelectron spectroscopy data measured on epitaxially grown Al0.52In0.48P(001) epilayers lattice matched to GaAs.
Kurtash, Vladislav; Mathew, Sobin; Thiele, Sebastian; Scheler, Theresa; Reiprich, Johannes; Hähnlein, Bernd; Stauffenberg, Jaqueline; Manske, Eberhard; Narasimha, Shilpashree; Abedin, Saadman; Jacobs, Heiko O.; Pezoldt, Jörg
Hysteresis associated with intrinsic-oxide traps in gate-tunable tetrahedral CVD-MoS2 memristor. - In: IEEE Xplore digital library, ISSN 2473-2001, (2022), S. 527-530

We introduce back gated memristor based on CVD-grown 30-40 nm thick MoS2 channel. The device demonstrates bipolar behaviour and the measurements are consistent with the simulations performed within the intrinsic-oxide traps model. This confirms the theory that the source of hysteresis in thin-film MoS2 memristors is charge trapping on MoS2/SiO2 interface and the grain boundaries. The impact of back gate voltage bias, voltage sweep range and channel area on memristive effect was studied and quantified using hysteresis area. Hysteresis in bipolar memristors can be tuned by back gate voltage, which makes these devices promising for neuromorphic computing.
Zare Pour, Mohammad Amin; Romanyuk, Oleksandr; Moritz, Dominik Christian; Paszuk, Agnieszka; Maheu, Clément; Shekarabi, Sahar; Hanke, Kai Daniel; Ostheimer, David; Mayer, Thomas; Hofmann, Jan Philipp; Jaegermann, Wolfram; Hannappel, Thomas
Band energy diagrams of n-GaInP/n-AlInP(100) surfaces and heterointerfaces studied by X-ray photoelectron spectroscopy. - In: Surfaces and Interfaces, ISSN 2468-0230, Bd. 34 (2022), 102384

Lattice matched n-type AlInP(100) charge selective contacts are commonly grown on n-p GaInP(100) top absorbers in high-efficiency III-V multijunction solar or photoelectrochemical cells. The cell performance can be greatly limited by the electron selectivity and valance band offset at this heterointerface. Understanding of the atomic and electronic properties of the GaInP/AlInP heterointerface is crucial for the reduction of photocurrent losses in III-V multijunction devices. In our paper, we investigated chemical composition and electronic properties of n-GaInP/n-AlInP heterostructures by X-ray photoelectron spectroscopy (XPS). To mimic an in-situ interface experiment with in-situ stepwise deposition of the contact material, 1 nm -50 nm thick n-AlInP(100) epitaxial layers were grown on n-GaInP(100) buffer layer on n-GaAs(100) substrates by metal organic vapor phase epitaxy. We observed (2 × 2)/c(4 × 2) low-energy electron diffraction patterns with characteristic diffuse streaks along the [011¯] direction due to PP dimers on both AlInP(100) and GaInP(100) as-prepared surfaces. Atomic composition analysis confirmed P-rich termination on both surfaces. Angle-resolved XPS measurements revealed a surface core level shift of 0.9 eV in P 2p peaks and the absence of interface core level shifts. We assigned the surface chemical shift in the P 2p spectrum to PP bonds on a surface. We found an upward surface band bending on the (2 × 2)/c(4 × 2) surfaces most probably caused by localized mid-gap electronic states. Pinning of the Fermi level by localized electronic states remained in n-GaInP/n-AlInP heterostructures. A valence band offset of 0.2 eV was derived by XPS and band alignment diagram models for the n-n junctions were suggested.
Koch, Juliane; Liborius, Lisa; Kleinschmidt, Peter; Weimann, Nils; Prost, Werner; Hannappel, Thomas
Electrical properties of the base-substrate junction in freestanding core-shell nanowires. - In: Advanced materials interfaces, ISSN 2196-7350, Bd. 9 (2022), 30, 2200948, S. 1-8

Well-defined hetero-interfaces with controlled properties are crucial for any high-performance, semiconductor-based, (opto-)electronic device. They are particularly important for device structures on the nanoscale with increased interfacial areas. Utilizing a ultrahigh-vacuum based multi-tip scanning tunneling microscope, this work reveals inadvertent conductivity channels between the nanowire (NW) base and the substrate, when measuring individual vertical core-shell III-V-semiconductor NWs. For that, four-terminal probing is applied on freestanding, epitaxially grown coaxial p-GaAs/i-GaInP/n-GaInP NWs without the need of nanoscale lithography or deposition of electrical contacts. This advanced analysis, carried out after composition-selective wet chemical etching, reveals a substantially degraded electrical performance of the freestanding NWs compared to detached ones. In an electron beam induced current mode of the nanosensor, charge separation at the substrate-to-NW base junction is demonstrated. An energy dispersive X-ray spectroscopic linescan shows an unintended compositional change of the epitaxially grown NW toward the planar layers caused by different incorporation mechanisms of Ga and In at the NW base. This approach provides direct insight into the NW-substrate transition area and leads to a model of the conductivity channels at the NW base, which should, in principle, be considered in the fabrication of all NW heterostructures grown bottom-up on heterogeneous substrate materials.
Moritz, Dominik Christian; Ruiz Alvarado, Isaac Azahel; Zare Pour, Mohammad Amin; Paszuk, Agnieszka; Frieß, Tilo; Runge, Erich; Hofmann, Jan Philipp; Hannappel, Thomas; Schmidt, W. Gero; Jaegermann, Wolfram
P-terminated InP (001) surfaces: surface band bending and reactivity to water. - In: ACS applied materials & interfaces, ISSN 1944-8252, Bd. 14 (2022), 41, S. 47255-47261

Stable InP (001) surfaces are characterized by fully occupied and empty surface states close to the bulk valence and conduction band edges, respectively. The present photoemission data show, however, a surface Fermi level pinning only slightly below the midgap energy which gives rise to an appreciable surface band bending. By means of density functional theory calculations, it is shown that this apparent discrepancy is due to surface defects that form at finite temperature. In particular, the desorption of hydrogen from metalorganic vapor phase epitaxy grown P-rich InP (001) surfaces exposes partially filled P dangling bonds that give rise to band gap states. These defects are investigated with respect to surface reactivity in contact with molecular water by low-temperature water adsorption experiments using photoemission spectroscopy and are compared to our computational results. Interestingly, these hydrogen-related gap states are robust with respect to water adsorption, provided that water does not dissociate. Because significant water dissociation is expected to occur at steps rather than terraces, surface band bending of a flat InP (001) surface is not affected by water exposure.