5 7 5 line defects on As Si 100 A general stress relief mechanism for V IV surfaces

An entire family of nano scale trenches, ridges, and steps has been observed experimentally on AsH3 exposed Si 100 . Some of these line structures have been observed previously, but their structures have remained a mystery. Theoretical modeling shows that they are all based upon the same stress relieving 5 7 5 core structure. The strong similarities between line structures on As Si 100 , P Si 100 , As Ge 100 , and other V IV surfaces lead to a much broader conclusion 5 7 5 line structures are a general form of stress relief for group V terminated Si and Ge surface

Photoelectrochemical Conditioning of MOVPE p-InP Films for Light-Induced Hydrogen Evolution: Chemical, Electronic and Optical Properties

Homoepitaxial p-InP(100) thin films prepared by MOVPE (metallorganic vapor phase epitaxy) were transformed into an InP/oxide-phosphate/Rh heterostructure by photoelectrochemical conditioning. Surface sensitive synchrotron radiation photoelectron spectroscopy indicates the formation of a mixed oxide constituted by In(PO_3)_3, InPO_4 and In_(2)O_3 as nominal components during photo-electrochemical activation. The operation of these films as hydrogen evolving photocathode proved a light-to-chemical energy conversion efficiency of 14.5%. Surface activation arises from a shift of the semiconductor electron affinity by 0.44 eV by formation of In-Cl interfacial dipoles with a density of about 10^(12) cm^(−2). Predominant local In2O3-like structures in the oxide introduce resonance states near the semiconductor conduction band edge imparting electron conductivity to the phosphate matrix. Surface reflectance investigations indicate an enhanced light-coupling in the layered architecture

Atomic scale analysis of the GaP Si 100 heterointerface by in situ reflection anisotropy spectroscopy and ab initio density functional theory

A microscopic understanding of the formation of polar on nonpolar interfaces is a prerequisite for well defined heteroepitaxial preparation of III V compounds on 100 silicon for next generation high performance devices. Energetically and kinetically driven Si 100 step formations result in majority domains of monohydride terminated Si dimers oriented either parallel or perpendicular to the step edges. Here, the intentional variation of the Si 100 surface reconstruction controls the sublattice orientation of the heteroepitaxial GaP film, as observed by in situ reflection anisotropy spectroscopy RAS in chemical vapor ambient and confirmed by benchmarking to surface science analytics in ultrahigh vacuum. Ab initio density functional calculations of both abrupt and compensated interfaces are carried out. For P rich chemical potentials at abrupt interfaces, Si P bonds are energetically favored over Si Ga bonds, in agreement with in situ RAS experiments. The energetically most favorable interface is compensated with an intermixed interfacial layer. In situ RAS reveals that the GaP sublattice orientation depends on the P chemical potential during nucleation, which agrees with a kinetically limited formation of abrupt interface

MOVPE growth of GaP/GaPN core-shell nanowires: N incorporation, morphology and crystal structure

Dilute nitride III-V nanowires (NWs) possess great potential as building blocks in future optoelectronical and electrochemical devices. Here, we provide evidence for the growth of GaP/GaPN core-shell NWs via metalorganic vapor phase epitaxy, both on GaP(111)B and on GaP/Si (111) hetero-substrates. The NW morphology meets the common needs for use in applications, i.e. they are straight and vertically oriented to the substrate as well as homogeneous in length. Moreover, no parasitical island growth is observed. Nitrogen was found to be incorporated on group V sites as determined from transmission electron microscopy (TEM) and Raman spectroscopy. Together with the incorporation of N, the NWs exhibit strong photoluminescence in the visible range, which we attribute to radiative recombination at N-related deep states. Independently of the N incorporation, a peculiar facet formation was found, with {110} facets at the top and {112} at the bottom of the NWs. TEM reveals that this phenomenon is related to different stacking fault densities within the zinc blende structure, which lead to different effective surface energies for the bottom and the top of the NWs.This work was supported by the Deutsche Forschungsgemeinschaft (DFG, proj. no. HA 3096/4-2 & DA 396/6-2). We thank D Roßberg and D Flock for preparation of the TEM lamellae via FIB, as well as A Müller for technical support of the MOVPE system and W Dziony for AES measurements. We appreciate fruitful discussions with A Paszuk and A Nägelein

Time resolved in situ spectroscopy during formation of the GaP Si 100 heterointerface

Though III V Si 100 heterointerfaces are essential for future epitaxial high performance devices, their atomic structure is an open historical question. Benchmarking of transient optical in situ spectroscopy during chemical vapor deposition to chemical analysis by X ray photoelectron spectroscopy enables us to distinguish between formation of surfaces and of the heterointerface. A terrace related optical anisotropy signal evolves during pulsed GaP nucleation on single domain Si 100 surfaces. This dielectric anisotropy agrees well with the one calculated for buried GaP Si 100 interfaces from differently thick GaP epilayers. X ray photoelectron spectroscopy reveals a chemically shifted contribution of the P and Si emission lines, which quantitatively corresponds to one monolayer and establishes simultaneously with the nucleation related optical in situ signal. We attribute that contribution to the existence of Si P bonds at the buried heterointerface. During further pulsing and annealing in phosphorus ambient, dielectric anisotropies known from atomically well ordered GaP 100 surfaces super impose the nucleation related optical in situ spectra. Figure Presente

Monolithic Photoelectrochemical Device for Direct Water Splitting with 19% Efficiency

Recent rapid progress in efficiencies for solar water splitting by photoelectrochemical devices has enhanced its prospects to enable storable renewable energy. Efficient solar fuel generators all use tandem photoelectrode structures, and advanced integrated devices incorporate corrosion protection layers as well as heterogeneous catalysts. Realization of near thermodynamic limiting performance requires tailoring the energy band structure of the photoelectrode and also the optical and electronic properties of the surface layers exposed to the electrolyte. Here, we report a monolithic device architecture that exhibits reduced surface reflectivity in conjunction with metallic Rh nanoparticle catalyst layers that minimize parasitic light absorption. Additionally, the anatase TiO2 protection layer on the photocathode creates a favorable internal band alignment for hydrogen evolution. An initial solar-to-hydrogen efficiency of 19.3 % is obtained in acidic electrolyte and an efficiency of 18.5 % is achieved at neutral pH condition (under simulated sunlight)