Zeitschriftenaufsätze und Buchbeiträge

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.

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.

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.

A method to synthesize the three-dimensional arrangement of bulk tetrahedral MoS2 thin films by solid source chemical vapor deposition of MoO3 and S is presented. The developed synthesizing recipe uses a temperature ramping with a constant N2 gas flow in the deposition process to grow tetrahedral MoS2 thin film layers. The study analyses the time-dependent growth morphologies, and the results are combined and presented in a growth model. A combination of optical, electron, atomic force microscopy, Raman spectroscopy, and X-ray diffraction are used to study the morphological and structural features of the tetrahedral MoS2 thin layers. The grown MoS2 is c-axis oriented 2H-MoS2. Additionally, the synthesized material is further used to fabricate back-gated field-effect transistors (FETs). The fabricated FET devices on the tetrahedral MoS2 show on/off current ratios of 10^6 and mobility up to ∼56 cm^2 V^-1 s^-1 with an estimated carrier concentration of 4 × 10^16 cm-3 for VGS = 0 V.

Monolithic integrated photovoltaic-driven electrochemical (PV-EC) artificial photosynthesis is reported for unassisted CO2 reduction. The PV-EC structures employ triple junction photoelectrodes with a front mounted semitransparent catalyst layer as a photocathode. The catalyst layer is comprised of an array of microscale triangular metallic prisms that redirect incoming light toward open areas of the photoelectrode to reduce shadow losses. Full wave electromagnetic simulations of the prism array (PA) structure guide optimization of geometries and length scales. An integrated device is constructed with Ag catalyst prisms covering 35% of the surface area. The experimental device has close to 80% of the transmittance with a catalytic surface area equivalent 144% of the glass substrate area. Experimentally this photocathode demonstrates a direct solar-to-CO conversion efficiency of 5.9% with 50 h stability. Selective electrodeposition of Cu catalysts onto the surface of the Ag triangular prisms allows CO2 conversion to higher value products enabling demonstration of a solar-to-C2+ product efficiency of 3.1%. This design featuring structures that have a semitransparent catalyst layer on a PV-EC cell is a general solution to light loss by shadowing for front surface mounted metal catalysts, and opens a route for the development of artificial photosynthesis based on this scalable design approach.