Matthias M. May

Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure.

Photosynthesis is natures route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators.

Epitaxial III–V Films and Surfaces for Photoelectrocatalysis

Efficient photoelectrochemical devices for water splitting benefit from the highest material quality and dedicated surface preparation achieved by epitaxial growth. InP(100)-based half-cells show significant solar-to-hydrogen efficiencies, but require a bias due to insufficient voltage. Tandem absorber structures may provide both adequate potential and efficient utilization of the solar spectrum. We propose epitaxial dilute nitride GaPNAs photocathodes on Si(100) substrates to combine close-to-optimum limiting efficiency, lattice-matched growth, and established surface preparation. Prior to a discussion of the challenging III-V/Si(100) heterojunction, we describe the closely related epitaxial preparation of InP(100) surfaces and its beneficial impact on photoelectrochemical water-splitting performance. Analogies and specific differences to GaP(100) surfaces are discussed based on in situ reflectance anisotropy and on two-photon photoemission results. Preliminary experiments regarding GaP/Si(100) photoelectrochemistry and dilute nitride GaPN heteroepitaxy on Si(100) confirm the potential of the GaPNAs/Si tandem absorber structure for future water-splitting devices.

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 superimpose the nucleation-related optical in situ spectra.

The interface of GaP(100) and H2O studied by photoemission and reflection anisotropy spectroscopy

We study the initial interaction of adsorbed H2O with P-rich and Ga-rich GaP(100) surfaces. Atomically well defined surfaces are prepared by metal-organic vapour phase epitaxy and transferred contamination-free to ultra-high vacuum, where water is adsorbed at room temperature. Finally, the surfaces are annealed in vapour phase ambient. During all steps, the impact on the surface properties is monitored with in situ reflection anisotropy spectroscopy (RAS). Photoelectron spectroscopy and low-energy electron diffraction are applied for further in system studies. After exposure up to saturation of the RA spectra, the Ga-rich (2 × 4) surface reconstruction exhibits a sub-monolayer coverage in form of a mixture of molecularly and dissociatively adsorbed water. For the p(2 × 2)/c(4 × 2) P-rich surface reconstruction, a new c(2 × 2) superstructure forms upon adsorption and the uptake of adsorbate is significantly reduced when compared to the Ga-rich surface. Our findings show that microscopic surface reconstructions of GaP(100) greatly impact the mechanism of initial interface formation with water, which could benefit the design of e.g. photoelectrochemical water splitting devices.

Formation of GaP/Si(100) Heterointerfaces in the Presence of Inherent Reactor Residuals.

Adequate silicon preparation is a prerequisite for defect-free III-V growth on Si. We transfer the silicon processing from clean to GaP containing metalorganic vapor phase epitaxy reactors, where we monitor the entire process in situ with reflection anisotropy spectroscopy and analyze the chemical composition of the surface with X-ray photoelectron spectroscopy. Beyond a certain submonolayer threshold value of (Ga,P) residuals found on the Si(100) surface, GaP grows with an inverted majority sublattice. Analogously to III-V growth on two-domain substrates, the coexistence of Si-Ga and Si-P interfacial bonds at terraces of the same type causes antiphase disorder in GaP epilayers.

Materials for light-induced water splitting: In situ controlled surface preparation of GaPN epilayers grown lattice-matched on Si(100)

Energy storage is a key challenge in solar-driven renewable energy conversion. We promote a photochemical diode based on dilute nitride GaPN grown lattice-matched on Si(100), which could reach both high photovoltaic efficiencies and evolve hydrogen directly without external bias. Homoepitaxial GaP(100) surface preparation was shown to have a significant impact on the semiconductor-water interface formation. Here, we grow a thin, pseudomorphic GaP nucleation buffer on almost single-domain Si(100) prior to GaPN growth and compare the GaP_(0.98)N_(0.02)/Si(100) surface preparation to established P- and Ga-rich surfaces of GaP/Si(100). We apply reflection anisotropy spectroscopy to study the surface preparation of GaP_(0.98)N_(0.02) in situ in vapor phase epitaxy ambient and benchmark the signals to low energy electron diffraction, photoelectron spectroscopy, and x-ray diffraction. While the preparation of the Ga-rich surface is hardly influenced by the presence of the nitrogen precursor 1,1-dimethylhydrazine (UDMH), we find that stabilization with UDMH after growth hinders well-defined formation of the V-rich GaP_(0.98)N_(0.02)/Si(100) surface. Additional features in the reflection anisotropy spectra are suggested to be related to nitrogen incorporation in the GaP bulk.

In situ controlled heteroepitaxy of single-domain GaP on As-modified Si(100)

Metalorganic vapor phase epitaxy of III-V compounds commonly involves arsenic. We study the formation of atomically well-ordered, As-modified Si(100) surfaces and subsequent growth of GaP/Si(100) quasisubstrates in situ with reflection anisotropy spectroscopy. Surface symmetry and chemical composition are measured by low energy electron diffraction and X-ray photoelectron spectroscopy, respectively. A two-step annealing procedure of initially monohydride-terminated, (1 × 2) reconstructed Si(100) in As leads to a predominantly (1 × 2) reconstructed surface. GaP nucleation succeeds analogously to As-free systems and epilayers free of antiphase disorder may be grown subsequently. The GaP sublattice orientation, however, is inverted with respect to GaP growth on monohydride-terminated Si(100).

CHAPTER 9:Epitaxial III-V Thin Film Absorbers: Preparation, Efficient InP Photocathodes and Routes to High Efficiency Tandem Structures

The application of III-V semiconductor compounds allow the design of highly efficient absorbers for light-induced water splitting due to their outstanding properties and flexibility. This includes the possibility to tune magnitude and nature of band gaps as well as lattice constants enabling well-defined homo- and heteroepitaxial growth by metal-organic vapor phase epitaxy. Reflection anisotropy spectroscopy enables optical in-situ growth control facilitating the preparation of abrupt interfaces, which are essential for high-efficiency applications. Following this approach, InP(100) absorbers were prepared featuring a stable and efficient photocathode. Surface functionalization could be achieved by in situ photoelectrochemical preparation of an n-type indium oxide layer, which contains phosphates and phosphites, creating a p-n+ junction. In addition to stabilizing the cathode against corrosion, the junction enables efficient charge transfer to the Rh electrocatalyst. Our recent progress in III-V heteroepitaxy on silicon substrates extends the parameter space aiming for a water splitting tandem structure on Si. With Si as bottom cell, lattice-matched GaPN is a promising candidate for the top cell. To gain a better understanding of initial surface transformations induced by the electrolyte, we employ model adsorption experiments with GaP(100), the material basis for GaPN. Furthermore, we describe the concept for quantum-well, nanostructured absorbers.

On the benchmarking of multi-junction photoelectrochemical fuel generating devices

Photoelectrochemical solar fuel generation is evolving steadily towards devices mature for applications, driven by the development of efficient multi-junction devices. The crucial characteristics deciding over feasibility of an application are efficiency and stability. Benchmarking and reporting routines for these characteristics are, however, not yet on a level of standardisation as in the photovoltaic community, mainly due to the intricacies of the photoelectrochemical dimension. We discuss best practice considerations for benchmarking and propose an alternative efficiency definition that includes stability. Furthermore, we analyse the effects of spectral shaping and anti-reflection properties introduced by catalyst nanoparticles and their impact on design criteria for direct solar fuel generation in monolithic devices.

In Situ Characterization of Interfaces Relevant for Efficient Photoinduced Reactions

Solar energy conversion and photoinduced bioactive sensors are representing topical scientific fields, where interfaces play a decisive role for efficient applications. The key to specifically tune these interfaces is a precise knowledge of interfacial structures and their formation on the microscopic, preferably atomic scale. Gaining thorough insight into interfacial reactions, however, is particularly challenging in relevant complex chemical environment. This review introduces a spectrum of material systems with corresponding interfaces significant for efficient applications in energy conversion and sensor technologies. It highlights appropriate analysis techniques capable of monitoring critical physicochemical reactions in situ during non-vacuum preparation and photoactivity studies including well-defined inorganic epitaxial reference surfaces, buried interfaces, and low-defect nucleation of disjunct epitaxial materials that are analyzed during preparation in chemical vapor environment. Their surfaces are then modified and functionalized in gaseous and liquid environment. Finally, even more complex coupling of inorganic stable photoactive materials with responsive soft matter for bioactivity is reviewed. Interface formation, structure, and/or artificial photochemical interfacial reactions are scrutinized down to the atomic scale in real time, also accounting for equilibrium versus non-equilibrium, kinetically driven processes, in order to accelerate progresses in the realization of efficient energy materials and in the exploitation of photoinduced processes at interfaces.