Evolution of epitaxial semiconductor nanodots and nanowires from supersaturated wetting layers

In this tutorial we review recent progress in the design and growth of epitaxial semiconductor nanostructures in lattice-mismatched material systems. We focus on the Ge on Si model system after pointing out the similarities to III–V and other growth systems qualitatively as well as quantitatively. During material deposition, the first layers of the epitaxial film wet the surface before the formation of strain-driven three-dimensional nanostructures. In particular, we stress that the supersaturation of the wetting layer (WL), whose relevance is often neglected, plays a key role in determining the nucleation and growth of nanodots (NDs), nanodot-molecules and nanowires (NWs). At elevated growth temperatures the Ge reservoir in the planar, supersaturated WL is abruptly consumed and generates NDs with highly homogeneous sizes – a process mainly driven by elastic energy minimization. Furthermore, the careful control of the supersaturated Ge layer allows us to obtain perfectly site-controlled, ordered NDs or ND-molecules on pit-patterned substrates for a broad range of pit-periods. At low growth temperatures subtle interplays between surface energies of dominant crystal facets in the system drive the material transfer from the supersaturated WL into the elongating NWs growing horizontally, dislocation- and catalyst-free on the substrate surface. Due to the similarities in the formation of nanostructures in different epitaxial semiconductor systems we expect that the observation of the novel growth phenomena described in this Tutorial Review for Ge/Si should be relevant for other lattice-mismatched heterostructure systems, too

Photoluminescence investigation of strictly ordered Ge dots grown on pit-patterned Si substrates

We investigate the optical properties of ordered Ge quantum dots (QDs) by means of micro-photoluminescence spectroscopy (PL). These were grown on pit-patterned Si(001) substrates with a wide range of pit-periods and thus inter QD-distances (425–3400 nm). By exploiting almost arbitrary inter-QD distances achievable in this way we are able to choose the number of QDs that contribute to the PL emission in a range between 70 and less than three QDs. This well-defined system allows us to clarify, by PL-investigation, several points which are important for the understanding of the formation and optical properties of ordered QDs. We directly trace and quantify the amount of Ge transferred from the surrounding wetting layer (WL) to the QDs in the pits. Moreover, by exploiting different pit-shapes, we reveal the role of strain-induced activation energy barriers that have to be overcome for charge carriers generated outside the dots. These need to diffuse between the energy minimum of the WL in and between the pits, and the one in the QDs. In addition, we demonstrate that the WL in the pits is already severely intermixed with Si before upright QDs nucleate, which further enhances intermixing of ordered QDs as compared to QDs grown on planar substrates. Furthermore, we quantitatively determine the amount of Ge transferred by surface diffusion through the border region between planar and patterned substrate. This is important for the growth of ordered islands on patterned fields of finite size. We highlight that the Ge WL-facets in the pits act as PL emission centres, similar to upright QDs

Optical properties of individual site-controlled Ge quantum dots

We report photoluminescence (PL) experiments on individual SiGe quantum dots (QDs) that were epitaxially grown in a site-controlled fashion on pre-patterned Si(001) substrates. We demonstrate that the PL line-widths of single QDs decrease with excitation power to about 16 meV, a value that is much narrower than any of the previously reported PL signals in the SiGe/Si heterosystem. At low temperatures, the PL-intensity becomes limited by a 25 meV high potential-barrier between the QDs and the surrounding Ge wetting layer (WL). This barrier impedes QD filling from the WL which collects and traps most of the optically excited holes in this type-II heterosystem. This work was supported by the Austrian Science Funds (FWF) via Schrödinger Scholarship J3328-N19 and the Project Nos. F2502-N17 and F2512-N17 of SFB025: IRON. M.G. and O.G.S. acknowledge support from the Center for Advancing Electronics Dresden, CfAED. T.T. was supported by the ICR-KU International Short-term Exchange Program for Young Researchers. The authors thank T. Fromherz and F. Hackl for helpful discussions

Switching between Proton Vacancy and Excess Proton Transfer Pathways in the Reaction between 7-Hydroxyquinoline and Formate

Bifunctional or amphoteric photoacids simultaneously present donor (acidic) and acceptor (basic) properties making them useful tools to analyze proton transfer reactions. In protic solvents, the proton exchange between the acid and the base is controlled by the acidity or basicity strength and typically occurs on two different pathways known as protolysis and hydrolysis. We report here how the addition of a formate base will alter the relative importance of the possible reaction pathways of the bifunctional photoacid 7-hydroxyquinoline (7HQ), which has been recently understood to predominantly involve a hydroxide/methoxide transport mechanism between the basic proton-accepting quinoline nitrogen site toward the proton-donating OH group with a time constant of 360 ps in deuterated methanol (CD3OD). We follow the reaction dynamics by probing the IR-active marker modes of the different charged forms of photoexcited 7HQ, and of formic acid (HCOOD) in CD3OD solution. A comparison of the transient IR spectra as a function of formate concentration, and classical molecular dynamics simulations enables us to identify distinct contributions of “tight” (meaning “contact”) and “loose” (i.e., “solvent-separated”) 7HQ–formate reaction pairs in our data. Our results suggest that depending on the orientation of the OH group with respect to the quinoline aromatic ring system, the presence of the formate molecule in a proton relay pathway facilitates a net proton transfer from the proton-donating OH group of 7HQ-N* via the methanol/formate bridge toward the quinoline N site

Ultra-steep side facets in multi-faceted SiGe/Si(001) Stranski-Krastanow islands

For the prototypical Ge/Si(001) system, we show that at high growth temperature a new type of Stranski-Krastanow islands is formed with side facets steeper than {111} and high aspect ratio. Nano-goniometric analysis of the island shapes reveals the presence of six new facet groups in addition to those previously found for dome or barn-shaped islands. Due to the highly multi-faceted island shape and high aspect ratio, the new island types are named "cupola" islands and their steepest {12 5 3} side facet is inclined by 68°to the substrate surface. Assessing the relative stability of the new facets from surface area analysis, we find that their stability is similar to that of {113} and {15 3 23} facets of dome islands. The comparison of the different island shapes shows that they form a hierarchical class of geometrical structures, in which the lower aspect ratio islands of barns, domes and pyramids are directly derived from the cupola islands by successive truncation of the pedestal bases without facet rearrangements. The results underline the key role of surface faceting in the process of island formation, which is as crucial for understanding the island's growth evolution as it is important for device applications