Optical and electronic functionality arising from controlled defect formation in nanoscale complex oxide lateral epitaxy.

Epitaxial crystallization of complex oxides provides the means to create materials with precisely selected composition, strain, and orientation, thereby controlling their functionalities. Extending this control to nanoscale three-dimensional geometries can be accomplished via a three-dimensional analog of oxide solid-phase epitaxy, lateral epitaxial crystallization. The orientation of crystals within laterally crystallized SrTiO3 systematically changes from the orientation of the SrTiO3 substrate. This evolution occurs as a function of lateral crystallization distance, with a rate of approximately 50° µm-1. The mechanism of the rotation is consistent with a steady-state stress of tens of megapascal over a 100-nanometer scale region near the moving amorphous/crystalline interface arising from the amorphous-crystalline density difference. Second harmonic generation and piezoelectric force microscopy reveal that the laterally crystallized SrTiO3 is noncentrosymmetric and develops a switchable piezoelectric response at room temperature, illustrating the potential to use lateral crystallization to control the functionality of complex oxides.

Thermal atomic layer deposition of Er2O3 films from a volatile, thermally stable enaminolate precursor.

Thin films of Er2O3 films were grown by atomic layer deposition using the Er precursor tris(1-(dimethylamino)-3,3-dimethylbut-1-en-2-olate)erbium(III) (Er(L1)3), with water as the co-reactant. Saturative, self-limited growth was observed at a substrate temperature of 200 °C for pulse lengths of ≥4.0 s for Er(L1)3 and ≥0.2 s for water. An ALD window was observed from 175 to 225 °C with a growth rate of about 0.25 Å per cycle. Er2O3 films grown at 200 °C on Si(100) and SiO2 substrates with a thickness of 33 nm had root mean square surface roughnesses of 1.75 and 0.75 nm, respectively. Grazing incidence X-ray diffraction patterns showed that the films were composed of polycrystalline Er2O3 at all deposition temperatures on Si(100) and SiO2 substrates. X-ray photoelectron spectroscopy revealed stoichiometric Er2O3, with carbon and nitrogen levels below the detection limits after argon ion sputtering to remove surface impurities. Transmission electron microscopy studies of Er2O3 film growth in nanoscale trenches (aspect ratio = 10) demonstrated conformal coverage.

Reconfiguration of Amorphous Complex Oxides: A Route to a Broad Range of Assembly Phenomena, Hybrid Materials, and Novel Functionalities.

Reconfiguration of amorphous complex oxides provides a readily controllable source of stress that can be leveraged in nanoscale assembly to access a broad range of 3D geometries and hybrid materials. An amorphous SrTiO3 layer on a Si:B/Si1- x Gex :B heterostructure is reconfigured at the atomic scale upon heating, exhibiting a change in volume of ≈2% and accompanying biaxial stress. The Si:B/Si1- x Gex :B bilayer is fabricated by molecular beam epitaxy, followed by sputter deposition of SrTiO3 at room temperature. The processes yield a hybrid oxide/semiconductor nanomembrane. Upon release from the substrate, the nanomembrane rolls up and has a curvature determined by the stress in the epitaxially grown Si:B/Si1- x Gex :B heterostructure. Heating to 600 °C leads to a decrease of the radius of curvature consistent with the development of a large compressive biaxial stress during the reconfiguration of SrTiO3 . The control of stresses via post-deposition processing provides a new route to the assembly of complex-oxide-based heterostructures in 3D geometry. The reconfiguration of metastable mechanical stressors enables i) synthesis of various types of strained superlattice structures that cannot be fabricated by direct growth and ii) technologies based on strain engineering of complex oxides via highly scalable lithographic processes and on large-area semiconductor substrates.

Phase Selection and Structure of Low-Defect-Density γ-Al2O3 Created by Epitaxial Crystallization of Amorphous Al2O3.

A multistep phase sequence following the crystallization of amorphous Al2O3 via solid-phase epitaxy (SPE) points to methods to create low-defect-density thin films of the metastable cubic γ-Al2O3 polymorph. An amorphous Al2O3 thin film on a (0001) α-Al2O3 sapphire substrate initially transforms upon heating to form epitaxial γ-Al2O3, followed by a transformation to monoclinic θ-Al2O3, and eventually to α-Al2O3. Epitaxial γ-Al2O3 layers with low mosaic widths in X-ray rocking curves can be formed via SPE by crystallizing the γ-Al2O3 phase from amorphous Al2O3 and avoiding the microstructural inhomogeneity arising from the spatially inhomogeneous transformation to θ-Al2O3. A complementary molecular dynamics (MD) simulation indicates that the amorphous layer and γ-Al2O3 have similar Al coordination geometry, suggesting that γ-Al2O3 forms in part because it involves the minimum rearrangement of the initially amorphous configuration. The lattice parameters of γ-Al2O3 are consistent with a structure in which the majority of the Al vacancies in the spinel structure occupy sites with tetrahedral coordination, consistent with the MD results. The formation of Al vacancies at tetrahedral spinel sites in epitaxial γ-Al2O3 can minimize the epitaxial elastic deformation of γ-Al2O3 during crystallization.

Alignment of semiconducting graphene nanoribbons on vicinal Ge(001).

Chemical vapor deposition of CH4 on Ge(001) can enable anisotropic growth of narrow, semiconducting graphene nanoribbons with predominately smooth armchair edges and high-performance charge transport properties. However, such nanoribbons are not aligned in one direction but instead grow perpendicularly, which is not optimal for integration into high-performance electronics. Here, it is demonstrated that vicinal Ge(001) substrates can be used to synthesize armchair nanoribbons, of which ∼90% are aligned within ±1.5° perpendicular to the miscut. When the growth rate is slow, graphene crystals evolve as nanoribbons. However, as the growth rate increases, the uphill and downhill crystal edges evolve asymmetrically. This asymmetry is consistent with stronger binding between the downhill edge and the Ge surface, for example due to different edge termination as shown by density functional theory calculations. By tailoring growth rate and time, nanoribbons with sub-10 nm widths that exhibit excellent charge transport characteristics, including simultaneous high on-state conductance of 8.0 µS and a high on/off conductance ratio of 570 in field-effect transistors, are achieved. Large-area alignment of semiconducting ribbons with promising charge transport properties is an important step towards understanding the anisotropic nanoribbon growth and integrating these materials into scalable, future semiconductor technologies.

Silicon Nanomembranes with Hybrid Crystal Orientations and Strain States.

Methods to integrate different crystal orientations, strain states, and compositions of semiconductors in planar and preferably flexible configurations may enable nontraditional sensing-, stimulating-, or communication-device applications. We combine crystalline-silicon nanomembranes, patterning, membrane transfer, and epitaxial growth to demonstrate planar arrays of different orientations and strain states of Si in a single membrane, which is then readily transferable to other substrates, including flexible supports. As examples, regions of Si(001) and Si(110) or strained Si(110) are combined to form a multicomponent, single substrate with high-quality narrow interfaces. We perform extensive structural characterization of all interfaces and measure charge-carrier mobilities in different regions of a 2D quilt. The method is readily extendable to include varying compositions or different classes of materials.

Gate fidelity and coherence of an electron spin in an Si/SiGe quantum dot with micromagnet.

The gate fidelity and the coherence time of a quantum bit (qubit) are important benchmarks for quantum computation. We construct a qubit using a single electron spin in an Si/SiGe quantum dot and control it electrically via an artificial spin-orbit field from a micromagnet. We measure an average single-qubit gate fidelity of ∼99% using randomized benchmarking, which is consistent with dephasing from the slowly evolving nuclear spins in the substrate. The coherence time measured using dynamical decoupling extends up to ∼400 µs for 128 decoupling pulses, with no sign of saturation. We find evidence that the coherence time is limited by noise in the 10-kHz to 1-MHz range, possibly because charge noise affects the spin via the micromagnet gradient. This work shows that an electron spin in an Si/SiGe quantum dot is a good candidate for quantum information processing as well as for a quantum memory, even without isotopic purification.

Electronic Transport Properties of Epitaxial Si/SiGe Heterostructures Grown on Single-Crystal SiGe Nanomembranes.

To assess possible improvements in the electronic performance of two-dimensional electron gases (2DEGs) in silicon, SiGe/Si/SiGe heterostructures are grown on fully elastically relaxed single-crystal SiGe nanomembranes produced through a strain engineering approach. This procedure eliminates the formation of dislocations in the heterostructure. Top-gated Hall bar devices are fabricated to enable magnetoresistivity and Hall effect measurements. Both Shubnikov-de Haas oscillations and the quantum Hall effect are observed at low temperatures, demonstrating the formation of high-quality 2DEGs. Values of charge carrier mobility as a function of carrier density extracted from these measurements are at least as high or higher than those obtained from companion measurements made on heterostructures grown on conventional strain graded substrates. In all samples, impurity scattering appears to limit the mobility.

Probing the electronic structure at semiconductor surfaces using charge transport in nanomembranes.

The electrical properties of nanostructures are extremely sensitive to their surface condition. In very thin two-dimensional crystalline-semiconductor sheets, termed nanomembranes, the influence of the bulk is diminished, and the electrical conductance becomes exquisitely responsive to the structure of the surface and the type and density of defects there. Its understanding therefore requires a precise knowledge of the surface condition. Here we report measurements, using nanomembranes, that demonstrate direct charge transport through the π* band of the clean reconstructed Si(001) surface. We determine the charge carrier mobility in this band. These measurements, performed in ultra-high vacuum to create a truly clean surface, lay the foundation for a quantitative understanding of the role of extended or localized surface states, created by surface structure, defects or adsorbed atoms/molecules, in modifying charge transport through semiconductor nanostructures.

Defect-free single-crystal SiGe: a new material from nanomembrane strain engineering.

Many important materials cannot be grown as single crystals in bulk form because strain destroys long-range crystallinity. Among them, alloys of group IV semiconductors, specifically SiGe alloys, have significant technological value. Using nanomembrane strain engineering methods, we demonstrate the fabrication of fully elastically relaxed Si(1-x)Ge(x) nanomembranes (NMs) for use as growth substrates for new materials. To do so, we grow defect-free, uniformly and elastically strained SiGe layers on Si substrates and release the SiGe layers to allow them to relax this strain completely as free-standing NMs. These SiGe NMs are transferred to new hosts and bonded there. We confirm the high structural quality of these new materials and demonstrate their use as substrates for technologically relevant epitaxial films by growing strained-Si layers and thick, lattice-matched SiGe alloy layers on them.

Symmetry in strain engineering of nanomembranes: making new strained materials.

Strain in a material changes the lattice constant and thereby creates a material with new properties relative to the unstrained, but chemically identical, material. The ability to alter the strain (its magnitude, direction, extent, periodicity, symmetry, and nature) allows tunability of these new properties. A recent development, crystalline nanomembranes, offers a powerful platform for using and tuning strain to create materials that have unique properties, not achievable in bulk materials or with conventional processes. Nanomembranes, because of their thinness, enable elastic strain sharing, a process that introduces large amounts of strain and unique strain distributions in single-crystal materials, without exposing the material to the formation of extended defects. We provide here prescriptions for making new strained materials using crystal symmetry as the driver: we calculate the strain distributions in flat nanomembranes for two-fold and four-fold elastically symmetric materials. We show that we can controllably tune the amount of strain and the asymmetry of the strain distribution in elastically isotropic and anisotropic materials uniformly over large areas. We perform the experimental demonstration with a trilayer Si(110)/Si((1-x))Ge(x)(110)/Si(110) nanomembrane: an elastically two-fold symmetric system in which we can transfer strain that is biaxially isotropic. We are thus able to make uniformly strained materials that cannot be made any other way.

Influence of surface properties on the electrical conductivity of silicon nanomembranes.

Because of the large surface-to-volume ratio, the conductivity of semiconductor nanostructures is very sensitive to surface chemical and structural conditions. Two surface modifications, vacuum hydrogenation (VH) and hydrofluoric acid (HF) cleaning, of silicon nanomembranes (SiNMs) that nominally have the same effect, the hydrogen termination of the surface, are compared. The sheet resistance of the SiNMs, measured by the van der Pauw method, shows that HF etching produces at least an order of magnitude larger drop in sheet resistance than that caused by VH treatment, relative to the very high sheet resistance of samples terminated with native oxide. Re-oxidation rates after these treatments also differ. X-ray photoelectron spectroscopy measurements are consistent with the electrical-conductivity results. We pinpoint the likely cause of the differences.PACS: 73.63.-b, 62.23.Kn, 73.40.Ty.

Semiconductor nanomembrane tubes: three-dimensional confinement for controlled neurite outgrowth.

In many neural culture studies, neurite migration on a flat, open surface does not reflect the three-dimensional (3D) microenvironment in vivo. With that in mind, we fabricated arrays of semiconductor tubes using strained silicon (Si) and germanium (Ge) nanomembranes and employed them as a cell culture substrate for primary cortical neurons. Our experiments show that the SiGe substrate and the tube fabrication process are biologically viable for neuron cells. We also observe that neurons are attracted by the tube topography, even in the absence of adhesion factors, and can be guided to pass through the tubes during outgrowth. Coupled with selective seeding of individual neurons close to the tube opening, growth within a tube can be limited to a single axon. Furthermore, the tube feature resembles the natural myelin, both physically and electrically, and it is possible to control the tube diameter to be close to that of an axon, providing a confined 3D contact with the axon membrane and potentially insulating it from the extracellular solution.

Influence of surface chemical modification on charge transport properties in ultrathin silicon membranes.

Ultrathin silicon-on-insulator, composed of a crystalline sheet of silicon bounded by native oxide and a buried oxide layer, is extremely resistive because of charge trapping at the interfaces between the sheet of silicon and the oxide. After chemical modification of the top surface with hydrofluoric acid (HF), the sheet resistance drops to values below what is expected based on bulk doping alone. We explain this behavior in terms of surface-induced band structure changes combined with the effective isolation from bulk properties created by crystal thinness.

Mechano-electronic superlattices in silicon nanoribbons.

Significant new mechanical and electronic phenomena can arise in single-crystal semiconductors when their thickness reaches nanometer dimensions, where the two surfaces of the crystal are physically close enough to each other that what happens at one surface influences what happens at the other. We show experimentally that, in silicon nanomembranes, through-membrane elastic interactions cause the double-sided ordering of epitaxially grown nanostressors that locally and periodically highly strains the membrane, leading to a strain lattice. Because strain influences band structure, we create a periodic band gap modulation, up to 20% of the band gap, effectively an electronic superlattice. Our calculations demonstrate that discrete minibands can form in the potential wells of an electronic superlattice generated by Ge nanostressors on a sufficiently thin Si(001) nanomembrane at the temperature of 77 K. We predict that it is possible to observe discrete minibands in Si nanoribbons at room temperature if nanostressors of a different material are grown.

Elastically relaxed free-standing strained-silicon nanomembranes.

Strain plays a critical role in the properties of materials. In silicon and silicon-germanium, strain provides a mechanism for control of both carrier mobility and band offsets. In materials integration, strain is typically tuned through the use of dislocations and elemental composition. We demonstrate a versatile method to control strain by fabricating membranes in which the final strain state is controlled by elastic strain sharing, that is, without the formation of defects. We grow Si/SiGe layers on a substrate from which they can be released, forming nanomembranes. X-ray-diffraction measurements confirm a final strain predicted by elasticity theory. The effectiveness of elastic strain to alter electronic properties is demonstrated by low-temperature longitudinal Hall-effect measurements on a strained-silicon quantum well before and after release. Elastic strain sharing and film transfer offer an intriguing path towards complex, multiple-layer structures in which each layer's properties are controlled elastically, without the introduction of undesirable defects.

Electronic transport in nanometre-scale silicon-on-insulator membranes.

The widely used 'silicon-on-insulator' (SOI) system consists of a layer of single-crystalline silicon supported on a silicon dioxide substrate. When this silicon layer (the template layer) is very thin, the assumption that an effectively infinite number of atoms contributes to its physical properties no longer applies, and new electronic, mechanical and thermodynamic phenomena arise, distinct from those of bulk silicon. The development of unusual electronic properties with decreasing layer thickness is particularly important for silicon microelectronic devices, in which (001)-oriented SOI is often used. Here we show--using scanning tunnelling microscopy, electronic transport measurements, and theory--that electronic conduction in thin SOI(001) is determined not by bulk dopants but by the interaction of surface or interface electronic energy levels with the 'bulk' band structure of the thin silicon template layer. This interaction enables high-mobility carrier conduction in nanometre-scale SOI; conduction in even the thinnest membranes or layers of Si(001) is therefore possible, independent of any considerations of bulk doping, provided that the proper surface or interface states are available to enable the thermal excitation of 'bulk' carriers in the silicon layer.