Publications

Large-scale on-chip integration of organic nanowire-based devices requires the deterministic assembly of organic small molecules into highly-aligned nanowires. In this work, phthalocyanine molecules are self-assembled into horizontally-aligned nanowires after generating parallel hydrophobic nanogrooves on a sapphire surface. In contrast to previous self-oriented inorganic nanowires, these molecular nanowires are separated from their supporting sapphire by an ultrathin amorphous layer, indicating a complete elimination of lattice matching between nanowires and substrates. Therefore, small molecules beyond phthalocyanines hold promise to form aligned nanowires using this graphoepitaxial self-assembly strategy. The excellent alignment and high crystallinity of these nanowires enable the desired in-situ integration of nanowire-based devices without additional postgrowth processing steps. As a proof of concept, self-oriented CuPc nanowires are integrated into photodetector arrays directly on their growth substrate after electrode arrays are transferred onto the nanowires. Compared to previous CuPc photodetectors constructed using other approaches, these detectors exhibit a faster response to the spectrum in the 488-780 nm range (rise and fall times are 0.05-0.43 s and 0.38-2.34 s, respectively) while offering comparable detectivities (2.49 x 10(10) Jones on average). This graphoepitaxial self-assembly offers new opportunities for the aligned growth of organic crystalline nanowires and their large-scale in-situ integration into functional devices.

Surface-guided growth has proven to be an efficient approach for the production of nanowire arrays with controlled orientations and their large-scale integration into electronic and optoelectronic devices. Much has been learned about the different mechanisms of guided nanowire growth by epitaxy, graphoepitaxy, and artificial epitaxy. A model describing the kinetics of surface-guided nanowire growth has been recently reported. Yet, many aspects of the surface-guided growth process remain unclear due to a lack of its observation in real time. Here we observe how surface-guided nanowires grow in real time by in situ scanning electron microscopy (SEM). Movies of ZnSe surface-guided nanowires growing on periodically faceted substrates of annealed M-plane sapphire clearly show how the nanowires elongate along the substrate nanogrooves while pushing the catalytic Au nanodroplet forward at the tip of the nanowire. The movies reveal the timing between competing processes, such as planar vs nonplanar growth, catalyst-selective vapor-liquid-solid elongation vs nonselective vapor-solid thickening, and the effect of topographic discontinuities of the substrate on the growth direction, leading to the formation of kinks and loops. Contrary to some observations for nonplanar nanowire growth, planar nanowires are shown to elongate at a constant rate and not by jumps. A decrease in precursor concentration as it is consumed after long reaction time causes the nanowires to shrink back instead of growing, thus indicating that the process is reversible and takes place near equilibrium. This real-time study of surface-guided growth, enabled by in situ SEM, enables a better understanding of the formation of nanostructures on surfaces.

Optoelectronic micro- A nd nanostructures have a vast parameter space to explore for modification and optimization of their functional performance. This paper reports on a data-led approach using high-throughput single nanostructure spectroscopy to probe >8000 structures, allowing for holistic analysis of multiple material and optoelectronic parameters with statistical confidence. The methodology is applied to surface-guided CsPbBr₃nanowires, which have complex and interrelated geometric, structural, and electronic properties. Photoluminescence-based measurements, studying both the surface and embedded interfaces, exploits the natural inter nanowire geometric variation to show that increasing the nanowire width reduces the optical bandgap, increases the recombination rate in the nanowire bulk, and reduces the rate at the surface interface. A model of carrier recombination and diffusion ascribes these trends to carrier density and strain effects at the interfaces and self-consistently retrieves values for carrier mobility, trap densities, bandgap, diffusion length, and internal quantum efficiency. The model predicts parameter trends, such as the variation of internal quantum efficiency with width, which is confirmed by experimental verification. As this approach requires minimal a priori information, it is widely applicable to nano- A nd microscale materials.

Aligned growth of planar semiconductor nanowires (NWs) on crystalline substrates has been widely demonstrated during the past two decades and was used for the fabrication of a large variety of devices. However, the dependence on single-crystal substrates is a major obstacle in the way of implementing NW-based applications in today's silicon- and glass-based technologies. Here, the guided growth of semiconductor NWs is demonstrated along nanoscale-depth scratches, created in a nonlithographic process on amorphous oxidized silicon wafers and soda-lime glass. Scratches are created on the substrates in a few seconds using a robust and scalable mechanical polishing process. Growth of planar NWs of different materials (CdS, CdSe, ZnSe, and ZnO) guided by scratches on Si/SiO₂ wafers and glass is demonstrated and studied. Photoluminescence measurements from individual NWs grown along scratches show that the interaction with the substrate preserves the optical properties of the material. Crystallographic analysis indicates that all materials grow as single crystals, and the influence of the scratches on the different materials is discussed in terms of morphology, crystallinity, and crystallographic orientations. This process opens the way to large-scale integration of NWs into functional devices by guided growth for various applications including displays, polarized light sensors, and smart windows.

Ferroelectric and ferroelastic domains have been predicted to enhance metal halide perovskite (MHP) solar cell performance. While the formation of such domains can be modified by temperature, pressure, or strain, established methods lack spatial control at the level of single domains. Here, we induce the formation of ferroelastic domains in CsPbBr3 nanowires at room temperature using an atomic force microscope (AFM) tip and visualize the domains using nanofocused x-ray diffraction with a 60 nm beam. Regions scanned with a low AFM tip force show orthorhombic 004 reflections along the nanowire axis, while regions exposed to higher forces exhibit 220 reflections. The applied stress locally changes the crystal structure, leading to lattice tilts that define ferroelastic domains, which spread spatially and terminate at {112}-type domain walls. The ability to induce individual ferroelastic domains within MHPs using AFM gives new possibilities for device design and fundamental experimental studies.

Surface-guided growth of planar nanowires offers the possibility to control their position, direction, length, and crystallographic orientation and to enable their large-scale integration into practical devices. However, understanding of and control over planar nanowire growth are still limited. Here, we study theoretically and experimentally the growth kinetics of surface-guided planar nanowires. We present a model that considers different kinetic pathways of material transport into the planar nanowires. Two limiting regimes are established by the GibbsThomson effect for thinner nanowires and by surface diffusion for thicker nanowires. By fitting the experimental data for the lengthdiameter dependence to the kinetic model, we determine the power exponent, which represents the dimensionality of surface diffusion, and results to be different for planar vs. nonplanar nanowires. Excellent correlation between the model predictions and the data is obtained for surface-guided Au-catalyzed ZnSe and ZnS nanowires growing on both flat and faceted sapphire surfaces. These data are compared with those of nonplanar nanowire growth under similar conditions. The results indicate that, whereas nonplanar growth is usually dominated by surface diffusion of precursor adatoms over the nanowire walls, planar growth is dominated by surface diffusion over the substrate. This mechanism of planar nanowire growth can be extended to a broad range of materialsubstrate combinations for higher control toward large-scale integration into practical devices.

The synthesis and characterization of nanotubes from misfit layered compounds (MLCs) of the type (LnS)(1+y)TaS2 (denoted here as LnS-TaS2; Ln=Pr, Sm, Gd, and Yb), not reported before, are described (the bulk compound YbS-LaS2 was not previously documented). Transmission electron microscopy and selected area electron diffraction showed that the interlayer spacing along the c axis decreased with an increase in the atomic number of the lanthanide atom, which suggested tighter interaction between the LnS layer and TaS2 for the late lanthanides. The Raman spectra of the tubules were studied and compared to those of the bulk MLC compounds. Similar to the bulk MLCs, the Raman spectra could be divided into the low-frequency modes (110-150cm(-1)) of the LnS lattice and the high-frequency modes (250-400cm(-1)) of the TaS2 lattice. The Raman spectra indicated that the vibrational lattice modes of the strained layers in the tubes were stiffer than those in the bulk compounds. Furthermore, the modes of the late lanthanides were higher in energy than those of the earlier lanthanides, which suggested larger charge transfer between the LnS and TaS2 layers for the late lanthanides. Polarized Raman measurements showed the expected binodal intensity profile (antenna effect). The intensity ratio of the Raman signal showed that the E-2g mode of TaS2 was more sensitive to the light-polarization effect than its A(1g) mode. These nanotubes are expected to reveal interesting low-temperature quasi-1D transport behavior.

1D core-shell heterojunction nanostructures have great potential for high-performance, compact optoelectronic devices owing to their high interface area to volume ratio, yet their bottom-up assembly toward scalable fabrication remains a challenge. Here the site-controlled growth of aligned CdS-CdSe core-shell nanowalls is reported by a combination of surface-guided vaporliquid-solid horizontal growth and selective-area vapor-solid epitaxial growth, and their integration into photodetectors at wafer-scale without postgrowth transfer, alignment, or selective shell-etching steps. The photocurrent response of these nanowalls is reduced to 200 ns with a gain of up to 3.8 x 10(3) and a photoresponsivity of 1.2 x 10(3) A W-1, the fastest response at such a high gain ever reported for photodetectors based on compound semiconductor nanostructures. The simultaneous achievement of sub-microsecond response and high-gain photocurrent is attributed to the virtues of both the epitaxial CdS-CdSe heterojunction and the enhanced charge-separation efficiency of the core-shell nanowall geometry. Surface-guided nanostructures are promising templates for wafer-scale fabrication of self-aligned core-shell nanostructures toward scalable fabrication of high-performance compact photodetectors from the bottom-up.

The organization of nanowires on surfaces remains a major obstacle toward their large-scale integration into functional devices. Surface-material interactions have been used, with different materials and substrates, to guide horizontal nanowires during their growth into well-organized assemblies, but the only guided nanowire heterostructures reported so far are axial and not radial. Here, we demonstrate the guided growth of horizontal core-shell nanowires, specifically of ZnSe@ZnTe, with control over their crystal phase and crystallographic orientations. We exploit the directional control of the guided growth for the parallel production of multiple radial p-n heterojunctions and probe their optoelectronic properties. The devices exhibit a rectifying behavior with photovoltaic characteristics upon illumination. Guided nanowire heterostructures enable the bottom-up assembly of complex semiconductor structures with controlled electronic and optoelectronic properties.

One-dimensional semiconductor nanostructures, such as nanowires (NWs), have attracted tremendous attention due to their unique properties and potential applications in nanoelectronics, nano-optoelectronics, and sensors. One of the challenges toward their integration into practical devices is their large-scale controlled assembly. Here, we report the guided growth of horizontal CdSe nanowires on five different planes of sapphire. The growth direction and crystallographic orientation are controlled by the epitaxial relationship with the substrate as well as by a graphoepitaxial effect of surface nanosteps and grooves. CdSe is a promising direct-bandgap II-VI semiconductor active in the visible range, with potential applications in optoelectronics. The guided CdSe nanowires were found to have a wurtzite single-crystal structure. Field-effect transistors and photodetectors were fabricated to examine the nanowire electronic and optoelectronic properties, respectively. The latter exhibited the fastest rise and fall times ever reported for CdSe nanostructures as well as a relatively high gain, both features being essential for optoelectronic applications.

A major challenge toward large-scale integration of nanowires is the control over their alignment and position. A possible solution to this challenge is the guided growth process, which enables the synthesis of well-aligned horizontal nanowires that grow according to specific epitaxial or graphoepitaxial relations with the substrate. However, the guided growth of horizontal nanowires was demonstrated for a limited number of materials, most of which exhibit unintentional n-type behavior. Here we demonstrate the vapor-liquid-solid growth of guided horizontal ZnTe nanowires and nanowalls displaying p-type behavior on four different planes of sapphire. The growth directions of the nanowires are determined by epitaxial relations between the nanowires and the substrate or by a graphoepitaxial effect that guides their growth along nanogrooves or nanosteps along the surface. We characterized the crystallographic orientations and elemental composition of the nanowires using transmission electron microscopy and photoluminescence. The optoelectronic and electronic properties of the nanowires were studied by fabricating photodetectors and top-gate thin film transistors. These measurements showed that the guided ZnTe nanowires are p-type semiconductors and are photoconductive in the visible range. The guided growth of horizontal p-type nanowires opens up the possibility of parallel nanowire integration into functional systems with a variety of potential applications not available by other means.

The incorporation of nanostructures into nanoelectronic and nanoelectromechanical systems is a long sought-after goal. In the present article, we report the first torsional electromechanical measurements of pure inorganic nanotubes. The WS₂ nanotubes exhibited a complex and reproducible electrical response to mechanical deformation. We combined these measurements with density-functional-tight-binding calculations to understand the interplay between mechanical deformation, specifically torsion and tension, and electrical properties of WS₂ nanotubes. This yielded the understanding that the electrical response to mechanical deformation may span several orders of magnitude on one hand and detect several modes of mechanical deformation simultaneously on the other. These results demonstrate that inorganic nanotubes could thus be attractive building blocks for nanoelectromechanical systems such as highly sensitive nanometric motion sensors.

Perfectly aligned horizontal ZnSe nanowires are obtained by guided growth, and easily integrated into high-performance blue-UV photodetectors. Their crystal phase and crystallographic orientation are controlled by the epitaxial relations with six different sapphire planes. Guided growth paves the way for the large-scale integration of nanowires into optoelectronic devices.

We report the guided growth of horizontal GaN nanowires (NWs) on spinel (MgAl₂O₄) substrates with three different orientations: (111), (100), and (110). The NWs form ordered arrays with distinct morphologies on the surface of the substrates, controlled by the interaction with the substrate. The geometry of the NWs matches the symmetry of the spinel surfaces: on MgAl₂O₄(111), (100), and (110) the NWs grow in six, four, and two directions, respectively. The epitaxial relations and morphologies of the NW-substrate interface were characterized by cross-sectional transmission electron microscopy. The substrate was found to be mobilized during the growth and either climb up or recede on/under one or two sides of the NW, depending on the substrate orientation. Possible reasons for the similarity and differences between the orientations of the NWs and thin GaN films grown on MgAl₂O₄ are proposed. These results demonstrate the generality and flexibility of the guided growth phenomenon in NWs and specifically show that MgAl₂O₄(111) could be a low-mismatch substrate for the growth of high-quality GaN layers and NWs.

The ability to assemble discrete nanowires (NWs) with nanoscale precision on a substrate is the key to their integration into circuits and other functional systems. We demonstrate a bottom-up approach for massively parallel deterministic assembly of discrete NWs based on surface-guided horizontal growth from nanopatterned catalyst. The guided growth and the catalyst nanopattern define the direction and length, and the position of each NW, respectively, both with unprecedented precision and yield, without the need for postgrowth assembly. We used these highly ordered NWarrays for the parallel production of hundreds of independently addressable single-NW field-effect transistors, showing up to 85% yield of working devices. Furthermore, we applied this approach for the integration of 14 discrete NWs into an electronic circuit operating as a three-bit address decoder. These results demonstrate the feasibility of massively parallel "self-integration" of NWs into electronic circuits and functional systems based on guided growth.

Semiconducting nanowires frequently have enhanced properties and unique functionality compared to their bulk counterparts. Controlling the geometry of nanowires is crucial for their integration into nanoscale devices because the shape of a device component can dictate its functionality, such as in the case of a mechanical spring or an antenna. We demonstrate a novel synthetic method for making polycrystalline CdSe nanowires with controlled geometries by using self-organized single-walled carbon nanotubes as a template for the selective electrodeposition of nanowires. Nanowires of up to hundreds of micrometers in length are formed as high-density straight arrays, as well as in the shape of serpentines and loops. These nanowires exhibit significant photoluminescence and photoconductivity applicable to photodetectors and respond to illumination up to 2 orders of magnitude faster than single crystalline CdSe.

The organization of carbon nanotubes into well-defined straight or curved geometries and arrays on surfaces is a critical prerequisite for their integration into nanocircuits and a variety of functional nanosystems. We review the recent development of a new approach to carbon nanotube organization based on self-organized growth directed by well-defined crystal surfaces, or "nanotube epitaxy". We identify three different modes of surface-directed growth, namely by atomic rows, atomic steps, and nanofacets. Particular emphasis is given here to the combinations of such surface-directed growth with external forces-like those exerted by an electric field or gas flow-for the creation of well-defined complex geometries, including crossbar architectures, serpentines, and coils.

We combine electromechanical measurements with ab initio density-functional calculations to settle the controversy about the origin of torsion-induced conductance oscillations in multiwall carbon nanotubes. Contrary to intuition, the observed oscillation period in multiwall tubes exhibits the same inverse-squared diameter dependence as in single-wall tubes with the same diameter. This finding suggests an intrawall origin of the oscillations and an effective electronic decoupling of the walls, which we confirm in calculations of multiwall nanotubes subject to differential torsion. We exclude the alternative origin of the conductance oscillations due to changes in the interwall registry, which would result in a different diameter dependence of the oscillation period.

(Figure Presented) Let's twist again! Torsion is a chiral deformation. It can turn achiral objects into chiral ones, and discriminate between left-handed and right-handed chiral objects. This article focuses on the significance of carbon nanotubes which can be elastically twisted by 180 without breaking and act as a single-molecule torsional pendulum (see transmission electron micrograph).

A new approach for the specific detection and mapping of single molecule recognition is presented, based on the nonlinear elastic behavior of a single polymer chain. The process of molecular recognition between a ligand and a receptor is inherently accompanied by a decrease in the translational and rotational degrees of freedom of the two molecules. We show that a polymeric tether linked to the ligand can effectively transduce the configurational constraint imposed by molecular recognition into a measurable force, which is dominated by the entropic elasticity of the polymer. This force is specifically characterized by a strong nonlinearity when the extension of the polymer approaches its contour length. Thus, a polymer chain tethering the ligand to an oscillating cantilevered tip gives rise to a highly anharmonic motion upon ligand-receptor binding. Higher-harmonics atomic force microscopy allows us to detect this phenomenon in real time as a specific signature for the probing and mapping of single-molecule recognition.

This work reports Raman spectroscopy measurements from single wall carbon nanotubes (SWNTs) addressing the nature of the G-band resonance Raman spectra. Experimental results on different samples are presented, i.e., aligned and misaligned SWNT samples, as well as isolated and bundled SWNTs. It is shown that the Raman spectra from nondefective SWNTs, both isolated and bundled, are composed of strong first-order single resonance Raman features. Defective materials, however, are found to exhibit lower intensity spectra with contributions from both single resonance and defect-induced double resonance features.

Photoinduced electron transfer between water-oil phases is accomplished in a water-in-oil microemulsion system using a "shuttle photosensitizer" as an electron transporter. The system consists of a water-in-oil microemulsion in which ethyl eosin, (1)EtEo(-), acts as a photosensitizer, Fe(CN)(6)(3-) as an electron acceptor, and tributylamine, Bu3N, as an electron donor. The hydrophilic photosensitizer and electron acceptor are solubilized in the aqueous microdroplets of the water-in-oil microemulsion, whereas the hydrophobic electron donor is present in the continuous oil phase. Photoinduced oxidative electron-transfer quenching in the water phase, k(q) = 1.7 x 10(5) s(-1), results in the oxidized photosensitizer, (2)EtEo(.), and Fe(CN)(6)(4-). The hydrophobic oxidized photosensitizer is extracted to the continuous oil phase, resulting in the phase separation of the photogenerated redox species, and the stabilization of the products against back electron transfer, k(rec) = 7.1 x 10(2) s(-1). The stabilization of the redox species against back electron transfer enables the reduction of the oxidized photosensitizer, (2)EtEo(.).by Bu3N in the oil phase, k(red) = 1.1 x 10(6) M-1.s(-1). The latter process regenerates the hydrophilic photosensitizer, (1)EoEt(-), that is transported back to the water microdroplets, a process leading to the electron transfer across the water-oil boundary by the shuttle photosensitizer. The photosensitized reduction of Fe(CN)63- by Bu3N, in the water-in-oil microemulsion system, proceeds with a quantum yield of phi = 0.04. The mechanism involved in the photoinduced electron transfer between the water-oil phases is elucidated by time-resolved laser flash photolysis experiments and steady-state irradiation. A detailed mathematical model, assuming a Poisson distribution of the quencher in the water droplets, is formulated. This accounts for the different processes involved in the electron transfer in the microheterogeneous system.

Carbon nanotubes combine a range of properties that make them well suited for use as probe tips in applications such as atomic force microscopy (AFM)1,2,3. Their high aspect ratio, for example, opens up the possibility of probing the deep crevices4 that occur in microelectronic circuits, and the small effective radius of nanotube tips significantly improves the lateral resolution beyond what can be achieved using commercial silicon tips5. Another characteristic feature of nanotubes is their ability to buckle elastically4,6, which makes them very robust while limiting the maximum force that is applied to delicate organic and biological samples. Earlier investigations into the performance of nanotubes as scanning probe microscopy tips have focused on topographical imaging, but a potentially more significant issue is the question of whether nanotubes can be modified to create probes that can sense and manipulate matter at the molecular level7. Here we demonstrate that nanotube tips with the capability of chemical and biological discrimination can be created with acidic functionality and by coupling basic or hydrophobic functionalities or biomolecular probes to the carboxyl groups that are present at the open tip ends. We have used these modified nanotubes as AFM tips to titrate the acid and base groups, to image patterned samples based on molecular interactions, and to measure the binding force between single proteinligand pairs. As carboxyl groups are readily derivatized by a variety of reactions8, the preparation of a wide range of functionalized nanotube tips should be possible, thus creating molecular probes with potential applications in many areas of chemistry and biology.