In situ observations of size effects in GaAs nanowire growth.

Lateral dimensions of III-V nanowires are known to affect the growth dynamics and crystal structure. Investigations into size effects have in the past relied on theoretical models and post growth observations, which only give a limited insight into the growth dynamics. Here we show the first experimental investigation into how nanowire diameter affects the growth dynamics by growing Au-seeded GaAs nanowires in an environmental transmission electron microscope. This was done by recording videos of nanowires during growth and analysing the Ga-limited incubation time and As-limited step-flow time. Our data show that the incubation time is stable across the investigated diameter range aside from a sharp increase for the smallest diameter, whereas the step-flow time is observed to steadily increase across the diameter range. We show using a simple model that this can be explained by the increasing vapour pressure in the droplet. In addition to the existing understanding of nanowire growth at small dimensions being limited by nucleation this work provides experimental evidence that growth is also limited by the inability to finish the step-flow process.

Enabling In Situ Studies of Metal-Organic Chemical Vapor Deposition in a Transmission Electron Microscope.

The world of environmental microscopy provides the possibility to study and analyze transformations and reactions during realistic conditions to understand the processes better. We report on the design and development of a metal-organic chemical vapor deposition (MOCVD) system integrated with an environmental transmission electron microscope intended for real-time investigations of crystal growth. We demonstrate methods for achieving a wide range of precisely controlled concentrations of precursor gas at the sample, as well as for calibrating the sample partial pressure using the pressure measured elsewhere in the microscope column. The influences of elevated temperature and reactive gas within the pole-piece gap are evaluated with respect to imaging and spectroscopy. We show that X-ray energy-dispersive spectroscopy can be strongly affected by temperatures beyond 500$^{\circ }$C, while the spatial resolution is largely unaffected by heat and microscope pressure for the relevant conditions. Finally, the influence of the electron beam on the investigated processes is discussed. With this work, we aim to provide crucial input in the development of advanced in situ electron microscopy systems for studies of complex reactions in real time under realistic conditions, for instance as used during formation of semiconductor crystals.

Direct Observations of Twin Formation Dynamics in Binary Semiconductors.

With the increased demand for controlled deterministic growth of III-V semiconductors at the nanoscale, the impact and interest of understanding defect formation and crystal structure switching becomes increasingly important. Vapor-liquid-solid (VLS) growth of semiconductor nanocrystals is an important mechanism for controlling and studying the formation of individual crystal layers and stacking defects. Using in situ studies, combining atomic resolution of transmission electron microscopy and controlled VLS crystal growth using metal organic chemical vapor deposition, we investigate the simplest achievable change in atomic layer stacking-single twinned layers formed in GaAs. Using Au-assisted GaAs nanowires of various diameters, we study the formation of individual layers with atomic resolution to reveal the growth difference in forming a twin defect. We determine that the formation of a twinned layer occurs significantly more slowly than that of a normal crystal layer. To understand this, we conduct thermodynamic modeling and determine that the propagation of a twin is limited by the energy cost of forming the twin interface. Finally, we determine that the slower propagation of twinned layers increases the probability of additional layers nucleating, such that multiple layers grow simultaneously. This observation challenges the current understanding that continuous uniform epitaxial growth, especially in the case of liquid-metal assisted nanowires, proceeds one single layer at a time and that its progression is limited by the nucleation rate.

Observation of the Multilayer Growth Mode in Ternary InGaAs Nanowires.

Au-seeded semiconductor nanowires have classically been considered to only grow in a layer-by-layer growth mode, where individual layers nucleate and grow one at a time with an incubation step in between. Recent in situ investigations have shown that there are circumstances where binary semiconductor nanowires grow in a multilayer fashion, creating a stack of incomplete layers at the interface between a nanoparticle and a nanowire. In the current investigation, the growth behavior in ternary InGaAs nanowires has been analyzed in situ, using environmental transmission electron microscopy. The investigation has revealed that multilayer growth also occurs for ternary nanowires and appears to be more common than in the binary case. In addition, the size of the multilayer stacks observed is much larger than what has been reported previously. The investigation details the implications of multilayers for the overall growth of the nanowires, as well as the surrounding conditions under which it has manifested. We show that multilayer growth is highly dynamic, where the stack of layers regularly changes size by transporting material between the growing layers. Another observation is that multilayer growth can be initiated in conjunction with the formation of crystallographic defects and compositional changes. In addition, the role that multilayers can have in behaviors such as growth failure and kinking, sometimes observed when creating heterostructures between GaAs and InAs ex situ, is discussed. The prevalence of multilayer growth in this ternary material system implies that, in order to fully understand and accurately predict the growth of nanowires of complex composition and structure, multilayer growth has to be considered.

Post-nucleation evolution of the liquid-solid interface in nanowire growth.

We study usingin situtransmission electron microscopy the birth of GaAs nanowires from liquid Au-Ga catalysts on amorphous substrates. Lattice-resolved observations of the starting stages of growth are reported here for the first time. It reveals how the initial nanostructure evolves into a nanowire growing in a zincblende 〈111〉 or the equivalent wurtzite〈0001〉 direction. This growth direction(s) is what is typically observed in most III-V and II-VI nanowires. However, the reason for this preferential nanowire growth along this direction is still a dilemma. Based on the videos recorded shortly after the nucleation of nanowires, we argue that the lower catalyst droplet-nanowire interface energy of the {111} facet when zincblende (or the equivalent {0001} facet in wurtzite) is the reason for this direction selectivity in nanowires.

Compositional Correlation between the Nanoparticle and the Growing Au-Assisted InxGa1-xAs Nanowire.

The nanowire geometry is favorable for the growth of ternary semiconductor materials, because the composition and properties can be tuned freely without substrate lattice matching. To achieve precise control of the composition in ternary semiconductor nanowires, a deeper understanding of the growth is required. One unknown aspect of seeded nanowire growth is how the composition of the catalyst nanoparticle affects the resulting composition of the growing nanowire. We report the first in situ measurements of the nanoparticle and InxGa1-xAs nanowire compositional relationship using an environmental transmission electron microscopy setup. The compositions were measured and correlated during growth, via X-ray energy dispersive spectroscopy. Contrary to predictions from thermodynamic models, the experimental results do not show a miscibility gap. Therefore, we construct a kinetic model that better predicts the compositional trends by suppressing the miscibility gap. The findings imply that compositional control of InxGa1-xAs nanowires is possible across the entire compositional range.

Time-resolved compositional mapping during in situ TEM studies.

In situ studies using transmission electron microscopy (TEM) can provide insights to how properties, structures and compositions of nanostructures are affected and evolving when exerted to heat or chemical exposure. While high-resolved imaging can be obtained continuously, at video-framerates of hundreds of frames per second (fps), compositional analysis struggles with time resolution due to the long acquisition times for a reliable analysis. This especially holds true when performing mapping (correlated spatial and compositional information). Hence, transient changes are difficult to resolve using mapping. In this work, the time-resolution of sequential mapping using scanning TEM (STEM) and energy dispersive spectroscopy (EDS) is improved by acquiring spectrum images during short times and filtering the spectroscopic data. The suggested algorithm uses regularization to smooth and prevent overfitting (known from compressed sensing) to fit model spectra to the data. The algorithm is applied on simulations as well as acquisitions of catalyzed crystal growth (nanowires), performed in situ in a specialized environmental TEM (ETEM). The results show the improved temporal resolution, where the compositional progression of the different regions of the nanostructure is revealed, here with a time-resolution as low as 16 s compared to the minutes usually needed for similar analysis.

Vapor-solid-solid growth dynamics in GaAs nanowires.

Semiconductor nanowires are promising material systems for coming-of-age nanotechnology. The usage of the vapor-solid-solid (VSS) route, where the catalyst used for promoting axial growth of nanowires is a solid, offers certain advantages compared to the common vapor-liquid-solid (VLS) route (using a liquid catalyst). The VSS growth of group-IV elemental nanowires has been investigated by other groups in situ during growth in a transmission electron microscope (TEM). Though it is known that compound nanowire growth has different dynamics compared to elemental semiconductors, the layer growth dynamics of VSS growth of compound nanowires have not been studied yet. Here we investigate for the first time controlled VSS growth of compound nanowires by in situ microscopy, using Au-seeded GaAs as a model system. The ledge-flow growth kinetics and dynamics at the wire-catalyst interface are studied and compared for liquid and solid catalysts under similar growth conditions. Here the temperature and thermal history of the system are manipulated to control the catalyst phase. In the first experiment discussed here we reduce the growth temperature in steps to solidify the initially liquid catalyst, and compare the dynamics between VLS and VSS growth observed at slightly different temperatures. In the second experiment we exploit thermal hysteresis of the system to obtain both VLS and VSS at the same temperature. The VSS growth rate is comparable or slightly slower than the VLS growth rate. Unlike in the VLS case, during VSS growth we frequently observe that a new layer starts before the previous layer is completely grown, i.e., 'multilayer growth'. Understanding the VSS growth mode enables better control of nanowire properties by widening the range of usable nanowire growth parameters.

Limits of III-V Nanowire Growth Based on Droplet Dynamics.

Crystal growth of semiconductor nanowires from a liquid droplet depends on the stability of this droplet's liquid-solid interface. Because of the assisting property of the droplet, growth will be hindered if the droplet is displaced onto the nanowire sidewalls. Using real-time observation of such growth by in situ transmission electron microscopy combined with theoretical analysis of the surface energies involved, we observe a reoccurring truncation at the edge of the droplet-nanowire interface. We demonstrate that creating a truncation widens the parameter range for having a droplet on the top facet, which allows continued nanowire growth. Combining experiment and theory provides an explanation for the previously reported truncation phenomenon of the growth interface based only on droplet wetting dynamics. In addition to determining the fundamental limits of droplet-assisted nanowire growth, this allows experimental estimation of the surface tension and the surface energies of the nanowire such as the otherwise metastable wurtzite GaAs {101̅0} facet.

Independent Control of Nucleation and Layer Growth in Nanowires.

Control of the crystallization process is central to developing nanomaterials with atomic precision to meet the demands of electronic and quantum technology applications. Semiconductor nanowires grown by the vapor-liquid-solid process are a promising material system in which the ability to form components with structure and composition not achievable in bulk is well-established. Here, we use in situ TEM imaging of Au-catalyzed GaAs nanowire growth to understand the processes by which the growth dynamics are connected to the experimental parameters. We find that two sequential steps in the crystallization process-nucleation and layer growth-can occur on similar time scales and can be controlled independently using different growth parameters. Importantly, the layer growth process contributes significantly to the growth time for all conditions and will play a major role in determining material properties such as compositional uniformity, dopant density, and impurity incorporation. The results are understood through theoretical simulations correlating the growth dynamics, liquid droplet, and experimental parameters. The key insights discussed here are not restricted to Au-catalyzed GaAs nanowire growth but can be extended to most compound nanowire growths in which the different growth species has very different solubility in the catalyst particle.

In situ analysis of catalyst composition during gold catalyzed GaAs nanowire growth.

Semiconductor nanowires offer the opportunity to incorporate novel structures and functionality into electronic and optoelectronic devices. A clear understanding of the nanowire growth mechanism is essential for well-controlled growth of structures with desired properties, but the understanding is currently limited by a lack of empirical measurements of important parameters during growth, such as catalyst particle composition. However, this is difficult to accurately determine by investigating post-growth. We report direct in situ measurement of the catalyst composition during nanowire growth for the first time. We study Au-seeded GaAs nanowires inside an electron microscope as they grow and measure the catalyst composition using X-ray energy dispersive spectroscopy. The Ga content in the catalyst during growth increases with both temperature and Ga precursor flux.

Kinetics of Au-Ga Droplet Mediated Decomposition of GaAs Nanowires.

Particle-assisted III-V semiconductor nanowire growth and applications thereof have been studied extensively. However, the stability of nanowires in contact with the particle and the particle chemical composition as a function of temperature remain largely unknown. In this work, we use in situ transmission electron microscopy to investigate the interface between a Au-Ga particle and the top facet of an ⟨1̅1̅1̅⟩-oriented GaAs nanowire grown via the vapor-liquid-solid process. We observed a thermally activated bilayer-by-bilayer removal of the GaAs facet in contact with the liquid particle during annealing between 300 and 420 °C in vacuum. Interestingly, the GaAs-removal rates initially depend on the thermal history of the sample and are time-invariant at later times. In situ X-ray energy dispersive spectroscopy was also used to determine that the Ga content in the particle at any given temperature remains constant over extended periods of time and increases with increasing temperature from 300 to 400 °C. We attribute the observed phenomena to droplet-assisted decomposition of GaAs at a rate that is controlled by the amount of Ga in the droplet. We suggest that the observed transients in removal rates are a direct consequence of time-dependent changes in the Ga content. Our results provide new insights into the role of droplet composition on the thermal stability of GaAs nanowires and complement the existing knowledge on the factors influencing nanowire growth. Moreover, understanding the nanowire stability and decomposition is important for improving processing protocols for the successful fabrication and sustained operation of nanowire-based devices.

Demonstration of Sn-seeded GaSb homo- and GaAs-GaSb heterostructural nanowires.

The particle-assisted epitaxial growth of antimonide-based nanowires has mainly been realized using gold as the seed material. However, the Au-seeded epitaxial growth of antimonide-based nanowires such as GaSb nanowires presents several challenges such as for example direct nucleation issues and crystal structure tuning. Therefore, it is of great importance to understand the role of seed material choice and properties in the growth behavior of antimonide-based nanowires to obtain a deeper understanding and a better control on their formation processes. In this report, we have investigated the epitaxial growth of GaSb and GaAs-GaSb nanowires using in situ-formed tin seeds by means of metalorganic vapor phase epitaxy technique. This comprehensive report covers the growth of in situ-formed tin seeds and Sn-seeded GaSb nanowires on both GaAs and GaSb (111)B substrates, as well as GaAs-GaSb nanowires on GaAs (111)B substrates. The growth behavior and structural properties of the obtained GaSb nanowires are further investigated and compared with the Au-seeded counterparts. The results provided by this study demonstrate that Sn is a promising seed material for the growth of GaSb nanowires.