In Situ TEM Studies of III-V Nanowire Growth Mechanism

Growing nanowires inside a transmission electron microscope (TEM) and observing the process in situ has contributed immensely to understanding nanowire growth mechanisms. Majority of such studies were on elemental semiconductors – either Si or Ge – both of which are indirect bandgap semiconductors. Several compound semiconductors on the other hand have a direct bandgap making them more efficient in several applications involving light absorption or emission. During compound nanowire growth using a metal catalyst, the difference in miscibility of the nanowire species inside the metal catalyst are different, making its growth dynamics different from elemental nanowires. Thus, studies specifically focusing on compound nanowires are necessary for understanding its growth dynamics. This chapter reviews the recent progresses in the understanding of compound semiconductor nanowire growth obtained using in situ TEM. The concentrations of the nanowire species in the catalyst was studied in situ. This concentration difference has been shown to enable independent control of layer nucleation and layer growth in nanowires. In situ TEM has also enabled better understanding of the formation of metastable crystal structures in nanowires

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 nanowire is a solid, offers certain advantages compared to the common vapor liquid solid (VLS) route (using liquid catalyst). The VSS growth of group-IV elemental nanowires have 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 monoatomic semiconductors, the dynamics of VSS growth of compound nanowires has not been understood. Here we investigate VSS growth of compound nanowires by in situ microscopy, using Au-seeded GaAs as a model system. The growth kinetics and dynamics at the wire-catalyst interface by ledge-flow is studied and compared for liquid and solid catalysts at similar growth conditions. Here the temperature and thermal history of the system is 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 VLS growth. Unlike in the VLS case, during VSS growth we see several occasions where 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

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 measurement of the catalyst composition of individual gold seeded GaAs nanowires inside an electron microscope as they grow. The Ga content in the catalyst during growth increased with both temperature and Ga precursor flux. A direct comparison of the calculated phase diagrams of the Au-Ga-As ternary system to the measured catalyst composition not only lets us estimate the As content in the catalyst but also indicates the relevance of phase diagrams to understanding nanowire growth

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

We study using in situ transmission 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 wurtzite0001 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

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 500C, 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

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 {101¯ 0} facet

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