Yi-Chia Chou

In-situ TEM observation of repeating events of nucleation in epitaxial growth of nano CoSi2 in nanowires of Si.

The formation of CoSi and CoSi2 in Si nanowires at 700 and 800 degrees C, respectively, by point contact reactions between nanodots of Co and nanowires of Si have been investigated in situ in a ultrahigh vacuum high-resolution transmission electron microscope. The CoSi2 has undergone an axial epitaxial growth in the Si nanowire and a stepwise growth mode was found. We observed that the stepwise growth occurs repeatedly in the form of an atomic step sweeping across the CoSi2/Si interface. It appears that the growth of a new step or a new silicide layer requires an independent event of nucleation. We are able to resolve the nucleation stage and the growth stage of each layer of the epitaxial growth in video images. In the nucleation stage, the incubation period is measured, which is much longer than the period needed to grow the layer across the silicide/Si interface. So the epitaxial growth consists of a repeating nucleation and a rapid stepwise growth across the epitaxial interface. This is a general behavior of epitaxial growth in nanowires. The axial heterostructure of CoSi2/Si/CoSi2 with sharp epitaxial interfaces has been obtained. A discussion of the kinetics of supply limited and source-limited reaction in nanowire case by point contact reaction is given. The heterostructures are promising as high performance transistors based on intrinsic Si nanowires.

Atomic-Scale Variability and Control of III-V Nanowire Growth Kinetics

Regular Nanowires For a range of nanotechnology applications, semiconductor nanowires will need to be grown with high precision and control. Chou et al. (p. 281) studied the growth of gallium phosphide (GaP) nanowires using chemical vapor deposition within a transmission electron microscope and worked out conditions that could generate regular and predictable wire growth. Fluctuations and defects in III-V nanowire growth can be avoided by growing at a low V/III ratio. In the growth of nanoscale device structures, the ultimate goal is atomic-level precision. By growing III-V nanowires in a transmission electron microscope, we measured the local kinetics in situ as each atomic plane was added at the catalyst-nanowire growth interface by the vapor-liquid-solid process. During growth of gallium phosphide nanowires at typical V/III ratios, we found surprising fluctuations in growth rate, even under steady growth conditions. We correlated these fluctuations with the formation of twin defects in the nanowire, and found that these variations can be suppressed by switching to growth conditions with a low V/III ratio. We derive a growth model showing that this unexpected variation in local growth kinetics reflects the very different supply pathways of the V and III species. The model explains under which conditions the growth rate can be controlled precisely at the atomic level.

Homogeneous nucleation of epitaxial CoSi2 and NiSi in Si nanowires.

Homogeneous nucleation is rare except in theory. We observed repeating events of homogeneous nucleation in epitaxial growth of CoSi(2) and NiSi silicides in nanowires of silicon by using high resolution TEM. The growth of every single atomic layer requires nucleation. Heterogeneous nucleation is prevented because of non-microreversibility between the oxide/Si and oxide/silicide interfaces. We determined the incubation time of homogeneous nucleation. The calculated and the measured nucleation rates are in good agreement. We used Zeldovich factor to estimate the number of molecules in the critical nucleus; it is about 10 and reasonable. A very high supersaturation is found for the homogeneous nucleation.

Synthesis of nanostructures in nanowires using sequential catalyst reactions

Nanowire growth by the vapor-liquid-solid process enables a high level of control over nanowire composition, diameter, growth direction, branching and kinking, periodic twinning, and crystal structure. The tremendous impact of VLS-grown nanowires is due to this structural versatility, generating applications ranging from solid state lighting and single photon sources to thermoelectric devices. Here we show that the morphology of these nanostructures can be further tailored by using the liquid droplets that catalyze nanowire growth as a “mixing bowl”, in which growth materials are sequentially supplied to nucleate new phases. Growing within the liquid, these phases adopt the shape of faceted nanocrystals that are then incorporated into the nanowires by further growth. We demonstrate this concept by epitaxially incorporating metal silicide nanocrystals into Si nanowires with defect-free interfaces, and discuss how this process can be generalized to create complex nanowire-based heterostructures.

Growth of Multiple Metal/Semiconductor Nanoheterostructures through Point and Line Contact Reactions

Forming functional circuit components in future nanotechnology requires systematic studies of solid-state chemical reactions in the nanoscale. Here, we report efficient and unique methods, point and line contact reactions on Si nanowires, fabricating high quality and quantity of multiple nanoheterostructures of NiSi/Si and investigation of NiSi formation in nanoscale. By using the point contact reaction between several Ni nanodots and a Si nanowire carried out in situ in an ultrahigh vacuum transmission electron microscopy, multiple sections of single-crystal NiSi and Si with very sharp interfaces were produced in a Si nanowire. Owing to the supply limited point contact reaction, we propose that the nucleation and growth of the sugar cane-type NiSi grains start at the middle of the point contacts between two Ni nanodots and a Si nanowire. The reaction happens by the dissolution of Ni into the Si nanowire at the point contacts and by interstitial diffusion of Ni atoms within a Si nanowire. The growth of NiSi stops as the amount of Ni in the Ni nanodots is consumed. Additionally, without lithography, utilizing the line contact reaction between PS nanosphere-mediated Ni nanopatterns and a nanowire of Si, we have fabricated periodic multi-NiSi/Si/NiSi heterostructure nanonowires that may enhance the development of circuit elements in nanoscale electronic devices. Unlike the point contact reaction, silicide growth starts at the contact area in the line contact reaction; the different silicide formation modes resulting from point and line contact reactions are compared and analyzed. A mechanism on the basis of flux divergence is proposed for controlling the growth of the nano-multiheterostructures.

High precision thermal stress study on flip chips by synchrotron polychromatic x-ray microdiffraction

The bending and residual stress of flip chips caused by the mismatch of thermal expansion between the chip and the substrate have been measured by polychromatic microfocused synchrotron x-ray beam. Precise orientation information as a function of position on the chip was obtained from Laue diffraction patterns, so that the bending angle with respect to a reference position at the center of the chip can be calculated at each position. This in turn allows deducing the local curvature of the entire flip chip. Local stress distribution was then mapped by applying a modified Stoney’s stress-strain equation to the measured curvature. Our study shows that thermal stress on the circuits and the solder joints in a flip chip strongly depend on temperature and the distance from the center of the chip, indicating that interconnects at the corner and edge of a flip chip are of reliability concerns.

Effect of Elastic Strain Fluctuation on Atomic Layer Growth of Epitaxial Silicide in Si Nanowires by Point Contact Reactions

Effects of strain impact a range of applications involving mobility change in field-effect-transistors. We report the effect of strain fluctuation on epitaxial growth of NiSi2 in a Si nanowire via point contact and atomic layer reactions, and we discuss the thermodynamic, kinetic, and mechanical implications. The generation and relaxation of strain shown by in situ TEM is periodic and in synchronization with the atomic layer reaction. The Si lattice at the epitaxial interface is under tensile strain, which enables a high solubility of supersaturated interstitial Ni atoms for homogeneous nucleation of an epitaxial atomic layer of the disilicide phase. The tensile strain is reduced locally during the incubation period of nucleation by the dissolution of supersaturated Ni atoms in the Si lattice but the strained-Si state returns once the atomic layer epitaxial growth of NiSi2 occurs by consuming the supersaturated Ni.

Nucleation and growth of epitaxial silicide in nanowire of silicon

When two nanowires cross each other, they form a point contact. Point contact reaction between a nano metal wire and a nano Si wire has been studied by using ultra-high vacuum and high resolution transmission electron microscopy. Axel epitaxial growth of nano silicides of NiSi and CoSi2 in nanowires of Si has been observed. The nucleation stage and stepwise growth stage of the reactive epitaxial growth of nano silicide on nano Si have been measured. A repeating event of homogeneous nucleation has been found, which enables us to estimate the number of molecules in a critical nucleus to be about 10 using the Zeldovich factor. A comparison to heterogeneous nucleation will be made. The nucleation-controlled or supply-controlled growth mode of point contact reactions is different from the well-known diffusion-controlled and interfacial-reaction-controlled modes of growth in thin film and bulk samples.

Nano silicide formation in nano Si wires

The review reports that the conductance of nanowire of Si is very sensitive to small changes in its surrounding potential and can be affected by the attachment of a small number of charged biological molecules. Using different receptors on the oxidized nano Si wire surface, the detection of the conductance change can be specific to the molecules absorbed on the wire surface. The combination of sensitivity and selectivity makes nanowire-based electronic device to be unique in having a great potential in bio-sensing. It is further reported that in order to have ultra-sensitivity for the detection of a single charged molecule or a virus, the length of the nanowire of Si has to be in the nm range or it requires a nanogapofSi.