1

2. UHV-CVD GROWTH OF SI/GE NWS

2.1. Growth Techniques

VAPOR-LIQUID-SOLID GROWTH
METAL CATALYST
2.2. NW Growth at BM32
SAMPLE PREPARATION
SI NWS
GE NWS
Source Precursor / Pressure Temperature Growth Mode
This work 10
-4
-10
-2
mbar Ge
2
H
6
280C - 340C VLS
(Boukhicha 2011) 10
-4
-10
-2
mbar Ge
2
H
6
280C - 400C VLS
(Kodambaka et al. 2007) 10
-7
-10
-5
Torr Ge
2
H
6
250C - 400C VLS+VSS
Two step growh, boukhicha and Conditions for subeutectic growth of
Ge nanowires by the vapor-liquid-solid mechanism

GE/SI RADIAL NW HETEROSTRUCTURES
Will be shown in chapter 4.
GE/SI AXIAL NW HETEROSTRUCTURES
Despite our numerous attempts, direct growth of Ge NWs on Si substrates has
turned out to be fruitless. Crawling NWs (Figure 2-1A) was observed when the same
growth condition that gave rise to nice Ge NWs in Ge(111) substrates was applied. The
2
presence of crawling NWs is understood as follows. In the early stages of growth, the
droplet sits on a tapering pedestal, which must introduce new facets to evolve into steady-
state nanowire growth. If the introduction of new facets is impeded, the initial base
continues to taper until the catalyst droplet rolls off. The catalyst then crawls along the
surface, growing into a lateral wire (Schwarz & Tersoff 2011). Various growth conditions
has been attempted for growth temperature between 270C and 360C with liquid or
intentionally solidified Au catalysts, but were still unfruitful (Figure 2-1B). Successful
growth has been reported elsewhere (Kodambaka et al. 2007; Jagannathan et al. 2006;
Woodruff et al. 2007), although it seems that only catalysts (and hence NWs) with very
small size (typically 10-40nm) were used in the majority of the cases. The possibility of
having a size limit (which eventually boils down to differences in surface energy,
supersaturation rate, etc.) only below which successful growth can take place agrees well
with our observations (Figure 2-1C), where small vertically aligned Ge NWs were seen
growing among crawling NWs with larger diameters. However, even with rather small
catalysts, the yield (Figure 2-1D) was still less than satisfactory.
3

Figure 2-1: 40 perspective view of direct growth of Ge NWs on Si (111) substrates with
2e-2 mbar of Ge
2
H
6
at 280C (A) The same condition that gives rise to nice Ge NWs on
Ge substrates: with 3ML of Au catalysts annealed at 500C for 25min. (B) with 3ML of
deliberately solidified Au catalysts. (C) with 3ML of Au catalysts annealed at 450C for
45min. (D) with 3ML of Au catalysts annealed at 450C for 15min
An easy solution to the problem is to grow Ge NWs on existing Si NWs instead,
the result of which is known as GeSi NW heterostructure. Although the size limit for
successful growth still exists, as is evident from Figure 2-2A, the barrier is significantly
lowered. As a matter of fact, Ge NW parts were seen growing on Si NWs with diameter
of as large as 80-100nm. By intentionally bombarding the reconstructed surface with Ar
+

and by lowering the temperature at which Au nucleation occurred, we were able to
synthesize GeSi NW heterostructures with an acceptable yield. Figure 2-2B shows a
zoom-in SEM image of such structures. The Ge part (upper half) resembles that of a Ge
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NW grown on Ge substrates. The variation in diameter along the axial direction is due to
intensive overgrowth under our relatively high partial gas pressure. The Si part (lower
half) is featured with large and irregular facets, which is also resulted from Ge
overgrowth during the process. A non-negligible amount of kinking was observed (Figure
2-2CD). As a matter of fact, the elevated level of kinking is expected due to disparate
growth temperatures and chemical potential-induced instabilities (Dick et al. 2007) in the
liquid growth seed upon switching between Si and Ge (Dayeh et al. 2011). The majority
of the kinking was found towards the <111> directions in our case, although <112>
kinking was also observed. Finally, it is worth mentioning that, despite absence of any
chemical analysis, we expect the Si-Ge heterojunction in our case to be rather smooth.
More compositional abrupt Si-Ge interface has been reported, by tuning the
semiconductor solubility in the alloy catalyst with either Al (Wen et al. 2009) or Ga
(Perea et al. 2011).
5

Figure 2-2: (A) 40 perspective view of Ge/Si axial NW heterostructures. The Si NW
parts were grown with 20min of 1e-5mbar Si
2
H
6
injection at 500C right after deposition
of 3ML Au. The sample was then cooled down to 285C for the growth of Ge NW parts
with 80min of 2e-2mbar of Ge
2
H
6
injection. Subsequent Ge growth occurred only for
NWs with smaller size. (C) Top view and (B)(D) 40 perspective view of nicer Ge/Si
axial NW heterostructures. Prior to the deposition of metal catalyst, the (77)
reconstructed surface was bombarded with 0.8mA of Ar
+
at RT to limit Au diffusion. The
temperature for the growth of Si NW parts (and for Au deposition) was also lowered to
450C in order to synthesize NWs with smaller diameters. The rest of the growth
conditions were kept the same.





6
SI/GE AXIAL NW HETEROSTRUCTURES

GROWTH WITH COLLOIDAL GOLD AND WITH PATTERNED SUBSTRATES
2.3. Conclusion








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