The Growth of Nanowires

FKA 196 : Fundamentals of micro and nanotechnology Mariana David, Maria Karani, Guilain Piraux, october 2013

Introduction
Nanowires are nanostructures that have a thickness/diameter of the order of a nanometer. Since the first studies of nanowires synthesis by VLS growth, many other growth methods have been developed and refined. The understanding of the different parameters involved in nanowires properties and of the possibilities offered by the known materials is constantly increasing. Many types of nanowires can now be synthetized, like metallic, semiconducting or insulating nanowires. Here is presented a panel of some of these growth techniques

Vapor Liquid Solid growth

It is a widely used method for 1D nanomaterials that includes elementals nanomaterials. It was firstly introduced by Wagner & Ellis in 1964.

MBE-based growths and their advantages

MBE = Molecular Beam Epitaxy [1]
One of the most used technique for single crystal deposition High vacuum environment Molecular beams created from solid source thermal evaporation Metal catalyst : crystallize the source atoms on the metal/substrate interface Many variations of the technique (CBE, SAE) Advantages : Low contamination and oxidation High purity Figure 3 : MBE growth chamber In situ deposition of metal seeds, semi-conductor materials and dopants Low growth Temperature + low growth rate No inter-diffusion in nanostructures Accurate control of layer thickness through the use of shutters

To grow a Si nanowire:

Figure 1: Si whisker growth from vapor phases via AuSi catalytic droplets [1]

Use Au catalyst on a Si substrate Deposition of a thin film of Au on Si should start at a specific Temperature: 363oC for Au catalyst, 800oC without a catalyst (Deposition can be applied by sputtering or thermal evaporation) Activation of Au particles in an Ar or H 2 environment *activation in too high temperature or low vacuum conditions could cause the evaporation of Au nanoparticles Au- Si Droplets are formed by annealing the thin film At 363oC :The Catalytic Effect : Au-Si droplets absorb vapor-phase Si particles Si atoms bond at the interface The liquid droplets rise from the Si substrate For d>20nm growth should be applied along the <111> direction. [1] Advantages : The nanowire grows only where the catalyst is put The diameter is determined by the size of the droplet Large quantities can be growth Disadvantages Usually results in unidirectional growth Contamination occurs by using a metal catalyst

An interesting evolution of MBE : Selective Area Epitaxy (SAE) [3]

The main purpose of using SAE is to avoid the use of any metal catalyst (Au, Al, Ti) SAE uses a patterned SiO2 layer as a mask and specific growth conditions to restrict the growth inside the apertures of this mask. Main disadvantage: Slow growth rate
Figure 4 : Selective Area Epitaxy [4]

Figure 2: Undirectional growth of Si nanowires [1]

What about controlling the growth parameters, such as diameter, composition, length?
An experiment from 2012[2]...
Fact: regarding to IIIV nitrides, the group III elements (In, Ga, Al) alloy readily with the metal seed, but the group V source (N) is generally insoluble, leading to diffusion processes . Hypothesis: different flows of III and V sources should change the rates of III source incorporation into and extraction out of the seed particle, providing control of the seed composition, nanowire diameter and growth rate Experiment: study of III-V nanowires synthesized by chemical vapor deposition via Au particle-mediated growth at 560 C

Nanowires:

InN Influences of V flow (N)

GaN

Influences of III flow (Ga) III source: H2 flow through a Ga-coated quartz injector during growth. H2 flow was reduced from 50 to 10 sccm 1 - the nanowire diameter decrease by (13 5%) 2- the growth rate decreased by 65 9% Figure 5 : (a) BF-TEM image of a GaN nanowire with different diameters along its length. Segments 14 correspond to the flows described in (b). (b) Average diameter of each nanowire segment normalized to the diameter of segment 2. The inset shows H2 flow through the Ga-coated quartz tube injector during the nanowire growth.

NH3 flow was reduced from 300 sccm to 25 sccm during the growth: 1 - In composition increased from (50 7)% to (71 6)% 2 - the nanowire diameter increased (34 9)% 3 - reduced NH3 flow also reduces the growth rate, since that for equal durations of low and high NH3 flow, the hillocks were 39 7% shorter than the valleys

Conclusion:

Research on nanowires is still in progress and there is no industrial use yet but nanowires are very promising and have many application perspectives in the electronic or medicine fields. The wide area they can cover promises a wide range of future applications

References :

(1) N.Wang,Y.Cai, R.Q.Zhang, Materials Science and Engineering R 60 (2008), 1-51 (2) S. K. Lim; S. Crawford; G. Haberfehlner; S. Gradeak, Nano Lett. (2013), 13, 331336. (3) D. Spirkoska, C. Colombo, M. Hei, M. Heigoldt,G. Abstreiter, A. Fontcuberta i Morral, Adv. in Solid State Physics, Vol.48 (2009), 13-26 (4) Mandl B, Stangl J, Hilner E, Zakharov AA, Hillerich K, Dey AW, Samuelson L, Bauer G, Deppert K, Mikkelsen A - Nano Lett. (2010)