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Probability of twin formation on self-catalyzed GaAs nanowires on Si substrate.
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PMID:  23043754     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
We attempted to control the incorporation of twin boundaries in self-catalyzed GaAs nanowires (NWs). Self-catalyzed GaAs NWs were grown on a Si substrate under various arsenic pressures using molecular beam epitaxy and the vapor-liquid-solid method. When the arsenic flux is low, wurtzite structures are dominant in the GaAs NWs. On the other hand, zinc blende structures become dominant as the arsenic flux rises. We discussed this phenomenon on the basis of thermodynamics and examined the probability of twin-boundary formation in detail.
Authors:
Masahito Yamaguchi; Ji-Hyun Paek; Hiroshi Amano
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Publication Detail:
Type:  Journal Article     Date:  2012-10-08
Journal Detail:
Title:  Nanoscale research letters     Volume:  7     ISSN:  1556-276X     ISO Abbreviation:  Nanoscale Res Lett     Publication Date:  2012  
Date Detail:
Created Date:  2012-11-13     Completed Date:  2012-11-19     Revised Date:  2013-02-19    
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Nlm Unique ID:  101279750     Medline TA:  Nanoscale Res Lett     Country:  United States    
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Languages:  eng     Pagination:  558     Citation Subset:  -    
Affiliation:
Department of Electrical Engineering and Computer Science, Nagoya University, C3-1 Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan. yamaguti@nagoya-u.jp.
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Journal ID (nlm-ta): Nanoscale Res Lett
Journal ID (iso-abbrev): Nanoscale Res Lett
ISSN: 1931-7573
ISSN: 1556-276X
Publisher: Springer
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Copyright ©2012 Yamaguchi et al.; licensee Springer.
open-access:
Received Day: 14 Month: 7 Year: 2012
Accepted Day: 22 Month: 9 Year: 2012
collection publication date: Year: 2012
Electronic publication date: Day: 8 Month: 10 Year: 2012
Volume: 7 Issue: 1
First Page: 558 Last Page: 558
PubMed Id: 23043754
ID: 3495757
Publisher Id: 1556-276X-7-558
DOI: 10.1186/1556-276X-7-558

Probability of twin formation on self-catalyzed GaAs nanowires on Si substrate
Masahito Yamaguchi1 Email: yamaguti@nagoya-u.jp
Ji-Hyun Paek1 Email: j_paek@nuee.nagoya-u.ac.jp
Hiroshi Amano1 Email: amano@nuee.nagoya-u.ac.jp
1Department of Electrical Engineering and Computer Science, Nagoya University, C3-1 Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan

Background

III-V compound semiconductor nanowires (NWs) have been attracting significant attention as fundamental structures of novel optical and electronic devices. Especially, vapor-liquid-solid (VLS) NWs grown on Si substrates have been investigated for optoelectronic integrated circuits [1,2].

Previously, we succeeded in growing self-catalyzed GaAs NWs on Si substrates using molecular beam epitaxy (MBE)-VLS method which is a combination of MBE and VLS method [3]. However, twin boundaries formed in the NWs during growth. The occurrence of twin boundaries is controlled by various methods such as control of supersaturation, growth temperature, and diameter [4-8]. To control the twin boundaries, we focused on the pressure of arsenic because self-catalyzed GaAs NW growth was nearly independent of Ga pressure, and arsenic flux plays an important role in the growth mechanism [3]. In addition, arsenic solubility in Ga solution is very low [9]. This means that the degree of supersaturation depends on arsenic pressure only.


Methods

Self-catalyzed GaAs NWs were grown on a (111)Si substrate by MBE-VLS method. The growth temperature was 580°C. When the arsenic flux varied from 5.0×10−6 to 1.9×10−5 Torr, the diameter and the length of the obtained GaAs NWs varied from 90 to 30 nm and 0.5 to 3.5 μm, respectively. We have previously discussed the tendency of the diameter and length to depend on the arsenic flux [3]. The obtained NWs were observed by transmission electron microscopy (TEM).


Results and discussion

TEM images of GaAs NWs are shown in Figure 1. In the case of low arsenic flux (5.0 × 10−6 Torr), wurtzite (WZ) structures are dominant as shown in Figure 1a. On the other hand, when the arsenic flux is high, Figure 1c shows that segments between the twin boundaries become large, and zinc blende (ZB) structures are dominant. The segment size follows the time between successive twin-crystal nucleation events. Furthermore, distribution of the segment sizes is exponential from a stochastic point of view [10].

Figure 2 shows the distribution histogram of the segment sizes obtained from Figure 1. We assume a segment size of x and fitted the histogram with an exponential curve of the form exp (x/a) to estimate the expectation value of segment α. The estimated expectation values were 1.1 and 6.5 monolayers at arsenic fluxes of 7.0 × 10−6 and 1.9 × 10−5 Torr, respectively. The reciprocal of the expectation value α−1 is equivalent to the probability of occurrence of twin-crystal nucleation. The probabilities were approximately 90% (7.0 × 10−6 Torr) and 15% (1.9 × 10−5 Torr). The dependence of the probability on the arsenic flux is in good agreement with [11] and [12].

To understand these phenomena, we calculate the degree of supersaturation and estimate the probability of twin-boundary formation, following the procedure presented by Glas [13]. The degree of supersaturation Δμ is as follows:

[Formula ID: bmcM1]
(1) 
Δμ=μGaL+μAsL−2μGaAs

where μGaAs is the half chemical potential of GaAs crystal nucleation; μGaL and μAsL are the chemical potentials of liquid gallium and liquid arsenic, respectively. We assume that the arsenic adatom was liquid arsenic existing on the gallium droplet. However, μGaL and μAsL include an interaction between gallium and arsenic in pure gallium and arsenic chemical potentials μGapL and μAspL, respectively. Therefore, μXL (X = Ga or As) is given by

[Formula ID: bmcM2]
(2) 
μXL=μXpL+RTlnaXL

where R is the gas constant, T is the growth temperature, and aLX is the activity of X in the liquid phase. At T0 = 298.15 K, when we adopt an enthalpy per mol in the X, the solid phase of hX,0pS, the degree of supersaturation Δμ is given by

[Formula ID: bmcM3]
(3) 
Δμ=RTlnaGaL+RTlnaAsL+μGaL−hGa,0pS+μAspL−hAs,0ps−2μGaAs−0.5hGa,0pS−0.5hAs,0pS.

All terms except the enthalpies depend on the growth temperature. The third, fourth, and fifth terms are the differences between the chemical potential and enthalpy of the pure gallium droplet, arsenic droplet, and GaAs crystal. Their values are tabulated in the paper of Ansara et al. [14]. The first and second terms are concerned with interactions in the alloy. They are denoted by the atomic concentration cX and the interaction parameter for gallium and arsenic ωGa,As as follows:

[Formula ID: bmcM4]
(4) 
RTlnaGaAsL=RTlncGaAs+cAsGa2ωGa,As=RTlncGaAs+cAsGa2VGaVAscGaVGa+cAsVAsδGa−δAs2−1.256×105χGa−χAs2VGaVAs

where VGa(As), χGa(As), and δGa(As) are the molar volume in the liquid phase, Pauling electronegativity, and Hildebrand solubility parameter, respectively. From these equations, we can obtain the relational expression for the supersaturation dependence on growth temperature and arsenic concentration in the gallium droplet.

Figure 3 shows the supersaturation as a function of the arsenic concentration in the gallium droplet at 580°C. In this calculation, the supersaturation per atom Δμ/NA, where NA is Avogadro's number, is adopted. In Figure 3, the equilibrium arsenic concentration is approximately 0.06% at Δμ/NA = 0. This value is in fair agreement with the arsenic concentration of approximately 0.1% in the gallium droplet at 580°C [9]. Therefore, when the arsenic concentration is positive because of an oversupply of arsenic atoms greater than 0.06%, GaAs VLS growth may occur.

From supersaturation Δμ/NA, we can obtain the probability of twin-boundary formation. When arsenic adatoms on the gallium droplet surface diffuse to the three-phase boundary of vapor, liquid, and solid phases, we assumed that the GaAs crystal nucleus would be formed into a rhombus shape with side length r at the vertex of the nanowire top surface. Figure 4 shows the growth model. When the ZB and WZ structures form, the amount of Gibbs free energy change in this growth system is given by

[Formula ID: bmcM5]
(5) 
ΔGZBWZ=−3r2hΔμ2ΩNA+2rhγSL,ZBWZ+ζγSV,ZBWZ−γLVsinβ+3r22γSN

where Ω is the solid volume of the Ga-As pair (4.51 × 10−29 m3), h is the height of crystal nucleus, β is the contact angle of the droplet, γLV (γSN) is the interface energy between the droplet and the vapor phase (between the crystal nucleus and the NW top surface), and γSL,ZB(WZ) and γSV,ZB(WZ) are the interface energies of the GaAs ZB (WZ) crystal nucleus top and side surfaces. Obviously, h is the (111) GaAs lattice spacing, which is 0.32639 nm. γSV,ZB and γSV,WZ are the surface energies of (1-10)GaAs and (11-20)GaAs, which are 0.62 and 0.54 J/m2, respectively [15]. The interface energy γLV depends on temperature, and we use the following relation: γLV = 0.708 − 0.66 × 10− 4 × (T − 303) (J/m2) [16]. If the crystal nucleus is ZB, γSN = 0. On the other hand, in the case of the WZ crystal nucleus, γSN is 0.023 (J/m2), which is half of the GaAs stacking fault energy [17]. We assumed that the contact angle β is 45° [18]. Since the NW side surface has a certain asperity, we adopted the parameter ζ (0 <ζ < 1). Therefore, the maximum ΔGZB(WZ) * and the critical nucleus of Equation 4 for r are obtained as follows:

[Formula ID: bmcM6]
(6) 
ΔGZBWZ*=2h2γSL,ZBWZ+ζγSV,ZBWZ−γLVsinβ23hΔμΩNAγSN

[Formula ID: bmcM7]
(7) 
rZBWZ*=2hγSL,ZBWZ+ζγSV,ZBWZ−γLVsinβ3hΔμΩNA−γSN

At steady state, it is known that the probability of crystal nucleation JZB(WZ) is proportional to the SZB(WZ) region, where a crystal nucleus can form, and Zeldovich factor ZZB(WZ)[19]. The relation is given by

[Formula ID: bmcM8]
(8) 
JZBWZ∝ZZBWZSZBWZexp−ΔGZBWZ*kT

where k is the Boltzmann constant, SZBWZ=33rZBWZ*2, and the Zeldovich factor is

[Formula ID: bmcM9]
(9) 
ZZBWZ=3hΔμΩNA−γSN/2πkT1/2

Therefore, the probability of twin-crystal nucleation P is

[Formula ID: bmcM10]
(10) 
P=JWZJZB+JWZ=ZWZSWZexp−ΔGWZ*kTZZBSZBexp−ΔGZB*kT+ZWZSWZexp−ΔGWZ*kT

This equation indicates that the probability depends on the growth temperature and arsenic concentration. When we assume that ζ is 0.8 at 580°C, the relation between the probability P and arsenic concentration cAs is shown in Figure 5. As the droplet arsenic concentration increases with increasing arsenic flux, the probability of twin-crystal nucleation decreases. This phenomenon agrees with the experimental results.

By using the probability of twin-crystal nucleation in Figure 2, we can calculate the arsenic concentration and supersaturation per atom. When the arsenic fluxes are 7.0 × 10−6 and 1.9 × 10−5 Torr, the arsenic concentrations are 0.11% and 0.38%, and the supersaturations per atom are 53 and 143 meV, respectively. These supersaturation values are smaller than those of Au-catalyzed GaAs NWs (230 to 1,570 meV) [20]. This difference might be due to the difference in the side facet surface. Glas et al. adopted the {111} and {1-100} facets in the ZB and WZ structures in their calculations, respectively. In addition, there might be a difference in the diffusion length between gold and gallium droplets. From the obtained arsenic concentration, we estimate the critical nucleus. When the arsenic fluxes are 7.0 × 10−6 and 1.9 × 10−5 Torr, the critical nuclei of ZB (WZ) are 1.1 (0.3) and 0.4 (0.1) nm, respectively. This means that the increase of arsenic flux decreases the critical nucleus and increases the growth rate. In the case of high arsenic flux, the size difference between critical ZB and WZ nuclei is small compared with the case of low arsenic flux. This means that the ZB structure appears easily as the arsenic flux increases. Therefore, we could improve the comprehension of the growth mechanism in the self-catalyzed GaAs NWs. This comprehension might support a technological feasibility of a novel device like twin-plane 1D superlattices [21].


Conclusions

Self-catalyzed GaAs NWs were grown on a (111)Si substrate by MBE-VLS method under various arsenic fluxes. From the TEM observations, we found that the segment size between the twin boundaries depends on the arsenic flux. In order to understand this phenomenon, we attempted to calculate the degree of supersaturation and estimate the probability of twin-boundary formation. When the supersaturation increased with increasing arsenic flux, the size difference between the critical ZB and WZ nuclei decreased. As a result, the ZB structures were easier to obtain as the arsenic flux increased. This qualitatively explained the experimental results and the high probability of the incorporation of twin boundaries.


Abbreviations

GaAs: gallium arsenide; MBE: molecular beam epitaxy; NW: nanowires; Si: silicon; TEM: transmission electron microscope; VLS: vapor-liquid-solid; WZ: wurtzite; ZB: zinc blende.


Competing interests

The authors declare that they have no competing interests.


Authors’ contributions

MY conceived, designed, and coordinated the study and drafted the manuscript. JP carried out the experiments and calculations and helped draft the manuscript. HA participated in the coordination of the study. All authors read and approved the final manuscript.


Authors’ information

MY is an associate professor, JP is a graduate school student, and HA is a professor at the Department of Electrical Engineering and Computer Science, Nagoya University.


Acknowledgments

This study was partly supported by the Grant-in-Aid for Scientific Research (KAKENHI) No. 23510148 of the Japan Society for the Promotion of Science (JSPS) and ‘Tatematsu Foundation.’ Nagoya University Venture Business Laboratory is gratefully acknowledged for allowing the use of facilities.


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Figures

[Figure ID: F1]
Figure 1 

TEM images of NWs grown under various arsenic fluxes. (a) 5.0 × 10−6, (b) 7.0 × 10−6, and (c) 1.9 × 10−5 Torr.



[Figure ID: F2]
Figure 2 

Histogram and distribution of segment size obtained from Figure1. Arsenic fluxes are (a) 7.0 × 10−6 and (b) 1.9 × 10−5 Torr. Solid lines are exponential fitting curves.



[Figure ID: F3]
Figure 3 

Supersaturation as a function of arsenic concentration in gallium droplet at 580°C.



[Figure ID: F4]
Figure 4 

Growth model adopted in the calculation.



[Figure ID: F5]
Figure 5 

Relation between the probability of the twin-crystal nucleus and arsenic concentration at 580°C (ζ= 0.8).



Article Categories:
  • Nano Express

Keywords: GaAs nanowire, Molecular beam epitaxy, Vapor-liquid-solid, Twin boundary, Supersaturation, Wurtzite, zinc blende.

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