Understanding Self-Catalyzed Epitaxial Growth of III–V Nanowires

Jan 19, 2017 - On that basis, we performed a pregrowth annealing strategy to promote the nanowire density by enhancing the pits formation on the subst...
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Understanding Self-Catalyzed Epitaxial Growth of III-V Nanowires Towards Controlled Synthesis Yunlong Zi, Sergey Suslov, and Chen Yang Nano Lett., Just Accepted Manuscript • DOI: 10.1021/acs.nanolett.6b04817 • Publication Date (Web): 19 Jan 2017 Downloaded from http://pubs.acs.org on January 22, 2017

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Understanding Self-Catalyzed Epitaxial Growth of III-V Nanowires Towards Controlled Synthesis Yunlong Zi†‡*, Sergey Suslov§⊥, Chen Yang†∥* †

Department of Physics and Astronomy, Purdue University, West Lafayette, IN 47907, United

States §





Birck Nanotechnology Center, Purdue University, West Lafayette, IN 47907, United States Department of Chemistry, Purdue University, West Lafayette, IN 47907, United States Current address: School of Materials Science and Engineering, Georgia Institute of

Technology, Atlanta, GA 30332 ⊥

Current address: Qatar Environment and Energy Research Institute, Hamad Bin Khalifa

University, Qatar Foundation, P.O. Box 5825 Doha, Qatar *

Corresponding Authors. Email: [email protected] and [email protected]

Keywords: self-catalyzed nanowire growth, InAs, epitaxial, growth mechanism

Abstract: Self-catalyzed growth of III-V nanowires has drawn plenty of attention due to the potentials of integration in current Si-based technologies. The homoparticle-assisted vaporliquid-solid growth mechanism has been demonstrated for self-catalyzed III-V nanowire growth. However, the understandings of the preferred growth sites of these nanowires are still limited, which obstructs the controlled synthesis and the applications of self-catalyzed nanowire arrays. Here we experimentally demonstrated that thermally created pits could serve as the preferred sites for self-catalyzed InAs nanowire growth. Based on that, we performed a pre-growth 1 ACS Paragon Plus Environment

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annealing strategy to promote the nanowire density by enhancing the pits formation on the substrate surface, and enable the nanowire growth on the substrate that was not capable to facilitate the growth. The discovery of the preferred self-catalyzed nanowire growth sites and the pre-growth annealing strategy have shown great potentials for controlled self-catalyzed III-V nanowire array growth with preferred locations and density.

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With high mobility and low effective mass of carriers, III-V nanowires have been demonstrated as promising semiconductor channel materials for nanowire transistors.1-3 Heteroparticle catalysts, such as Au or Ni nanoparticles, have been successfully demonstrated for high quality III-V nanowire growth4-10. However, III-V nanowires produced by heteroparticlecatalyzed growth have shown the problem of thermal stability. Taking InAs nanowires as an example, at around 500 °C, the presence of Au catalysts promotes catalytic decomposition of InAs material greatly11; besides, at 220-300 °C, Ni nanoparticles will react with semiconductor InAs nanowires to form fully-conducted NixInAs nanowires12. These effects of metal catalysts limit the processing temperature of III-V nanowires and nanowire-based devices. Additionally, to be compatible with current Si-based technologies, nanowires without Au nanoparticles are always preferred, since Au can form deep level traps in Si. Therefore, heteroparticle-free III-V nanowire growth methods are highly demanded for further applications and integrations in Sibased technologies. Here we mainly focus on InAs nanowires, since among III-V nanowires, InAs nanowires have attracted particularly substantial attention due to the outstanding electrical performances.6, 7, 13-15 Different methods to achieve heteroparticle-free nanowire growth have been demonstrated for InAs nanowires. Selective area epitaxial growth of self-catalyzed InAs nanowires was performed on SiO2/Si and SiO2/InAs substrates, with pre-patterning and wetetching steps to define the growth sites for nanowires.16, 17 Van der Waals epitaxial growth of InAs nanowires was also reported on mechanical exfoliated and CVD grown graphene18, 19, in which ledges, kinks and defects were considered as preferred nucleation sites. However, these methods often require complex additional pre-growth steps, such as pre-deposition and patterning of SiO2 layer, transfer of graphene, etc., which make the whole process challenging

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for large scale production. At the same time, the homoparticle-assisted vapor-liquid-solid (VLS) growth mechanism has been shown as applicable for self-catalyzed InAs nanowire growth on Si and III-V substrates without pre-patterning steps required.20-27 However, understandings of the preferred sites for this homoparticle-assisted self-catalyzed InAs nanowire growth are still very little, which limits the controlled synthesis and further applications of these self-catalyzed nanowires, particularly in the applications requiring position/density controls. In our work, epitaxial self-catalyzed InAs nanowire growth was performed directly on III-V substrates. The distinct growth behaviors of epitaxial self-catalyzed InAs nanowires on different III-V substrates, especially InAs, GaSb, and GaAs, were compared. We found that thermally created pits observed on III-V substrates were correlated to the self-catalyzed growth. Through cross-sectional transmission electron microscopy imaging of as-grown samples, such pits were confirmed as the preferred sites for nanowire growth. This new finding allows us to develop a pre-growth annealing strategy to promote nanowire density by creating more pits before growth. Through this strategy we can also enable growth on the substrate that was previously not capable to facilitate the growth. Our results open the potentials for synthesis of self-catalyzed III-V nanowires with controlled locations and density. Self-catalyzed InAs nanowire growth was performed in a simple vapor deposition system with a multi-zone tube furnace. InAs powder (99.9999% from Alfa Aesar) was placed in the upstream zone as the solid precursor. Growth was tested out on different III-V substrates (from MTI Corporation), including InAs, GaSb, and GaAs. Prior to the growth, III-V substrates were cleaned by sonication in acetone, isopropyl alcohol and ethanol. These cleaned substrates were placed in the downstream zone as growth substrates. The tube was evacuated and a base pressure of a few mtorr was achieved before the growth starts. Then the upstream zone (precursor) and

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the downstream zone (substrate) were heated to the desirable source temperature (820-850 °C) and substrate temperature (490-500 °C), respectively, under 2.2 Torr pressure condition maintained by the carrier gas H2. The typical growth period was 45 min to 1h.

Table 1. Self-catalyzed InAs nanowire growth on different substrates. Substrates InAs (111)B InAs (111)A GaSb (111)A GaSb (110) GaAs (111)B

Melting T °C NW Growth? 942

712 1238

Yes Yes Yes Yes No

Scanning electron microscope (SEM) was utilized to image as-grown samples. As shown in Table 1, InAs nanowire growth was observed on all the InAs and GaSb substrates (Figure 1 a~d); however, there is no nanowire growth on GaAs substrates, which will be further discussed later. All the nanowires are grown along B directions. The diameters of nanowires are in the range of 20-100 nm, while the length is up to 1 µm for 45 min growth. Transmission electron microscope (TEM) equipped with energy-dispersive X-ray spectrometer (EDX) was used to confirm the composition of nanowires (Figure 1 e and f). For nanowires grown on all the III-V substrates tested, the In:As ratio in nanowires was confirmed as about 1:1. As shown in Figure 1g, high-resolution TEM (HRTEM) images taken on nanowires also confirm the zinc blende crystal structure with lattice constant of about 0.606 nm, which is consistent with the bulk value of InAs.

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Figure 1. Self-catalyzed InAs nanowire growth on (a) InAs (111)B substrate (85° tilt view, inset is the 70° tilt view), (b) InAs (111)A substrate (top view), (c) GaSb (111)A substrate (top view), and (d) GaSb (110) substrate (top view). The insets in b~d show projections of three B directions of the substrate. (e) TEM image of an InAs nanowire and (f) EDX spectrum taken from it showing In and As peaks, in which Fe and Cu peaks are from pole pieces in the TEM column and the TEM grid. (g) High-resolution TEM image of InAs nanowire with growth direction of B. B: zone axis. The inset shows fast fourier transform (FFT) of the TEM image. Scale bars are: (a) 400 nm; inset of (a) 400 nm; (b) 800 nm; (c) 1 µm; (d) 2 µm; (e) 500 nm; (g) 5 nm.

Growth on GaSb (111)A was studied in details to identify the preferred sites of the selfcatalyzed InAs nanowire growth. SEM snapshots were taken on the GaSb substrate surfaces 6 ACS Paragon Plus Environment

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before growth and at different growth time. Before loading the substrate to the growth furnace, the surface of the GaSb (111)A substrate was smooth without any features observed (Figure 2a). At 5 min after all the zones achieve the desired temperature, there was no nanowire but pits observed all over the substrate surface (Figure 2b). The formation of these pits is due to the thermal annealing effect under the growth temperature in the first 5 min.28 At 45 min of growth, there are nanowires observed on GaSb (111)A substrate, as shown in Figure 1b. After removing the nanowires from this substrate by 10 min sonication in ethanol, there are also pits observed on the remaining substrate surface (Figure 2c). We estimated the pits density after 5 min growth, the nanowires density after 45 min growth, and the pits density after removal of the nanowires. The results are compared in Figure 2d, indicating these density values are correlated. Therefore, we hypothesized that thermally created pits on the substrate surface can be the preferred sites for InAs nanowire growth. A proposed growth process is illustrated in Figure 3. Within the initial several minutes under the growth temperature, there are pits formed on substrates due to the thermal annealing effect (Figure 3b). Due to capillary condensation, these pits serve as preferred sites to absorb indium droplets (Figure 3c).21 Then InAs nanowire growth was catalyzed by these indium droplets (Figure 3d).

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Figure 2. (a): GaSb (111)A substrate before nanowire growth; (b): GaSb (111)A substrate after growth starts for 5 min; (c): as-grown GaSb (111)A substrate shown in Figure 1b after 10 min sonication in ethanol; (d): comparison of the density of nanowires obtained from the sample of 45 min growth (Fig. 1b), the density of pits obtained from the sample of 5 min growth (Fig. 2b), and the density of pits after removing nanowires from the sample of 45 min growth (Fig. 2c). The white arrows in (b) and (c) indicate the locations of the pits. Scale bars: 200 nm.

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Figure 3. The proposed growth process of self-catalyzed InAs nanowires. (a): the substrate before growth; (b): pits formation on substrates due to thermal annealing effect; (c): indium droplets absorption inside pits; (d): The InAs nanowire growth. The legends are shown above the figure. Please be notice that the shape of pits is drawn as pyramid just for convenience.

As shown in Table 1, in addition to InAs and GaSb substrates, growth tests were also performed on GaAs (111)B substrates. At the identical growth condition, there was no nanowire growth observed on GaAs (111)B substrate. SEM images of GaAs as-grown samples after the 45 min growth show that the substrate surface is smooth without any pits (Figure S1, supporting information). This could be due to the high melting point of GaAs (1238 ºC), and thus the growth temperature (490-500 °C) is not high enough to thermally evaporate the GaAs material surface to create pits before growth. Consequentially, there is no nanowire growth. These results support our hypothesis that pits created on the substrate surface can be the preferred sites for InAs 9 ACS Paragon Plus Environment

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nanowire growth. Based on this observation, we expect that introducing pits through a pregrowth thermal annealing step at a suitable temperature could promote the InAs nanowire growth on the GaAs substrate. Selected-area annealing was performed on GaAs (111)B substrate to demonstrate the promotion of the InAs nanowire growth through pits formation. Sample preparation process was illustrated in Figure 4a. 20 nm SiO2 layer was deposited on part of the GaAs (111)B substrate surface (area A). The other part of the GaAs substrate was covered by a Si substrate during the deposition, thus there is no SiO2 layer deposited in this area (area B). Prior to the annealing step, the substrate surface in the both areas were observed to be clean without any features (Figure S2 a and b, supporting information). The entire substrate was then thermally annealed in 20 sccm H2 at 650 °C for 5 min. The SiO2 layer protected the substrate surface in area A from being evaporated in the annealing step. Thus the area A was still clean with no features observed, and high density pits were observed only in area B. (Figure S2 c and d, supporting information) The pits formatted are in irregular shape, which is consistent with a previous report.29 The SiO2 layer was then completely removed by etching in buffered oxide etch (BOE) for 25 second. Lowdensity pits were observed in area A, which might be created in the etching step. In comparison, the formation of the higher density pits observed in area B was mainly due to the enhanced surface evaporation in the annealing step (Fig. 3c). The self-catalyzed InAs nanowire growth was then performed on the substrate prepared, resulting in low-density nanowires in area A (Fig. 3d) and high-density nanowires in area B (Fig. 3e). We notice that the lengths of the high-density nanowires in area B are usually short, which might be attributed to the competition of source elements between nanowires, similar to a previous reported result.30 The direct correlation between the density of pits and the density of nanowires on the corresponding areas supports our

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hypothesis, and suggests that the designed fabrication/creation process of pits could promote self-catalyzed InAs nanowire growth on the substrate which was not capable to facilitate the growth.

Figure 4. Self-catalyzed InAs nanowire growth on GaAs (111)B substrates after selected-area annealing. (a) Schematic of substrate preparation and growth process. Areas A (left) was deposited by a SiO2 layer while area B (right) was not deposited. (b) and (c) SEM images taken from areas A (b) and B (c) of the as-prepared substrate after removal of SiO2 through 25 s etching in BOE solution (top view). The locations of the pits in (b) are indicated by the white arrows. The pits’ locations in (c) are not marked since the pits are with obviously high density. (d) and (e) SEM images taken from areas A (d) and B (e) of the as-grown sample (20° tilted view). 11 ACS Paragon Plus Environment

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A key in our hypothesis is that the indium droplets condensed in the pits initiated the nanowire growth. Noticeably, in the TEM image shown in Figure 1c, in which the TEM sample was prepared through dispersion of sonicated nanowires from as-grown substrates, no obvious contrast indicated In droplets on tips of grown nanowires, which is attributed to the fact that these indium droplets were crystallized to be InAs during the final stage of nanowire growth, as reported previously21. To directly confirm the presence of pits for nanowire growth, we have carried out the cross-sectional TEM study of as-grown samples. Cross-sectional TEM samples were prepared using a focused ion beam (FIB) liftout method (Note S1, supporting information) from the area B of GaAs (111)B substrates as shown in Figure 4. Protective layers of Pt/C were deposited locally in the area of interest to avoid surface damage. In the TEM images for the cross-sectional sample (Figure 5a), the InAs nanowire (indicated in the figure), the amorphous Pt/C layer, and the GaAs substrate (the region below the dashed white straight line) were identified. The Moiré patterns (indicated in the figure and circled by the dashed line) below the nanowire area were identified to have a horizontal spacing of 2.5-2.6 nm and a vertical spacing of about 3 nm, which are expected for InAs and GaAs lattices with overlap of (11ത3) (horizontal) and (220) planes (vertical), respectively (Note S2, supporting information). Such pattern outlines a pit area filled by the InAs material inside the GaAs substrate. As we observed in TEM for different nanowires, there was always a pit area with Moiré patterns at the root of each nanowire (Figure S3, supporting information), which were all identified as formed by overlapping InAs and GaAs lattices. Notably, a small area of Moiré patterns was also observed at the bottom part of the nanowire, which is attributed to the

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fact that the observation direction is a little tilt away from the cross-sectional view, therefore there is a small overlap of the GaAs substrate with the root of the InAs nanowire. From the TEM images, the average depth of the pits was identified as about 52.30±4.13 nm. As shown in Figure 5 b and c, the depth of representative pits on a GaAs substrate after annealing at the same condition was measured to be 48.10±5.96 nm by atomic force microscopy (AFM), consistent with the observation in the TEM images. (Figure 5d) More AFM images showing the pits depth are illustrated in Figure S4, supporting information. The pits with similar sizes on the annealed GaAs substrates were also reported previously.29 Additionally, in the EDX elemental mapping carried out in the scanning TEM (STEM) mode, an area consisted of indium, gallium and arsenic was observed at the root of a nanowire from the cross-sectional sample, which was identified as the pit area (Figure S5, Supporting information). These results confirm our hypothesis that the pits are the preferred sites for the nanowire growth, and support that the pre-growth annealing step enhanced the nanowire growth by creating pits on the substrate surface.

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Figure 5. Direct observation of the pits. (a) Cross-sectional TEM image on the sample made from area B shows InAs nanowire, GaAs substrate (below the white straight dash line), and the pit area. (b) and (c): AFM analysis on the tomography of annealed GaAs substrate surface. (d): Comparison between the average depths measured from TEM and AFM, respectively (each method with ~10 pits). Scale bars are (a) 20 nm; (b) 200 nm.

We have demonstrated the pre-growth annealing method as an effective method to promote nanowire growth on GaAs substrates based on the formation of pits as the preferred sites. We also tested this strategy on InAs (100) substrates. Here the pre-growth annealing step was carried in 20 sccm H2, 500 °C for 2 min. Growth conditions were kept identical. Figure 6 14 ACS Paragon Plus Environment

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shows SEM images taken from as-grown samples without (Fig. 6a) and with (Fig. 6b) the pregrowth annealing step. Specifically, the nanowire density was estimated and compared in Figure 6c, showing ~0.3 /µm2 for the sample without annealing and ~4.5 / µm2 for that with annealing. Our results suggest that such pre-annealing step is applicable for InAs substrates for the promoted self-catalyzed InAs nanowire growth, and offers a convenient way to greatly improve the density of InAs nanowires.

Figure 6. Applying the pre-growth annealing step on InAs (100) substrate. InAs nanowire growth on InAs (100) substrate (a) (top view) without annealing and (b) (cross-sectional view) with 2 min 500 °C pre-growth annealing step. The green arrows in the top right inset of (b) indicate the B directions. The bottom left inset of (b) shows the top view. (c) is the nanowire densities estimated for (a) and (b). Scale bars are: (a) 400 nm; (b) 200 nm; inset of (b) 500 nm.

In conclusion, self-catalyzed InAs nanowire growth was demonstrated on varieties of IIIV substrates. Thermally created pits on the substrate surface were hypothesized to provide preferred sites for self-catalyzed InAs nanowire growth. However, even though nanowire growth

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was observed on all InAs and GaSb substrates, no growth was found on the GaAs (111)B substrate, which was due to few thermally created pits on the substrate. Selected-area growth with a pre-growth annealing step on the GaAs (111)B substrate confirms the correlations between the density of pits and the density of nanowires. The pits were also directly observed to support the nanowire growth in cross-sectional TEM images, with the depth of the pits confirmed by AFM analysis. Pre-growth annealing step was also successfully demonstrated on the InAs (100) substrate to promote nanowire growth density dramatically. The discovery of the preferred self-catalyzed nanowire growth sites provides the potentials for controlled selfcatalyzed III-V nanowire growth with preferred locations and density.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge via the Internet at http://pubs.acs.org. Figure S1-S5 Note S1-S2 Additional SEM, TEM, AFM images, Scanning TEM image with elemental mappings, crosssectional TEM sample preparation by FIB, and identification of the Moiré patterns.

AUTHOR INFORMATION Corresponding Author * Y. Z. (email: [email protected]) and C. Y. (email: [email protected]) Author Contributions 16 ACS Paragon Plus Environment

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The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by Army Research Office grant 57975-EL. Authors gratefully acknowledge Dr. Sammy Saber for helps in TEM sample preparation.

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16. Tomioka, K.; Motohisa, J.; Hara, S.; Fukui, T. Nano Letters 2008, 8, (10), 3475-3480. 17. Tomioka, K.; Mohan, P.; Noborisaka, J.; Hara, S.; Motohisa, J.; Fukui, T. Journal of Crystal Growth 2007, 298, (0), 644-647. 18. Hong, Y. J.; Fukui, T. ACS Nano 2011, 5, (9), 7576-7584. 19. Hong, Y. J.; Lee, W. H.; Wu, Y.; Ruoff, R. S.; Fukui, T. Nano Letters 2012, 12, (3), 1431-1436. 20. Mandl, B.; Stangl, J.; Mårtensson, T.; Mikkelsen, A.; Eriksson, J.; Karlsson, L. S.; Bauer, G.; uuml; nther; Samuelson, L.; Seifert, W. Nano Letters 2006, 6, (8), 1817-1821. 21. Mandl, B.; Stangl, J.; Hilner, E.; Zakharov, A. A.; Hillerich, K.; Dey, A. W.; Samuelson, L.; Bauer, G. n.; Deppert, K.; Mikkelsen, A. Nano Letters 2010, 10, (11), 4443-4449. 22. Tersoff, J. Nano Letters 2015, 15, (10), 6609-6613. 23. Jing, Y.; Bao, X.; Wei, W.; Li, C.; Sun, K.; Aplin, D. P. R.; Ding, Y.; Wang, Z.-L.; Bando, Y.; Wang, D. The Journal of Physical Chemistry C 2014, 118, (3), 1696-1705. 24. Biermanns, A.; Dimakis, E.; Davydok, A.; Sasaki, T.; Geelhaar, L.; Takahasi, M.; Pietsch, U. Nano Letters 2014, 14, (12), 6878-6883. 25. Wang, X.; Yang, X.; Du, W.; Ji, H.; Luo, S.; Yang, T. Journal of Crystal Growth 2014, 395, 55-60. 26. Wang, X.; Du, W.; Yang, X.; Zhang, X.; Yang, T. Journal of Crystal Growth 2015, 426, 287-292. 27. Dubrovskii, V. G.; Sibirev, N. V.; Berdnikov, Y.; Gomes, U. P.; Ercolani, D.; Zannier, V.; Sorba, L. Nanotechnology 2016, 27, (37), 375602. 28. Campos, C. E. M.; Pizani, P. S. Applied Surface Science 2002, 200, (1–4), 111-116. 29. Guillén-Cervantes, A.; Rivera-Alvarez, Z.; López-López, M.; López-Luna, E.; Hernández-Calderón, I. Thin Solid Films 2000, 373, (1–2), 159-163. 30. Jensen, L. E.; Björk, M. T.; Jeppesen, S.; Persson, A. I.; Ohlsson, B. J.; Samuelson, L. Nano Letters 2004, 4, (10), 1961-1964.

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