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Interface dynamics and crystal phase switching in GaAs nanowires

Nature volume 531, pages 317–322 (2016)Cite this article

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Abstract

Controlled formation of non-equilibrium crystal structures is one of the most important challenges in crystal growth. Catalytically grown nanowires are ideal systems for studying the fundamental physics of phase selection, and could lead to new electronic applications based on the engineering of crystal phases. Here we image gallium arsenide (GaAs) nanowires during growth as they switch between phases as a result of varying growth conditions. We find clear differences between the growth dynamics of the phases, including differences in interface morphology, step flow and catalyst geometry. We explain these differences, and the phase selection, using a model that relates the catalyst volume, the contact angle at the trijunction (the point at which solid, liquid and vapour meet) and the nucleation site of each new layer of GaAs. This model allows us to predict the conditions under which each phase should be observed, and use these predictions to design GaAs heterostructures. These results could apply to phase selection in other nanowire systems.

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Figure 1: Interface dynamics during WZ and ZB growth of GaAs.
Figure 2: Changes in droplet volume during phase switching.
Figure 3: Growth of a WZ nanowire containing multiple narrow ZB segments.
Figure 4: Model relating droplet size to interface morphology.

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References

  1. Krogstrup, P. et al. Structural phase control in self-catalyzed growth of GaAs nanowires on silicon (111). Nano Lett. 10, 4475–4482 (2010)

    Article  ADS  CAS  PubMed  Google Scholar 

  2. Ikejiri, K., Kitauchi, Y., Tomioka, K., Motohisa, J. & Fukui, T. Zinc blende and wurtzite crystal phase mixing and transition in indium phosphide nanowires. Nano Lett. 11, 4314–4318 (2011)

    Article  ADS  CAS  PubMed  Google Scholar 

  3. Husanu, E., Ercolani, D., Gemmi, M. & Sorba, L. Growth of defect-free GaP nanowires. Nanotechnology 25, 205601 (2014)

    Article  ADS  PubMed  CAS  Google Scholar 

  4. Caroff, P. et al. Controlled polytypic and twin-plane superlattices in III–V nanowires. Nature Nanotechnol. 4, 50–55 (2009)

    Article  ADS  CAS  Google Scholar 

  5. Koguchi, M., Kakibayashi, H., Yazawa, M., Hiruma, K. & Katsuyama, T. Crystal structure change of GaAs and InAs whiskers from zinc-blende to wurtzite type. Jpn J. Appl. Phys. 31, 2061–2065 (1992)

    Article  ADS  CAS  Google Scholar 

  6. Wallentin, J. et al. Changes in contact angle of seed particle correlated with increased zincblende formation in doped InP nanowires. Nano Lett. 10, 4807–4812 (2010)

    Article  ADS  CAS  PubMed  Google Scholar 

  7. Lehmann, S., Wallentin, J., Jacobsson, D., Deppert, K. & Dick, K. A. A general approach for sharp crystal phase switching in InAs, GaAs, InP, and GaP nanowires using only group V flow. Nano Lett. 13, 4099–4105 (2013)

    Article  ADS  CAS  PubMed  Google Scholar 

  8. Joyce, H. J., Wong-Leung, J., Gao, Q., Tan, H. H. & Jagadish, C. Phase perfection in zinc blende and wurtzite III–V nanowires using basic growth parameters. Nano Lett. 10, 908–915 (2010)

    Article  ADS  CAS  PubMed  Google Scholar 

  9. Lehmann, S., Jacobsson, D. & Dick, K. A. Crystal phase control in GaAs nanowires: opposing trends in the Ga- and As-limited growth regimes. Nanotechnology 26, 301001 (2015)

    Article  PubMed  CAS  Google Scholar 

  10. Algra, R. E. et al. The role of surface energies and chemical potential during nanowire growth. Nano Lett. 11, 1259–1264 (2011)

    Article  ADS  CAS  PubMed  Google Scholar 

  11. Dheeraj, D. L. et al. Controlling crystal phases in GaAs nanowires grown by Au-assisted molecular beam epitaxy. Nanotechnology 24, 015601 (2013)

    Article  ADS  CAS  PubMed  Google Scholar 

  12. Johansson, J. et al. Effects of growth conditions on the crystal structure of gold-seeded GaP nanowires. J. Cryst. Growth 310, 5102–5105 (2008)

    Article  ADS  CAS  Google Scholar 

  13. Yuan, X. et al. Tunable polarity in a III–V nanowire by droplet wetting and surface energy engineering. Adv. Mater. 27, 6096–6103 (2015)

    Article  CAS  PubMed  Google Scholar 

  14. Xu, T. et al. Faceting, composition and crystal phase evolution in III–V antimonide nanowire heterostructures revealed by combining microscopy techniques. Nanotechnology 23, 095702 (2012)

    Article  ADS  PubMed  CAS  Google Scholar 

  15. De, A. & Pryor, C. E. Predicted band structures of III–V semiconductors in the wurtzite phase. Phys. Rev. B 81, 155210 (2010)

    Article  ADS  CAS  Google Scholar 

  16. Akopian, N., Patriarche, G., Liu, L., Harmand, J. C. & Zwiller, V. Crystal phase quantum dots. Nano Lett. 10, 1198–1201 (2010)

    Article  ADS  CAS  PubMed  Google Scholar 

  17. Vainorius, N. et al. Confinement in thickness-controlled GaAs polytype nanodots. Nano Lett. 15, 2652–2656 (2015)

    Article  ADS  CAS  PubMed  Google Scholar 

  18. Assali, S. et al. Direct band gap wurtzite gallium phosphide nanowires. Nano Lett. 13, 1559–1563 (2013)

    Article  ADS  CAS  PubMed  PubMed Central  Google Scholar 

  19. Dick, K. A., Thelander, C., Samuelson, L. & Caroff, P. Crystal phase engineering in single InAs nanowires. Nano Lett. 10, 3494–3499 (2010)

    Article  ADS  CAS  PubMed  Google Scholar 

  20. Glas, F., Harmand, J. C. & Patriarche, G. Why does wurtzite form in nanowires of III–V zinc blende semiconductors? Phys. Rev. Lett. 99, 146101 (2007)

    Article  ADS  PubMed  CAS  Google Scholar 

  21. Dubrovskii, V. G., Sibirev, N. V., Harmand, J. C. & Glas, F. Growth kinetics and crystal structure of semiconductor nanowires. Phys. Rev. B 78, 235301 (2008)

    Article  ADS  CAS  Google Scholar 

  22. Dubrovskii, V. G. Influence of the group V element on the chemical potential and crystal structure of Au-catalyzed III–V nanowires. Appl. Phys. Lett. 104, 053110 (2014)

    Article  ADS  CAS  Google Scholar 

  23. Krogstrup, P. et al. Advances in the theory of III–V nanowire growth dynamics. J. Phys. D 46, 313001 (2013)

    Article  CAS  Google Scholar 

  24. Johansson, J. et al. Effects of supersaturation on the crystal structure of gold seeded III−V nanowires. Cryst. Growth Des. 9, 766–773 (2009)

    Article  CAS  Google Scholar 

  25. Krogstrup, P. et al. Impact of the liquid phase shape on the structure of III–V nanowires. Phys. Rev. Lett. 106, 125505 (2011)

    Article  ADS  PubMed  CAS  Google Scholar 

  26. Munshi, A. M. et al. Crystal phase engineering in self-catalyzed GaAs and GaAs/GaAsSb nanowires grown on Si(111). J. Cryst. Growth 372, 163–169 (2013)

    Article  ADS  CAS  Google Scholar 

  27. Cirlin, G. E. et al. Self-catalyzed, pure zincblende GaAs nanowires grown on Si(111) by molecular beam epitaxy. Phys. Rev. B 82, 035302 (2010)

    Article  ADS  CAS  Google Scholar 

  28. Spirkoska, D. et al. Structural and optical properties of high quality zinc-blende/wurtzite GaAs nanowire heterostructures. Phys Rev B 80, 245325 (2009)

    Article  ADS  CAS  Google Scholar 

  29. Ross, F. M. Controlling nanowire structures through real time growth studies. Rep. Prog. Phys. 73, 114501 (2010)

    Article  ADS  CAS  Google Scholar 

  30. Chou, Y.-C. et al. Atomic-scale variability and control of III–V nanowire growth kinetics. Science 343, 281–284 (2014)

    Article  ADS  CAS  PubMed  Google Scholar 

  31. Wen, C. Y. et al. Periodically changing morphology of the growth interface in Si, Ge, and GaP nanowires. Phys. Rev. Lett. 107, 025503 (2011)

    Article  ADS  PubMed  CAS  Google Scholar 

  32. Prince, A. A., Raynor, G. V. & Evans, D. S. Phase Diagrams of Ternary Gold Alloys 123–132 (Institute of Metals, 1990)

  33. Wen, C. Y., Reuter, M. C., Tersoff, J., Stach, E. A. & Ross, F. M. Structure, growth kinetics, and ledge flow during vapour–solid–solid growth of copper-catalyzed silicon nanowires. Nano Lett. 10, 514–519 (2010)

    Article  ADS  CAS  PubMed  Google Scholar 

  34. Oh, S. H. et al. Oscillatory mass transport in vapor-liquid-solid growth of sapphire nanowires. Science 330, 489–493 (2010)

    Article  ADS  CAS  PubMed  Google Scholar 

  35. Gamalski, A. D., Ducati, C. & Hofmann, S. Cyclic supersaturation and triple phase boundary dynamics in germanium nanowire growth. J. Phys. Chem. C 115, 4413–4417 (2011)

    Article  CAS  Google Scholar 

  36. Hilner, E. et al. Au wetting and nanoparticle stability on GaAs(111)B. Appl. Phys. Lett. 89, 251912 (2006)

    Article  ADS  CAS  Google Scholar 

  37. Schwarz, K. W. & Tersoff, J. Elementary processes in nanowire growth. Nano Lett. 11, 316–320 (2011)

    Article  ADS  CAS  PubMed  Google Scholar 

  38. Yu, X. et al. Evidence for structural phase transitions induced by the triple phase line shift in self-catalyzed GaAs nanowires. Nano Lett. 12, 5436–5442 (2012)

    Article  ADS  CAS  PubMed  Google Scholar 

  39. Krogstrup, P. et al. In-situ x-ray characterization of wurtzite formation in GaAs nanowires. Appl. Phys. Lett. 100, 093103 (2012)

    Article  ADS  CAS  Google Scholar 

  40. Takahasi, M., Kozu, M., Sasaki, T. & Hu, W. Mechanisms determining the structure of gold-catalyzed GaAs nanowires studied by in situ X-ray diffraction. Cryst. Growth Des. 15, 4979–4985 (2015)

    Article  CAS  Google Scholar 

  41. Johansson, J., Zanolli, Z. & Dick, K. A. Polytype attainability in III–V semiconductor nanowires. Cryst. Growth Des. 16, 371–379 (2016)

    Article  CAS  Google Scholar 

  42. Schmidt, V., Senz, S. & Gösele, U. The shape of epitaxially grown silicon nanowires and the influence of line tension. Appl. Phys. A 80, 445–450 (2005)

    Article  ADS  CAS  Google Scholar 

  43. Jiang, N. et al. Understanding the true shape of Au-catalyzed GaAs nanowires. Nano Lett. 14, 5865–5872 (2014)

    Article  ADS  CAS  PubMed  Google Scholar 

  44. Hillerich, K. et al. Strategies to control morphology in hybrid group III–V/group IV heterostructure nanowires. Nano Lett. 13, 903–908 (2013)

    Article  ADS  CAS  PubMed  Google Scholar 

  45. Larsen, C. A., Buchan, N. I. & Stringfellow, G. B. Reaction mechanisms in the organometallic vapor phase epitaxial growth of GaAs. Appl. Phys. Lett. 52, 480–482 (1988)

    Article  ADS  CAS  Google Scholar 

  46. Tamaru, K. The decomposition of arsine. J. Phys. Chem. 59, 777–780 (1955)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

D.J., S.L. and K.A.D. acknowledge financial support from the Knut and Alice Wallenberg Foundation (KAW), the Swedish Research Council (VR) and the Nanometer Structure Consortium at Lund University (nmC@LU). F.P. and S.H. acknowledge support from ERC Grant 279342: InSituNANO. We acknowledge A. Ellis for technical support.

Author information

Authors and Affiliations

  1. Solid State Physics and NanoLund, Lund University, Box 118, Lund, 221 00, Sweden

    Daniel Jacobsson, Sebastian Lehmann & Kimberly A. Dick

  2. Centre for Analysis and Synthesis, Lund University, Box 124, Lund, 221 00, Sweden

    Daniel Jacobsson & Kimberly A. Dick

  3. Department of Engineering, University of Cambridge, 9 JJ Thomson Avenue, Cambridge, CB3 0FA, UK

    Federico Panciera & Stephan Hofmann

  4. IBM T. J. Watson Research Center, 1101 Kitchawan Road, Yorktown Heights, New York, 10598, USA

    Federico Panciera, Jerry Tersoff, Mark C. Reuter & Frances M. Ross

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  1. Daniel Jacobsson
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Contributions

D.J. and F.P. performed experiments and data analysis, J.T. developed the model, M.C.R. developed the UHVTEM technique, S.L. provided growth expertise, and K.A.D., S.H. and F.M.R. designed the experiments and coordinated the analysis.

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Correspondence to Daniel Jacobsson or Frances M. Ross.

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Extended data figures and tables

Extended Data Figure 1 Distinguishing crystal phases using dark-field imaging.

a, Dark-field images recorded using three spots in the diffraction pattern showing how WZ and the two variants of ZB (ZB1 and ZB2) are distinguished in the 〈110〉 direction. The right panel shows a bright-field (BF) image for comparison. b, Diffraction pattern with the three spots indicated. These are post-growth images recorded in a JEOL 3000 TEM. c, Image recorded during growth, also in the 〈110〉 direction, showing the dark-field contrast and the measured angle of the truncated corner. d, A schematic showing the hexagonal cross-section as seen from the side (beam direction) and from above. Seen from the side, the droplet contact angle ϕ and corner-facet angle θ are shown. Seen from above, the electron beam direction is shown.

Extended Data Figure 2 Kinetics of WZ growth.

a, Step-flow kinetics measured for the WZ nanowire shown in Supplementary Video 1 and Fig. 1a. b, Length of a WZ nanowire versus the number of step-flow events. The average gradient of the graph confirms that each step is 0.33 nm in height, that is, a WZ(0001) bilayer. The red line shows the calculated length, assuming that each new bilayer (red squares) adds 0.33 nm in length. The black data are measured lengths, with error bars defined by the standard deviation of each subset (length measured in 3–4 different movie frames for each data point). c, Growth rate versus AsH3 pressure, estimated by measuring the increase in the length of the nanowire shown in Fig. 2 during growth intervals at different AsH3 pressures, and by fitting a linear function to the length versus time plot. Error bars are defined by the standard error of the fits. The growth temperature was 550 °C and TMGa pressure was constant at 3.5 × 10−8 Torr.

Extended Data Figure 3 Droplet angle at the transition does not change with Au composition in the droplet.

a–c, During growth, the crystal structure of a nanowire was switched back and forth several times by changing the AsH3 pressure. Data shows the measured angles and absolute droplet volumes at which the switch from WZ to ZB (red) and ZB to WZ (blue) occurred (a, b). During this time the wire also grew radially (c). a, Switch angles versus nanowire diameter. Shading indicates the range of observed angles at which WZ switches to ZB (red) and ZB to WZ (blue). Some hysteresis in switching is visible, perhaps because the droplet angle continues to change in the time before the switched layer grows. The data are scattered, but there is no strong dependence of angle on diameter (especially for the blue data points). For example, ZB switches to WZ at angles between 123° and 132° at both large and small diameter, and WZ switches to ZB at angles between 127° and 136°. b, Switch angle versus inferred composition, as calculated from the measured h/d ratio assuming that the amount of Au does not change. The data are scattered, but there is no strong dependence of angle on composition. For example, for the first few data points, for which the nanowire had a diameter of 30 mn, ZB switched to WZ for a Ga fraction of less than 60%. For subsequent data points, for which the nanowire had a diameter of 40 nm, the switch did not occur until the composition had a Ga fraction of about 75%. The fact that droplet angles are similar despite the change in diameter suggests that droplet geometry controls the switch, whereas droplet volume and composition do not appear to be important.

Supplementary information

WZ growth at higher V/III ratio (stills in Fig. 1a)

Dark-field conditions, speeded up 60×, field of view 100 nm, nanowire diameter 55 nm; scale bar 10 nm. T = 550 °C, AsH3 = 1 × 10−5 Torr, TMGa = 3.5 × 10−8 Torr. Sharp corners are visible with slow step flow. Steps originate from both sides of the nanowire. The adjacent graph shows the step position as a function of time. (AVI 13985 kb)

ZB growth at large h/d ratio, then a transition to WZ as the droplet shrinks (stills in Fig. 1b, d)

The video starts with a large droplet, which decreases in size as the AsH3 pressure is increased. For the first ¾ of the movie h/d is large enough that ZB grows, showing truncated corners that slowly fill in, then jump back again as the step flows. Four layers of ZB can be seen growing in this way. The droplet shrinks continuously and after the fourth layer, growth continues in the WZ structure with no further corner truncation. The graph shows h/d and ϕ, as well as the AsH3 pressure and the time of each facet truncation, marked with an arrow. Dark-field conditions, speeded up 30×, field of view 100 nm, nanowire diameter 30 nm; scale bar 10 nm; T=550 °C, AsH3 = 1.4 × 10−5 Torr, TMGa = *2.0 × 10−8 Torr. (AVI 9481 kb)

Droplet size change on changing the V/III ratio

Bright-field conditions, speeded up 60×, field of view 120 nm, nanowire diameter 35 nm. The initial AsH3 = 1.1 × 10-5 Torr drops to 1 × 10-9 Torr; TMGa = 2 × 10-8 Torr, T = 550 °C. Scale bar 10 nm. Inset is a graph showing pressure and droplet volume from each frame. (AVI 18648 kb)

WZ to ZB transition (still in Fig. 1c, data in Fig. 2)

The video starts with WZ growth at low h/d ratio. Layer growth appears as slightly brighter contrast at the growth interface (although it is indistinct due to the imaging conditions). Then AsH3 is reduced for a short time to trigger ZB growth. The first ZB layer that forms appears as a bright line 7 s after the start of the video. As it appears, a truncated facet forms which cuts down into the WZ below. Three ZB layers grow in this way, at 7, 10 and 11 s. The growth rate increases because AsH3 has already been increased again during this time. Eventually growth transitions back to WZ. The segment of WZ is not clearly visible in the images until 19 s into the video, when the imaging conditions are changed and it shows as a brighter band above the ZB, which now appears as a darker band. Speeded up 30×, field of view 90 nm, nanowire diameter 30 nm. Initially, AsH3 = 1.4 × 10−5 Torr, then lowered to 1 × 10−7 Torr then returned to 1.4 × 10−5; TMGa = 2 × 10−8 Torr, T = 550 °C. Scale bar 10 nm. (AVI 5347 kb)

ZB growth showing two examples of simultaneous oscillations on opposite sides of a nanowire.

Dark-field conditions. The first nanowire is shown speeded up 6×, field of view 100 nm, nanowire diameter ~50 nm. AsH3 = (1.3–1.4) × 10−5 Torr; TMGa = 2 × 10−8 Torr, T = 500 °C. Five layers grow. The corner truncation is more visible on the left hand side, but its size changes simultaneously on both sides. The second wire is shown speeded up 6×, field of view 100 nm, nanowire diameter ~50 nm. AsH3 = 1.5 × 10−5 Torr; TMGa = 2 × 10−7 Torr, T = 550 °C. Two layers grow. The contrast is weaker, but a symmetrical oscillation is visible on both sides. Scale bars 10 nm. (AVI 15575 kb)

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Jacobsson, D., Panciera, F., Tersoff, J. et al. Interface dynamics and crystal phase switching in GaAs nanowires. Nature 531, 317–322 (2016). https://doi.org/10.1038/nature17148

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