Raman study on zinc-blende single InAs nanowire grown on Si (111) substrate
© Li et al.; licensee Springer. 2013
Received: 26 October 2012
Accepted: 2 January 2013
Published: 14 January 2013
We report polarized Raman scattering studies on single InAs nanowires (NWs). The NWs were grown by metalorganic chemical vapor deposition on Si (111) substrates without external catalyst and showed a zinc-blende crystal structure. The single NWs were studied for different polarization excitation of the incident laser beam relative to the NW axis. The transverse optical (TO) mode exhibits maximum intensity when both the incident and analyzed light polarizations are parallel to the NW axis. The TO mode of InAs NWs is found to act like a nearly perfect dipole antenna, which can be attributed to the one-dimensional NW geometry and Raman selection rules.
KeywordsNanowires (NWs) Raman spectroscopy Phonon property Polarize 62.23.Hj 81.07.Gf 63.22.Gh 61.46.Km
Semiconductor nanowires (NWs) have been intensively studied in the last decade due to their novel physical properties and potential applications in high-performance devices, such as field-effect transistors, lasers, photodetectors, and photovoltaic devices [1–5]. Among them, InAs NWs possess excellent electron transport properties such as high bulk mobility, small effective mass, and low ohmic contact resistivity, which can be used for making high-performance electronic devices such as high-mobility transistors [6–8]. For their device applications, it is important to understand the physical properties of these InAs NWs, including phonon scattering information. Although NWs with low defect density have been reported, many NW material systems suffer from various types of planar defects, predominantly rotational twins and twinning superlattices, alternating zinc-blende (ZB)/wurtzite polytypes, as well as point defects [9–12]. Raman scattering, a nondestructive contactless characterization technique, provides an effective approach to probe phonon properties. Combined with advanced confocal microscopy, Raman scattering can be well used to investigate the phonon properties of single NWs with a spatial resolution of roughly half the excitation wavelength. Phonon energies, scattering cross sections, and symmetry properties of optical phonons are determined by analyzing inelastically scattered light, providing information about crystal structure and composition, electronic properties, and electron–phonon and phonon-phonon interactions . In the meantime, Raman scattering in NWs is expected to be different from that in their bulk materials due to their one-dimensional geometry , where the polarized excitation will show a significant effect on phonon modes. Indeed, some previous studies on NWs do show an obvious polarization effect [15–20]. Though some works [21, 22] have reported on the Raman spectra of InAs NW assemblies, little attention has been devoted to the Raman scattering in single InAs NWs [23, 24], especially the effect of excitation polarization on phonon vibration. In this work, we present a Raman study on single zinc-blende InAs NWs. The effect of excitation polarization on the phonon properties of single InAs NWs is also investigated in detail.
Theoretical considerations of zinc-blende InAs
where R is the Raman tensor and and are the polarization of the incident radiation and the scattered radiation, respectively. The zone-center optical phonon in the zinc-blende structure is split into a doubly degenerate transverse optical (TO) mode and a longitudinal optical (LO) mode, and the Raman tensor elements are different for the TO and LO modes. As calculated, the TO mode can be observed in backscattering from the (110) and (111) surfaces, while the LO mode is allowed from the (100) and (111) surfaces .
In order to calculate the polar patterns of Is for NWs, one has to take into account the additional degree of freedom associated with the rotation of θ around the NW axis since it can influence the polar patterns of the optical modes. Based on , this angular dependence is a clear signature of the presence of zinc-blende TO modes and can be used for their assignation.
Results and discussion
Raman measurements were performed in a backscattering configuration on single InAs NWs and from the (110) surface of a bulk InAs single crystal as reference. The general measurement geometry for a single NW is shown in Figure 1. The laboratory coordinate system x, y, z is chosen according to the NW geometry and the basis of the NW crystal coordinate system: (). Based on the calculated selection rules in , the TO phonon mode can be observed in the backscattering from the (110) and (111) InAs surfaces, while the LO phonon mode can be observed from the (100) and (111) InAs surfaces. The Raman spectra of the single InAs NW and bulk InAs obtained are shown in Figure 4b, which are measured under the configuration . The coordinates y and z are chosen perpendicular and parallel to the NW growth axis, respectively. Incident and scattered light polarizations were selected parallel to the NW growth axis. The Raman spectra of both nanowire and bulk InAs have been normalized with respect to the intensity of the TO phonon mode of bulk InAs for easy comparison. For bulk InAs (110), the TO mode is found at 217.2 cm−1. The Raman scattering spectrum of InAs NWs is composed mainly by the TO mode at 215.8 cm−1, slightly lower than that for the reference bulk InAs (110) sample. In addition, the LO mode of the single NW is also visible at around 236 cm−1, the appearance of which might be caused by the disorder and an imperfect scattering geometry . In addition, the TO mode of InAs NWs exhibits a downshift of about 2 to 3 cm−1 compared to the TO mode of bulk ZB InAs. Along with the downshift, a remarkable increase of the full width at half maximum to 14 cm−1 is observed. It should be mentioned that the downshift of the TO mode was also observed in the Raman measurements on the as-grown NW ensemble samples. Generally, there are two factors which might induce the downward shift of phonon mode frequency and the broadening of the Raman peak. One is laser heating effect. As reported before [27–30], local heating might also cause the downshift of phonon mode frequency and the broadening of phonon peak. To reduce the laser heating effect, we use the lowest laser power and the monodisperse wires were placed on high thermal conductivity HOPG to avoid substrate effects. An excitation power-dependent Raman measurement was performed on the single NWs, and no shifting of the phonon peak was observed when the excitation power is 0.05 mW (data not shown here), which may be due to high-thermal conductivity substrate (HOPG) and low nanowire coverage over the substrate . Thus, this heating effect can be lowered in our measurements; the other is quantum confinement effect. It is well demonstrated before in theory and experiments that for small-sized crystals like quantum wires, nanowires, etc., the quantum confinement effect will be very obvious and result in the downward frequency shift and linewidth broadening of the TO and LO phonon modes. Such change of phonon mode frequency and linewidth is mainly due to the relaxation of the q = 0 selection rule in the Raman scattering [14, 15, 22, 29–33].
For better understanding of phonon properties in single NWs, excitation polarization-dependent Raman measurements were also performed on the single NWs. Figure 4c shows the Raman spectra of single NWs measured under four main polarization configurations (, , , and ). It is observed that the intensity of the TO mode measured with parallel configuration, i.e., and , when the incident and scattered light polarizations are parallel to each other, is much stronger than that with perpendicular configuration, and the intensity measured under the configuration is much stronger than that under the configuration. This indicates that the highest scattering intensity occurs when both the incident and analyzed light linear polarization are parallel to the NW growth axis. These results observed here are in accordance with those of ZB GaAs NWs reported in , which is mainly caused by the selection rules of the crystal. The excitation polarization-dependent Raman scattering measurements were performed by rotating the half-wave plate in 10° ± 2° increments and thus changing the angle, ϕ, between the electric vector of the incident light and the long axis of the NW. Figure 4d shows the polar scan of the intensity of the TO phonon mode of single InAs NWs as a function of the angle measured under two scattering configurations and , where . As shown in Figure 4d, for the configuration, the maximum intensity occurs at 5° and 175°, while the minimum intensity occurs at 85° and 265°. Some experimental points slightly deviate from the trend, which might be caused by the experimental artifact. For the configuration, there is a weakly preferential value of ϕ giving a maximum scattering intensity (maximum intensity is around 75° and minimum intensity is around 340°). It is noted that the maximum intensity measured under the polarization is around seven times that measured under the polarization, which indicates that the Raman scattering under the configuration is much more efficient than that under the configuration. This particular distribution of the maximum/minimum Raman peak intensity in the polar scan, as shown in Figure 4d, agrees well with that obtained with theoretical calculation for ZB InAs nanowires . This further confirms that the InAs NWs studied here is mainly composed of ZB phase, which accords with the HRTEM results discussed before [16, 23]. The TO mode of InAs NWs is found to act like a nearly perfect dipole antenna. The same behavior has been found in the other one-dimensional systems, such as SWNTs , 20-nm WS2 nanotubes , GaP NWs , and GaAs NWs . The origin of this effect has been attributed to the scattering of the electromagnetic field from a dielectric cylinder of nanoscale dimensions . Furthermore, it is observed that the light is preferentially absorbed when the incident light is polarized along the nanowire axis . These theories about Raman selection rules and the one-dimensional geometry of the NW may be used to explain our experimental data.
Raman scattering experiments have been performed on single InAs NWs. In the single NW spectra, a striking TO mode is observed at 215.8 cm−1, slightly lower than that of the reference bulk InAs (110) sample. This downward shift of the phonon frequency is mainly caused by defects or disorders that existed in the NW. The excitation polarization-dependent Raman measurements indicate that the TO phonon mode in the NW presents the highest scattering efficiency when both the incident and analyzed polarization are parallel to the NW growth axis. The TO mode of InAs NWs is found to act like a nearly perfect dipole antenna. This is a combined consequence of both the selection rules and the one-dimensional geometry of the NW.
High-resolution transmission electron microscopy
Metalorganic chemical vapor deposition
Scanning electron microscopy
The authors would like to acknowledge Shuai Luo and Xiaoye Wang for their help with the MOCVD work. The work was supported by the 973 Program (no. 2012CB932701) and the National Natural Science Foundation of China (nos. 60990313, 60990315, and 21173068).
- Yan RX, Gargas D, Yang PD: Nanowire photonics. Nature Photonics 2009, 3: 569. 10.1038/nphoton.2009.184View Article
- Lu W, Lieber CM: Semiconductor nanowires. J Phys D 2006, 39: R387. 10.1088/0022-3727/39/21/R01View Article
- Patolsky F, Lieber CM: Nanowire nanosensors. Mater Today 2005, 8: 20.View Article
- Li Y, Qian F, Xiang J, Lieber CM: Battery betters performance energy generation. Mater Today 2006, 9: 18.View Article
- Wei W, Bao XY, Soci C, Ding Y, Wang ZL, Wang DL: Direct heteroepitaxy of vertical InAs nanowires on Si substrates for broad band photovoltaics and photodetection. Nano Lett 2009, 9: 2926. 10.1021/nl901270nView Article
- Adachi S: Properties of Group-IV, III-V and II-VI Semiconductors. New York: Wiley; 2005.View Article
- Dayeh SA, Aplin D, Zhou XT, Yu PKL, Yu ET, Wang DL: High electron mobility InAs nanowire field-effect transistors. Small 2007, 3: 326. 10.1002/smll.200600379View Article
- Jiang XC, Xiong QH, Nam SW, Qian F, Li Y, Lieber CM: InAs/InP radial nanowire heterostructures as high electron mobility devices. Nano Lett 2007, 7: 3214. 10.1021/nl072024aView Article
- Dick KA, Caroff P, Bolinsson J, Messing ME, Johansson J, Deppert K, Wallenberg LR, Samuelson L: Control of III-V nanowire crystal structure by growth parameter tuning. Semicond Sci Technol 2010, 25: 024009. 10.1088/0268-1242/25/2/024009View Article
- Hsu YF, Xi YY, Tam KH, Djurisic AB, Luo JM, Ling CC, Cheung CK, Ng AMC, Chan WK, Deng X, Beling CD, Fung S, Cheah KW, Fong PWK, Surya CC: Undoped p-type ZnO nanorods synthesized by a hydrothermal method. Adv Funct Mater 2008, 18: 1020. 10.1002/adfm.200701083View Article
- Xiong QH, Wang J, Eklund PC: Coherent twinning phenomena towards twinning superlattices in III-V semiconducting nanowires. Nano Lett 2006, 6: 2736. 10.1021/nl0616983View Article
- Algra RE, Verheijen MA, Borgstrom MT, Feiner LF, Immink G, Enckevort WJP, Vlieg E, Bakkers EPAM: Twinning superlattices in indium phosphide nanowires. Nature 2008, 456: 369. 10.1038/nature07570View Article
- Cardona M, Guntherodt G: Light Scattering in Solids II: Basic Concepts and Instrumentation. Berlin: Springer; 1982.View Article
- Adu KW, Gutierrez HR, Kim UJ, Sumanasekera GU, Eklund PC: Confined phonons in Si nanowires. Nano Lett 2005, 5: 409. 10.1021/nl0486259View Article
- Adu KW, Xiong Q, Gutierrez HR, Chen G, Eklund PC: Raman scattering as a probe of phonon confinement and surface optical modes in semiconducting nanowires. Appl Phys A: Mater Sci Process 2006, 85: 287. 10.1007/s00339-006-3716-8View Article
- Zardo I, Conesa-Boj S, Peiro F, Morante JR, Arbiol J, Uccelli E, Abstreiter G, Morral AF: Raman spectroscopy of wurtzite and zinc-blende GaAs nanowires: polarization dependence, selection rules, and strain effects. Phys Rev B 2009, 80: 245324.View Article
- Frechette J, Carraro C: Diameter-dependent modulation and polarization anisotropy in Raman scattering from individual nanowires. Phys Rev B 2006, 74: 161404.View Article
- Chen G, Wu J, Lu QJ, Gutierrez HR, Xiong QH, Pellen ME, Petko JS, Werner DH, Eklund PC: Optical antenna effect in semiconducting nanowires. Nano Lett 2008, 8: 1341. 10.1021/nl080007vView Article
- Xiong Q, Chen G, Gutierrez HR, Eklund PC: Raman scattering studies of individual polar semiconducting nanowires: phonon splitting and antenna effects. Appl Phys Mater Sci Process 2006, 85: 299. 10.1007/s00339-006-3717-7View Article
- Livneh T, Zhang J, Cheng G, Moskovits M: Polarized Raman scattering from single GaN nanowires. Phys Rev B 2006, 74: 03520.View Article
- Li TF, Chen YH, Lei W, Zhou XL, Luo S, Hu YZ, Wang LJ, Yang T, Wang ZG: Effect of growth temperature on the morphology and phonon properties of InAs nanowires on Si substrates. Nanoscale Res Lett 2011, 6: 463. 10.1186/1556-276X-6-463View Article
- Begum N, Bhatti AS, Jabeen F, Rubini S, Martelli F: Line shape analysis of Raman scattering from LO and SO phonons in III-V nanowires. J Appl Phys 2009, 106: 114317. 10.1063/1.3267488View Article
- Moller M, Lima MM, Cantarero A, Dacal LCO: Polarized and resonant Raman spectroscopy on single InAs nanowire. Phys Rev B 2011, 84: 085318.View Article
- Hormann NG, Zardo I, Hertenberger S, Funk S, Bolte S, Doblinger M, Koblmuller G, Abstreiter G: Effects of stacking variations on the lattice dynamics of InAs nanowires. Phys Rev B 2011, 84: 155301.View Article
- Yu PY, Cardona M: Fundamentals of Semiconductors. Berlin: Springer; 2005.
- Wu J, Zhang D, Lu Q, Gutierrez HR, Eklund PC: Polarized Raman scattering from single GaP nanowires. Phys Rev B 2010, 81: 165415.View Article
- Yazji S, Zardo I, Soini M, Postorino P, Morral AFI, Abstreiter G: Local modification of GaAs nanowires induced by laser heating. Nanotechnology 2011, 22: 325701. 10.1088/0957-4484/22/32/325701View Article
- Soini M, Zardo I, Uccelli E, Funk S, Koblmuller G, Morral AFI, Abstreiter G: Thermal conductivity of GaAs nanowires studied by micro-Raman spectroscopy combined with laser heating. Appl Phys Lett 2010, 97: 263107. 10.1063/1.3532848View Article
- Gupta R, Xiong Q, Adu CK, Kim UJ, Eklund PC: Laser-induced Fano resonance scattering in silicon nanowires. Nano Lett 2003, 3: 627. 10.1021/nl0341133View Article
- Piscanec S, Cantoro M, Ferrari AC, Zapien JA, Lifshitz Y, Lee ST, Hofmann S, Robertson J: Raman spectroscopy of silicon nanowires. Phys Rev B 2003, 68: 241312.View Article
- Adu KW, Gutierrez HR, Kim UJ, Eklund PC: Inhomogeneous laser heating and phonon confinement in silicon nanowires: a micro-Raman scattering study. Phys Rev B 2006, 73: 155333.View Article
- Lei W, Chen YH, Xu B, Ye XL, Zeng YP, Wang ZG: Raman study on self-assembled InAs/InAlAs/InP(001) quantum wires. Nanotechnology 1974, 2005: 16.
- Campbell IH, Fauchet PM: The effect of microcrystal size and shape on the one phonon Raman spectra of crystalline semiconductors. Solid State Commum 1986, 58: 739. 10.1016/0038-1098(86)90513-2View Article
- Duesberg GS, Loa I, Burghhard M, Syassen K, Roth S: Polarized Raman spectroscopy on isolated single-wall carbon nanotubes. Phys Rev Lett 2000, 85: 5436. 10.1103/PhysRevLett.85.5436View Article
- Rafailov PM, Thomsen C, Gartsman K, Kaplan-Ashiri I, Tenne R: Orientation dependence of the polarizability of an individual WS2 nanotube by resonant Raman spectroscopy. Phys Rev B 2005, 72: 205436.View Article
- Wang JF, Gudiksen MS, Duan XF, Cui Y, Lieber CM: Highly polarized photoluminescence and photodetection from single indium phosphide nanowires. Science 2001, 293: 1455–1457. 10.1126/science.1062340View Article
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.