Co-reporter:Ruth A. Schlitz, KunHo Yoon, Lisa A. Fredin, Young-geun Ha, Mark A. Ratner, Tobin J. Marks, and Lincoln J. Lauhon
The Journal of Physical Chemistry Letters November 18, 2010 Volume 1(Issue 22) pp:
Publication Date(Web):November 4, 2010
DOI:10.1021/jz101325r
The effect of thermal annealing on leakage current and dielectric breakdown in self-assembled nanodielectric (SAND) metal−insulator−semiconductor (MIS) devices is investigated. Annealing at temperatures of ≥300 °C for 120 s in a reducing atmosphere significantly reduces the leakage current density at typical operating voltages (Vg = 3 V) while greatly narrowing the distribution of breakdown voltages. The threshold breakdown voltage is characterized by a Weibull distribution of slope β ≈ 4.5 prior to thermal annealing, and by β ≥ 12 post annealing. A comparison of the breakdown characteristics of conventional inorganic dielectrics with those of SAND demonstrates that self-assembly is a viable approach to fabricating highly reliable dielectric materials for unconventional electronics.Keywords (keywords): dielectric breakdown; metal−insulator−semiconductor device; self-assembled monolayer; self-assembled nanodielectric; thermal processing; Weibull analysis;
Co-reporter:Zhiyuan Sun, David N. Seidman, and Lincoln J. Lauhon
Nano Letters July 12, 2017 Volume 17(Issue 7) pp:4518-4518
Publication Date(Web):June 28, 2017
DOI:10.1021/acs.nanolett.7b02071
Dopants modify the electronic properties of semiconductors, including their susceptibility to etching. In semiconductor nanowires doped during growth by the vapor–liquid–solid (VLS) process, it has been shown that nanofaceting of the liquid–solid growth interface influences strongly the radial distribution of dopants. Hence, the combination of facet-dependent doping and dopant selective etching provides a means to tune simultaneously the electronic properties and morphologies of nanowires. Using atom-probe tomography, we investigated the boron dopant distribution in Au catalyzed VLS grown silicon nanowires, which regularly kink between equivalent ⟨112⟩ directions. Segments alternate between radially uniform and nonuniform doping profiles, which we attribute to switching between a concave and convex faceted liquid–solid interface. Dopant selective etching was used to reveal and correlate the shape of the growth interface with the observed anisotropic doping.Keywords: atom-probe tomography; dopant; liquid−solid interface; Nanowire; selective etching; vapor−liquid−solid growth;
Co-reporter:Dr. Titel Jurca;Michael J. Moody;Dr. Alex Henning;Dr. Jonathan D. Emery;Dr. Binghao Wang;Dr. Jeffrey M. Tan;Dr. Tracy L. Lohr; Lincoln J. Lauhon; Tobin J. Marks
Angewandte Chemie 2017 Volume 129(Issue 18) pp:5073-5077
Publication Date(Web):2017/04/24
DOI:10.1002/ange.201611838
AbstractWet chemical screening reveals the very high reactivity of Mo(NMe2)4 with H2S for the low-temperature synthesis of MoS2. This observation motivated an investigation of Mo(NMe2)4 as a volatile precursor for the atomic layer deposition (ALD) of MoS2 thin films. Herein we report that Mo(NMe2)4 enables MoS2 film growth at record low temperatures—as low as 60 °C. The as-deposited films are amorphous but can be readily crystallized by annealing. Importantly, the low ALD growth temperature is compatible with photolithographic and lift-off patterning for the straightforward fabrication of diverse device structures.
Co-reporter:Deep Jariwala, Sarah L. Howell, Kan-Sheng Chen, Junmo Kang, Vinod K. Sangwan, Stephen A. Filippone, Riccardo Turrisi, Tobin J. Marks, Lincoln J. Lauhon, and Mark C. Hersam
Nano Letters 2016 Volume 16(Issue 1) pp:497-503
Publication Date(Web):December 10, 2015
DOI:10.1021/acs.nanolett.5b04141
The recent emergence of a wide variety of two-dimensional (2D) materials has created new opportunities for device concepts and applications. In particular, the availability of semiconducting transition metal dichalcogenides, in addition to semimetallic graphene and insulating boron nitride, has enabled the fabrication of “all 2D” van der Waals heterostructure devices. Furthermore, the concept of van der Waals heterostructures has the potential to be significantly broadened beyond layered solids. For example, molecular and polymeric organic solids, whose surface atoms possess saturated bonds, are also known to interact via van der Waals forces and thus offer an alternative for scalable integration with 2D materials. Here, we demonstrate the integration of an organic small molecule p-type semiconductor, pentacene, with a 2D n-type semiconductor, MoS2. The resulting p–n heterojunction is gate-tunable and shows asymmetric control over the antiambipolar transfer characteristic. In addition, the pentacene/MoS2 heterojunction exhibits a photovoltaic effect attributable to type II band alignment, which suggests that MoS2 can function as an acceptor in hybrid solar cells.
Co-reporter:KunHo Yoon, Jae-Hyeok Lee, Joohoon Kang, Junmo Kang, Michael J. Moody, Mark C. Hersam, and Lincoln J. Lauhon
Nano Letters 2016 Volume 16(Issue 12) pp:7370-7375
Publication Date(Web):November 10, 2016
DOI:10.1021/acs.nanolett.6b02691
The decreasing cost of silicon-based photovoltaics has enabled significant increases in solar electricity generation worldwide. Silicon photoanodes could also play an important role in the cost-effective generation of solar fuels, but the most successful methods of photoelectrode passivation and performance enhancement rely on a combination of precious metals and sophisticated processing methods that offset the economic arguments for silicon. Here we show that metal-free carbon-based nanomaterial coatings deposited from solution can protect silicon photoanodes carrying out the oxygen evolution reaction in a range of working environments. Purified semiconducting carbon nanotubes (CNTs) act as a hole extraction layer, and a graphene (Gr) capping layer both protects the CNT film and acts as a hole exchange layer with the electrolyte. The performance of semiconducting CNTs is found to be superior to that of metallic or unsorted CNTs in this context. Furthermore, the insertion of graphene oxide (GO) between the n-Si and CNTs reduces the overpotential relative to photoanodes with CNTs deposited on hydrogen-passivated silicon. The composite photoanode structure of n-Si/GO/CNT/Gr shows promising performance for oxygen evolution and excellent potential for improvement by optimizing the catalytic properties and stability of the graphene protective layer.Keywords: Carbon nanotube; graphene; graphene oxide; photoanode; solar fuel; water-splitting;
Co-reporter:Xiaochen Ren, Arunima K. Singh, Lei Fang, Mercouri G. Kanatzidis, Francesca Tavazza, Albert V. Davydov, and Lincoln J. Lauhon
Nano Letters 2016 Volume 16(Issue 10) pp:6064-6069
Publication Date(Web):September 7, 2016
DOI:10.1021/acs.nanolett.6b02104
Impurity doping in two-dimensional (2D) materials can provide a route to tuning electronic properties, so it is important to be able to determine the distribution of dopant atoms within and between layers. Here we report the tomographic mapping of dopants in layered 2D materials with atomic sensitivity and subnanometer spatial resolution using atom probe tomography (APT). APT analysis shows that Ag dopes both Bi2Se3 and PbSe layers in (PbSe)5(Bi2Se3)3, and correlations in the position of Ag atoms suggest a pairing across neighboring Bi2Se3 and PbSe layers. Density functional theory (DFT) calculations confirm the favorability of substitutional doping for both Pb and Bi and provide insights into the observed spatial correlations in dopant locations.Keywords: 2D materials; Atom probe tomography; DFT; doping; materials genome initiative;
Co-reporter:Sarah L. Howell, Deep Jariwala, Chung-Chiang Wu, Kan-Sheng Chen, Vinod K. Sangwan, Junmo Kang, Tobin J. Marks, Mark C. Hersam, and Lincoln J. Lauhon
Nano Letters 2015 Volume 15(Issue 4) pp:2278-2284
Publication Date(Web):March 25, 2015
DOI:10.1021/nl504311p
The thickness-dependent band structure of MoS2 implies that discontinuities in energy bands exist at the interface of monolayer (1L) and multilayer (ML) thin films. The characteristics of such heterojunctions are analyzed here using current versus voltage measurements, scanning photocurrent microscopy, and finite element simulations of charge carrier transport. Rectifying I–V curves are consistently observed between contacts on opposite sides of 1L/ML junctions, and a strong bias-dependent photocurrent is observed at the junction. Finite element device simulations with varying carrier concentrations and electron affinities show that a type II band alignment at single layer/multilayer junctions reproduces both the rectifying electrical characteristics and the photocurrent response under bias. However, the zero-bias junction photocurrent and its energy dependence are not explained by conventional photovoltaic and photothermoelectric mechanisms, indicating the contributions of hot carriers.
Co-reporter:Chang-Hua Liu, In Soo Kim, and Lincoln J. Lauhon
Nano Letters 2015 Volume 15(Issue 10) pp:6727-6731
Publication Date(Web):September 10, 2015
DOI:10.1021/acs.nanolett.5b02586
Two-dimensional (2-D) materials including graphene and transition metal dichalcogenides (TMDs) are an exciting platform for ultrasensitive force and displacement detection in which the strong light–matter coupling is exploited in the optical control of nanomechanical motion. Here we report the optical excitation and displacement detection of a ∼ 3 nm thick MoS2 resonator in the strong-coupling regime, which has not previously been achieved in 2-D materials. Mechanical mode frequencies can be tuned by more than 12% by optical heating, and they exhibit avoided crossings indicative of strong intermode coupling. When the membrane is optically excited at the frequency difference between vibrational modes, normal mode splitting is observed, and the intermode energy exchange rate exceeds the mode decay rate by a factor of 15. Finite element and analytical modeling quantifies the extent of mode softening necessary to control intermode energy exchange in the strong coupling regime.
Co-reporter:Nari Jeon, Bernhard Loitsch, Stefanie Morkoetter, Gerhard Abstreiter, Jonathan Finley, Hubert J. Krenner, Gregor Koblmueller, and Lincoln J. Lauhon
ACS Nano 2015 Volume 9(Issue 8) pp:8335
Publication Date(Web):July 30, 2015
DOI:10.1021/acsnano.5b04070
GaAs-AlxGa1–xAs (AlGaAs) core–shell nanowires show great promise for nanoscale electronic and optoelectronic devices, but the application of these nonplanar heterostructures in devices requires improved understanding and control of nanoscale alloy composition and interfaces. Multiple researchers have observed sharp emission lines of unknown origin below the AlGaAs band edge in photoluminescence (PL) spectra of core–shell nanowires; point defects, alloy composition fluctuations, and self-assembled quantum dots have been put forward as candidate structures. Here we employ laser-assisted atom probe tomography to reveal structural and compositional features that give rise to the sharp PL emission spectra. Nanoscale ellipsoidal Ga-enriched clusters resulting from random composition fluctuations are identified in the AlGaAs shell, and their compositions, size distributions, and interface characteristics are analyzed. Simulations of exciton transition energies in ellipsoidal quantum dots are used to relate the Ga nanocluster distribution with the distribution of sharp PL emission lines. We conclude that the Ga rich clusters can act as discrete emitters provided that the major diameter is ≥4 nm. Smaller clusters are under-represented in the PL spectrum, and spectral lines of larger clusters are broadened, due to quantum tunneling between clusters.Keywords: atom probe tomography; heterostructure; III−V; nanowire; photoluminescence; quantum dot;
Co-reporter:Aaron Holsteen, In Soo Kim, and Lincoln J. Lauhon
Nano Letters 2014 Volume 14(Issue 4) pp:1898-1902
Publication Date(Web):March 5, 2014
DOI:10.1021/nl404678k
Nanomechanical resonators provide a compelling platform to investigate and exploit phase transitions coupled to mechanical degrees of freedom because resonator frequencies and quality factors are exquisitely sensitive to changes in state, particularly for discontinuous changes accompanying a first-order phase transition. Correlated scanning fiber-optic interferometry and dual-beam Raman spectroscopy were used to investigate mechanical fluctuations of vanadium dioxide (VO2) nanowires across the first order insulator to metal transition. Unusually large and controllable changes in resonator frequency were observed due to the influences of domain wall motion and anomalous phonon softening on the effective modulus. In addition, extraordinary static and dynamic displacements were generated by local strain gradients, suggesting new classes of sensors and nanoelectromechanical devices with programmable discrete outputs as a function of continuous inputs.
Co-reporter:In Soo Kim, Vinod K. Sangwan, Deep Jariwala, Joshua D. Wood, Spencer Park, Kan-Sheng Chen, Fengyuan Shi, Francisco Ruiz-Zepeda, Arturo Ponce, Miguel Jose-Yacaman, Vinayak P. Dravid, Tobin J. Marks, Mark C. Hersam, and Lincoln J. Lauhon
ACS Nano 2014 Volume 8(Issue 10) pp:10551
Publication Date(Web):September 15, 2014
DOI:10.1021/nn503988x
Ultrathin transition metal dichalcogenides (TMDCs) of Mo and W show great potential for digital electronics and optoelectronic applications. Whereas early studies were limited to mechanically exfoliated flakes, the large-area synthesis of 2D TMDCs has now been realized by chemical vapor deposition (CVD) based on a sulfurization reaction. The optoelectronic properties of CVD grown monolayer MoS2 have been intensively investigated, but the influence of stoichiometry on the electrical and optical properties has been largely overlooked. Here we systematically vary the stoichiometry of monolayer MoS2 during CVD via controlled sulfurization and investigate the associated changes in photoluminescence and electrical properties. X-ray photoelectron spectroscopy is employed to measure relative variations in stoichiometry and the persistence of MoOx species. As MoS2−δ is reduced (increasing δ), the field-effect mobility of monolayer transistors increases while the photoluminescence yield becomes nonuniform. Devices fabricated from monolayers with the lowest sulfur content have negligible hysteresis and a threshold voltage of ∼0 V. We conclude that the electrical and optical properties of monolayer MoS2 crystals can be tuned via stoichiometry engineering to meet the requirements of various applications.Keywords: chemical vapor deposition; field-effect mobility; molybdenum disulfide; photoluminescence; stoichiometry; transition metal dichalcogenides; X-ray photoelectron spectroscopy;
Co-reporter:KunHo Yoon, Jerome K. Hyun, Justin G. Connell, Iddo Amit, Yossi Rosenwaks, and Lincoln J. Lauhon
Nano Letters 2013 Volume 13(Issue 12) pp:6183-6188
Publication Date(Web):November 13, 2013
DOI:10.1021/nl4035412
Barrier heights between metal contacts and silicon nanowires were measured using spectrally resolved scanning photocurrent microscopy (SPCM). Illumination of the metal-semiconductor junction with sub-bandgap photons generates a photocurrent dominated by internal photoemission of hot electrons. Analysis of the dependence of photocurrent yield on photon energy enables quantitative extraction of the barrier height. Enhanced doping near the nanowire surface, mapped quantitatively with atom probe tomography, results in a lowering of the effective barrier height. Occupied interface states produce an additional lowering that depends strongly on diameter. The doping and diameter dependencies are explained quantitatively with finite element modeling. The combined tomography, electrical characterization, and numerical modeling approach represents a significant advance in the quantitative analysis of transport mechanisms at nanoscale interfaces that can be extended to other nanoscale devices and heterostructures.
Co-reporter:Sarah L. Howell, Sonal Padalkar, KunHo Yoon, Qiming Li, Daniel D. Koleske, Jonathan J. Wierer, George T. Wang, and Lincoln J. Lauhon
Nano Letters 2013 Volume 13(Issue 11) pp:5123-5128
Publication Date(Web):October 7, 2013
DOI:10.1021/nl402331u
GaN–InGaN core–shell nanowire array devices are characterized by spectrally resolved scanning photocurrent microscopy (SPCM). The spatially resolved external quantum efficiency is correlated with structure and composition inferred from atomic force microscope (AFM) topography, scanning transmission electron microscope (STEM) imaging, Raman microspectroscopy, and scanning photocurrent microscopy (SPCM) maps of the effective absorption edge. The experimental analyses are coupled with finite difference time domain simulations to provide mechanistic understanding of spatial variations in carrier generation and collection, which is essential to the development of heterogeneous novel architecture solar cell devices.
Co-reporter:James R. Riley, Sonal Padalkar, Qiming Li, Ping Lu, Daniel D. Koleske, Jonathan J. Wierer, George T. Wang, and Lincoln J. Lauhon
Nano Letters 2013 Volume 13(Issue 9) pp:4317-4325
Publication Date(Web):August 6, 2013
DOI:10.1021/nl4021045
Correlated atom probe tomography, cross-sectional scanning transmission electron microscopy, and cathodoluminescence spectroscopy are used to analyze InGaN/GaN multiquantum wells (QWs) in nanowire array light-emitting diodes (LEDs). Tomographic analysis of the In distribution, interface morphology, and dopant clustering reveals material quality comparable to that of planar LED QWs. The position-dependent CL emission wavelength of the nonpolar side-facet QWs and semipolar top QWs is correlated with In composition.
Co-reporter:Nari Jeon, Shadi A. Dayeh, and Lincoln J. Lauhon
Nano Letters 2013 Volume 13(Issue 8) pp:3947-3952
Publication Date(Web):July 30, 2013
DOI:10.1021/nl402117b
We propose layer-by-layer growth mechanisms to account for planar defect generation leading to kinked polytype nanowires. Cs-corrected scanning transmission electron microscopy enabled identification of stacking sequences of distinct polytype bands found in kinked nanowires, and Raman spectroscopy was used to distinguish polytype nanowires from twinned nanowires containing only the 3C diamond cubic phase. The faceting and atomic-scale defect structures of twinned 3C are compared with those of polytype nanowires to develop a common model linking nucleation pinning to nanowire morphology and phase.
Co-reporter:Vinod K. Sangwan, Deep Jariwala, Stephen A. Filippone, Hunter J. Karmel, James E. Johns, Justice M. P. Alaboson, Tobin J. Marks, Lincoln J. Lauhon, and Mark C. Hersam
Nano Letters 2013 Volume 13(Issue 3) pp:1162-1167
Publication Date(Web):February 7, 2013
DOI:10.1021/nl3045553
The full potential of graphene in integrated circuits can only be realized with a reliable ultrathin high-κ top-gate dielectric. Here, we report the first statistical analysis of the breakdown characteristics of dielectrics on graphene, which allows the simultaneous optimization of gate capacitance and the key parameters that describe large-area uniformity and dielectric strength. In particular, vertically heterogeneous and laterally homogeneous Al2O3 and HfO2 stacks grown via atomic-layer deposition and seeded by a molecularly thin perylene-3,4,9,10-tetracarboxylic dianhydride organic monolayer exhibit high uniformities (Weibull shape parameter β > 25) and large breakdown strengths (Weibull scale parameter, EBD > 7 MV/cm) that are comparable to control dielectrics grown on Si substrates.
Co-reporter:Justin G. Connell, KunHo Yoon, Daniel E. Perea, Edwin J. Schwalbach, Peter W. Voorhees, and Lincoln J. Lauhon
Nano Letters 2013 Volume 13(Issue 1) pp:199-206
Publication Date(Web):December 13, 2012
DOI:10.1021/nl3038695
The vapor–liquid–solid (VLS) process of semiconductor nanowire growth is an attractive approach to low-dimensional materials and heterostructures because it provides a mechanism to modulate, in situ, nanowire composition and doping, but the ultimate limits on doping control are ultimately dictated by the growth process itself. Under widely used conditions for the chemical vapor deposition growth of Si and Ge nanowires from a Au catalyst droplet, we find that dopants incorporated from the liquid are not uniformly distributed. Specifically, atom probe tomographic analysis revealed up to 100-fold enhancements in dopant concentration near the VLS trijunction in both B-doped Si and P-doped Ge nanowires. We hypothesize that radial and azimuthal inhomogeneities arise from a faceted liquid–solid interface present during nanowire growth, and we present a simple model to account for the distribution. As the same segregation behavior was observed in two distinct semiconductors with different dopants, the observed inhomogeneity is likely to be present in other VLS grown nanowires.
Co-reporter:Chung-Chiang Wu, Deep Jariwala, Vinod K. Sangwan, Tobin J. Marks, Mark C. Hersam, and Lincoln J. Lauhon
The Journal of Physical Chemistry Letters 2013 Volume 4(Issue 15) pp:2508-2513
Publication Date(Web):July 17, 2013
DOI:10.1021/jz401199x
The mechanisms underlying the intrinsic photoresponse of few-layer (FL) molybdenum disulfide (MoS2) field-effect transistors are investigated via scanning photocurrent microscopy. We attribute the locally enhanced photocurrent to band-bending-assisted separation of photoexcited carriers at the MoS2/Au interface. The wavelength-dependent photocurrents of FL MoS2 transistors qualitatively follow the optical absorption spectra of MoS2, providing direct evidence of interband photoexcitation. Time and spectrally resolved photocurrent measurements at varying external electric fields and carrier concentrations establish that drift-diffusion currents dominate photothermoelectric currents in devices under bias.Keywords: MoS2; nanoelectronics; scanning photocurrent microscopy; transition metal dichalcogenides;
Co-reporter:Francisco J. Lopez, Jerome K. Hyun, Uri Givan, In Soo Kim, Aaron L. Holsteen, and Lincoln J. Lauhon
Nano Letters 2012 Volume 12(Issue 5) pp:2266-2271
Publication Date(Web):April 12, 2012
DOI:10.1021/nl204537d
Diameter-dependent Raman scattering in single tapered silicon nanowires is measured and quantitatively reproduced by modeling with finite-difference time-domain simulations. Single crystal tapered silicon nanowires were produced by homoepitaxial radial growth concurrent with vapor–liquid–solid axial growth. Multiple electromagnetic resonances along the nanowire induce broad band light absorption and scattering. Observed Raman scattering intensities for multiple polarization configurations are reproduced by a model that accounts for the internal electromagnetic mode structure of both the exciting and scattered light. Consequences for the application of Stokes to anti-Stokes intensity ratio for the estimation of lattice temperature are discussed.
Co-reporter:Eric R. Hemesath, Daniel K. Schreiber, Emine B. Gulsoy, Christian F. Kisielowski, Amanda K. Petford-Long, Peter W. Voorhees, and Lincoln J. Lauhon
Nano Letters 2012 Volume 12(Issue 1) pp:167-171
Publication Date(Web):November 23, 2011
DOI:10.1021/nl203259f
Scanning and transmission electron microscopy was used to correlate the structure of planar defects with the prevalence of Au catalyst atom incorporation in Si nanowires. Site-specific high-resolution imaging along orthogonal zone axes, enabled by advances in focused ion beam cross sectioning, reveals substantial incorporation of catalyst atoms at grain boundaries in ⟨110⟩ oriented nanowires. In contrast, (111) stacking faults that generate new polytypes in ⟨112⟩ oriented nanowires do not show preferential catalyst incorporation. Tomographic reconstruction of the catalyst–nanowire interface is used to suggest criteria for the stability of planar defects that trap impurity atoms in catalyst-mediated nanowires.
Co-reporter:In Soo Kim and Lincoln J. Lauhon
Crystal Growth & Design 2012 Volume 12(Issue 3) pp:1383-1387
Publication Date(Web):January 17, 2012
DOI:10.1021/cg201488w
Single-crystal vanadium dioxide (VO2) nanobeams are attractive materials to investigate the influence of dimensions on the metal–insulator transition, so simple strategies to control yield and morphology are desirable. In a physical vapor transport process, three distinctive morphologies of VO2 nanostructures, nanoparticles, nanowires, and nanosheets, were observed depending on local source supersaturation and temperature. On the basis of these observations, a practical two-step synthetic approach was devised to modify the supersaturation during growth, separately optimizing nucleation density and nanobeam aspect ratio. Increased yield and uniformity in length associated with simultaneous nucleation could be achieved with modulation of oxygen flow or seeding the substrate with nuclei. The ability to lower the supersaturation while maintaining high densities of nanobeams also improved control over the morphology.
Co-reporter:James R. Riley ; Daniel E. Perea ; Liang He ; Frank Tsui
The Journal of Physical Chemistry C 2012 Volume 116(Issue 1) pp:276-280
Publication Date(Web):December 16, 2011
DOI:10.1021/jp208553g
Atom probe tomography (APT) was used to quantify inhomogeneities in the distribution of Mn and Co in doped epitaxial Ge thin films for which X-ray diffraction (XRD) studies indicate single phase material. The segregation of dopants into Co and Mn-rich regions with characteristic sizes was evident upon visual inspection of the APT reconstruction and a frequency distribution analysis of the concentration of Co, Mn, and Ge atoms verified that the composition fluctuations exceeded those of a random alloy. Isoconcentration surfaces were generated to establish the connectedness of regions enriched in Mn that have been proposed to enhance the Curie temperature in dilute magnetic semiconductors. The analysis demonstrates important contributions that APT can make to the understanding of magnetism in these materials.
Co-reporter:James R. Riley, Rodrigo A. Bernal, Qiming Li, Horacio D. Espinosa, George T. Wang, and Lincoln J. Lauhon
ACS Nano 2012 Volume 6(Issue 5) pp:3898
Publication Date(Web):April 20, 2012
DOI:10.1021/nn2050517
GaN nanowires oriented along the nonpolar a-axis were analyzed using pulsed laser atom probe tomography (APT). Stoichiometric mass spectra were achieved by optimizing the temperature, applied dc voltage, and laser pulse energy. Local variations in the measured stoichiometry were observed and correlated with facet polarity using scanning electron microscopy. Fewer N atoms were detected from nonpolar and Ga-polar surfaces due to uncorrelated evaporation of N2 ions following N adatom diffusion. The observed differences in Ga and N ion evaporation behaviors are considered in detail to understand the influence of intrinsic materials characteristics on the reliability of atom probe tomography analysis. We find that while reliable analysis of III–N alloys is possible, the standard APT procedure of empirically adjusting analysis conditions to obtain stoichiometric detection of Ga and N is not necessarily the best approach for this materials system.Keywords: atom probe tomography; GaN; semiconductor nanowires
Co-reporter:Ruth A. Schlitz, Young-geun Ha, Tobin J. Marks, and Lincoln J. Lauhon
ACS Nano 2012 Volume 6(Issue 5) pp:4452
Publication Date(Web):April 27, 2012
DOI:10.1021/nn3011834
Uniformity of the dielectric breakdown voltage distribution for several thicknesses of a zirconia-based self-assembled nanodielectric was characterized using the Weibull distribution. Two regimes of breakdown behavior are observed: self-assembled multilayers >5 nm thick are well described by a single two-parameter Weibull distribution, with β ≈ 11. Multilayers ≤5 nm thick exhibit kinks on the Weibull plot of dielectric breakdown voltage, suggesting that multiple characteristic mechanisms for dielectric breakdown are present. Both the degree of uniformity and the effective dielectric breakdown field are observed to be greater for one layer than for two layers of Zr-SAND, suggesting that this multilayer is more promising for device applications.Keywords: dielectric breakdown; reliability; SAND; self-assembly; Weibull analysis
Co-reporter:Jerome K. Hyun and Lincoln J. Lauhon
Nano Letters 2011 Volume 11(Issue 7) pp:2731-2734
Publication Date(Web):June 6, 2011
DOI:10.1021/nl201021k
Semiconducting nanowires have been demonstrated as promising light-harvesting units with enhanced absorption compared to bulk films of equivalent volume. However, for small diameter nanowires, the ultrahigh aspect ratio constrains the absorption to be polarization selective by responding primarily to the transverse magnetic (TM) light. While this effect is useful for polarization-sensitive optoelectronic devices, practical light-harvesting applications demand efficient light absorption in both TM and transverse electric (TE) light. In this study, we engineer the polarization sensitivity and the charge carrier generation in a 50 nm Si nanowire by decorating the surface with plasmonic Au nanoparticles. Using scanning photocurrent microscopy (SPCM) with a tunable wavelength laser, we spatially and spectrally resolve the local enhancement in the TE photocurrent resulting from the plasmonic near-field response of individual nanoparticles and the broad-band enhancement due to surface-enhanced absorption. These results provide guidance to the development and the optimization of nanowire–nanoparticle light-harvesting systems.
Co-reporter:Shixiong Zhang, In Soo Kim, and Lincoln J. Lauhon
Nano Letters 2011 Volume 11(Issue 4) pp:1443-1447
Publication Date(Web):March 23, 2011
DOI:10.1021/nl103925m
Coexisting monoclinic M1 (insulating) and rutile (metallic) domains were observed in free-standing vanadium dioxide nanobeams at room temperature. Similar domain structures have been attributed to interfacial strain, which was not present here. Annealing under reducing conditions indicated that a deficiency of oxygen stabilizes the rutile phase to temperatures as low as 103 K, which represents an unprecedented suppression of the phase transition by 238 K. In a complementary manner, oxygen-rich growth conditions stabilize the metastable monoclinic M2 and triclinic T (or M3) phases. A pseudophase diagram with dimensions of temperature and stoichiometry is established that highlights the accessibility of new phases in the nanobeam geometry.
Co-reporter:Francisco J. Lopez, Uri Givan, Justin G. Connell, and Lincoln J. Lauhon
ACS Nano 2011 Volume 5(Issue 11) pp:8958
Publication Date(Web):October 21, 2011
DOI:10.1021/nn2031337
Silicon nanowires with predominant 9R, 27T, 2H and other polytype structures with respective hexagonalities of 50, 40 and 35.3% were identified by Raman microscopy. Transmission electron microscopy indicates that intrinsic stacking faults form the basic building blocks of these polytypes. We propose a generation mechanism in which polytypes are seeded from incoherent twin boundaries and associated partial dislocations. This mechanism explains observed prevalence of polytypes and trends in stacking for longer period structures. The percentage of hexagonal planes in a polytype is extracted from its Raman spectrum after correcting the zone-folded phonon frequencies to account for changes of the in-plane lattice parameter with respect to diamond cubic (3C) Si. The correction is found to be (i) of the same order of magnitude as frequency differences between modes of low period polytypes and (ii) proportional to the hexagonality. Corrected phonon frequencies agree with experimentally found values to within 0.4 cm–1. Homostructures in which a central polytype region is bounded by 3C regions, with the planes (111)3C║(0001)polytype parallel to the nanowire axis, are found in ⟨112⟩ oriented nanowires. Strain-induced shifts of the Raman modes in such structures enable a rough estimation of the lattice misfit between polytypes, which compares favorably with first-principles calculations. Considerations presented here provide a simple and quantitative framework to interpret Raman frequencies and extract crystallographic information on polytype structures.Keywords: grain boundary; homostructure; polytype; Raman spectroscopy; silicon nanowire
Co-reporter:Shixiong Zhang, Francisco J. Lopez, Jerome K. Hyun, and Lincoln J. Lauhon
Nano Letters 2010 Volume 10(Issue 11) pp:4483-4487
Publication Date(Web):October 26, 2010
DOI:10.1021/nl102316b
We report the direct detection of hole accumulation in the core of Ge−Si core−shell nanowire heterostructures by a Fano resonance between free holes and the F2g mode in Raman spectra. Raman enhancements of 10−10 000 with respect to bulk were observed and explained using finite difference time domain simulations of the electric fields concentrated in the nanowire. Numerical modeling of the radial carrier concentration revealed that the asymmetric line-shape is strongly influenced by inhomogeneous broadening.
Co-reporter:Justin G. Connell, Zakaria Y. Al Balushi, Kwonnam Sohn, Jiaxing Huang, and Lincoln J. Lauhon
The Journal of Physical Chemistry Letters 2010 Volume 1(Issue 23) pp:3360-3365
Publication Date(Web):November 12, 2010
DOI:10.1021/jz101436a
Elemental metal nanoparticles are widely used to catalyze semiconductor nanowire growth, but size-controlled alloy nanoparticles have not been explored in this context. We present a simple aqueous synthesis of Au−Cu2O core−shell nanoparticles to produce Au−Cu alloy nanoparticles of controlled size and composition by vacuum annealing. Colloidal Au nanoparticles were used as size-controlled seeds, and fine control of the Cu2O shell thickness enabled tuning of the average Au−Cu alloy composition. The alloy nanoparticles were found to catalyze Ge nanowire growth in a low-pressure chemical vapor deposition environment. The nanowire growth rate for Au−Cu nanoparticles was intermediate to that of Cu (slowest) and Au (fastest) nanoparticles under identical conditions, suggesting a vapor−solid−solid growth process. These catalysts provide a useful platform to explore the influence of catalyst phase and chemistry on nanowire growth mechanisms that determine important variables including the doping rate and junction abruptness.Keywords (keywords): alloy; core−shell; nanoparticle; nanowire; semiconductor; vapor−solid−solid;
Co-reporter:Jonathan E. Allen;Daniel E. Perea;Eric R. Hemesath
Advanced Materials 2009 Volume 21( Issue 30) pp:3067-3072
Publication Date(Web):
DOI:10.1002/adma.200803865
Co-reporter:Shixiong Zhang, Jung Yen Chou and Lincoln J. Lauhon
Nano Letters 2009 Volume 9(Issue 12) pp:4527-4532
Publication Date(Web):2017-2-22
DOI:10.1021/nl9028973
The electrical resistance of single VO2 nanobeams was measured while simultaneously mapping the domain structure with Raman spectroscopy to investigate the relationship between structural domain formation and the metal−insulator transition. With increasing temperature, the nanobeams transformed from the insulating monoclinic M1 phase to a mixture of the Mott-insulating M2 and metallic rutile phases. Domain fractions were used to extract the temperature dependent resistivity of the M2 phase, which showed an activated behavior consistent with the expected Mott−Hubbard gap. Metallic monoclinic phases were also produced by direct injection of charge into devices, decoupling the Mott metal−insulator transition from the monoclinic to rutile structural phase transition.
Co-reporter:Shixiong Zhang, Eric R. Hemesath, Daniel E. Perea, Edy Wijaya, Jessica L. Lensch-Falk and Lincoln J. Lauhon
Nano Letters 2009 Volume 9(Issue 9) pp:3268-3274
Publication Date(Web):2017-2-22
DOI:10.1021/nl901548u
We quantitatively examine the relative influence of bulk impurities and surface states on the electrical properties of Ge nanowires with and without phosphorus (P) doping. The unintentional impurity concentration in nominally undoped Ge nanowires is less than 2 × 1017 cm−3 as determined by atom probe tomography. Surprisingly, P doping of ∼1018 cm−3 reduces the nanowire conductivity by 2 orders of magnitude. By modeling the contributions of dopants, impurities, and surface states, we confirm that the conductivity of nominally undoped Ge nanowires is mainly due to surface state induced hole accumulation rather than impurities introduced by catalyst. In P-doped nanowires, the surface states accept the electrons generated by the P dopants, reducing the conductivity and leading to ambipolar behavior. In contrast, intentional surface-doping results in a high conductivity and recovery of n-type characteristics.
Co-reporter:Francisco J. Lopez, Eric R. Hemesath and Lincoln J. Lauhon
Nano Letters 2009 Volume 9(Issue 7) pp:2774-2779
Publication Date(Web):June 15, 2009
DOI:10.1021/nl901315s
Correlated Raman microscopy and transmission electron microscopy were used to study the ordering of {111} planar defects in individual silicon nanowires. Detailed electron diffraction and polarization-dependent Raman analysis of individual nanowires enabled assessments of the stacking fault distribution, which varied from random to periodic, with the latter giving rise to local domains of 2H and 9R polytypes rather than the 3C diamond cubic structure. Some controversies and inconsistencies concerning earlier reports of polytypes in Si nanowires were resolved.
Co-reporter:Jonathan E. Allen, Eric R. Hemesath and Lincoln J. Lauhon
Nano Letters 2009 Volume 9(Issue 5) pp:1903-1908
Publication Date(Web):March 27, 2009
DOI:10.1021/nl803924z
High-performance field-effect transistors were fabricated by etching the channel regions of surface-doped Si nanowires. On/off ratios of 106 and field effect mobilities up to 525 cm2/(V·s) represent significant improvements over transistors fabricated from uniformly doped n-Si nanowires. Analysis by scanning photocurrent microscopy (SPCM) confirmed that the devices function similarly to traditional metal-oxide semiconductor field-effect transistors; in accumulation, the device current is controlled by channel conductance modulation, while n+−n junctions determine subthreshold characteristics as the channel is depleted. The principles of operation and the drain current saturation mechanisms were investigated by correlating current versus voltage data with integrated photocurrent profiles from SPCM.
Co-reporter:Jessica L. Lensch-Falk, Eric R. Hemesath, Daniel E. Perea and Lincoln J. Lauhon
Journal of Materials Chemistry A 2009 vol. 19(Issue 7) pp:849-857
Publication Date(Web):07 Jan 2009
DOI:10.1039/B817391E
Metal impurities have been used to mediate the growth of anisotropic crystalline semiconductor nanowires for a variety of applications. A majority of efforts have employed the vapor-liquid-solid approach at growth temperatures above the metal-semiconductor eutectic. Sub-eutectic vapor-solid-solid (VSS) growth has received less attention but may provide advantages including reduced processing temperatures and more abrupt heterojunctions. We present a review of the VSS growth of Si and Ge nanowires together with new studies of Mn-mediated Ge and Si nanowires to assess the generality of sub-eutectic nanowire growth and highlight key requirements.
Co-reporter:Jessica L. Lensch-Falk, Eric R. Hemesath and Lincoln J. Lauhon
Nano Letters 2008 Volume 8(Issue 9) pp:2669-2673
Publication Date(Web):August 12, 2008
DOI:10.1021/nl800933s
We report the growth of free-standing one-dimensional Ge/Mn-germanide nanowire heterostructures by chemical vapor deposition and provide a detailed description of the growth mechanism. Self-assembled manganese-germanide particles seed the growth of Ge nanowires (GeNWs) and simultaneously elongate along a parallel axis, resulting in syntaxial growth of the two phases. The GeNW growth is limited by GeH4 decomposition, whereas the germanide growth is limited by reaction of Mn at the growth interface. This syntaxial growth mechanism provides a novel route to axial metal/semiconductor nanowire heterostructures.
Co-reporter:D.E. Perea, E. Wijaya, J.L. Lensch-Falk, E.R. Hemesath, L.J. Lauhon
Journal of Solid State Chemistry 2008 Volume 181(Issue 7) pp:1642-1649
Publication Date(Web):July 2008
DOI:10.1016/j.jssc.2008.06.007
We describe the application of pulsed-laser atom probe (PLAP) tomography to the analysis of dopants and unintentional impurities in Si and Ge nanowires grown by the vapor–liquid–solid mechanism. PLAP tomography was used to determine the concentration of phosphorous in Ge nanowires and B in Si nanowires, enabling comparisons of the atomic concentrations of the reactants with those of the reaction products. Oxygen impurities were also detected, but the contribution from background gas adsorption was not ruled out. Gold catalyst impurities were not detected, and an upper bound of 5 ppm was established. Intrinsic and extrinsic origins of the detection limits of dopants and other impurities are described in detail. A tapered nanowire geometry was found to improve the mass resolution and signal-to-noise ratio by increasing the tip cooling rate. Simulations of nanowire cooling under laser pulsing were used to validate this improved approach to PLAP analysis of nanowires.Scanning electron micrograph of a P-doped Ge nanowire including the Au catalyst tip (top). The corresponding 3D reconstruction (middle) and mass spectrum (bottom) of the boxed region produced via atom probe tomography. From the 3D reconstruction and mass spectrum, the concentration and distribution of dopants can be determined.
Co-reporter:S. J. May;J.-G. Zheng;B. W. Wessels;L. J. Lauhon
Advanced Materials 2005 Volume 17(Issue 5) pp:
Publication Date(Web):3 MAR 2005
DOI:10.1002/adma.200401332
Dendritic growth of multiply branched InAs nanowires (see Figure and cover) is initiated by the controlled introduction of a Mn precursor in the context of vapor–liquid–solid nanowire growth by chemical vapor deposition. Self-assembly of Mn clusters leads to the nucleation and epitaxial growth of Mn-terminated InAs branches. The results provide a new route to the formation of hierarchical nanowire structures for nanoscale electronics and photonics.
Co-reporter:S. J. May;J.-G. Zheng;B. W. Wessels;L. J. Lauhon
Advanced Materials 2005 Volume 17(Issue 5) pp:
Publication Date(Web):3 MAR 2005
DOI:10.1002/adma.200590026
The dendritic nanostructures shown on the cover background were generated by self-assembled Mn clusters deposited from the vapor phase during vapor–liquid–solid growth of InAs nanowires. By carefully controlling the timing and amount of the Mn precursor, on p. 598 Lauhon and co-workers demonstrate a route to the formation of ordered hierarchical nanowire structures shown from various perspectives in the cover insets.
Co-reporter:Jessica L. Lensch-Falk, Eric R. Hemesath, Daniel E. Perea and Lincoln J. Lauhon
Journal of Materials Chemistry A 2009 - vol. 19(Issue 7) pp:NaN857-857
Publication Date(Web):2009/01/07
DOI:10.1039/B817391E
Metal impurities have been used to mediate the growth of anisotropic crystalline semiconductor nanowires for a variety of applications. A majority of efforts have employed the vapor-liquid-solid approach at growth temperatures above the metal-semiconductor eutectic. Sub-eutectic vapor-solid-solid (VSS) growth has received less attention but may provide advantages including reduced processing temperatures and more abrupt heterojunctions. We present a review of the VSS growth of Si and Ge nanowires together with new studies of Mn-mediated Ge and Si nanowires to assess the generality of sub-eutectic nanowire growth and highlight key requirements.