AVS2016 Session EM+NS+SP+SS-WeA: Nanoscale Imaging of Metals and Compound Semiconductor based Nanostructures, Surfaces and Interfaces

Contact resistance is one of the most important factors which could potentially limit the performance of novel electronic and optoelectronic devices based on two-dimensional (2D) materials like graphene, black phosphorus, various transition metal dichalcogenides (TMDs) like MoS₂, WSe₂ and beyond [1-3]. It is now widely accepted that metal-2D contacts are mostly Schottky barriers type [1-3]. Hence, various contact engineering strategies have been adopted to minimize the Schottky barrier height at the metal-2D interface and thereby reduce the contact resistance. In this talk I will provide a comprehensive overview of different contact engineering schemes metal work function engineering, interface engineering and phase engineering [4-6]. Additionally, I will also talk about the scalability of the contact resistance since an aggressively scaled 2D device will also have aggressively scaled contacts.

1. Das S, Chen H-Y, Penumatcha AV, Appenzeller J: High performance multilayer MoS2 transistors with scandium contacts. Nano letters 2012, 13(1):100-105

2. Das S, Appenzeller J: WSe2 field effect transistors with enhanced ambipolar characteristics. Applied Physics Letters 2013, 103(10):103501

3. Das S, Demarteau M, Roelofs A: Ambipolar phosphorene field effect transistor. ACS nano 2014, 8(11):11730-11738.

4. Das S, Appenzeller J: Where does the current flow in two-dimensional layered systems?Nano letters 2013, 13(7):3396-3402

5. Das S, Gulotty R, Sumant AV, Roelofs A: All two-dimensional, flexible, transparent, and thinnest thin film transistor. Nano letters 2014, 14(5):2861-2866.

6. Kappera R, Voiry D, Yalcin SE, Branch B, Gupta G, Mohite AD, Chhowalla M: Phase-engineered low-resistance contacts for ultrathin MoS2 transistors. Nature materials 2014, 13(12):1128-1134.

We have previously demonstrated that a patterned elastic stress field can be used to change the near-surface atomic composition in an epitaxial compound semiconductor film.¹ This compositional patterning laterally manipulates quantum barriers within the film in a press-and-print manner. In this example, an array of silicon pillars is pressed against a relaxed Si_0.8Ge_0.2 substrate in a mechanical press, and the entire assembly is heated to high temperatures. This serves to promote a diffusive separation of the germanium into highly localized regions. Here, the difficulty in analyzing these structures is due to the lack of surface detail on the stress-annealed substrate as there is only elastic deformation observed during the fabrication process. To visualize the regions compressively stressed by the pillars and therefore compositionally altered regions, we report the use of μ-Raman spectroscopy to produce a 2D compositional map of a substrate. The substrate is patterned with feature sizes on the order of 1 to 3 microns to remain within the spatial resolution of μ-Raman spectroscopy for the purpose of demonstration. The first-order Raman spectrum for pure silicon and germanium produces peaks at 520.2 and 300.7 cm^-1, respectively. The deviations from these relaxed silicon and germanium peaks have been attributed to residual tensile stress in the Ge-depleted regions. Lateral line scans are performed to map the compositions of the stressed and annealed substrate, which provides a clear image of the resulting diffusion process. This imaging also allows the quantum structures to be addressable.

¹ S. Ghosh, D. Kaiser, J. Bonilla, T. Sinno, and S. M. Han, "Stress-Directed Compositional Patterning of SiGe Substrates for Lateral Quantum Barrier Manipulation," Applied Physic Letters 107, 072106-1:5 (2015).

III-V semiconductor nanowires (NWs) have a large technological potential within electronics, optoelectronics, and energy harvesting [1]. With their flexibility in creating heterostructures, by radial and axial stacking during epitaxial growth, comes an increasing complexity of device structure. Furthermore, due to their small diameter and their very large surface-to-volume-ratio, the performance of NW devices is strongly determined by surface properties. It is therefore essential to study the structural and electronic properties of NW surfaces down to the atomic level and across interfaces regarding doping, material composition, or crystal phase.

We recently obtained atomically resolved scanning tunneling microscopy (STM) images of various GaAs, InAs, and InP NW surfaces [2,3]. By combining STM imaging with scanning tunneling spectroscopy (STS) measurements, we correlate the surface structure and local electronic properties [3]. Here, we will present examples from InAs NWs with interfaces between different crystal phase. Our low-temperature STM/S results show that even the smallest possible insertion of zincblende phase within a wurtzite segment, a single bilayer stacking fault, shows a clear zincblende signature. We observe transitions in the local density of states with sub-nm lateral resolution. Furthermore, we map the interface band alignment and measure quantum confinement energies of single and double bilayer stacking faults.

Beyond traditional steady-state surface characterization, it is desirable to even investigate nanostructure devices in-situ, meaning while they are operating under an applied bias. We are now using simultaneous STM, AFM, and electrical transport measurements for studying individually contacted NWs during device operation [4], complemented by Kelvin probe force microscopy and scanning photoemission microscopy. We will present initial results of such combined in-situ studies on axial pn-junctions in InP and GaInP NWs, where we also investigate the influence of NW surface modification (e.g. removal of native oxide by atomic hydrogen) on photovoltaic properties.

[1] E. Lind et al., IEEE J. El. Dev. Soc. 3, 96 (2015); J. Wallentin et al., Science 339, 1057 (2013).

[2] M. Hjort et al., ACS Nano 6, 9679 (2012); J. Knutsson et al., ACS Appl. Mat. & Interf. 7, 5748 (2015).

[3] M. Hjort et al., Nano Lett. 13, 4492 (2013); M. Hjort et al., ACS Nano 8, 12346 (2014).

[4] O. Persson et al., Nano Lett. 15, 3684 (2015); J. L. Webb et al., Nano Res. 7, 877 (2014).

Scattering-type scanning near-field optical (s-SNOM) microscopy enable spectroscopic imaging with nanoscale resolution and provide chemical and structural information of surfaces [1]. In this work, we investigate identification of material type using an approach based on analyzing near fields at the sample edge [2]. We develop theoretical approach that includes full-wave numerical simulations and calculations of s-SNOM signal in different demodulation orders. This model allow characterization of structures of any shape and material, as well as different tips, and does not include any fitting parameters. In this way, we defined that metallic edge has bright and dark fringes in near-field characterization, whereas a bright edge of dielectric material has no outside fringe. Similar behavior is observed for anisotropic material with hyperbolic dispersion (boron nitride in mid-IR range): depending on the wavelength, it shows either metallic or dielectric properties.

1. Y. Abate, R.E. Marvel, J.I. Ziegler, S. Gamage, M.H. Javani, M.I. Stockman, and R.F. Haglund "Control of plasmonic nanoantennas by reversible metal-insulator transition" Sci. Rep. 5, 13997 (2015).

2. Y. Abate, S. Gamage, L. Zhen, S.B. Cronin, H. Wang, V. Babicheva, M.H. Javani, M.I. Stockman, “Nanoscopy reveals metallic black phosphorus,” Light: Science & Applications, accepted (2016). http://arxiv.org/abs/1506.05431

Morphology is one essential element that gives rise to extraordinary physical, chemical, and mechanical properties in nanomaterials. Precise morphology control of nanomaterials is a notorious task, which heavily relies on fundamental understanding of the governing atomistic mechanisms and kinetics at the nanoscale. Despite numerous studies on the growth and application of nanostructures, current understanding of kinetics that governs the nanocrystal evolution is yet limited.

By programming deposition conditions at time domain, we observed the wedding cake growth mechanism in the formation of 2D ZnO nanostructures. Within a narrow growth window, the surfaces of 2D structures were covered with a unique concentric terrace feature. This mechanism was further validated by comparing the characteristic growth rates to the screw dislocation-driven model. An interesting 1D to 2D morphology transition was also found during the wedding cake growth, when the adatoms overcome the Ehrlich-Schwoebel (ES) barrier along the edge of the top crystal facet triggered by lowering the supersaturation. The evolution of 2D plate structure from 1D pillars represents a dynamic crystal growth behavior transition when the local deposition conditions were tuned in-situ. It lively recorded the wedding cake growth model in nanostructure formation from vapor phase, which was rare to be observed when the deposition conditions were remained constant. The terrace feature on these nanostructures provided a valuable platform for understanding the wedding cake growth kinetics that could be an important mechanism to design and predict the nanocrystal morphology formation from the bottom-up. Analyzing the supersaturation and temperature-related growth behavior provides a new insight into nanostructure growth mechanisms and morphology control.

As heterogeneous materials scale below 10 nm, a suitable combination of single digit nanocrystals with their rich variety of tunable surfaces and interfaces allows tailoring unprecedented materials with novel structure-function relationships. The design of new catalysts [1], investigations of polymers at atomic resolution [2] or analyses of deviations from a random doping distributions at atomic resolution [3] may serve as examples. This contribution describes research that aims at exploiting the emerging ability to analyze and understand such materials by directly determining their atom arrangement in three-dimensions using aberration-corrected transmission electron microscopy [4]. Attempts to unravel the atomic structure of such nanoscale composites in this manner must explicitly address their pronounced sensitivity to the probing radiation that can unintentionally alter their pristine structure, often beyond recognition. We address this challenge by applying low dose-rate in-line holography [5], which allows operating electron microscopes with dose rates as low as 5-10 e/Ųs that help maintaining structural integrity at atomic resolution to an unexplored end. The approach mimics best practices in biological research but achieves atomic resolution with single atom sensitivity by the acquisition of large image series. We observe a variety of previously unknown atom configurations in surface proximity of CoO_x nanocrystals and coatings that are hidden behind unusually broadened diffraction patterns but become visible in real space images because the phase problem is solved. The observed structures are drastically altered by an exposure of the material to water vapor or other gases, which is investigated at atomic resolution in environmental electron microscopy. It is shown for Rh/W catalysts that electron beam-induced atom dynamics can be entirely suppressed even for atom clusters made from less than 10 atoms. Resultantly, chemical compositions can be determined by contrast measurements alone and functional processes can be triggered and tracked in real time at atomic resolution.[6]

[1] J. A. Haber et al., Advanced Energy Materials 5 (2015) 1402307

[2] D. Lolla et al., Nanoscale 8 (2016) 120 - 128

[3] P. Specht, C. Kisielowski, On the chemical homogeneity of InxGa1-xN alloys - Electron microscopy at the edge of technical limits, submitted (2016)

[4] F.R. Chen et al., Nature Commun. 7:10603 doi: 10.1038/ ncomms10603 (2016)

[5] C. Kisielowski, Advanced Materials 27 (2015) 5838-5844

[6] The Molecular Foundry, which is supported by the Office of Science, the Office of Basic Energy Sciences, the U.S. Department of Energy under Contract No. DE-AC02-05CH11231