AVS2015 Session 2D+EM+MG+NS+SS+TF-ThA: Heterostructures of 2D Materials

Thursday, October 22, 2015 2:20 PM in 212C

Thursday Afternoon

Time Period ThA Sessions | Abstract Timeline | Topic 2D Sessions | Time Periods | Topics | AVS2015 Schedule

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2:20 PM 2D+EM+MG+NS+SS+TF-ThA-1 Dielectrics Layer Deposition on 2D Materials by Functionalization with Polar Titanyl Phthalocyanine
JunHong Park (UC San Diego); Sara Fathipour (University of Notre Dame); Il Jo Kwak (UC San Diego); Hema Movva (UT-Austin); Suresh Vishwanath, Huili Xing (Cornell University); Sanjay Banerjee (UT-Austin); Alan Seabaugh (University of Notre Dame); Andrew C. Kummel (University of California at San Diego)

Several novel designs for beyond CMOS devices have emerged using two-dimensional semiconductors. These devices require deposition of thin insulators on 2D semiconductors or between two sheets of 2D semiconductors. However, 2D semiconductors are nearly inert surfaces thereby making uniform nucleation of oxide growth challenging preventing scaling of the insulator thickness. A new technique has been developed to employ a monolayer of ordered metal phthalocyanines (MPc) on 2D semiconductors directly as a nucleation layer for growth of ALD dielectric. TiOPc monolayers were deposited on HOPG surfaces and WSe2 by organic molecular beam epitaxy. TiOPc forms a monolayer with only few defects, and the crystal structure of monolayer has four-fold symmetry in a 1.6 x 1.6 nm grid on both HOPG and WSe2. Observation of bright protrusions on each O-TiPc indicates that each O-TiPc in the monolayer is directed outward to vacuum. After exposure O-TiPc monolayer to 5 cycles ALD pulse (tri-methyl-aluminum (TMA)+H2O), insulating aluminum oxide was deposited uniformly on TiOPc/HOPG. After formation of AlOx on TiOPc/HOPG, the band gap of surface increases from 1.7 eV to 3.4 eV, while the conductance decreased. A metal-oxide-TiOPc-graphene capacitor has the lower thickness and the higher capacitance value than any reported graphene MOSCAPs. In the dual gated graphene FET with 40 cycles of AlOx, TiOPc assisted AlOx shows very low leakage current. Employing the TiOPc seeding layer also can be expanded to other TMD materials. The bottom gated WSe2 FET was fabricated. On the bottom gated WSe2 FET, the TiOPc monolayer was deposited, then 50 cycle of AlOx was deposited via ALD. In this dual gated WSe2 FET, the leakage current of the AlOx is measured as ~0.05 pA/μm2 at 0.5 VTG. As a control, 20 cycles of Al2O3, and 140 cycles of HfO2 were deposited on bare WSe2. The leakage current of the TiOPc assisted 50 cycle Al2O3 oxide is 3 orders of magnitude lower than HfO2/Al2O3/WSe2, consistent with a high nucleation.

2:40 PM 2D+EM+MG+NS+SS+TF-ThA-2 Direct Probing of the Electronic Structure of Bilayer Homo- and Hetero-Structures and Tracking their Evolution with Interlayer Twist-Angle
Nader Zaki, Po-Chun Yeh, Wencan Jin, Richard Osgood, Jr. (Columbia University)

2D atomic layer materials such as graphene and transition-metal dichalcogenides such as MoS2 have garnered much interest over the last few years due to their surprising electronic properties. For example, graphene possesses an exceptionally high mobility while monolayer MoS2 possesses a direct bandgap with an exceptionally high light-matter interaction. One of the directions the 2D materials community is now pursuing is one in which these materials are combined together by way of vertical stacking in order to fabricate custom layered structures with potentially rich physics and unique device properties. Naturally, determining the electronic structure of these custom assembled structures is a necessary task to understanding their electronic behavior. While the electronic structure of the constituent materials have already been studied for monolayer form, the electronic structure of the stacked structures has only recently started to be deciphered. This talk will report on the direct determination of the electronic structure of two bilayer systems: twisted bilayer MoS2 and twisted graphene/MoS2. Using LEEM, μLEED, and μARPES, the stack quality, stack orientation, and stack electronic structure are directly probed and resolved with few μm and higher spatial resolution. To be discussed will be the evolution of the electronic structure with twist angle and its implications on the electronic properties of the respective homo- and hetero-structures.

3:00 PM 2D+EM+MG+NS+SS+TF-ThA-3 In Situ Microscopy on 2D Materials: Heterostructures, Nanostructures, Novel Materials Systems
Peter Sutter (University of Nebraska - Lincoln)

Two-dimensional (2D) materials, such as graphene, hexagonal boron nitride, and a family of metal dichalcogenides have fascinating properties and show promise for applications. The broad exploration and use of these materials depends on the development of scalable synthesis methods, and of a fundamental understanding of their properties. I will discuss recent advances in understanding the synthesis, processing, and properties of 2D materials derived primarily from in-situ surface imaging.

In-situ microscopy provides the basis for creating complex heterostructures of different 2D materials, such as graphene and hexagonal boron nitride, and for studying atomically precise graphene nanostructures. Real-time imaging yields quantitative information on the growth and processing of new classes of 2D materials, such as metal dichalcogenide semiconductors. Finally, the combination of in-situ microscopy with synchrotron-based spectroscopy represents a unique approach for exploring the electronic band structure of 2D materials.

Our results illustrate that in-situ microscopy can be a powerful tool for realizing and probing the unique characteristics of two-dimensional materials.

4:00 PM 2D+EM+MG+NS+SS+TF-ThA-6 Direct Growth of Graphene/h-BN(0001) Multilayer Heterostructures for Novel Device Applications
Marcus Driver, John Beatty, Opeyemi Olanipekun, Kimberly Reid, Jeffry Kelber (University of North Texas)

We report the direct layer-by-layer growth of h-BN(0001) multilayers on Co(0001) by atomic layer epitaxy (ALE), and the direct growth of graphene multilayers on h-BN(0001) by molecular beam epitaxy (MBE). For the first time, this allows the growth of graphene/BN heterostructures with graphene and BN thicknesses controlled with atomic precision, and with all graphene and BN layers in azimuthal registry. Such control is a prerequisite for many proposed spintronic and electronic applications that emphasize charge or spin transport perpendicularly through the heterojunction. Further, the growth by direct, scalable methods without physical transfer, is essential for industrial development of such devices. h-BN(0001) multilayers have been deposited on Co(0001)/Al2O3(0001), using a BCl3/NH3 ALE process at 600 K. X-ray photoelectron spectroscopy (XPS) indicates B:N atomic ratios of 1:1 with negligible Cl contamination or reaction with the metallic substrate. Low energy electron diffraction (LEED) data indicate BN domain sizes of ~ 300 A or greater, with the lattice in registry with that of the Co(0001) substrate. LEED data also indicate BN domains larger than those of the Co substrate, suggesting BN overgrowth of Co domain boundaries. The XPS-derived average BN film thickness scales linearly with the number of BCl3/NH3 cycles, and the lack of Co oxidation after ambient exposure of a BN bilayer indicates that these films are macroscopically continuous over the 1 cm x 1 cm sample size. Graphene formation on h-BN(0001) was achieved using MBE with a graphite rod source, with deposition carried out at 800 K. LEED data show the expected 6-fold LEED pattern in exact registry with that of the h-BN(0001)/Co(0001) substrate. XPS C 1s spectra indicate a C 1s binding energy near 284.5 eV and with the expected pi-to-pi* transition. A heterojunction consisting of ~ 3 monolayers (ML) graphene/3 ML h-BN on Co(0001) proved stable in vacuum to at least 1000 K, indicating the adaptability of this growth process to a variety of industrial applications. Other recent results indicate the adaptability of this process to other substrates, such as Ru(0001) or CoSi2(111). These developments make possible a variety of spin filters, spin valves, and tunneling transistors proposed on the basis of close BN/graphene lattice matching, but not readily achievable with physically transferred films.

Acknowledgements: This work was supported by CSPIN, a MARCO/DARPA STARnet Center, under tasks 2381.001

and 2381.003, and by a UNT ROP grant. Peter Dowben and Jian-Ping Wang are acknowledged for stimulating and informative discussions.

4:20 PM 2D+EM+MG+NS+SS+TF-ThA-7 Al2O3 on Black Phosphorus by Atomic Layer Deposition: An in situ Interface S tudy
Hui Zhu, Stephen McDonnell, Xiaoye Qin, Angelica Azcatl, Lanxia Cheng, Rafik Addou, Jiyoung Kim (UT-Dallas); Peide Ye (Purdue University); Robert Wallace (UT-Dallas)

Black phosphorus (“black-P”) is considered to be an appealing 2D material because of its novel properties and potential application in few-layer transistor structures.1,2,3 However, a clear challenge in the implementation of black-P is the strong hydrophilic4 and oxidation5 reactions during device processing and thereafter. Thus, efficient isolation layers are necessary for black-P to preserve its electronic properties. Al2O32 or HfO26 dielectric layers deposited by atomic layer deposition (ALD) have been used as isolation layers in recent black-P transistors. In this work, three different samples oxidized by ambient air were investigated to understand the interfacial chemistry, and nucleation of atomic layer deposited Al2O3 on black-P using in situ X-ray photoelectron spectroscopy (XPS). This work suggests that exposing a sample that is initially free of phosphorus oxide to the ALD precursors does not result in detectable oxidation. However, when the phosphorus oxide is formed on the surface prior to deposition, the black-P can react with both the surface adventitious oxygen contamination and the H2O precursor at the deposition temperature of 200 °C. As a result, the concentration of the phosphorus oxide increases after both annealing and the atomic layer deposition process. The nucleation rate of Al2O3 on black-P is correlated with the amount of oxygen on samples prior to the deposition. The growth of Al2O3 follows a “substrate inhibited growth” behavior where an incubation period is required. Ex situ atomic force microscopy is also used to investigate the deposited Al2O3 morphologies on black-P where the Al2O3 tends to form islands on the exfoliated black-P simples.

This work was supported in part by the SWAN Center, a SRC center sponsored by the Nanoelectronics Research Initiative and NIST, the Center for Low Energy Systems Technology (LEAST), one of the six SRC STARnet Centers, sponsored by MARCO and DARPA, and the US/Ireland R&D Partnership (UNITE) under the NSF award ECCS-1407765.


1 L. Li, Y. Yu, G.J. Ye, Q. Ge, X. Ou, H. Wu, D. Feng, X.H. Chen, and Y. Zhang, Nat. Nanotech. 9, 372 (2014).

2 H. Liu, A.T. Neal, Z. Zhu, Z. Luo, X. Xu, D. Tománek, and P.D. Ye, ACS Nano 8, 4033 (2014).

3 F. Xia, H. Wang, and Y. Jia, Nat. Comm. 5, 4458 (2014).

4 J.D. Wood, S.A. Wells, D. Jariwala, K. Chen, E. Cho, V.K. Sangwan, X. Liu, L.J. Lauhon, T.J. Marks, and M.C. Hersam, Nano Lett. 14, 6964 (2014).

5 A. Favron, E. Gaufrès, F. Fossard, P.L. Lévesque, Anne-Laurence, Phaneuf-L’ Heureux, N.Y.-W. Tang, A. Loiseau, R. Leonelli, S. Francoeur, and R. Martel, arXiv:1408.0345 (2014).

6 N. Haratipour, M.C. Robbins, and S.J. Koester, arXiv:1409.8395 2 (2014).

4:40 PM 2D+EM+MG+NS+SS+TF-ThA-8 Topological Winding Number Change and Broken Inversion Symmetry in a Hofstadter’s Butterfly
Marc Bockrath (UC Riverside)
Recently several research groups have demonstrated accurate placement of graphene on hexagonal BN (hBN) with crystallographic alignment. Due to the resulting superlattice formed in the graphene/hBN heterostructures, an energy gap, secondary Dirac Points, and Hofstadter quantization in a magnetic field have been observed. Using aligned layer transfer we are able to produce graphene/hBN heterostructures with ~1 degree alignment accuracy, and measure the transport properties of the resulting systems. We observe an additional π Berry’s phase shift in the magneto-oscillations when tuning the Fermi level past the secondary Dirac points, originating from a change in topological winding number from odd to even when the Fermi-surface electron orbit begins to enclose the secondary Dirac points. At large hole doping inversion symmetry breaking generates a distinct hexagonal pattern in the longitudinal resistivity versus magnetic field and charge density. This results from a systematic pattern of replica Dirac points and gaps, reflecting the fractal spectrum of the Hofstadter butterfly.
5:00 PM 2D+EM+MG+NS+SS+TF-ThA-9 Compliant Substrate Epitaxy: Au on MoS2
Yuzhi Zhou, Chrzan Daryl (UC Berkeley)
The heteroepitaxial growth of Au on MoS2, a layered van der Waals bonded dichalcongenide, is analyzed. It is argued that the weak coupling between the layers in the dichalcogenides enables the first substrate layer to deform elastically almost independently from the substrate layers below, and hence enables epitaxial growth for a larger mismatch than might otherwise be expected. Linear, continuum elasticity theory and density functional theory are used to show that a {111} oriented Au film is the preferred over an {001} oriented Au film, despite the fact that the {111} orientation leads to a much higher elastic strain. During the initial stages of growth, the {111} orientation is favored over the {001} orientation due to its lower surface and interfacial energies. As the Au film grows thicker, the elastic relaxation of the first layer of the substrate leads to a reduction in the elastic energy of the growing film. This reduces the elastic energy difference between the {001} and {111} orientations enabling the {111} orientation to remain stable for all film thicknesses. This work is supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
5:20 PM 2D+EM+MG+NS+SS+TF-ThA-10 Direct Synthesis of 2D van der Waals Heterostructures
Judy Cha (Yale University)

Two-dimensional (2D) chalcogenides have gained renewed interest due to their interesting electrical properties such as topological insulator surface states in Bi2Se3 and hydrogen evolution catalytic activities in MoS2. Our ability to thin them down to a single layer and their anisotropic bonding nature opens up possibilities for novel heterostructures where we can tailor their electronic properties. I will present one-step, scalable heterostructure synthesis method to synthesize these chalcogenide nanostructures and examine their electronic transport properties. Intercalation into 2D materials will be considered as a novel way to design 2D heterostructures, in which the optical and electrical properties of the host 2D materials can drastically change. I will also discuss ways to control the alignment of molecular layers in these 2D chalcogenides, which exploits stress and strain built in the film during the growth. Electron tomography will be used to reconstruct the 3D structure of vertically oriented molecular layers in MoS2 thin films. In the second part of the talk, I will present synthesis and electronic properties of SnTe topological crystalline insulator nanoplates. Although SnTe is cubic and not a layered material, large SnTe nanoplates expanding hundreds of microns in lateral dimension with ~ 100 nm in thickness are possible. I will discuss effects of substrates and growth conditions to promote thin film growth of non-layered materials.

Time Period ThA Sessions | Abstract Timeline | Topic 2D Sessions | Time Periods | Topics | AVS2015 Schedule