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 AlO_x 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 AlO_x, TiOPc assisted AlO_x 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 AlO_x was deposited via ALD. In this dual gated WSe₂ FET, the leakage current of the AlO_x 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.

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.

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.

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.

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.

Reference:

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).

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.