AVS 61st International Symposium & Exhibition
    2D Materials Focus Topic Tuesday Sessions
       Session 2D+AS+BI+PS+SS-TuM

Paper 2D+AS+BI+PS+SS-TuM13
Dielectrics Layer Deposition on Graphene Surface by Functionalization with Polar Titanyl Phthalocyanine

Tuesday, November 11, 2014, 12:00 pm, Room 310

Session: 2D Materials: Surface Chemistry, Functionalization, Bio and Sensor Applications
Presenter: Jun Hong Park, University of California at San Diego
Authors: J.H. Park, University of California at San Diego
I.J. Kwak, University of California at San Diego
K. Sardashti, University of California at San Diego
A.C. Kummel, University of California at San Diego
Correspondent: Click to Email
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 monolayer low-k dielectric or as a nucleation layer for growth of high-k insulators. This study demonstrates the molecular scale observation of formation of O-TiPc mono and bilayers on graphene with UHV scanning tunneling microscopy (STM). O-TiPc monolayers were deposited on HOPG surfaces by organic molecular beam epitaxy. After deposition, O-TiPc forms a monolayer with only few defects, and the crystal structure of monolayer has four-fold symmetry in a 1.4 x 1.4 nm grid. Observation of bright protrusions on each O-TiPc indicates that each O-TiPc in the monolayer is directed outward to vacuum. STS shows the band gap of the monolayer is 1.7 eV and the band gap of the bilayer is 2.3 eV. The monolayer or bilayer can directly be employed for sub-nanometer insulators on 2D semiconductors at low bias. Multiple cycles of TMA and water were dosed onto O-TiPc/HOPG to investigate nucleation of Al2O3 on the O-TiPc layers. The first cycle of TMA was observed to chemisorb on a 1.4 x 1.4 nm grid on the TiOPc monolayer. After exposure O-TiPc monolayer to 5 cycles ALD pulse (tri-methyl-aluminum (TMA)+H2O), insulating aluminum oxide was deposited uniformly on O-TiPc/HOPG. After formation of Al2O3 on O-TiPc/HOPG, the band gap of surface increases from 1.7 eV to 2.7 eV, while the conductance decreased. As shown in XPS spectra, the quality of Al2O3 can be improved by post annealing, consisting with transition of chemical states in O 1s peak and Al 2p. The chemical shifts of O and Al indicate that post annealing converts remained the Al-OH to Al2O3. Consequently, O-TiPc can not only act as a low-K dielectric but also induce high density ordered nucleation of ALD on central ion of O-TiPc for high-k dielectric growth.