Center for Nanoscale Science and Engineering, Department of Chemistry, University of California, Riverside, California 92521, USA.
J Am Chem Soc. 2010 Oct 20;132(41):14429-36. doi: 10.1021/ja101706j.
We report the effect of electrochemical oxidation in nitric acid on the electronic properties of epitaxial graphene (EG) grown on silicon carbide substrates; we demonstrate the availability of an additional reaction channel in EG, which is not present in graphite but which facilitates the introduction of the reaction medium into the graphene galleries during electro-oxidation. The device performance of the chemically processed graphene was studied by patterning the EG wafers with two geometrically identical macroscopic channels; the electro-oxidized channel showed a logarithmic increase of resistance with decreasing temperature, which is ascribed to the scattering of charge carriers in a two-dimensional electronic gas, rather than the presence of an energy gap at the Fermi level. Field-effect transistors were fabricated on the electro-oxidized and pristine graphene channels using single-walled carbon nanotube thin film top gate electrodes, thereby allowing the study of the effect of oxidative chemistry on the transistor performance of EG. The electro-oxidized channel showed higher values for the on-off ratio and the mobility of the graphene field-effect transistor, which we ascribe to the availability of high-quality internal graphene layers after electro-oxidation of the more defective top layers. Thus, the present oxidative process provides a clear contrast with previously demonstrated covalent chemistry in which sp(3) hybridized carbon atoms are introduced into the graphitic transport layer of the lattice by carbon-carbon bond formation, thereby opening an energy gap.
我们报告了电化学氧化在硝酸中的作用对在碳化硅衬底上生长的外延石墨烯(EG)的电子性质的影响;我们证明了 EG 中存在一个额外的反应通道,在石墨中不存在,但在电氧化过程中有利于将反应介质引入到石墨烯的层间。通过用两个几何形状相同的宏观通道对 EG 晶片进行图案化,研究了经过化学处理的石墨烯的器件性能;电氧化通道的电阻随温度的降低呈对数增加,这归因于二维电子气中的载流子散射,而不是费米能级处存在能隙。使用单壁碳纳米管薄膜顶栅电极在电氧化和原始石墨烯通道上制造了场效应晶体管,从而可以研究氧化化学对 EG 晶体管性能的影响。电氧化通道的开关比和石墨烯场效应晶体管的迁移率更高,我们将其归因于电氧化更有缺陷的顶层后,可获得高质量的内部石墨烯层。因此,与之前通过碳-碳键形成将 sp(3)杂化碳原子引入晶格的石墨输运层中从而打开能隙的共价化学相比,目前的氧化过程提供了一个明显的对比。