title: Covalent attachment of diamondoid phosphonic acid dichlorides to tungsten oxide surfaces.
abstract: Diamondoids (nanometer-sized diamond-like hydrocarbons) are a novel class of carbon nanomaterials that exhibit negative electron affinity (NEA) and strong electron-phonon scattering. Surface-bound diamondoid monolayers exhibit monochromatic photoemission, a unique property that makes them ideal electron sources for electron-beam lithography and high-resolution electron microscopy. However, these applications are limited by the stability of the chemical bonding of diamondoids on surfaces. Here we demonstrate the stable covalent attachment of diamantane phosphonic dichloride on tungsten/tungsten oxide surfaces. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy revealed that diamondoid-functionalized tungsten oxide films were stable up to 300-350 °C, a substantial improvement over conventional diamondoid thiolate monolayers on gold, which dissociate at 100-200 °C. Extreme ultraviolet (EUV) light stimulated photoemission from these diamondoid phosphonate monolayers exhibited a characteristic monochromatic NEA peak with 0.2 eV full width at half-maximum (fwhm) at room temperature, showing that the unique monochromatization property of diamondoids remained intact after attachment. Our results demonstrate that phosphonic dichloride functionality is a promising approach for forming stable diamondoid monolayers for elevated temperature and high-current applications such as electron emission and coatings in micro/nano electromechanical systems (MEMS/NEMS).
authors.affiliation: Geballe Laboratory for Advanced Materials, Stanford University, 476 Lomita Mall, Stanford, California 94305, United States.
authors.forename: Fei Hua
authors.initials: FH
authors.lastname: Li
authors.forename: Jason D
authors.initials: JD
authors.lastname: Fabbri
authors.forename: Raisa I
authors.initials: RI
authors.lastname: Yurchenko
authors.forename: Alexander N
authors.initials: AN
authors.lastname: Mileshkin
authors.forename: J Nathan
authors.initials: JN
authors.lastname: Hohman
authors.forename: Hao
authors.initials: H
authors.lastname: Yan
authors.forename: Hongyuan
authors.initials: H
authors.lastname: Yuan
authors.forename: Ich C
authors.initials: IC
authors.lastname: Tran
authors.forename: Trevor M
authors.initials: TM
authors.lastname: Willey
authors.forename: Michael
authors.initials: M
authors.lastname: Bagge-Hansen
authors.forename: Jeremy E P
authors.initials: JE
authors.lastname: Dahl
authors.forename: Robert M K
authors.initials: RM
authors.lastname: Carlson
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Fokin
authors.forename: Peter R
authors.initials: PR
authors.lastname: Schreiner
authors.forename: Zhi-Xun
authors.initials: ZX
authors.lastname: Shen
authors.forename: Nicolas A
authors.initials: NA
authors.lastname: Melosh
mesh_terms: D002712:Chlorides / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D010316:Particle Size; D010757:Phosphorous Acids / Q000737:chemistry*; D013499:Surface Properties; D014414:Tungsten / Q000737:chemistry*
chemical_list: D002712:Chlorides; D010087:Oxides; D010757:Phosphorous Acids; C570063:phosphonic acid; C511604:tungsten oxide; D014414:Tungsten