Layer-by-layer, self-limiting chemisorptive siloxane self-assembly using Si3O2Cl8 as the
precursor affords thin, conformal, relatively dense, largely pinhole-free dielectric films that
can be deposited on oxide surfaces with sub-nanometer control of film thickness (8.3(1)
Å/layer). Deposition chemistry, microstructure, and hole injection/work function modification
properties of these (SiO2)
x
-like films on single-crystal Si(111) and polycrystalline indium tin
oxide (ITO) substrates have been characterized by synchrotron specular X-ray reflectivity,
cyclic voltammetry, X-ray and UV photoelectron spectroscopy, and atomic force microscopy.
Chemisorption of these (SiO2)
x
films onto the ITO anodes of three-layer, vapor-deposited
organic electroluminescent devices (ITO/(SiO2)
x
/TPD/Alq/Al) nearly triples the external
quantum and luminous efficiencies. The efficiency enhancement is attributed to hole and
electron injection fluence balance caused by modification of the effective voltage profile
brought about by the assembly of well-ordered siloxane layers. Interestingly, as a function
of increasing (SiO2)
x
layer thickness, device turn-on voltage first increases (x = 0 → 1),
progressively decreases (x = 1 → 2 → 3), and then increases (x = 3 → 4). A theoretical model
based upon computation at the ab initio level is proposed in which the self-assembled
dielectric layers induce an additional, thickness-dependent “built-in” electric field across
the organic transport layers, thereby simultaneously enhancing electron injection from the
cathode (increasing luminescence efficiency) and decreasing the efficiency of hole injection
(changing the turn-on voltage).