Potential of Thermodynamic Evaluation
of the Efficiency of Adhesion Promoters
V. A. Titov
, V. I. Rakhlin
, and E. E. Grinberg
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Favorskii Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
State Research Institute of Chemical Reagents and Special-Purity Chemical Substances,
Federal State Unitary Enterprise, Moscow, Russia
Received December 15, 2009
Abstract—Method for evaluation of the efficiency of photoresist adhesion promoters is suggested. The method
is based on a thermodynamic simulation of the reactivity of organosilicon compounds with respect to hydroxy-
containing derivatives. The adequacy of the chosen technique was verified experimentally.
ORGANIC SYNTHESIS AND INDUSTRIAL
ISSN 1070-4272, Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 3, pp. 431–436. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.A. Titov, V.I. Rakhlin, E.E. Grinberg, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 3, pp. 439–444.
Of high importance for improving the repro-
ducibility of manufacture processes and raising the
yield of high-quality products in fabrication of micro-
electronic devices with micro- and submicrometer
elements are procedures for preparation of wafers in
microphotolithographyic processes and, in particular,
their treatment with a photoresist adhesion promoter.
Improving the photoresist adhesion to the substrate
surface diminishes deviations of element sizes in
exposure, development, and etching.
Compounds with silicon–nitrogen bonds find wide
practical application in these processes. They serve as
precursors in growth of dielectric layers  and as
adhesion promoters in deposition of a photoresist .
At present, the most widely used compound is
hexamethyldisilazane; however, it can hardly be
considered the optimal reagent. This is due both to an
unfortunate ratio between the film-forming elements
(Si : N = 2 : 1) and to the comparatively low
hydrolysis susceptibility of this compound.
In recent years, steadily increasing interest for use
in this field has been attracted by organosilicon
derivatives of 1,1-dimethylhydrazine. Efficient methods
have been developed for synthesis of a number of
volatile derivatives of compounds belonging to this
class [3, 4]: trimethyl(2,2-dimethylhydrazino)silane
, and 1,1-dimethyl-2,2-
methods are simple, technologically convenient, and
enable synthesis of target products in up to 90% yields,
which makes prospects for their application rather
Also accessible are organylaminosilanes of general
= H, Alk, Ar; n = 1–
3), which are formed in high yield in reactions of
with an excess amount of the
The goal of our study was to make an attempt to
theoretically evaluate the efficiency of compounds
used as adhesion promoters for the example of various
classes of nitrogen-containing organosilicon compounds.
The role of an adhesion promoter consists in that
hydrophobic properties are imparted to the substrate
surface, with adsorbed water removed and surface
hydroxy groups blocked. The rates of these processes
are different, but it is apparent that their variation must
be symbate for various reagents. This makes it possible
to evaluate the efficiency of an adhesion promoter by
data on how easily it interacts with hydroxyl-