ISSN 10637397, Russian Microelectronics, 2010, Vol. 39, No. 3, pp. 199–209. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.Yu. Vasilyev, 2010, published in Mikroelektronika, 2010, Vol. 39, No. 3, pp. 219–229
This paper is a generalization of the original submis
sions which were presented in 2006–2009 at various inter
national conferences and published in conference pro
ceedings and in journals by a group of authors, including
the author of this work (see [27–39] in ). In the first
part of , the features of the equipment and methods of
pulse deposition of thin layers through the example of
deposition on metal ruthenium (Ru) at low temperatures
were analyzed. In the second part, the results of all exper
imental data on the growth of layers of Ru with the partic
ipation of the carbonyldiene precursor
ther, the precursor), in the presence of reductant
, were presented. In contrast to previously
published qualitative data, in the investigated range of
experimental conditions of the growth of kinetics, the
data is analyzed quantitatively, taking into account impor
tant experimental details.
The final goal of the kinetic studies was to find deposi
tion conditions corresponding to the socalled mode of
growth of layers “Atomic Layer Deposition” (ALD, which
is sometimes referred to in the Russian literature as
“molecular layering”). In case of the ALD regime, the
interaction of the monolayer precursor chemical
adsorbed on the surface with a second reagent coming
from gas phase limits the stage of the growth process .
Implementation of the deposition process in a sequential
pulse mode is necessary for the realization of ALD.
Method of deposition of the ruthenium layer
. For the
pulsed deposition of Ru, two variants of the organization
of the cyclic process HOGF with consistent impulses of
initial reagents were used. Option 1 included a 4step, 8
second cycle, with the following sequence of supply of
reagents: (1) fumes of the precursor in a mixture with
argon, 1 s, (2) argon, 3 s, (3) the second component, 1 s,
and (4) argon, 3 s. In the case of Option 2, the cycle time
was 20 s, and the 8step cycle includes the following
sequence: (1) fumes of the precursor in a mixture with
argon, 1 s, (2) exhausting, 1–3 s, (3) argon, 1–3 s, (4)
exhausting, 1–3 s, (5) the second component, 1–5 s, (6)
exhausting, 1–3 s, (7) argon, 1–3 s, and (8) exhausting,
1–3 s. The optimization of the pulse duration of the
reagents, purge gas argon, and vacuum pumping between
pulses are discussed in .
The initial carbonyldiene ruthenium precur
, is not a purchasable reagent. In appear
ance, under normal conditions it is described as a light
yellow opalescent liquid [3, 4], with a molecular weight of
265.23 g/mol and mass content of ruthenium of 38.1%.
According to , the vapor pressure of the precursor (
in the temperature range
was 0.28–5 Torr.
According to these data, for the six experimental points
presented in , the classical temperature dependence of
the vapor pressure of the precursor can be described by the
= 5.316 – 1642/
. Note that I used a
precursor with a much higher vapor pressure in compari
son with other known and used ruthenium precursors.
Low Temperature Pulsed GasPhase Deposition of Thin Layers
of Metallic Ruthenium for Micro and Nanoelectronics:
Part 2. Kinetics of the Growth of Ruthenium Layers
V. Yu. Vasilyev
Department of semiconductor devices and microelectronics (SDaME), Novosibirsk State Technical University,
Received April 17, 2009
—Experimental data of growth kinetics of layers of ruthenium in a temperature range of
by pulsed deposition from the gas phase with the participation of the carbonyldiene precursor complex
, as well as
as the second reagent are generalized.