ISSN 1063-7397, Russian Microelectronics, 2010, Vol. 39, No. 4, pp. 262–272. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.Yu. Vasilyev, 2010, published in Mikroelektronika, 2010, Vol. 39, No. 4, pp. 284–294
262
INTRODUCTION
In this article, we generalize the materials pre-
sented in 2006–2009 at different international confer-
ences as well as materials published by my fellow cow-
riters with my active participation in the works of con-
ferences and journals (see references [27–39] in [1]).
In the first part of [1], the data on the equipment and
procedure of carrying out the experiment as applied to
the pulsed low-temperature vapor-phase deposition of
metal ruthenium (Ru) were systematized. In the sec-
ond part of the work [2], in the studied range of exper-
imental conditions, the main peculiarities of the
growth kinetics of the Ru layers with the participation of
the complex carbonyl-diene precursor tricarbonyl[η
4
-
cyclohexa-1,3-diene]ruthenium, Ru(CO)
3
(C
6
H
8
) (fur-
ther precursor) in the presence of reducing agents NH
3
or H
2
or oxidizing agent N
2
O as second reagents are
generalized and analyzed. The goal of the kinetics
investigations was the search for the so-called deposi-
tion mode of the Ru layer by the Atomic Layer Depo-
sition (ALD) mechanism, at which the limiting stage
of the growth process is the interaction of the precur-
sor monolayer chemisorbed on the surface with the
second reagent arriving from the vapor phase [3]. By
their appearance, the ruthenium layers under all stud-
ied experimental conditions were granulated and had
different granularity and continuity [2]. By virtue of
this fact, no pronounced temperature range of the
growth of ruthenium layers by the ALD mechanism
was revealed, but the most probable in case of its exist-
ence, temperature range of 160 to 190°C was sug-
gested.
The found character of the growth of the layers (as
well as the data of a series of sources in the literature,
indicating a similar character of the growth of the Ru
layers from other precursors and under other condi-
tions (see, for example, [4–6]), indicated the necessity
of the analysis of the initial stages of the growth of the
layers, at which the ruthenium nuclei are formed. In
this connection, in the third part of the work, I mainly
systematized the results of the performed investiga-
tions of nucleation and growth of the Ru layers on dif-
ferent surfaces of the samples, mainly in the region of
low deposition temperatures (<~200°C).
EXPERIMENTAL
The instrumental and methodical experimental
details were presented in [1, 2]. For investigations, in
this work we used an eight-step cycle for the supply of
reagents 20 s long (referred to in [1, 2] as Variant 2).
This cycle involved the following sequence of puffing
the reagents into the deposition chamber: (i) precursor
with argon, 1s; (ii) pumping, 1–3 s; (iii) argon, 1–3 s;
(iv) pumping, 1–3 s; (v) second component, 1–5 s;
(vi) pumping, 1–3 s; (vii) argon, 1–3 s; and (viii)
pumping, 1–3 s. Precursor vapors were supplied in a
mixture with argon; a bubbler was cyclically filled with
argon with a flow rate of 20 cm
3
/min (henceforth, the
consumptions are given under standard conditions) in
the time interval between the precursor pulses, i.e., for
19 s. The consumptions of blow argon and second
reagents were 50 cm
3
/min. The experiments were per-
formed with the use of the most stable portion of pre-
cursor no. 4 (see comments for revealed peculiarities
of the studied portions of the precursor in [2]). The
experiments were performed at bubbler temperatures
of 35, 45, and 55°C, which corresponded to the mea-
sured precursor consumptions of ~0.7, ~1.1, and
Low-Temperature Pulsed CVD of Thin Layers
of Metallic Ruthenium for Microelectronics and Nanoelectronics.
Part 3: Nucleation Phenomena during the Growth
of Ruthenium Layers
V. Yu. Vasilyev
Novosibirsk State Technical University, pr. K. Marksa 20, Novosibirsk, 630092 Russia
e-mail: vladislav_v_2000@yahoo.com
Received March 13, 2009
Abstract—The data on the peculiarities of nucleation and initial stages of the growth of ruthenium layers on
different surfaces in the temperature range 110–350°C under the pulsed deposition from the vapor phase with
the participation of the carbonyl–diene precursor Ru(CO)
3
C
6
H
8
, as well as NH
3
, N
2
O, and H
2
as the second
reagent are generalized.
DOI: 10.1134/S1063739710040049
MANUFACTURING PROCESSES
AND EQUIPMENT