ISSN 1063-7397, Russian Microelectronics, 2017, Vol. 46, No. 2, pp. 75–81. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © D.G. Gromov, S.V. Bulyarskii, S.V. Dubkov, A.A. Pavlov, S.N. Skorik, A.Yu. Trifonov, A.S. Shulyat’ev, Yu.P. Shaman, E.P. Kitsyuk, A.A. Dudin,
A.P. Sirotina, S.A. Gavrilov, 2017, published in Mikroelektronika, 2017, Vol. 46, No. 2, pp. 83–90.
CVD-Growth of CNT with the Use of Catalutic Ct–Me–N–O
Thin Films Incorporated in the Technology
D. G. Gromov
*, S. V. Bulyarskii
**, S. V. Dubkov
, A. A. Pavlov
, S. N. Skorik
, A. Yu. Trifonov
A. S. Shulyat’ev
, Yu. P. Shaman
, E. P. Kitsyuk
, A. A. Dudin
, A. P. Sirotina
, and S. A. Gavrilov
MIET National Research University of Electronic Technology, Zelenograd, Russia
Institute for Nanotechnology of Microelectronics RAS, Moscow, 119991 Russia
Research and Manufacturing Complex Technology Center MIET, Moscow, Zelenograd, 124498 Russia
Lukin R&D Institute of Physical Problems, Zelenograd, Russia
Received July 4, 2016
Abstract⎯The process of the formation of carbon nanotube arrays on Ct–Me–N catalytic alloys of low
nickel content (10–20 at %) by chemical vapor deposition, where Ct is a catalytic metal from the group of Ni, Co,
Fe, and Pd, and Me is a transition metal of group IV–VII of the periodic table, was investigated. It is shown that
CNT grow effectively when the alloy contains Ti, V, Cr, Zr, Hf, Nb, and Ta. The addition of nitrogen and oxygen
to the alloy’s composition gives rise to a buildup of oxynitrides, expelling of the catalyst, and formation of its clusters
on the surface. The replacement of metals in the alloy has an effect on the diameter of the CNT. Moreover, the
alloy films 10–500 nm thick can be used for the CNT growth, which is responsible for high degree of homogeneity
and the repeatability of the process. CNT growth was not observed when the alloy contained W and Re.
The carbon nanotubes discovered by Iijima almost
25 years ago , still attract significant attention of
scientists and remain among the advanced nanomate-
rials. The unique structure of the carbon nanotubes is
responsible for their specific mechanical, physical,
and electrical properties in combination with their
chemical inertness. The unusual properties of this
material have opened new attractive areas of research
in nano- and microelectronics .
Chemical vapor deposition (CVD) in which the
hydrocarbons are thermally and under the action of
plasma (PECVD) decomposed over a metal catalyst is
the most technologically attractive method for micro-
electronics technology among the existing methods
used to form CNT. In this case, the growth of CNT
takes place on the site-specific areas of the solid-phase
surface and at lower temperatures, especially in the
case of the stimulation of this process by plasma
(~350°C). It has a capacity for using the hydrocarbons
in any state (solid, liquid, or vapor) and deposition of
carbon structures onto the substrates of any type [3, 4].
The metals of group VIII of the periodic table, for
example, Fe, Ni, or Co, are used as the catalysts .
There are also reports of using alloys of these catalysts
with other metals in which, however, the content of
the catalysts is always most abundant [3–8]. In such a
case, an auxiliary noncatalytic metal in the alloy makes
an impact upon the process of CNT growth and, among
other things, upon the diameter of the tubes.
Recently it was shown that an array of multiwall
carbon nanotubes can be formed on a thin film of the
catalyst-containing Co–Zr–N–O amorphous alloy
with a low (~15 at %) content of Co . A specific
character of this process is that the process can be per-
formed on films of the Co–Zr–N–O alloy of various
thicknesses, which makes it technologically attractive.
It was demonstrated in this report that a similar
process can also be performed on a number of alloys of
the catalyst with other transition metals and with met-
als of group V–VII of the periodic table. This process
depends on a wide range of factors that allow con-
trolling the parameters of the CNT arrays such as
height, density, and diameter.
The (100) silicon substrates coated by thermally
were used to manufacture the samples.
The substrates were standardly rinsed in Caro’s solution
= 1 : 1) and then flushed with deionized
water and dried by the fumes of isopropyl alcohol.
Layers of the Ct–Me–N alloys with thicknesses
ranging from 10 to 500 nm, with the catalytic metal