THE SPRAY DEPOSITION OF TRANSITION METAL NITRIDE THIN
FILMS USING ALCOHOL BASED PRECURSOR SOLUTIONS
K.S. WEIL AND P.N. KUMTA
Department of Materials Science and Engineering, Carnegie Mellon University,
Pittsburgh, PA 15213
ABSTRACT
A new alcohol solution based approach has been developed for preparing transition
metal nitride thin films and coatings. In this technique, the metal of interest is dissolved as a
chloride in acetonitrile, then chelated with triethanolamine to form a highly viscous solution
which settles out of the solvent phase. The acetonitrile is then evaporated off and the
remaining thick liquid precursor is easily diluted with water or methanol, yielding a semi-
viscous liquid which can be used directly to coat various substrates. When heat treated under
the appropriate conditions in ammonia, the precursor coating transforms to yield the
corresponding nitride. This approach is currently being considered for preparing nitride-
based thin film electrical components and has been successfully used thus far to spray deposit
TaN and NbN nitride films onto silicon substrates. Results of the preliminary study on these
two nitride films are discussed in this paper.
INTRODUCTION
Transition metal nitride materials, such as TiN, ZrN, and Fe4N are important in a
wide range of applications including wear and corrosion resistant coatings, high-temperature
structural components, and magnetic storage devices. However, the most immediate use of
transition metal nitrides may depend on their electrical properties. Thin tantalum nitride and
niobium nitride films are of particular interest. Tantalum nitride films are used extensively in
microelectronic applications such as in resistors and capacitors because of their low thermal
coefficients of resistance and stable resistance values under long term operating conditions
(1). The 8 phase of NbN is a type II superconductor with a useful T, of 17.3 K and high
breakdown current value, and it has found important applications in devices such as dc-
superconducting quantum interference devices, Josephson junctions, and switches for pulsed
power applications (2).
In recent years, a number of synthesis techniques have been developed for preparing
transition metal nitride coatings and films. These include: reaction sputtering (3), laser
ablation (4), the ammonolysis of sol-gel derived spin coated films (5), and thermal
decomposition of [(CH
3
)
3
Si]
2
NH based compounds (6). Synthetic approaches based on
liquid precursor techniques may offer several advantages over line of sight physical film
deposition methods, such as sputtering, including the opportunity to better control the
stoichiometry and microstructure of nitride thin films. We have recently demonstrated a new
solution based approach which offers the potential to synthesize a number of ternary
transition metal nitride powders (7,8). The focus of the present study is to demonstrate the
utility of this approach in preparing nitride thin films for electronic device applications. The
process involves dissolving a metal chloride in acetonitrile and chelating the metal species
with an alkanolamine complexing agent to form a liquid precursor. Depending on the choice
of the alkanolamine, this liquid can be further modified to prepare precursors for generating a
nitride powder or coating. Precursors for the powders, for example, are prepared using a low
molecular weight bidentate chelating agent, such as ethanolamine, followed by subsequent
hydrolysis to form a metallo-organic hydroxide precipitate which can be filtered and dried.
Thin film precursors, on the other hand, can be prepared by chelating the transition metal
chloride species with a higher molecular weight alkanolamine, such as triethanolamine. The
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Mat. Res. Soc. Symp. Proc. Vol. 495 © 1998 Materials Research Society