Fabrication of Aluminum Nitride Coating by Atmospheric Plasma Spray

M. Yamada1, M. Shahien2, T. Yasui1, M. Fukumoto1

1
Toyohashi University of Technology, Toyohashi, Aichi, Japan
2
Graduate student, Toyohashi University of Technology, Toyohashi, Aichi, Japan

Abstract: Reactive plasma spraying is a promising process upon fabrication of thick alumi-
num nitride coating. In this study, aluminum nitride based coatings were fabricated by reac-
tive plasma spraying with using atmospheric DC plasma and aluminum metal powder as
feedstock material. It was possible to fabricate cubic structured aluminum nitride based coat-
ing without containing the oxide.

Keywords: Plasma spray, Aluminum nitride, Atmospheric plasma, Nitriding reaction

1. Introduction The particles are quasi-spherical shape. Blasted soft steel

Aluminum nitride (AlN) has emerged as an important (SS400) plates were prepared as substrate. The substrate
material with its outstanding properties such as high was reciprocated by X-Y drive system to form uniform
thermal conductivity (180-220 W/m• K sintered com- thickness coating.
pacts), low thermal expansion (the value is similar to sili- The existence of AlN in the deposited coating was veri-
con) and high resistance of halogen plasma. AlN is appli- fied by X-ray diffraction (XRD: RINT-2500, Rigaku) with
cable for heat sink, semiconductor equipment and several CuKα radiation. Cross section microstructure of the coat-
structural and electrical components. Especially, thermal ings was observed by scanning electron microscope
sprayed AlN coating is expected to apply to reaction ves- (SEM: JSM-6390, JEOL). The hardness of the coatings
sel of CVD and etching which is a part of semiconductor was examined by micro Vickers hardness tester (HMV-1,
equipment. In these applications, thermal sprayed AlN SHIMADZU).
coating is required. However, it was impossible to fabri-
cate AlN coating by conventional thermal spray processes
Al Powder
due to thermal decomposition of AlN particles during
Powder
spraying. Therefore, fabrication of AlN including com-
Powder Plasma
posite coatings has been studied in order to obtain high feeder H2O stream
thermal conductivity ceramic coatings [1-4].
Plasma
In our previous studies, it was possible to fabricate AlN -
Unit
based coating by reactive plasma spraying with using +
radio frequency (RF) plasma spray equipment [5-7]. H2O Coating
Ar
However, it was difficult to fabricate dense coating due to
or Water-cooled Substrate
low particle velocity in the RF plasma spray system. Fur- N2
H2 N2 Cathode Insulator
anode
thermore, the RF plasma spray was carried out in vacuum
ambient. The particle velocity of RF plasma spray is Fig. 1 Schematic diagram of APS system.
much lower than that of DC plasma spray [8]. In this
study, AlN coating was fabricated by Atmospheric DC
Plasma Spray system (APS) with using reaction between
feedstock Al powder and nitrogen plasma. Feasibility of
fabrication of AlN coating by APS and the influence of
spray parameters were investigated.

2. Experimental Procedure
All experiments were carried out by atmospheric
plasma spray system (APS: 9MB, Sulzer Metco), using
primary gas of N2 and secondary gas of H2. The schematic
diagram of APS system is shown in Fig. 1. Feedstock
powder is supplied with carrier gas of Ar or N2. Typical
20μm
spray conditions are shown in Table 1. Pure aluminum Fig. 2 Morphology of feedstock powder.
powder (average particle size of 30µm) was used as feed-
stock powder. The feedstock powder is shown in Fig. 2.
 Table 1 Typical spray conditions Al
(a)
Primary gas : Pressure (psi) 48 c-AlN
(N2) : Flow rate (l/min) 100
Secondary gas : Pressure (psi) 50
(H2) : Flow rate (l/min) 5
Spray distance (mm) 150, 200, 300
Carrier gas: flow rate (l/min) Ar or N2:1
Substrate material SS400

(b)
3. Results and Discussion
3.1 Influence of Spray Distance
XRD spectra of the coatings fabricated with different
spray distance are shown in Fig. 3. It indicates that the
coatings consist of Al and cubic-AlN phases. Furthermore,

Intensity (arbit.unit)
in the case of 200 and 300 mm of spray distance, c-AlN
based coating was fabricated. It became clear that fabrica-
tion of AlN based coating by APS using reaction between
Al feedstock powder and N2/H2 plasma. Generally, alu-
minum nitride forms hexagonal structure. It is considered (c)
that the c-AlN in the coatings was formed due to the rapid
cooling of sprayed particles at the collision to the sub-
strate surface. The concentration of the nitride phase was
increased with the spray distance. It is considered that the
sprayed particle velocity of APS system is much higher
than RF plasma spray system which has the experience of
fabrication of AlN coating. If the nitriding reaction of
sprayed particles occurred during flight in the plasma,
longer spray distance is better for the reaction. It is con-
sidered that the nitriding reaction of sprayed particles on (d)
APS system occurred during flight in the plasma and en-
hanced in longer spray distance, consequently. However,
the concentration of AlN phase was almost same in the
case of spray distance of 200 and 300 mm. It means that
the nitriding reaction of flight particles is finished around
the spray distance of 200 mm.
Cross section microstructures of the coatings fabri- 35 40 45
cated with different spray distance are shown in Fig. 4. Diffraction angle, 2θ (CuKα)
The thickness of the coating fabricated with the spray
Fig. 3 XRD spectra of feedstock powder (a) and coatings
distance of 150 mm was approximately 100 μm. The
hardness of the coating was 540 Hv which is much higher fabricated with carrier gas of Ar and spray distance of (b)
than Al i.e. AlN phase in the coating increased the hard-
150 mm, (c) 200 mm and (d) 300 mm.
ness of the coating. Therefore, it was possible to fabricate
thick Al/AlN composite coating with dense microstructure
by APS. However, the thickness of the coatings decreased Therefore, the sprayed particle which completely reacted
with increasing of the spray distance. The sprayed parti- during flight could not deposit on the substrate. Increasing
cles deviated from the substrate by increasing the spray of the spray distance enhances the nitriding reaction. Thus
distance i.e. the deposition efficiency of sprayed particles the deposition efficiency of sprayed particles was de-
was decreased with spray distance. It was also considered creased with increasing of spray distance. In order to ob-
that the particles which completely reacted during flight tain AlN based thick and dense coating, spray distance
in the plasma. Molten or semi-molten particles are re- should be mentioned. The optimum spray distance in this
quired in order to deposit on the substrate in thermal spray study was 200 mm.
process. However, AlN does not have the molten phase.
 (a) (b) (c)

Fig. 4 SEM images of coatings fabricated with carrier gas of Ar and spray distance of (a) 150 mm, (b) 200 mm and
(c) 300 mm.

3.2 Influence of Carrier Gas

The influence of carrier gas species was investigated
with changing from Ar to N2. Cross section microstruc-
ture of the coating fabricated with using N2 for the carrier
gas is shown in Fig. 4. The thickness of the coating was
approximately 50 μm. It was possible to fabricate thick
coating with using N2 for carrier gas. The hardness of the
coating was 1020 Hv. It was similar as the hardness of
sintered AlN bulk. It means that the metal Al particles
were almost completely transformed into ceramic coating
in this process.
XRD spectrum of the coating is shown in Fig. 5. The
coating included oxide (Al2O3) phase, however, the coat- Fig. 4 SEM image of coating fabricated with carrier
ing consisted of completely c-AlN. It indicates that the N2 gas of N2 and spray distance of 100 mm.
gas as the carrier gas enhanced the nitriding reaction of
the sprayed particles during flight in the plasma.

4. Conclusions c-AlN
AlN coating was fabricated by reactive atmospheric Al2O3
plasma spray process with using Al feedstock powder and
Intensity (arbit.unit)

N2/H2 plasma. The following results were obtained in this

study.
1) It was possible to fabricate thick and dense cubic AlN
based coating by APS system.
2) Increase of spray distance enhanced the nitriding re-
action of sprayed particles during flight.
3) Increase of spray distance decreased the deposition
efficiency of sprayed particles and the thickness.
4) Carrier gas species affect to the nitriding reaction
during flight of the sprayed particles.
5) Thick c-AlN based coating with high hardness was 35 40 45
successfully fabricated with using N2 as the carrier Diffraction angle, 2θ (CuKα)
gas.
Fig. 5 XRD spectrum of coating fabricated with car-
Acknowledgment rier gas of N2 and spray distance of 100 mm.
This research was supported partly by Research for
Promotiong Technological Seeds in Japan Science and
Technology Agent.
[2] L.R. Krishna, D. Sen, Y.S. Rao, G.V.N. Rao and G.
References Sundararajan, J. Mater. Res., 17-10 (2002) 2514-2523
[1] H. Yang, W. Luan and S.-T. Tu, Mater. Trans., 47-7 [3] A. Ohmori, M. Wakamatsu and K. Kamada, Trans.
(2006) 1649-1653 JWRI, 22-2 (1993) 227-232
[4] F. Kassabji, F. Tourenne, A. Derradji and P. Fauchais, [7] M. Yamada, C.C. Lee, T. Yasui, M. Fukumoto and K.
Proc. 10th ITSC, 80 (1983) 82-84 Takahashi, Proc. ISPC-18 (2007) CD
[5] M. Yamada, H. Nakamura, T. Yasui, M. Fukumoto [8] P. Fauchais, A. Vardelle and A. Denoirjean, Surf.
and K. Takahashi, Mater. Trans., 47-7 (2006) Coat. Technol., 97 (1997) 66-78
1671-1676
[6] M. Yamada, T. Yasui, M. Fukumoto and K. Takahashi,
Thin Solid Films, 515 (2007) 4166-4171