ARTICLE IN PRESS

Journal of Crystal Growth 281 (2005) 639–645

www.elsevier.com/locate/jcrysgro

Direct nitridation of molten Al(Mg,Si) alloy to AlN

J. Haiboa, K. Chena,b, Z. Hepinga, S. Agathopoulosb,
O. Fabrichnayac, J.M.F. Ferreirab,
a
State Key Laboratory of New Ceramics and Fine Processing, Tsinghua University, Beijing 100084, PR China
b
Department of Ceramics and Glass Engineering, CICECO, University of Aveiro, Aveiro 3810-193, Portugal
c
Max-Planck-Institut fuer Metallforschung, Heisenbergstr 3, 70569 Stuttgart, Germany
Received 22 June 2004; accepted 10 April 2005
Available online 26 May 2005
Communicated by T.F. Kuech

Abstract

The growth of AlN rod-like crystals, successfully produced via direct nitridation of Al-alloy doped with 5 wt% Mg
and 2 wt% Si at 1273 K is predominantly based on capillary mass-transfer phenomena, which occur through a network
of micro-channels developed in the empty space among the AlN columnar crystals as well as the hollows inside these
crystals. The diffusion of N2 in the liquid alloy is the rate-determining step of the process. Mg and Mg3N2 resulting after
nitridation maintain a very low partial pressure of oxygen during the entire process and favour the formation of AlN.
r 2005 Elsevier B.V. All rights reserved.

Keywords: A1. Capillarity; A1. Crystal morphology; A1. Mass transfer; A1. Thermodynamics; A2. Growth from melt; B1. Alloys;
B1. Nitrides

1. Introduction There are several methods that have been

The properties of aluminium nitride, such as
high thermal conductivity, low dielectric constant,
high electrical resistance and good matching of
thermal expansion coefficient with silicon, indicate
AlN as potential material for producing substrates
and packaging materials in high-power integrated
circuits [1–3].
Corresponding author. Tel.: +351 234 370242;
fax: +351 234 425300.
E-mail address: jmf@cv.ua.pt (J.M.F. Ferreira).
developed to prepare AlN powders on an indus-
trial scale. These methods include the following: (i)
carbothermal reduction of aluminium oxide fol-
lowed by nitridation is a reliable but expensive and
time-consuming method [4]. (ii) Combustion
synthesis (CS) methods are of low cost but the
conversion degree is poor and the final product
consists of coarse particles with broad particle size
distribution [5,6]. (iii) Chemical vapour deposition
(CVD) has been attempted for preparing ultra-fine
aluminium nitride powders [7], but this method is
difficult to implement at industrial scale and the

0022-0248/$ - see front matter r 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2005.04.024
 ARTICLE IN PRESS
640 J. Haibo et al. / Journal of Crystal Growth 281 (2005) 639–645
very fine powders exhibit high chemical activity
and readily hydrolyse in humid air. (iv) Direct
synthesis of AlN powders via nitridation reactions
is a method widely used industrially but under
proprietary know-how.
This study addresses its interest to the last
production method (iv), and particularly to direct
nitridation of molten Al-alloy, doped with Mg and
Si. According to the experimental results presented
and discussed in Section 3, the production of AlN
powder through this method occurs via a mechan-
ism that actually involves the formation of AlN/Al
composites.
The approach followed was based on the
acquired technological and scientific knowledge
of producing Al2O3/Al composites via direct
oxidation of Al–Mg–Si alloys, widely known as
DIMOXTM [8–12]. According to the model of
Newkirk et al. [13], the structure of polycrystalline
Al2O3/Al composite, which comprises a randomly
developed network of micro-channels among the
Al2O3 grains, facilitates mass-transfer phenomena
of the molten alloy to the surface during produc-
tion process. Based on experimental results of
micro-structural and thermal (TGA) analysis,
Salas et al. [14] showed that the formation of a
continuous MgO-film and a non-continuous
MgAl2O4 layer on the Al-alloy surface precedes
the formation of Al2O3/Al composites. Antolin et
al. [15] showed that these protective MgO and
MgAl2O4 films could be eliminated by adding Si to
Al–Mg–Si alloys.
With regard to direct nitridation of molten Al-
alloys doped with Mg and Si alloys, the published
studies mainly address themselves to the fabrica-
tion process. In particular, Cerber et al. [16]
investigated the preparation process of AlN/Al
composites. Lehuy and Dallarie [17] analysed the
effect of additive elements (Mg and Si) on the
kinetics of nitridation reaction. The work of
Breval et al. [18] aimed at increasing the density
of AlN/Al composites. Scholz and Greil [19]
studied the influence of additive elements (Mg
and Si) in the alloy and of the oxygen content in
the furnace atmosphere on phase formation and
conversion of Al to AlN.
On the basis of experimental results, this work
proposes a mechanism of AlN crystal growth
during direct nitridation of molten Al–Mg–Si alloy.
The optimal result of this reaction should be the
complete transformation of metallic Al to high-
quality AlN, which means high purity, especially
with regard to the lowest possible contamination
with Al2O3. It is known that exposure of AlN-
powder in air results in spontaneous formation of
superficial Al2O3 [20,21], which can cause lowering
of thermal conductivity of AlN due to the low
mobility of the oxygen atoms dissolved in the lattice
of AlN [22]. On the other hand, in the light of the
production of substrates and packaging materials
for high-power integrated circuits, the presence of
Si in the final product should not seriously harm the
final properties.
2. Materials and experimental procedure
For the preparation of the Al-alloy, commercial
pure Al (99.9%) was melted in a vacuum furnace
and alloyed in situ with 5.0 wt% Mg and 2.0 wt%
Si, with respect to the resulting alloy. The molten
alloy was cast into a carbon mould. After cooling,
the alloy blocks were cut in prismatic samples of
10
10
15 mm3 in size.
Ultrasonically cleaned (in acetone) samples were
placed into alumina (purity 99.9%) crucibles
(20 mm diameter, 20 mm height). Prior heat
treatment, the furnace chamber was depleted in
oxygen by evacuating (103 mbar) and filling the
chamber with pure N2 (purity 99.999%) for three
consecutive times. Nitridation reaction took place
in a high-temperature furnace (MoSi2 heating
elements) under flown N2 atmosphere (flow rate
10 cm3/min) at 1273 K for different periods of time
(from 30 min to 10 h). The heating rate was 40 K/
min. After the experiments, cooling was either
slow inside the furnace in the protective stream of
flowing N2, or rapid by quenching (immersion of
the hot samples into cold water).
X-ray diffraction (XRD, Rigaku Geigerflex D/
Mac, C Series, Cu Ka radiation, Japan), scanning
electron microscopy (SEM, H-800, Hitachi Ltd.,
Japan), and electron probe micro-analysis
(EPMA, H-900, Hitachi Ltd., Japan) were em-
ployed to analyse the samples after the experi-
ments. For micro-structure observations, several
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J. Haibo et al. / Journal of Crystal Growth 281 (2005) 639–645 641

samples were chemically etched with HF solution

(immersion into 10 vol% HF solution for 10 min). AlN
Al

3. Results

At the end of prolonged (9–10 h) experiments, a

white coloured layer of MgO (identified by XRD)
was always adhered at the internal walls of the
furnace. Thorough investigation revealed that at 20 30 40 50 60 70 80
short nitridation times (e.g. 30 min) this adhered (a) 2θ
layer was yellowish and consisted of Mg3N2
(identified by XRD), turning itself into white
MgO over increasing time. AlN
Analysis of quenched alloys after 30 min of Si
heating showed that the Mg-concentration had
dramatically dropped down to 0.049 wt%, con-
firming that extensive volatilization of Mg rapidly
took place.
The X-ray analysis indicates that AlN forms
from the very beginning of the process but the
overall crystalline state of the alloy changes over
increasing reaction time (Fig. 1). In particular, the
20 30 40 50 60 70
peaks of Al registered at short reaction times (1 h,
( b) 2θ
Fig. 1a) were totally vanished in the prolonged
experiments (10 h), and peaks of Si were clearly Fig. 1. XRD spectra of the samples after 1 h (a), and 10 h (b)
registered (Fig. 1b). nitridation at 1273 K. (JCPDS cards: AlN: 25-1133; Al: 04-
Fig. 2 aims at presenting concisely but thor- 0787; Si: 27-1402).
oughly the general features of the micro-structure
of the alloy surface after 10 h of nitridation. Single The micro-structure observed after 10 min of
rod-like crystals have grown perpendicularly to the etching with 10 vol% HF solution (Fig. 2d) shows
surface (Fig. 2a). Cross section of this superficial that only the matter at the centre and at the brims
bunch-like bed revealed a network of parallel of the crystals was dissolved (arrow of Fig. 2d).
micro-channels formed among the rod-like crystals EPMA confirmed that the rod-like crystals consist
(Fig. 2b). This configuration represents the most of AlN, while the matter at the centre and the
usual case. However, if enough space for growth is brims is composed of Al and Si.
given, then AlN whiskers of several forms and
orientations can be formed (Fig. 2c and inset).
To shed light on the mechanism of crystal
growth, two important observations should be 4. Discussion
underlined:
(a) The AlN crystals are hollow. The hollowed The shape, the orientation and the hollow rod-
crystals form a second type of network of micro- like AlN crystals, together with the important
channels (the first type of micro-channels network finding of the liquid metallic droplets at the top of
is the one formed among the crystals). the crystals (Fig. 2) indicate that mass transfer of
(b) After cooling, solidified liquid droplets of Al liquid alloy through the network of micro-chan-
and Si (ascertained by EPMA) appear at the top of nels is the key point of the entire process, as
the AlN rod-like crystals (Fig. 2a and inset). schematically depicted in Fig. 3.
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642 J. Haibo et al. / Journal of Crystal Growth 281 (2005) 639–645

Fig. 2. AlN rod-like crystals generally grow perpendicularly to the outer surface of the Al–Mg–Si alloy during direct nitridation at
1273 K (10 h, slow cooling) (a). There is evidence of presence of liquid alloy at the top of the AlN crystals (inset of a). The columnar
AlN-crystals usually grow in parallel configuration of one to another (b and inset), but if space is given for crystal growth, then AlN
whiskers of several different morphologies can be developed (c and inset). Two types of micro-channels networks are formed: one of
the space among the AlN crystals, and the other of the hollows inside the crystals, as confirmed after etching with 10% HF acid
solution for 10 min (d).

According to this scheme, after the formation of N2

the first AlN crystals, capillary forces govern the
transfer of liquid alloy to the surface through the
micro-channels. In the opposite direction, nitrogen
diffuses into the liquid alloy. The Al mass transfer
may also occur via surface diffusion mechanism on
the walls of the AlN micro-tubes, which in such [N], [Al], [Si]
tiny configurations and at the investigated tem-
perature, may also result in a significant Al mass
transfer towards the reaction front. However, the AlN + Si AlN +Si
occurrence of capillary phenomena should be
beyond any doubt because at the investigated
temperature the viscosity of the alloy should be
very low while the size of the micro-channels fits AlN AlN
well the size of capillaries. This claim is supported
in conjunction with the fact of the good wetting + +
regime observed between the molten alloy and the
Si Liquid alloy Si
ceramic crystals of AlN (Fig. 2a).
AlN crystals should be precipitated immediately
after the concentration of the dissolved N2 Fig. 3. Schematic representation of the mechanism of the
in the Al alloy reaches the saturation point, production and the growth of the AlN rod-like crystals during
since thermodynamics (at 1273 K, DG1f;AlN ¼ direct nitridation of Al–Mg–Si alloy (see the text).
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J. Haibo et al. / Journal of Crystal Growth 281 (2005) 639–645
179:84 kJ=mol [23]) and experimental results
(Fig. 1) indicate high chemical affinity between
Al and N and fast reaction kinetics, respectively.
The formation of AlN evidently enriches the liquid
alloy in the doping metals. The experimental
results showed, however, that Mg is rapidly and
intensively evaporated. Therefore, in prolonged
experiments, the alloy will be enriched only in Si.
According to the Al–Si binary phase diagram, at
1273 K, Si crystals (Fig. 1b) should be precipitated
at concentrations higher than 45 wt% Si in the
alloy [24].
According to this mechanism, the opposite
directions of the N and Al fluxes imply that the
precipitation of AlN should occur at an interface
which must feature saturation of N in Al.
Assuming that there is a regime of steady-state
growth of AlN crystals, there must be accumula-
tion of neither Al nor N at this interface, where the
following reaction takes place:
½Al þ ½N ! AlN: (1)
Therefore, the mass flow, W, of Al and N towards
this interface must maintain the ratio
W A1 =W N ¼ 27
14, while the rate of increasing mass
of AlN, WAlN, should be related to the mass
transfer rates of Al and N according to the
following:
41 41
W AlN ¼ ; WN ¼ W Al . (2)
14 27
Earlier studies have shown that the capillary
flow rate of liquid Al significantly exceeds the
actual growth rate of AlN [25]. Accordingly, the
diffusion of N2 into the liquid alloy should be
the rate-determining step for the formation and
the growth of AlN crystals rather than the capillary
mass transfer of aluminium. However, increasing
amount of accumulated Al due to capillary flow
will reduce the overall saturation of nitrogen in the
liquid droplet. Therefore, it is suggested that a
steady state is only achieved at the vapour–liquid–
solid (VLS) interface, leading to the precipitation
of AlN along the thin walls of the micro-tubes
through a VLS mechanism [26,27], and thus
elongating the capillaries observed in Fig. 2.
To describe the mechanism of formation of
Al2O3 crystals in DIMOX, Newkirk et al. have
643
proposed a similar micro-channel model [13].
There is, however, a striking difference between
the proposed model in the case of AlN and
DIMOX (Al2O3), with regard to the mass-transfer
process through the network of the capillaries. In
the latter case (i.e. Al2O3), the network of micro-
channels is only formed among the rod-like
crystals [8], whereas in the present case of AlN
there is also a significant capillary network formed
by the hollow rod-like crystals of AlN.
With regard to the direction of crystal growth,
the VLS interface located at the walls of the hollow
AlN rod-like crystals (Figs. 2a and 3) is shifted
upwards over increasing reaction time and leads
the uniaxial crystal growth. It has been shown that
the c-axis is the dominating growth direction of the
AlN crystals grown perpendicularly to the surface
h0 0 0 1i [19]. In the case of DIMOX, Al3O2
crystals are grown along the h0 0 1i direction [13].
The presence of Mg thermodynamically favours
the formation of AlN. The experimental results
showed that Mg was rapidly (i.e. in the first 30 min
of the reaction) and intensively (i.e. dramatic
decrease of Mg concentration) evaporated from
the alloy. These findings agree fairly well with
earlier studies reporting that the ratio of the partial
pressure values of the three metals involved in this
study at 1273 K is PMg =PAl =PSi ¼ 106 =1=103 [28].
Our experimental results showed that after
evaporation, Mg reacted with N2 to form Mg3N2
(yellowish layer adhered at the walls of the furnace
chamber), turning progressively itself into MgO
(white layer) over prolonged experiments, plausi-
bly according to the following:
3Mg þ N2 ! Mg3 N2 ; (3)
2Mg3 N2 þ 3O2 ! 6MgO þ 2N2 : (4)
The partial pressure of O2 at the equilibrium
state of,
2Mg þ O2 # 2MgO; (5)
which is the sum of Eqs. (3) and (4), at 1273 K can
be estimated as 1038 atm, according to the
Ellingham diagrams. This low value of PO2
indicates the important role of Mg-evaporation
in deoxidation of furnace atmosphere and the
formation of AlN. In particular, the partial
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644 J. Haibo et al. / Journal of Crystal Growth 281 (2005) 639–645

pressure of oxygen at the equilibrium state of in the range of 5.57
1023 atm4Po2 4
1:19
1025 atm, the stable assemblage is Al2O3
Al2 O3 þ N2 #2AlN þ 32 O2 ; (6)
(0.96 mol) and b-sialon (0.04 mol). The gas phase
calculated by mostly consists of N2. Next abundant species are
" !#2=3 SiO and NO (PSiO ¼ 8:6
1010 atm and
DG0f PNO ¼ 2:56
1015 atm, at Po2 ¼ 1
1023 atm).
PO2 ¼ PN2 exp  , (7) At Po2 o1:19
1025 atm, the stable phase assem-
RT
blage is AlN (0.96 mol) and b-sialon (0.06 mol).
is PO2 ¼ 1:16
1025 atm at 1273 K. (For the The gas phase consists mainly of N2 with next
calculations we have neglected the slight abundant species SiO, Al and NO (PSiO ¼ 4:4

N2-overpressure in the chamber due to the 1011 atm, PAl ¼ 6:3
1015 atm and PNO ¼ 2:6

flown N2, assuming PN2 1 atm; DG f;Al2 O3 ¼ 1016 atm). Therefore, the calculations show that
1271:16 kJ=mol [29] and DG f;AlN ¼ 179:84 kJ= AlN forms in very reducing atmosphere at
mol [23], so DGr;eqð6Þ ¼ 911:5 kJ=mol.) This value is Po2 o1:19
1025 atm with gas phase mainly
several orders of magnitude higher than the containing N2 and very low amount of other
pressure anticipated at the equilibrium state of species.
Eq. (5) (i.e. 1038 atm51:16
1025 atm). More-
over, owing to the fact that the molten alloy is
rapidly depleted of Mg (even after 30 min), the
5. Conclusions
synthesis of AlN and the absence of Al2O3 in the
X-ray spectra in prolonged experiments (9–10 h,
AlN rod-like crystals were successfully grown
Fig. 1b) should be attributed to the continuous
via direct nitridation of Al–Mg–Si alloy at 1273 K.
deoxidation which occurs due to the oxidation of
AlN columnar crystals developed in a parallel
Mg3N2, according to Eq. (4). However, the rate of
configuration, perpendicularly to the outer surface
reaction and probably the nature of the products
of the molten alloy, forming two types of porous
should change over reaction time as Mg is
networks: one among the AlN crystals and the
consumed or might be kinetically inhibited from
other comprising the micro-channel of the hollow
reacting sufficiently rapid due to the formation of
rod-like crystals. Capillary forces should predomi-
reaction products. Moreover, the reduction of
nantly drive mass transfer of liquid Al-alloy
oxygen partial pressure is system specific: If small
through the micro-channels to form droplets at
amount of reactants were hypothetically put inside
their top. The reaction front is located at the
a large chamber with infinite volume, then the
growing walls of the hollow AlN rod-like crystals
evaporated Mg would cause a negligible reduction
leading to uniaxial crystal growth. The experi-
of oxygen partial pressure. Calculations of phase
mental results in conjunction with earlier studies
relations in the Si-Al-O-N system at 1273 K have
indicate that the diffusion of N2 in the liquid alloy
been performed using thermodynamics database
is seemingly the rate-determining step of the
for solid and liquid phases from [30] and gas phase
process. Mg plays a key role on reducing the
from the SGTE database [31] including N2, O2,
partial pressure of oxygen in the furnace chamber
SiO, SiO2, NO, AlO, Al2O, Al2O2, AlO2 and other
during the entire process favouring the formation
species. The calculations indicate that gas phase
of AlN and suppressing the formation of Al2O3.
consists mainly of N2. At partial pressure of
oxygen Po2 45:57
1023 atm, the stable phase
assemblage is Al2O3 (0.86 mol) and mullite
(0.14 mol); the gas phase contains small amounts Acknowledgement
of SiO and other species (PSiO ¼ 2:5
109 atm,
PNO ¼ 6:06
1015 atm). Al2O and other sub- The financial support of the Foundation of
oxide species form in remarkably lower amounts Science and Technology (FCT) of Portugal is
(less than 1020 atm). At partial pressure of oxygen gratefully acknowledged.
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J. Haibo et al. / Journal of Crystal Growth 281 (2005) 639–645
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