Thin Solid Films 519 (2011) 5539–5543

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

Effect of thermal cycling on the adhesion strength of Ti/Ni/Ag films on AlN substrate
Wei-Luen Jang, Tsung-Chieh Chiu ⁎, Kwang-Lung Lin
Department of Materials Science and Engineering, National Cheng Kung University, Tainan 70101, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: The adhesion strength of Ti/Ni/Ag multi-layers on AlN substrates before and after thermal cycling treatment
Received 29 June 2010 was studied. The Ti/Ni/Ag layers with thicknesses of 0.6, 1.0, and 0.2 μm, respectively, were deposited
Received in revised form 11 February 2011 sequentially on bulk AlN substrates using direct current (DC) sputtering. Thermal cycling test (TCT) was
Accepted 16 February 2011
conducted for 0, 15, 100, and 300 cycles to measure the adhesion strength of Ti/Ni/Ag on AlN. The adhesion
Available online 24 February 2011
strength of the deposited specimen increased slightly over 15 thermal cycles and increased abruptly after 100
Keywords:
thermal cycles. After 100 thermal cycles, Ti reacted with AlN substrate to form TiN and TiO. The formation of
Adhesion strength TiN and TiO at the Ti/AlN interface may be responsible for the increase of the adhesion strength after a large
Ti/Ni/Ag number of thermal cycles.
AlN © 2011 Elsevier B.V. All rights reserved.
Thermal cycling test

1. Introduction Ni protection layer and as a layer appropriate for silver epoxy die
attachment.
Light-emitting diodes (LEDs) are an important light source in many AlN is a potential candidate for the submount material for the flip-
applications due to their small size, long life time, and low power chip technique because its high heat transfer coefficient is higher than
consumption. Introduced as a practical electronic component in 1962 that of sapphire [12,13]. However, the mechanical properties of AlN
[1], early LEDs emitted low-intensity red light. Modern versions are substrates with metallization prior to soldering have rarely been
available across the visible, ultraviolet, and infrared wavelengths, with reported. In the present study, Ti/Ni/Ag films are deposited on AlN
very high brightness. Research priorities for LED devices are high power substrates and the adhesion strength of the deposited specimens is
and high luminous efficiency. Heat dissipation is thus a critical issue. measured under thermal cycling test prior to soldering. The adhesion
High temperature in high-power devices decreases the luminous strength of the deposited specimens is investigated to evaluate the
efficiency and expected life time [2]. application and feasibility of AlN substrates with Ti/Ni/Ag for the flip-
Sapphire is currently the most widely used substrate for LED devices. chip technique.
However, the heat transfer coefficient of sapphire is too low for high-
power LED devices. Recently, a flip-chip technique was used for heat
dissipation [3]. The heat generated in devices is transferred to a
submount through a flip-chip solder bump. The application of the flip-
chip technique to high-power diodes decreases the temperature and
improves the luminous efficiency [3]. Ohmic metallization is also an
important factor in luminous efficiency. Titanium base metal, alumi-
num, and gold have been used for ohmic metallization. It has been found
that titanium base metal has the lowest specific contact resistance,
which can improve the luminous efficiency of LED devices [4–9]. Ti/Ni/
Ag thin films were widely used for metallization [10,11]. The Ti layer
forms an adherent bond to the substrate and acts as a diffusion barrier,
preventing the intermixing of Ni and the substrate element. The Ni layer
generally acts as a surface that is convenient for soldering and as a
barrier layer between the base metal and solder. The Ag layer serves as a

⁎ Corresponding author. Tel.: +886 6 2757575x62929; fax: +886 6 2759602.

E-mail address: longman@mail.mse.ncku.edu.tw (T.-C. Chiu). Fig. 1. Microstructure of the as-sintered AlN substrate.

0040-6090/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.02.052
5540 W.-L. Jang et al. / Thin Solid Films 519 (2011) 5539–5543

Fig. 2. Fracture surfaces of (a) TCT 15 and (b) TCT 100 specimens.

2. Experimental details
AlN substrates (1 cm × 1 cm × 0.66 mm) were prepared using
powder sintering with Y2O3 as the sintering aid. Ti, Ni, and Ag films
were deposited sequentially on AlN substrates using direct current (DC)
sputtering (3-inch targets, 99.99%). Before the deposition of materials
on AlN, the substrates were sputter-etched to remove contaminants.
The working pressure was 1.07 Pa under an Ar atmosphere. The output
power was 150 W and the film thicknesses of Ti, Ni, and Ag were
controlled to be 0.6, 1.0, and 0.2 μm, respectively.
Deposited specimens underwent the thermal cycling test (TCT) to
evaluate the adhesion ability of Ti/Ni/Ag on AlN. For the thermal cycling
test, the specimens were cooled to −40 °C and then heated to 125 °C.
The dwell times for the maximum and minimum temperatures were
both 15 min. The cooling and heating rates were controlled at 11 °C/
min. The procedure mentioned above was defined as one cycle. The
numbers of thermal cycles were 0, 15, 100, and 300, respectively.
The pull-off test is widely used to measure the interfacial adhesion
strength [14–16]. In the present study, the specimens were adhered to
an Al stud with a diameter of 0.27 cm; the strength of the epoxy on the
Al stud was 70 MPa. The pull-off test instrument applied a force to the
Al stud at 89.0 N/s and stopped automatically when the Al stud
separated from the specimen. The adhesion strength of the deposited
film was recorded on a computer.

Fig. 3. XPS depth profiles of (a) as-prepared, (b) TCT 15, (c) TCT 100, and (d) TCT 300 specimens.
 W.-L. Jang et al. / Thin Solid Films 519 (2011) 5539–5543 5541

A conventional stylus surface-roughness detector (AlphaStep 200) attributed to the strengthening of the bond strength between the Ti
was used to measure the film thickness. The surface morphologies and layer and the AlN substrate, as discussed later.
fracture planes were observed using a field-emission scanning Fig. 3 shows the XPS depth profiles of the specimens before and
electron microscope (FE-SEM, JEOL JSM-6700F, 10 kV beam voltage) after thermal cycling test. Oxygen was detected in the Ti layer and the
equipped with an energy-dispersive X-ray spectrometer (EDS, AlN substrate for the as-prepared specimen, as shown in Fig. 3(a).
Oxford). Glancing incident angle X-ray diffraction (GIA-XRD) mea- Titanium is an excellent getter material for absorbing oxygen due to
surements for film crystallography were carried out to identify the its high oxygen affinity. The oxygen detected in the as-deposited Ti
types of phase using a thin film diffractometer (Rigaku D/MAX2500) layer is believed to be due to the reaction between Ti and residual
with monochromatic Cu Kα radiation. The composition profile and oxygen in the vacuum chamber during the deposition process.
chemical bonding state of the deposited specimens were measured by However, the signals of oxygen in the AlN substrate may come from
X-ray photoelectron spectroscopy (XPS, PHI 5000 VersaProbe) with the constituent of the sintered substrate that is composed of AlN and
monochromatic Al Kα radiation. The absolute binding energies of AlYO3, as shown in Fig. 1. In addition, the atomic percent of oxygen
deposited films were calibrated using C 1s line at 284.8 eV. slightly increased in the Ti layer after thermal cycling test. According
to the phase diagrams of titanium and oxygen [23], the solubility of
3. Results and discussion oxygen in α-Ti is large (~30 at.%). As a result, the increase of oxygen
concentration in the Ti layer can be attributed to the thermal energy of
Fig. 1 shows the backscattered electron image (BEI) of the as- cycle treatment accelerating the out-diffusion of oxygen atoms from
sintered AlN substrate without Ti/Ni/Ag deposition. The dark region is the AlN substrate. In addition to the diffusion of oxygen in Ti, the
the AlN matrix and the white particles are AlYO3, as identified by EDS overlapping region between Ni and Ti was found to broaden after
and GIA-XRD. The presence of the sintering aid resulted in the thermal cycling test, as shown in Fig. 3. According to the Ni–Ti binary
formation of a liquid phase during sintering, which eventually phase diagram, several types of intermetallic compounds (IMC) and
crystallized. The formation of AlYO3 distributed randomly in the AlN solid solutions form between Ni and Ti under isothermal aging [24].
substrate can be attributed to the reaction between AlN and liquid The XPS depth profile demonstrates that the broadened overlap
Y2O3 during the sintering process [17]. In addition, the surface of the region between Ni and Ti is a result of the interdiffusion that occurred
AlN substrate is not smooth, as shown in Fig. 1. between Ni and Ti despite the low temperature of the thermal cycling
From the pull-off test, the adhesion strengths of the as-prepared, test. It has been reported that the diffusivity of Ni in Ti is higher than
TCT 15, TCT 100, and TCT 300 specimens were measured to be 4.45, that of Ti in Ni [25]. The results of XPS depth profile, shown in Fig. 3,
6.47, 52.47, and 51.91 MPa, respectively. The adhesion strength also reveal that the diffusion of Ni into the Ti layer is more significant
increased with the number of cycles in the test. In particular, the than that of Ti into the Ni layer under thermal cycling test.
adhesion strength increased abruptly after 100 cycles of the test. The Fig. 4 shows the GIA-XRD patterns of the specimens with and
results of adhesion strength indicate that the reliability of the without thermal cycling test. The overall patterns are quite similar
deposited specimen increased after 100 thermal cycles. Accordingly, with corresponding phases of Ag, Ni, AlYO3, and AlN. No signals of
the interfacial bonding may be strengthened after 100 thermal cycles. interfacial compounds and the Ti layer were observed in the GIA-XRD
Fig. 2 shows the fracture morphology of TCT 15 and TCT 100
specimens after the pull-off test. The fracture plane of TCT 15 was
found at the interface between the AlN substrate and the Ti layer, as
shown in Fig. 2(a). The fracture behavior of the as-prepared specimen
(not shown) was quite similar to that of TCT 15; their adhesion
strengths are very similar. For TCT 100 and TCT 300 (not shown)
specimens, two types of interface were found on the fracture plane, as
shown in Fig. 2(b). Most of the fracture was found not at the Ti/AlN
interface, but at locations between the epoxy and Al stud, with a small
proportion of the fracture occurring at the Ti/AlN interface, as shown
in Fig. 2(b). A bare fracture surface of AlN after the pull-off test for the
as-prepared or TCT 15 specimen was observed, as shown in Fig. 2(a).
This occurrence suggests that the fracture may have begun at the Ti/
AlN interface and then propagated along it after the pull-off test,
resulting in the specimen without the thermal cycling test having the
lowest value of adhesion strength. However, for specimens TCT 100
and TCT 300 after the pull-off test, the Ti/AlN interface exhibits strong
bonding such that most of the interfaces withstand the pull test. The
pull fracture mainly occurs at the Al stud/epoxy interface. According-
ly, it is believed that interaction exists between Ti and AlN after
thermal cycling test.
The results show that the weakest bond was obtained for the
specimen without the thermal cycling test. In general, the mechanical
properties decrease and the electrical resistance increases for solder
joints that undergo the thermal cycling test [18–21]. The adhesion
strength of an as-reflowed specimen is usually higher than that of a
joint that undergoes thermomechanical stressing [19]. Cracks that
form in the matrix or at the interface are responsible for weak joints
after thermal cycling stressing [18,19,22]. However, the results of the
present study reveal the opposite phenomenon; the specimen that
underwent thermal cycling stressing exhibited better adhesion
strength than that of the as-prepared specimen. The significant Fig. 4. GIA-XRD patterns of (a) as-prepared, (b) TCT 15, (c) TCT 100, and (d) TCT 300
increase of adhesion strength after 100 thermal cycles may be mainly specimens.
5542 W.-L. Jang et al. / Thin Solid Films 519 (2011) 5539–5543

patterns. In this study, the peak temperature of the thermal cycling energies of AlN and TiN at 300 K have been reported as −276.303 kJ/
test was only 125 °C. For the deposited films on the AlN substrate, this mol and − 299.341 kJ/mol [27], respectively. Accordingly, it is
temperature may be too low to allow the formation of a thick possible for Ti to react with AlN to form TiN during thermal cycling
compound. Thin interfacial compounds formed at the Ti/AlN interface, test. The formation of TiN or TiO compounds at the Ti/AlN interface
as indicated by the XPS depth profile in Fig. 3. Furthermore, the increases the bond strength of the specimen. Therefore, the adhesion
thickness of the residual pure Ti layer was less than 0.6 μm after the strength increased after 100 thermal cycles.
thermal cycling test. The surface morphology of the AlN substrate is
rough, which may scatter the signals and lower the intensity of Ti
4. Conclusion
detected by GIA-XRD. As a result, the thin interfacial compounds and
residual Ti layers and the signals scattered by the geometry of the AlN
The adhesion strength of Ti/Ni/Ag films on AlN substrates before and
substrate may result in the absence of intensities in the GIA-XRD
after thermal cycling test was studied. The adhesion strength signifi-
patterns.
cantly increased with increasing number of thermal cycles. The fracture
In addition, the out-diffusion of oxygen in Fig. 3 implies the
behaviors of the as-prepared and TCT 15 specimens were similar; the
interaction between the Ti layer and the AlN substrate under thermal
fractures were mostly found at the interface between the Ti layer and
cycling test. To study this phenomenon in detail, the chemical
the AlN substrate. After 100 thermal cycles, Ti tended to react with AlN
bonding state of Ti was investigated. Fig. 5 shows the Ti 2p1/2 and
to form interfacial TiN and TiO, resulting in an increase in adhesion
2p3/2 core level spectra of the deposited specimens for various etching
strength. Therefore, the combination of Ti/Ni/Ag on AlN may be suitable
times. The intensity of all XPS spectra decreases with increasing
for flip-chip application after prolonged thermal cycling test.
etching time, which indicates that the Ti content decreases with
depth. For the as-prepared and TCT 15 specimens, the positions of Ti
2p1/2 and 2p3/2 peaks do not obviously change in the spectra. Acknowledgment
However, the positions of Ti 2p1/2 and 2p3/2 peaks for TCT 100 and
TCT 300 move to significantly higher binding energies with increasing The authors would like to thank the National Science Council of
etching time. In Fig. 5(d), the position of Ti 2p3/2 shifts to about Taiwan for financially supporting this research under grant NSC 98-
457 eV, which can be identified as TiN or TiO [26]. The formation 2627-E-006-002.

Fig. 5. XPS Ti 2p1/2 and 2p3/2 core level spectra of deposited films for various etching times.
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