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Electrical and microstructural properties of thermally annealed Ni/Au and

Ni/Pt/Au Schottky contacts on AlGaN/GaN heterostructures

Article  in  Semiconductor Science and Technology · July 2014

DOI: 10.1088/0268-1242/29/9/095005

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 Semiconductor Science and Technology

Semicond. Sci. Technol. 29 (2014) 095005 (10pp) doi:10.1088/0268-1242/29/9/095005

Electrical and microstructural properties of

thermally annealed Ni/Au and Ni/Pt/Au
Schottky contacts on AlGaN/GaN
heterostructures
Benedict Ofuonye1, Jaseun Lee1, Minjun Yan1, Changwoo Sun2,3,
Jian-Min Zuo2 and Ilesanmi Adesida1,2
1
Micro and Nanotechnology Laboratory, and Department of Electrical and Computer Engineering,
University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
2
Material Research Laboratory, and Department of Materials Science and Engineering, University of
Illinois at Urbana-Champaign, Urbana, Illinois 6180, USA
3
Department of Materials Science and Engineering, KAIST, Daejeon 305-701, Republic of Korea

E-mail: myan@illinois.edu

Received 8 May 2014

Accepted for publication 20 June 2014
Published 23 July 2014

Abstract
High work-function metals such as Ni, Pt, and Au in the form of multilayer structures, Ni/Au and
Ni/Pt/Au, have been investigated as Schottky metallizations on AlGaN/GaN heterostructures
under thermal annealing. As-deposited Ni/Pt/Au had slightly higher Schottky barrier height than
its Ni/Au counterpart. Schottky barrier heights for Ni/Au diodes on AlGaN/GaN increased by
about 20% from 1.02 eV for as-deposited to 1.21 eV after annealing at 500 °C for 2 min. Similar
trends were observed for Ni/Pt/Au Schottky diodes. Thermal stability study for these devices
showed that the interposition of Pt in Ni/Au systems improved the characteristics of the Schottky
diodes after short-term anneal but cause significant degradation after long-term anneal at 500 °C.
Ni/Au Schottky contacts exhibited excellent leakage response under thermal annealing for long
periods. Microstructural studies were carried out on Ni/Pt/Au and Ni/Au Schottky contacts to
elucidate the role of the Pt interlayer in the degradation of the Ni/Pt/Au metallization under long-
term thermal anneal.
Keywords: Schottky contact, AlGaN/GaN heterostructure, microstructure, thermal annealing

(Some figures may appear in colour only in the online journal)

1. Introduction ohmic contacts due to the high barrier to metals. Although

The high bandgap of GaN and AlGaN semiconductors puts a
restriction on the choice of metals for Schottky contacts to
only high work-function metals. n-GaN, for example, which
has a bandgap of 3.4 eV and an electron affinity of 4.1 eV
requires metals with work functions significantly higher than
4.1 eV to form Schottky contacts with appreciable Schottky
barrier heights (SBHs). With increasing Al mole fraction in
AlGaN, the electron affinity drops, so the barrier height
increases for the same work function metals [1, 2]. However,
high Al mole fraction make it more difficult to form excellent
methods for enhancing the effective barrier heights by
exploiting the piezoelectric effects have been explored [3],
engineering the Schottky metal stack is perhaps a more pre-
ferable approach. Schmitz et al [4, 5] undertook a compre-
hensive study of metal contacts to n-GaN and found that they
were ohmic or rectifying depending on the metal work-
function. The high work function metals had strong rectifying
behavior, however, the best gate metallizations for GaN-
based high electron mobility transistors (HEMTs) especially
for high temperature operation still remains to be determined.

0268-1242/14/095005+10$33.00 1 © 2014 IOP Publishing Ltd Printed in the UK

Semicond. Sci. Technol. 29 (2014) 095005 B Ofuonye et al

Table 1. High work function metals. contact metallizations to AlGaN/GaN HEMTs under thermal
Metal Work
annealing.
Function Φm Calculated Max SBH Contact
Metal [eV] ΦB = Φm − χGaN [eV] good for
2. Experiment
Ta 4.25 0.15 Ohmic
Al 4.28 0.18 Ohmic A comprehensive investigation of the annealing effects on Pt
Ti 4.33 0.23 Ohmic interposed Ni-based metals on n-GaN and AlGaN/GaN
Mo 4.6 0.5 Ohmic/
Schottky contacts at a range of temperatures from 275 °C to
Schottky
Au 5.1 1.0 Schottky
575 °C was carried out. The layer structure of AlGaN/GaN
Pd 5.12 1.02 Schottky high electron mobility transistor (HEMT) consisted of 30 nm
Ni 5.15 1.05 Schottky of AlGaN with Al concentration of 25%, followed by 1.7 μm
Ir 5.25 1.15 Schottky of undoped GaN buffer layer. The following metallization
Pt 5.65 1.55 Schottky options were studied; (1) Ni/Au (30/50 nm), (2) Ni/Pt/Au
(2.5/30/50 nm), and (3) Ni/Pt/Au (7.5/30/50 nm). To fabricate
Schottky diodes, optical lithography was used to define pat-
terns with 300 μm diameter circular gaps. Mo/Al/Mo/Au (15/
Table 1 summarizes the metal work functions for some 60/35/50 nm) ohmic contact metallization was deposited in
selected metals [6, 7]. As can be seen, the choice of metals for the outer region by e-beam evaporation. Prior to ohmic con-
Schottky metallization is limited to Pd, Ir, Ni, Au, and Pt, tact deposition, SiCl4 plasma treatment at −300 V for 1 min in
which are the metals that provide the highest barrier heights. a reactive ion etching (RIE) system was performed on the
Indeed, experimentally measured barrier heights on GaN have ohmic region. After lift-off, the ohmic metallization for the
shown that the high work function metals gave high barrier AlGaN/GaN layers was annealed at 575 °C for 20 min in a
heights [5, 6]. However, some of these metals do not have furnace under N2 ambient and was verified to have excellent
excellent adhesion to GaN [5]. Apart from excellent adhesion, ohmic behavior. Schottky contact metallizations were then
thermal stability is also critical to metallization for Schottky patterned and deposited by e-beam evaporation in the inner
gate contacts in order to obtain high performance GaN-based 250 μm diameter circle. Before ohmic and Schottky metal
HEMTs. The Schottky barrier height and leakage properties evaporations, surface oxide was removed by dipping samples
of the Schottky contacts determine which contacts will pro- in 2:1 DI water: HCl solution for 1 min. For microstructural
vide the best gate control in AlGaN/GaN HEMTs. Ni-based characterization, Ni/Au (30/50 nm) and Ni/Pt/Au (30/30/
and Pt-based Schottky diodes are the most commonly used 50 nm) metal schemes on AlGaN/GaN heterostructures were
gate structures for AlGaN/GaN HEMTs [1, 8–19]. Pt-based studied. Thicker interfacial Ni was used so that evolutions in
Schottky diodes attracted recent interests for their applications the metallizations could be quantified more clearly for
in hydrogen sensors [20–22]. Ir and Re Schottky contacts microstructure analysis. Current–voltage (I–V) characteristics
have also been investigated as possible gate metals with good were measured using a semiconductor parameter analyzer.
thermal stability and leakage behavior [23, 24]. Se with a high Auger electron spectroscopy (AES) and scanning transmis-
work function of 5.9 eV has been investigated for Schottky sion electron microscopy (STEM) were performed to inves-
contacts on n-GaN recently [25]. TiN and RuOx were used on tigate microstructural characteristics of the Schottky contacts.
AlGaN/GaN and InAlN/GaN heterostructures, with Schottky
barrier heights of 0.75 eV and 1.24 eV, respectively [26, 27].
Despite having a lower metal work function, Ni is more often 3. Results and discussion
used than Pt as the Schottky metal especially for HEMT
devices. A major reason for using Ni over Pt is the stronger Current–voltage measurements were used to characterize the
adhesion of Ni to GaN than Pt. It should be noted that Au also barrier heights of the AlGaN/GaN Schottky diodes. Ther-
has very poor adhesion to GaN [5]. mionic emission theory was used to extract the SBHs and
Miura et al [8, 9] have investigated the interposition of Pt ideality factors for the AlGaN/GaN HEMT structures using
between Ni and Au as a possible gate metallization for GaN- the electrical properties of AlGaN with aluminum con-
based HEMTs. This serves two purposes. First, these metals centration of 0.25. The values extracted in this manner are
have the highest work functions and hence give the very high relative because the impact of polarization and piezoelectric
Schottky barrier necessary for good gate control. Secondly, a charges from the 2-DEG formation were neglected
thin interfacial Ni layer ensures good metal-semiconductor [10, 12, 13]. However, relative comparison of those values for
adhesion. The performance of this contact scheme showed the different metallizations would give an indication of the
promise under thermal test in their study. A detailed study of metallization with the best Schottky characteristics.
these Ni-based metallization schemes needs to be undertaken SBH characteristics for three different metal schemes
both electrically and in terms of their microstructures to extracted from I–V measurements for the as-deposited and
determine the stack with the most ideal characteristics. In this furnace-annealed diodes in an N2 ambient are presented in
paper, we report a comprehensive electrical and micro- figure 1, as functions of annealing temperature. Squares are
structural characterization of Ni/Au and Ni/Pt/Au Schottky for Ni/Pt/Au (2.5/30/50 nm), circles are for Ni/Pt/Au (7.5/30/

2
Semicond. Sci. Technol. 29 (2014) 095005 B Ofuonye et al

Figure 1. Schottky barrier height of Schottky contacts to Figure 2. Schottky barrier height of Schottky contacts to
Al0.25Ga0.75N/GaN under 2 min furnace anneal. * Calculated relative Al0.25Ga0.75N/GaN under cumulative furnace anneal at 500 °C. *
to Al0.25Ga0.75N. Calculated relative to Al0.25Ga0.75N.

50 nm), and triangles are for Ni/Au (30/50 nm) as shown in

the figure. The addition of Pt between Ni and Au enhanced
the barrier height of the as-deposited diodes significantly. It is
seen that all the metal schemes showed the same trend in
behavior for Schottky diode samples annealed from 275 °C to
575 °C. Initially, the SBHs at 275 °C decreased slightly from
their as-deposited values, then steadily increased to maximum
values at 500 °C and dropped with further increase in tem-
perature. These results imply that 500 °C might be the optimal
temperature for a 2 min anneal. It is not clear why SBHs
dropped below the as-deposited values after 2 min annealing
at 275 °C for all the metallizations. However, we have
observed that, after annealing for a longer period at 275 °C,
the typical SBH gradually increased above the as-deposited
value, indicating the quantity of heat applied to the Schottky
contacts might affect the barrier height. It is likely that
annealing enabled the e-beam evaporated Schottky metalli- Figure 3. Ideality of Schottky contacts to Al0.25Ga0.75N/GaN under
zations to form more intimate contacts to the GaN and cumulative furnace anneal at 500 °C. * Calculated relative to
AlGaN/GaN, creating enhanced barrier heights due to the Al0.25Ga0.75N.
difference in the metal work-function and the semiconductor
electron affinity. AlGaN/GaN HEMT epilayer. The interposition of Pt between
The leakage of Schottky metallizations to GaN under the thin interfacial Ni (2.5 nm and 7.5 nm of Ni) and Au as
thermal storage is important because it impacts the perfor- contacts resulted in SBHs of about 1.0 eV after 4 h anneal and
mance of the contacts. Several authors have used different was fairly constant at this value up to 8 h of annealing. The
techniques to reduce leakage currents in n-GaN and AlGaN/ corresponding value of SBH for the equivalent Ni/Au was
GaN Schottky contacts [28–35]. Optimal thermal annealing ∼1.3 eV, which was 30% larger than that of Ni/Pt/Au. The
generally produces improvements in SBH and leakage char- degradation (i.e. higher values) in the ideality factors of the
acteristics for Schottky diodes to n-GaN and AlGaN/GaN Schottky diodes in the Ni/Pt/Au system as shown in figure 3
[7, 8, 30]. Improvement in barrier height almost always implies that under thermal anneal the diode quality degraded.
implies reduction in leakage current. Figures 2 and 3 show The thinner the thickness of Ni, the sooner the degradation of
SBH and ideality dependences on cumulative anneal time for Schottky contact occurred under thermal stress. The SBH of
the different metallizations on AlGaN/GaN HEMT structure, the Ni (2.5 nm)/Pt/Au system dropped to ∼1.0 eV after
when subjected to thermal annealing in the furnace at 500 °C 30 min of annealing, whereas the Ni (7.5 nm)/Pt/Au dropped
for up to a cumulative time of 8 h. to 1.0 eV after 4 h of annealing. It was observed that Ni/Au
Figure 2 shows that after 2 h of annealing, the Ni/Au exhibited the most increased barrier height and stability under
metallization produced SBH greater than 1.2 eV on the thermal stress, even though Ni/Pt/Au contacts had higher

3
Semicond. Sci. Technol. 29 (2014) 095005
SBH values at the initial stages of annealing. Contrary to
earlier investigations on Ni/Pt/Au [8, 9], our study here
showed that Ni/Pt/Au Schottky diodes did not possess higher
barrier heights compared to Ni/Au Schottky diodes under
long-term thermal stress. The SBH of Ni/Au diodes increased,
albeit slowly, with the annealing time within the time
investigated.
In order to further investigate the behavior of the
Schottky diodes, it is essential to undertake microstructural
studies of contact metallizations. AES and STEM techniques
were used to analyze the contacts for intermetallic and
interfacial reactions after annealing. In order to elucidate the
interfacial and intermetallic evolution after anneal, thicker
interfacial metal layers were deposited. The thickness of
30 nm Ni layer was adopted as the metal stacks of Ni/Au (30/
50 nm) and Ni/Pt/Au (30/30/50 nm), instead of Ni (7.5 nm)/
Pt/Au or Ni (2.5 nm)/Pt/Au.
AES analyses of the Ni/Au (30/50 nm) and Ni/Pt/Au (30/
30/50 nm) Schottky contacts to AlGaN/GaN before and after
500 °C anneal for 2 min and 1 h are shown in figures 4(a)–(f).
After a 2 min anneal, the Ni/Au metal stack showed a trace of
out-diffusion of Ni to the surface, as shown in figure 4(b).
Complete mixing of Ni and Au occurred after 1 h anneal as
shown in figure 4(c). Up to 80% of the composition at the
surface was Ni while Au had also spread towards the interface
with AlGaN. It has been reported that many Ni-Au phases
were formed at 500 °C [36], due to the affinity between Ni
and Au. Comparing AES profiles in figures 4(d)–(f) for the
Ni/Pt/Au metallization stack, it is evident that there is mixing
of the metals after 1 h anneal because of Ni out-diffusion
through Pt, all the way to the metal surface. Up to 70%
composition of the surface was Ni. A significant amount of Pt
(40%) and Ni (30%) composition near the AlGaN interface
suggests the possibility of Ni-Pt phase formation. There exist
some Ni-Pt and Ni-Au alloy phases which form at 500 °C
such as NiPt, Ni3Pt, Pt3Ni, and NixAuy [36–38]. This explains
the diffusion of Ni into Pt during anneal. The formation of
these Ni-Pt phases could be related to the degradation of the
Schottky contact as a function annealing time as the thin Ni
layer gradually intermixed with Au and Pt to form Ni-Pt and
Ni-Au alloys. The Ni-Pt and Ni-Au alloys contact the AlGaN
layer in parallel, resulting in a mixed-metal/semiconductor
interface. Consequently, these changed the Schottky proper-
ties of the Ni/Pt/Au metallization.
Figure 5 shows STEM images of Ni/Au (30/50 nm) and
Ni/Pt/Au (30/30/50 nm) contacts to AlGaN/GaN for as-
deposited and for 1 h annealing at 500 °C. For the Ni/Au
contact, after 1 h anneal at 500 °C, the low magnification
STEM image exhibited the accumulation of Au at the inter-
face between the semiconductor and metal, as seen in
figure 5(b).
The high resolution image for Ni/Au in figure 6(a) shows
the in-diffusion inlet of gold to the AlGaN interface with Ni
out-diffusing away from the surface, corroborating the
observation in the AES in figure 4(c). No interfacial reaction
was observed at the metal–AlGaN interface for 1 h annealing
at 500 °C, as the high resolution STEM image in figure 6(b)
indicates. A Z-intensity profile characterization of the
4
B Ofuonye et al
interface area is shown in figure 6(c). The Z-intensity is
proportional to the atomic number, Z, of the element. The
atomic number of Au is 79 and that of Ni is 28. With the high
Z-intensity at the metal–AlGaN interface, it was observed that
a thin Au-layer of at least 2 nm wide had uniformly formed at
the interface. The sharpness of the Z-intensity profile at the
interface indicates that no interfacial reaction occurred
between the metals and AlGaN. Therefore, the mechanism of
increased Schottky barrier height in the Ni/Au Schottky
contact to AlGaN/GaN in figure 2 could be explained from
the observation of a sustained accumulation of gold at the
interface, which created a uniform layer of Au contact to
AlGaN/GaN. As the thickness of the accumulated Au layer
increases beyond the critical Debye length necessary for
Schottky contacts, a higher barrier height is obtained that
approximates an Au-AlGaN Schottky contact. Since the metal
work function of Au is close to that of Ni, an increase in SBH
is seen when the metal contacting the AlGaN (NixAuy)
becomes more of Au. After 1 h anneal, enough Au had
accumulated to form a 2 nm Au-rich region at the interface
(y ≫ x). Away from the interface, the Ni concentration
increased such that x ≫ y until it got into the very Au-rich
near outer surface regions, as shown in figures 4(c), 6(a),
and (b).
Under annealing, the Ni/Pt/Au metallization exhibited
the formation of Ni-Pt phases as shown in figure 5(d). Au also
accumulated at the interface, but unlike the case in the Ni/Au
metallization, there was no uniform accumulation of Au at the
interface. No interfacial reaction was observed, as shown in
the high resolution image in figure 7(a). The formation of
mixed interface of Au-AlGaN and/or (Ni-Pt)-AlGaN explains
the degradation of barrier height in this metallization as
observed in the anneal results in figure 3. The degradation of
idealities further solidifies the impact of the observed mixed
interfaces. Even though a thick Ni (30 nm) was used in the Ni/
Pt/Au contact for STEM studies, mixed interfaces were
observed. Hence, in the Ni/Pt/Au Schottky contacts, where Ni
was either 2.5 nm or 7.5 nm, it could be expected that the Ni
was more aggressively consumed in forming Ni-Pt such that a
more mixed interface of Pt, Au, and thin Ni–Pt mixtures to
AlGaN resulted. The thicker the interfacial Ni, the more
degradation increased with annealing time. The reason for this
was due to the formation of Ni–Pt mixtures. The thicker the
interfacial Ni, the more Ni there was for the formation of Ni-
Pt alloys. Therefore, as the contact was continually annealed,
a more mixed interface resulted in degrading the Schottky
contact until all the interfacial Ni was consumed in forming
Ni–Pt. In the thinner interfacial Ni metallization (2.5 nm), this
happened sooner than in the thicker interfacial Ni (7.5 nm)
and so it reached a constant SBH value during annealing
sooner, as seen in figure 2. Also, the Ni–Pt phases formed at
the grain boundaries with dark spots segregating at these grain
boundaries, as shown in figures 7(b)–(d). The dark spots were
probably due to some types of voids. These spots and the Ni-
Pt mixture boundary structures may also have contributed to
the degradation in barrier heights and diode idealities.
Due to the fact that the metallization at the AlGaN
interface is no longer uniform after annealing, the barrier
Semicond. Sci. Technol. 29 (2014) 095005 B Ofuonye et al

Figure 4. Auger electron spectroscopy profiles of Ni/Au (30/50 nm) (a) to (c) and Ni/Pt/Au (30/30/50 nm) (d) to (f) before and after anneal
at 500 °C.

became a mixture of many paths from the metal to the alone. Annealing thus created multi-paths due to a mixed
AlGaN. This is like resistors in parallel where the net resis- interface of (Ni–Pt)–AlGaN and Au–AlGaN as shown in the
tance is smaller than the smallest value. Hence, the SBH is illustrative schematic in figure 8. Hence, the degradation of
smaller than one would expect for either Ni, Ni–Pt, Pt or Au the Ni/Pt/Au metallization can be attributed to the presence of

5
Semicond. Sci. Technol. 29 (2014) 095005 B Ofuonye et al

Figure 5. STEM images of Ni/Au and Ni/Pt/Au on AlGaN/GaN before and after anneal at 500 °C for 1 h. (a) Ni/Au (30/50 nm) as deposited
on AlGaN/GaN, (b) Ni/Au (30/50 nm) on AlGaN/GaN after 500 °C anneal for 1 h, (c) Ni/Pt/Au (30/30/50 nm) as deposited on AlGaN/GaN
and (d) Ni/Pt/Au (30/30/50 nm) on AlGaN/GaN after 500 °C anneal for 1 h.

Ni–Pt and Ni–Au phases and the formation of mixed interface reactions of the metal with the AlGaN layer were observed
during thermal anneal, while the improved performance of the even after 1 h anneal for both metallization contacts. There-
Ni/Au contact was due to the accumulation of a uniform Au- fore, STEM analyses of the Ni/Au and Ni/Pt/Au contact
rich area at the interface. It should be noted that no interfacial

6
Semicond. Sci. Technol. 29 (2014) 095005 B Ofuonye et al

Figure 6. High resolution STEM images of Ni/Au on AlGaN/GaN after 500 °C annealing for 1 h, (a) and (b), showing accumulation of Au at
the metal-AlGaN interface, (c) Z-intensity profile of the Au/Ni-AlGaN/GaN interface showing a sharp interface and Au accumulation.

7
Semicond. Sci. Technol. 29 (2014) 095005 B Ofuonye et al

Figure 7. High resolution STEM images of Ni/Pt/Au on AlGaN/GaN after 500 °C annealing for 1 h. (a) No interface reactions (b) Ni-Pt
phases formed, (c) Ni-Pt grain boundaries and (d) Dark spots at grain boundary.

metallizations to AlGaN do confirm the inter-metal mixing
observed in the AES plots in figure 4.
It has been reported that Ni/Ti/Pt/Au, Ni/Mo, and Ni/Au
Schottky contacts on n-type GaN under thermal annealing
have the similar trends, i.e. the optimal temperatures for
highest SBHs [39–42]. There was a significant increase of Ni/
Ti/Pt/Au’s SBH at an annealing temperature of 400 °C [39].
The Ni/Mo Schottky contact got the maximum SBH at
500 °C [40]. For an annealing temperature of 600 °C for
5 min, the Ni/Au contact obtained a highest SBH of 0.86 eV
[41]. For the same Ni/Au Schottky contact, another research
group achieved the optimal value around 400 °C [42]. After
that, Schottky contacts got deteriorated. Schottky contacts
turned into Ohmic contacts when rapidly annealed at much

8
Semicond. Sci. Technol. 29 (2014) 095005
Figure 8. Schematic showing mixed interface in Ni/Pt/Au after
500 °C anneal for 1 h.
higher temperature of 750 °C [43]. The variance of SBHs and
associated ideality factors might be attributed to the interface
states or deep level defects below these Schottky contacts
[44, 45]. The surface treatment with ammonium sulfide or
tetramethylammonium hydroxide can reduce the interface
sate density and improve the electrical properties of Schottky
diodes [46, 47]. Different surface passivation schemes with
additional thermal annealing and the temperature dependence
of SBHs will be explored for Ni-based Schottky contacts.
4. Conclusion
A comparative study of Ni/Au and Ni/Pt/Au Schottky contact
metallizations to AlGaN/GaN heterostructure has been
investigated under thermal anneal temperatures up to 575 °C.
These Schottky contacts exhibited the same behaviors as they
were progressively annealed for 2 min The interposition of Pt
improved the performance of the as-deposited Schottky
behavior. However, after annealing at 500 °C for hours, the
Schottky characteristics of Ni/Pt/Au metallization degraded
due to the formation of Ni–Pt phases causing the Ni to diffuse
upward into the Pt and creating mixed interfaces, which
resulted in the lowering of the Schottky barrier heights. For
Ni/Au metallization, the uniform accumulation of Au at the
interface contributed to the increase of Schottky barrier
heights and also the stability of the contacts. Therefore, Ni/Au
contacts should be preferred to Ni/Pt/Au as Schottky gate
contacts for AlGaN/GaN HEMTs designed for operations at
temperature up to 500 °C.
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