Thin Solid Films 527 (2013) 158–163

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Thin Solid Films

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Structure zone model for extreme shadowing conditions

S. Mukherjee, D. Gall ⁎
Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, USA

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

Article history: Previously reported data on the microstructure of glancing angle deposited (GLAD) metal layers is used to extend
Received 17 July 2012 the qualitative arguments of the structure zone model for physical vapor deposition to growth conditions with
Received in revised form 15 October 2012 exacerbated atomic shadowing. At low growth temperatures Ts relative to the melting point Tm, the microstruc-
Accepted 7 November 2012
tural development is governed by atomic shadowing for both normal deposition and GLAD, resulting in fibrous
Available online 15 November 2012
grains with voided boundaries (Zone I). As the homologous growth temperature θ=Ts / Tm is raised above ap-
Keywords:
proximately 0.3, GLAD layers continue to exhibit well separated columns while conventional thin films show
Structure zone model dense columnar microstructures (Zone II). θ> 0.5 leads to equiaxed grains independent of deposition angle
Physical vapor deposition (Zone III). Therefore, strong shadowing during GLAD suppresses Zone II microstructures, causing a direct transi-
Glancing angle deposition tion from Zone I to Zone III. GLAD microstructures can be divided into four distinct zones: rods, columns,
Atomic shadowing protrusions, and equiaxed grains: separated self-affine rods form for θ b θc =0.24±0.2, while considerably broader
Surface diffusion columns develop at θ >θc, due to exacerbated self-shadowing associated with an increased growth front rough-
Whisker ness, causing larger growth exponents. Above θ ≈0.35, protrusions develop on top of some columns as they cap-
ture an overproportionate amount of deposition flux and grow much higher than the surrounding layer. At
θ >0.5, diffusion processes dominate over atomic shadowing, leading to faceted rough layers with equiaxed
grains. In addition, the large mass transport facilitates the formation of whiskers that form for many metal
GLAD layers at θ > 0.4.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction In contrast, glancing angle deposition (GLAD) [17,18] is a PVD tech-

The microstructure of films deposited by physical vapor deposi-
tion (PVD) depends on the processing parameters such as substrate
temperature Ts [1–5], gas pressure [1,4,6–9], ion bombardment
[9–11], impurities [5], deposition geometry [11,12], substrate rough-
ness [13] and substrate rotation [14]. The systematic analysis of the
microstructure of films grown by a normal deposition flux led to the
development of the structure zone model (SZM) [1,4,15,16], which
qualitatively explains the morphology development as a function of
adatom mobility controlled by the process parameters. The funda-
mental physical processes at play during growth are shadowing and
surface diffusion [2]. Shadowing depends on the deposition angle
and causes preferential deposition on mounds, leading to the forma-
tion of a rough, porous, columnar microstructure. On the other
hand, diffusion leads to a reduction in porosity and a smoothening
of the film surface. It is controlled by Ts, ion bombardment, impurities
and the material system [1]. The initial SZM and the later revisions ex-
plain morphological changes in terms of the interplay between the
competing phenomena of shadowing and diffusion, and classify the
different film morphologies into zones (I, T, II and III) [1,4,5,15,16]
as a function of increasing adatom mobility, while keeping the “de-
gree” of shadowing constant.
⁎ Corresponding author. Tel.: +1 518 276 8471; fax: +1 518 276 8554.
E-mail address: galld@rpi.edu (D. Gall).
nique where the shadowing effect is purposely exacerbated by a grazing
incident angle α > 80° of the deposition flux. This leads to the formation
of self-affine [19] isolated columnar nanorod structures with a high
level of porosity [20] and surface roughness [21] in a wide range of ma-
terial systems [16,22] including metals [23] and covalently bonded ma-
terials [24]. Most research on GLAD is done at low temperatures, so that
surface diffusion is kinetically limited and the dominance of atomic
shadowing can be exploited to create arrays of nanostructures including
straight and slanted pillars [18], springs [25], spirals [26], tubes [27] and
branched [28,29] or multi-component nanorods [30,31]. The rod width
w broadens with height h [28], which is attributed to growth competi-
tion [32,33] and is described by a power law scaling relationship [19,34]
p
w∝h ; ð1Þ
where p is the growth exponent [23,24,35,36] which depends on pro-
cess parameters including the angle of incidence [21,23,37], the sub-
strate rotation [38–40], substrate patterning [18,32,39,41,42], the
material system under consideration [36] and Ts [43–45].
Recent studies on the microstructural evolution of GLAD layers at el-
evated temperatures [46–54] provide a motivation to revisit the funda-
mental competition between atomic shadowing and surface diffusion.
The SZM cannot correctly describe GLAD microstructures because it as-
sumes limited shadowing conditions which do not account for large de-
position angles. Conversely, models that describe GLAD microstructural

0040-6090/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2012.11.007
 S. Mukherjee, D. Gall / Thin Solid Films 527 (2013) 158–163
features including layer porosity [55,56] and column tilt [57,58] and
broadening [19,34] assume negligible or limited surface diffusion and
therefore do not account for temperatures that exceed ~1/3 of the melt-
ing point. The question arises regarding what layer microstructure is
expected at both a high growth temperature and a large deposition
angle, that is, for large surface diffusion and strong atomic shadowing.
In this article, we review recent experimental work on the tempera-
ture dependence of the microstructure of GLAD layers and discuss it
within the framework of the SZM. For this purpose, the growth temper-
ature is normalized by the melting point Tm of the deposited material, to
yield the homologous growth temperature θ= Ts /Tm. At low tempera-
ture, GLAD layers consist of high-aspect-ratio rods. Increasing θ leads to
a continuous increase in their width. This is exacerbated by anomalous
broadening at θ>~0.24, resulting in relatively broad columns. Growth
competition at θ >~0.35 yields protrusions that extend above the surface
of the surrounding film. At θ >~0.5, considerable mass transport results
in approximately equiaxed grains and, for many metals, in the formation
of whiskers. In contrast to the structure zone model for normal deposi-
tion, GLAD results in highly underdense microstructures up to θ~ 0.5.
That is, there is a direct transition from a Zone I to a Zone III microstruc-
ture, while Zone II is suppressed due to the large shadowing length scale
that limits the densification through surface diffusion for θ =0.3–0.5.
2. Experimental data
In this section, we summarize and discuss previously reported mi-
crostructural data of GLAD layers as a function of Ts. The temperature
dependence of GLAD microstructures has only relatively recently
gained interest. Thus, most data that is discussed in this section has
been reported within the last five years and stems primarily from four
different research groups, including our own. It includes GLAD layers
deposited by sputtering and by evaporation from angles α ≥ 80°, with
typically a continuously rotating substrate such that the net nanostruc-
ture growth direction is perpendicular to the substrate surface. The pri-
mary focus of this discussion is to understand the impact of increasing
surface diffusion, facilitated by increasing θ, on the microstructural de-
velopment of layers deposited by GLAD. Other deposition parameters,
including the angular distribution of the deposition flux as well as
growth rate and substrate rotation rate may also affect the microstruc-
ture but are, for clarity purposes, not discussed here. Instead, our partic-
ular interest is in temperature-induced qualitative changes in the
microstructure which are observable for various material systems and
scale with the homologous deposition temperature. They are all a direct
result of the competition between atomic shadowing and surface
diffusion.
High temperature GLAD was pioneered by Suzuki et al., [47,48]
who reported Al layer microstructures which exhibit rough surfaces,
approximately equiaxed grains, and whiskers. They attribute the mi-
crostructural evolution to diffusion at elevated temperatures [47]
which suppresses the formation of separated columns typical for
low-temperature GLAD. Similarly, the formation of whiskers is also
facilitated by considerable diffusion [48], and is reported for various
other metals including Cu, Ag, Au, Mn, Fe, Co, Ni and Zn deposited
at 390 °C [49,50]. Comparing the reported micrographs for Al as a
function of temperature indicates a transition from a microstructure
that is dominated by separated columns at Ts = 85 °C to a continuous
layer with whiskers at Ts = 290 °C [48]. This indicates a transition
from a shadowing dominated to a diffusion-dominated microstruc-
tural development. At an intermediate temperature of Ts = 180 °C,
Al layers are porous and exhibit a columnar microstructure. However,
their surface is very rough and the columns are of irregular shape,
with some columns extending well above the column tips of their
neighbors [48], a microstructural feature that we refer to as protrusions
[33]. These results are summarized in Fig. 1, which is a plot that includes
the microstructural information from all temperature dependent GLAD
data discussed in this section. For the case of aluminum deposited by
159
Suzuki et al., the columns and protrusions at Ts =85 and 180 °C are indi-
cated by symbols “c” and “p” at θ=0.38 and 0.49, respectively, while
Ts ≥290 °C leads to dense layers with equiaxed grains and whiskers, indi-
cated by overlaying symbols “e” and “w”. Due to the relatively low melt-
ing point Tm =933 K of Al, none of the reported Al GLAD microstructures
is described as rods “r”. The low-temperature rod-microstructure is char-
acterized by vertical rods which are narrower and exhibit a smaller
broadening rate than the columns. The transition from rods to columns
is due to a transition from a 2D to a 3D island growth mode, as discussed
in more detail below.
Suzuki et al. also reported the microstructure of Fe deposited by
GLAD as a function of Ts [50]. They found conventional GLAD columns
at Ts ≤ 300 °C and irregular microstructures with protrusions for
Ts ≥ 330 °C. In addition, whiskers start to develop above 330 °C, indi-
cating that surface diffusion is sufficient for whisker formation at
330 °C (θ = 0.33), while the columnar microstructure with protru-
sions suggests that atomic shadowing dominates over surface diffu-
sion in determining the overall microstructural development up to
θ ~ 0.44 for Fe [49,50], as indicated in Fig. 1 for the Fe melting point
of 1811 K.
Deniz et al. [51] studied the microstructure of various metals and ox-
ides deposited by GLAD as a function of Ts. They introduced the interesting
concept of a threshold temperature ΘT above which no nanostructuring
occurs. The deposited layers are considered “nanostructured” if they
consist of nanostructures that are separated by >2 nm and exhibit a
height-to-width aspect ratio of ~10 or more. This is a good definition
from a practical perspective, as it provides the useful temperature regime
over which arrays of distinct GLAD nanostructure arrays can be deposited.
In the context of the current discussion, microstructures characterized by
rods or columns are considered to be “nanostructured”, as they consist of
well-separated structures that exhibit a large height-to-width aspect
ratio. In contrast, protrusions and equiaxed grains do not satisfy the
“nanostructuring” definition by Deniz et al., since the width of the
protrusions can approach their height, and equiaxed grains have an aspect
ratio of ~1 and also exhibit no gap between them. Thus, within the se-
quence of microstructures with increasing temperature from r to c to p
Fig. 1. High-temperature GLAD microstructural data from Refs. [23,32,33,43–54,59] for
metallic and non-metallic systems classified into four zones: rods r, columns c, protrusions
p, and equiaxed e grains. Microstructures that exhibit whiskers w are also labeled. The
y-axis corresponds to the melting point Tm and the x-axis shows the homologous deposi-
tion temperature θ=Ts /Tm. Each row of data points is labeled on the right, indicating the
material as well as the relevant references. Italic symbols indicate non-metallic systems.
160 S. Mukherjee, D. Gall / Thin Solid Films 527 (2013) 158–163
to e, the threshold temperature ΘT lies at the boundary between c and p.
Fig. 1 includes data from Deniz et al. [51] for various metals, Sn, Al, Au,
Ru, and W, as well as oxides RuO2, SnO2, and WO3. For Sn and Al,
room temperature deposition is already above ΘT, leading to e and p mi-
crostructures, respectively. In contrast, room temperature corresponds
to θ = 0.11 and 0.08 for Ru and W, yielding rods for both of these
high-melting point metals. Au was studied as a function of Ts. It exhibits
columns up to θ = 0.32, protrusions from θ = 0.32–0.38, and equiaxed
grains for θ ≥0.48. RuO2, which has a melting point of 1473 K, shows
a sequence from r to c to p to e for θ = 0.35 to 0.43 to 0.50 to 0.58.
That is, ΘT is between θ = 0.43–0.50, which is considerably higher
than for metals, with ΘT ~ 0.33. This is attributed to the covalent bonding
and the related surface reconstruction, which yields a higher homolo-
gous activation energy for surface diffusion (Em / kTm) [43], and is also
consistent with the data for WO3 and SnO2, which show columns for all
reported temperatures Ts ≤866 K [51], indicating ΘT >0.50 and>0.45,
respectively. Fig. 1 shows overlaying c and p symbols for these oxides,
as the published micrographs do not clearly indicate if some columns ex-
hibit protrusions. Also, italic symbols are used for these covalently bond-
ed materials, in order to distinguish the data from the majority of metals
presented in Fig. 1.
Khare et al. has reported GLAD microstructures of Ag and Ge de-
posited at 300–623 K [52–54]. Room temperature deposition of Ag,
which corresponds to θ = 0.24, leads to a columnar microstructure.
In contrast, deposition at 573 and 623 K, corresponding to θ = 0.46
and 0.50, respectively, results in equiaxed grains with approximately
semi-spherical shapes, indicating considerable mass transport and a
tendency for dewetting on the higher-surface-energy Si substrate.
Such deposition at high temperature also leads to the formation of
whiskers, which are preferentially formed when the deposition flux
is collimated, likely due to the related higher average deposition
angle and/or lower deposition rate. Khare et al. also found that the
column width at low temperature can be increased by initial sub-
strate pattering. The effect of patterning prior to GLAD has been studied
by various researchers [53,59], and has been found to affect the broad-
ening rate due to the initially lower intercolumnar competition [32,33].
This makes a distinction between r and c microstructures typically less
obvious. The micrographs of Ge layers reported by Khare et al. indicate
columns for θ = 0.25–0.39, protrusions for θ = 0.47, and equiaxed grains
at θ = 0.51 [54]. This suggests that Ge exhibits a microstructural trend
similar to the metals discussed above, despite the transition from an
amorphous to a crystalline microstructure with increasing θ. In addi-
tion, they also report an increasing probability for column merging
with increasing θ, consistent with previous work from our group on
Ta columns which show an increase in the probability for merging
from negligible at 473 K to 20% at 973 K [33]. Related work by Patzig
et al. on Si shows that the nanostructure width increases from 115 to
140 nm with Ts increasing from room temperature to 633 K [46]. The
broadening is found to be qualitatively similar for GLAD columns, spi-
rals, and screws, suggesting that an understanding of the temperature
effects for GLAD rods/columns can likely be extended to include more
complex GLAD nanostructure shapes. This work by Patzig et al. is con-
sistent with data by Karabacak et al., who found an r microstructure
and a growth exponent p =0.32 for Si growth at room temperature
[23]. This data as well as room temperature data for Cu, Co, and W
from the same Ref. [23] are also included in Fig. 1.
Our own work on the temperature effects during GLAD has primar-
ily focused on statistically analyzing the nanostructure width distribu-
tion for metal layers including Al, Cr, Nb, and Ta [43–45] as well as on
growth competition [32,33] and probabilities for column branching
and merging [18,29,33,60]. Fig. 2 shows micrographs of typical GLAD
nanostructures deposited from an angle of 84° onto continuously rotat-
ing Si(001) substrates. The microstructures are comparable to those de-
scribed and discussed in detail in Refs. [44,45]. Here, they are primarily
shown to illustrate the characteristic r, c, p and w microstructural fea-
tures with increasing θ. The Ta rods in Fig. 2(a) were deposited at
room temperature, corresponding to θ = 0.09. They have a total height
of 500 nm and their width increases with height, following a power
law with p = 0.43, reaching a width of 100 nm near the top. Increasing
Ts results in an increase in the width at a given height [43] and a de-
crease in the broadening rate [44], which is due to a reduction in the
growth front roughness and hence a reduced self-shadowing of the
nanorods with increasing adatom mobility [45]. However, for metallic
systems there exists a critical homologous temperature θc at which
the surface roughness of the growth front increases due to a change
from a 2D to a 3D island growth mode. This leads to a discontinuity in
the p vs θ curve, that is, p increases steeply at the transition temperature
θc [44,45]. Within the context of this paper, the transition from r to c mi-
crostructures is defined by this transition of the growth mode. Accord-
ingly, Fig. 1 includes the data from Cr, Nb, and Ta layers from Ref. [45] for
a large range of θ values. Based on the plot, the transition from r to c oc-
curs between θ = 0.20 and 0.26 for most metals, which is in good agree-
ment with previously published values for the critical temperature of
θc = 0.20 ± 0.03 from Ref. [43] and θc = 0.24± 0.02 from Ref. [45]. We
note here that the distinction between r and c is in principle rigorous,
based on statistical analyses of the nanostructure width vs height
data. However, for many studies included in Fig. 1, such detailed data
in not available and the classification into r or c microstructures includes
considerable uncertainty, as it is based on the observed nanostructure
width and apparent broadening rate from published micrographs.
Fig. 2(b) shows an example of a c microstructure, from Cr deposited at
Ts =350 °C corresponding to θ=0.29. The columns have a maximum
height of 860 nm. They are 2.6 times wider than the Ta rods in Fig. 2(a),
at a fixed height of 500 nm. The Cr columns also exhibit stronger broad-
ening, with p=0.53. Based on the argument above, this large p value is
attributed to θ>θc.
Increasing the homologous temperature further results in an in-
creasing mass transport on the growth front which causes secondary
shadowing instabilities. In particular, a nanostructure may develop a
height that is sufficiently above those of its neighbors such that it cap-
tures an overproportional fraction of the deposition flux, resulting in
exacerbated growth both perpendicular and parallel to the substrate
surface. This leads to the development of protrusions which develop
on top of columns and may be considerably wider and taller than
the columns themselves. For example, we reported a p microstruc-
ture for Ta growth at Ts = 900 °C (θ = 0.36), where the protrusions
are twice as wide and three times as tall as the surrounding columns
[33]. The micrograph in Fig. 2(c) shows comparable protrusions, for
the case of Nb deposition at Ts = 850 °C, corresponding to θ = 0.41.
The overall microstructure is columnar, however, with a very rough
surface and columns of irregular shape. In particular, the micrograph
shows various “regular” grains that are 100–300 nm wide and 200–
400 nm tall, but also a few grains with a ten times larger volume
and a width and height of 600 and 1000 nm, respectively, exhibiting
pointed sharp tops. We refer to these grains as protrusions, as they ex-
tend well above the surrounding layer.
Similar to the reports by Suzuki et al. discussed above and summa-
rized in Fig. 1, we have also observed the development of a microstruc-
ture with equiaxed grains and whiskers for growth temperatures larger
than approximately half the melting point. Fig. 2(d) is an example of
an e and w microstructure, showing an Al GLAD layer deposited at
Ts = 250 °C, corresponding to θ = 0.56. This layer has a thickness of
1.2 μm, but shows 1–2 μm wide rod-shaped whiskers that extend
3–10 μm above the layer. The surface is rough with facets that ap-
proach the size of the layer thickness, indicating a microstructure
with equiaxed grains.
3. Discussion of the structure zone model
Fig. 3(a) shows the SZM initially proposed by Movchan and
Demchishin (MD) [15] and later revised by Thornton [1] for metallic
layers grown by PVD as a function of increasing homologous temperature
 S. Mukherjee, D. Gall / Thin Solid Films 527 (2013) 158–163
Fig. 2. Cross-sectional SEM micrographs from Ta, Cr, Nb, and Al GLAD layers deposited with continuous substrate rotation at homologous temperatures θ = Ts /Tm = 0.09, 0.29, 0.41,
and 0.56, showing typical microstructural features including (a) rods, (b) columns, (c) protrusions, and (d) equiaxed grains with whiskers.
θ=Ts/Tm. Increasing temperature (or in some cases ion bombardment)
causes an increase in the diffusion length scale which results, in turn, in
changing microstructures that are divided into 3 Zones I, II and III [15].
Each zone has its unique texture, porosity and range of process parame-
ters [2].
Shadowing controls the film microstructure and texture in Zone I,
and the film is columnar with tapered voids between columns [2].
The structure in Zone I has been further classified into Zone Ia, Ib
and Ic in an extended SZM [5]. Zone Ia is characterized by ballistic
Fig. 3. (a) Structure zone model for thin films deposited by physical vapor deposition with
a normal deposition flux [2,15]. The x-axis shows the homologous deposition temperature
θ=Ts /Tm. (b) Corresponding schematic for layers deposited by glancing angle deposition
with continuous substrate rotation, showing rods r, columns c, protrusions p, equiaxed
grains e, and whiskers w.
161
growth with a low adatom mobility at low Ts that leads to the forma-
tion of columnar structures. Zone Ib occurs at low Ts but in the pres-
ence of ion bombardment, which increases the adatom mobility and
leads to densification of the columnar structure. Zone Ic occurs at
slightly higher Ts, sufficient to cause adatom motion and the forma-
tion of crystalline islands. This leads to faceted columnar structures
with facets being planes with the lowest crystallographic growth
rate [5]. In Zone II, surface diffusion is the leading process that con-
trols morphological evolution, and the film consists of columnar
grains with defined dense grain boundaries, faceted top surfaces,
and an increased grain width. In Zone III, the microstructure is
governed by bulk diffusion, and the microstructure exhibits equiaxed
grains. The relative position of the zones in the SZM varies with the
deposition parameters and material system under consideration
[5]. Thornton, extended the initial MD model by adding the deposi-
tion pressure as a parameter to describe the effect of adatom mo-
bility induced by energetic particle bombardment in a sputtering
system [2]. In Thornton's model, an additional transition zone T be-
tween Zones I and II is included. Films in Zone T exhibit a fibrous
texture, as in Zone I, however, they show no voids and domes,
due to the additional adatom transport associated with energetic
bombardment.
Fig. 3(b) is a corresponding schematic, illustrating qualitative
changes with increasing homologous deposition temperatures θ of
the microstructure of GLAD layers deposited with substrate rotation.
It is based on the experimental observations summarized above,
which show distinct microstructural features, in particular rods,
columns, protrusions, equiaxed grains, and whiskers. At low tempera-
tures, the microstructure is characterized by well separated rods.
The rods are self-affine structures with an average width that follows
a power law relation with the height as described in Eq. (1) [23,45].
At the zero-temperature limit (θ = 0), the growth exponent p tends
to an analytical value of 0.5, which is an average of the two in-plane
orthogonal exponents during GLAD with a stationery substrate [23].
Also, in the absence of surface diffusion at θ = 0, the morphology is ma-
terial independent and is governed by geometric shadowing alone [43],
comparable to Zone Ia in the SZM. Fig. 3(b) also shows some rods that
are shorter than their neighbors. Their growth was terminated prema-
turely due to intercolumnar shadowing competition which has been
162 S. Mukherjee, D. Gall / Thin Solid Films 527 (2013) 158–163
reported to cause rod extinction [32,33], and provides space for broad-
ening of the neighboring rods, i.e. p > 0.
Increasing θ increases the diffusion length-scale and results in a
faceted columnar structure with a high level of porosity, resembling
the Zone I structure with a normal incident deposition flux. The
higher adatom mobility at higher θ also increases the width of the
rods at a given height [43], similar to the increasing columnar width
in the SZM. The broadening rate or p decreases with increasing θ,
due to a reduction in growth front roughness of individual rods
which, in turn, reduces rod self-shadowing. At a critical homologous
temperature θc = 0.24 ± 0.02 for metallic systems [45], a change
from 2D to 3D island growth mode occurs as the adatoms overcome
the Ehrlich–Schwoebel barrier [61,62], leading to an increase in the
roughness of the nanorod growth fronts. This dramatically increases
the self-shadowing and consequently the nanostructure broadening
rate, such that we refer to microstructures grown above θc as col-
umns. The easy observable difference between rods and columns is
the width, which is larger for the columns. However, the fundamental
difference is their broadening rate with increasing height. This rate is
quantified by p, which is 0.39 and 0.80 just below and above θc for
rods and columns, respectively [44,45]. Increasing θ (>θc) results in
a gradual decrease of p from the anomalous high value at θc. This is at-
tributed to a decreasing roughness of the growth front with increas-
ing diffusion length. That is, for θ > θc, the column broadening rate
decreases with increasing θ, while the column width at a constant h
increases with increasing θ.
Increasing θ further to ~ 0.35 results in the development of protru-
sions. Protrusions are microstructural features that extend a column
above the tips of the neighboring columns. They are typically consid-
erably wider than the columns and exhibit irregular shapes with
strong broadening. We attribute the formation of protrusions to the
larger diffusion length which causes an increase in the lateral length
scale of surface mounds on the growth front of individual columns.
This, in turn, leads to a chaotic instability where the surface mound
on one column extends vertically and captures an over-proportional
fraction of the deposition flux in comparison to the neighboring col-
umns. Consequently, this column will grow at a higher rate than its
neighbors and, once its height is clearly above its neighbors, it will ex-
hibit a strong lateral growth rate, leading to strong broadening and
the formation of irregularly shaped protrusions. The onset tempera-
ture for the formation of protrusions coincides with the threshold
temperature for nanostructuring, that has been introduced by Deniz
et al. [51]. According to their study and also evident from Fig. 1, the
transition from columns to protrusions occurs at θ = 0.30–0.35 for
various metals. In contrast, ceramics including RuO2, WO3 and SnO2
exhibit higher threshold temperatures of ΘT = 0.4–0.5. As discussed
above, this is related to the ratio of the activation energy for surface
diffusion over the melting temperature, which is typically higher for
covalently bonded materials than for metals, and is also typically
higher for compounds than for pure elements.
As θ is increased above ≈0.5, the surface and/or bulk diffusion
length becomes comparable or greater than the length scale for
shadowing interactions for any realistic layer thickness. Thus, diffusion
starts to dominate the microstructural evolution, causing a transition
from a Zone I to a Zone III microstructure, as illustrated in Fig. 3(b). At
approximately the same temperature, many metals also form whiskers.
Whiskers may nucleate at a crystalline defect or impurity and form due
to a not-well-understood strong preferential growth along certain crys-
talline orientations. While their formation is not well understood, it is
clear that they only occur if there is considerable surface and/or bulk
mass transport. This is consistent with the observation, also evident in
Fig. 1, that they only form at relatively large θ > 0.4. Also, based on
Refs. [47,48], a large deposition angle is required for their formation.
We attribute this to two possible mechanisms: (i) the large surface
roughness associated with strong shadowing conditions results in a con-
siderably higher probability for the nucleation of whiskers; or (ii) the
growth of whiskers is facilitated by the over-proportionally large fraction
of the glancing deposition flux that impinges on whiskers rather than
onto the vertical surface.
Comparing Fig. 3(a) and (b) indicates that the microstructure for
normal deposition [Fig. 3(a)] is similar to that for oblique deposition an-
gles [Fig. 3(b)], for both the low and high temperature limits, but the
microstructures qualitatively differ in the intermediate temperature
range. We attribute the resemblance at low θ to a dominance of atomic
shadowing, irrespective of deposition angle. Therefore, GLAD micro-
structures at low θ qualitatively resemble a Zone I microstructure,
which is underdense and exhibits separated columns, with the quanti-
tative difference being the degree of porosity, which is considerably
larger for GLAD. Similarly, we attribute the resemblance at high θ to a
dominance of atomic diffusion, irrespective of deposition angle. Conse-
quently, GLAD layers deposited at θ > 0.5 show an equiaxed grain struc-
ture, similar to a Zone III microstructure, with a noteworthy distinction
that GLAD layers have a higher tendency for whisker formation.
At intermediate deposition temperatures of approximately
0.3 b θ b 0.5, the deposition angle strongly affects the competition be-
tween diffusion and shadowing processes. This leads to qualitatively
different microstructures in Fig. 3(a) and (b): for normal deposition,
surface diffusion processes densify grain boundaries, leading to a
dense columnar Zone II microstructure. In contrast, GLAD causes strong
atomic shadowing effects, resulting in underdense microstructures
with well separated columns and, particularly at high θ, irregular pro-
trusions. That is, GLAD layers resemble underdense Zone I microstruc-
tures for θ up to ~0.5, above which there is a direct transition to a
Zone III microstructure.
In the context of discussing the competition between shadowing
and surface diffusion, we note a fundamental difference in the length
scale of these two competing processes: the surface diffusion length is
primarily determined by θ. That is, it is constant for given deposition
conditions and a given material system. In contrast, atomic shadowing
is purely geometric and therefore scales with the length scale of the sur-
face morphological features. Thus, with increasing layer thickness,
when both the vertical and lateral length scales of the surface roughness
increase, the length scale of atomic shadowing also increases and ulti-
mately dominates over surface diffusion, which has a constant length
scale. Therefore, for any given θ, there is a critical layer thickness
above which the length scale of atomic shadowing will be larger than
that for surface diffusion, leading to a shadowing dominated micro-
structure. This argument is independent of the deposition angle and
suggests that shadowing always wins, as long as the deposition flux
has an oblique component and the thickness is sufficiently large. There-
fore, the structure zone model in Fig. 3 is, in principle, dependent on the
thickness of the deposited layer. However, the realistic layer thicknesses
over which a discussion of microstructural development is reasonably
useful is also limited by practical aspects. In particular, thin films that
are thinner than ~30 nm have a microstructure that is primarily deter-
mined by nucleation processes which are not described by the SZM. On
the other hand, the range of achievable PVD deposition rates also limits
the maximum thickness, with many applications having thicknesses in
the ~1 μm range, and almost all thin films being thinner than 100 μm.
Thus, the structure zone model in Fig. 3 should be considered applicable
for thin films with thickness from ~100 nm to ~10 μm, since all data
discussed in this manuscript are for layers in that thickness range. A con-
siderable increase in thickness yields, in principle, a shift of transition-
temperatures to smaller θ values.
4. Conclusions
The morphology evolution of GLAD layers as a function of increasing
substrate temperature is described by four distinct zones: rods, columns,
protrusions and equiaxed grains with whiskers. Well separated, self-
affine columnar rods with high aspect ratio grow under conditions of
limited surface diffusion. The self-affinity of the rods is manifested by
 S. Mukherjee, D. Gall / Thin Solid Films 527 (2013) 158–163
their broadening as a function of their height and is characterized by the
growth exponent p. The growth exponent decreases with increasing sur-
face diffusion due to reduction in growth front roughness. At a critical ho-
mologous growth temperature θc =0.24±0.2, the morphology changes
from rods to columns, characterized by a higher column width and a dis-
crete increase in p. This transition is driven by an increased growth front
roughness at higher θ, leading to exacerbated self-shadowing. Beyond
θ=ΘT (~0.35 for metals), the morphology exhibits protrusions, which
are characterized by their higher column width and low aspect ratio com-
pared to columns. This is attributed to a diffusion-assisted chaotic instabil-
ity for self-shadowing such that some rods capture an overproportional
flux and grow much higher than the surrounding film. The value of ΘT in-
creases for covalently bonded systems to 0.4–0.5, due to associated higher
homologous activation energies for surface diffusion (Em /kTm). Beyond
θ=0.5, surface and bulk diffusion overcome the shadowing length
scale, resulting in continuous films with equiaxed grains which also exhib-
it a high probability for the formation of whiskers. This last morphological
transition is equivalent to a direct transition from Zone I to Zone III of the
SZM for films deposited from a normal angle. Thus, the development of a
Zone II structure, characterized by a dense columnar microstructure and
facilitated by considerable surface diffusion, is suppressed during GLAD.
Acknowledgments
This research was supported by the National Science Foundation,
under grant nos. 0645312 and 1234872.
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