7124 J. Phys. Chem.

B 2000, 104, 7124-7129

Polymorphism in Phthalocyanine Thin Films: Mechanism of the r f β Transition

S. Heutz, S. M. Bayliss, R. L. Middleton, G. Rumbles, and T. S. Jones*

Centre for Electronic Materials and DeVices and Department of Chemistry, Imperial College of Science,
Technology and Medicine, London SW7 2AY, U.K.
ReceiVed: January 6, 2000; In Final Form: May 9, 2000

Two different polymorphic forms of free base phthalocyanine films have been grown on glass substrates by
ultrahigh vacuum organic molecular beam deposition. Postgrowth annealing of films grown at room temperature
leads to transformation from the R to the β1 phase. The effects of annealing lead to a number of transition
states whose morphological, structural, and spectroscopic properties can be identified using atomic force and
optical interference microscopy, X-ray diffraction, and Raman and electronic absorption spectroscopy. Detailed
morphological studies indicate that the transition occurs via a discrete number of nucleations and is preceded
by an elongation of the R crystallites. Quantitative analysis of the crystallites and domain size shows that the
individual β1 crystals grow but are confined to domains of similar orientation. The film thickness plays a
critical role and three regimes have been identified. The R f β1 transformation is only complete for films
thicker than ∼940 Å, and thick films lead to a higher degree of orientation and larger domains.

1. Introduction the two phases. In this paper, we study the evolution of an R

There is considerable interest in the growth of thin films of
molecular materials as an alternative to more conventional
inorganic technology for applications in electronics and opto-
electonics. Phthalocyanine films have been particularly well
studied and are found as components in solar cells, field effect
transistors,1 and organic light emitting devices (OLEDs), in the
last case as a buffer layer at the ITO anode.2 Their structure is
highly conjugated and the polyaromatic ring (abbreviated Pc)
can be bound to a divalent transition metal (MPc) or to hydrogen
(H2Pc).3 The metal-free phthalocyanines (H2Pc) crystallize as
a variety of polymorphs, and the two main phases identified as
R and β. They are both characterized by a herringbone structure
with the molecules stacked along the b-axis, but the polymorphs
are differentiated by the angle between the plane of the molecule
and the stacking axis.4 The two phases are monoclinic and
crystallize in the C2/c and P21/a space groups for the R and β
polymorphs, respectively.5,6
The R and β phases can be grown in ultrahigh vacuum by
organic molecular beam deposition (OMBD). The R phase is
obtained by growth at room temperature on weakly interacting
substrates such as glass.7 High-temperature growth or post-
growth annealing of an R film leads to the formation of β films.8
The β-phase is commonly accepted as the stable form above a
critical crystal size.9 The two polymorphs differ in terms of their
morphological, spectroscopic, and structural properties. The R
phase grows as small spherical crystallites, while the β crystals
are large and slender.10 The β-crystals can be randomly oriented
or highly ordered over a short range (about 100 µm2) for growth
at high substrate temperature or annealing of an R film,
respectively. The high substrate temperature and annealed film
can also be differentiated structurally. These two structures have
recently been characterized by powder X-ray diffraction and
are labeled β1 and β2, respectively.10,11
The different films have been fully characterized as pure
phases, but little is known about the actual transition between
* Corresponding author. Tel: +44 (0)20-7594-5794. Fax: +44 (0)20-
7594-5801. E-mail: t.jones@ic.ac.uk.
10.1021/jp0000836 CCC: $19.00 © 2000 American Chemical Society
Published on Web 07/08/2000
film submitted to annealing for different times by a variety of
ex situ techniques. The early stages of the transformation are
identified and an elongation of the R crystallites is seen in atomic
force microscopy (AFM) studies. The sizes of the crystallites
(either R or β1) and of the oriented domains of β1 crystallites
have been analyzed quantitatively and used to determine the
mechanism of the transition. The influence of the thickness of
the film on its morphology has also been studied and three
different regimes have been observed. These show that continu-
ity of the films is a critical factor for the completion of the
transition.
2. Experimental Section
The films were grown in an OMBD chamber with a base
pressure of about 2 × 10-9 Torr. The H2Pc powder (SynTech,
99%) was outgassed for 15-20 h before growth and sublimed
onto the substrate using a miniature Knudsen effusion cell. The
cell temperature was ∼330 °C, which corresponds to a growth
rate of ∼5 Å s-1, as determined by a quartz crystal microbalance
positioned near the substrate. The film thickness was also
calibrated ex situ using scanning electron microscopy measure-
ments on cleaved silicon samples.
The substrates were cut from glass microscope slides (BDH
super premium) and cleaned thoroughly in a methanol sonic
bath for 15 min before being mounted and transferred into the
chamber. No in situ cleaning was performed, since this appeared
to have no obvious effect on the morphology and spectroscopic
characteristics of the deposited films.
The R f β1 transition was affected by in situ annealing of
samples grown at room temperature. Two series of samples were
investigated. First, 2330 Å thick films were submitted to an
annealing at 325 °C for various times, up to a maximum of 2
h. Second, the annealing temperature and time were kept
constant (325 °C for 2 h), but the thickness of the initial R film
was varied. Five thicknesses have been considered: 560, 660,
940, 2330, and 4810 Å.
Ex situ morphology analyses were performed using a Nomar-
Polymorphism in Phthalocyanine Thin Films
Figure 1. Powder XRD 2θ scans recorded from 2330 Å thick H2Pc
films after annealing for (a) 0, (b) 0.75, (c) 1.0, (d) 1.25, and (e) 1.5 h.
The last two scans have been scaled by a factor of 20. The transition
from R to β1 characteristics is very abrupt and occurs between 1 and
1.25 h annealing.
ski interference optical microscope (Olympus BH2-UMA) and
an AFM (Burleigh instruments) operated in the tapping (non-
contact) mode. The electronic properties of the films were
assessed using a Unicam UV4 spectrometer and a Siemens
D5000 powder diffractometer was used to record 2θ scans.
Raman spectra were also obtained by excitation with a 632.8
nm laser source and detection by a microscope, spectrograph
and CCD detection system (ISA-Horiba infinity).
3. Results and Discussion
The film properties were probed using powder X-ray dif-
fraction and electronic absorption spectroscopy. Each data point
for a different annealing time represents a different sample. It
was observed that gradual sublimation of the films occurred
with increased annealing time; for example, annealing for 3 h
resulted in complete sublimation of the material from the
substrate.
XRD 2θ scans are shown in Figure 1, for (a) a reference R
film, and samples annealed for (b) 0.75, (c) 1.0, (d) 1.25, and
(e) 1.5 h. It should be noted that the intensities of the samples
annealed for 1.25 and 1.5 h have been scaled by a factor of 20
for the sake of clarity. Films annealed up to 1 h (a-c) show
peaks characteristic of the R phase, with diffraction from the
(200) and (400) planes giving 2θ values at 6.82 and 13.6°,
respectively.12 Longer annealing (d,e) results in a diffractogram
typical of the β1 phase, where the peaks due to diffraction from
the (001), (002) and (41h3h) planes appear at 2θ ) 7.0, 14.1, and
15.5°.13 The transition is abrupt, with no intermediate state
containing diffraction signals typical of both polymorphs. The
fwhm of the diffraction peaks do not change with increased
annealing time, indicating little or no growth of the crystal size
for either the R or β1 form.
The same abrupt transition is also seen in electronic absorp-
tion spectroscopy. The spectra of the samples submitted to
different annealing times are shown in Figure 2; (a) no anneal
and (b) 0.75, (c) 1.0, (d) 1.25, (e) 1.5, and (f) 2.0 h annealing.
A rather sharp transition from R character to β character is again
observed between 1 and 1.25 h annealing. Samples that are
annealed for 1 h or less (a-c) show absorption features
characteristic of the R phase, with a peak at 630 nm and a high-
J. Phys. Chem. B, Vol. 104, No. 30, 2000 7125
Figure 2. Electronic absorption spectra recorded from 2330 Å thick
H2Pc films after annealing for (a) 0, (b) 0.75, (c) 1.0, (d) 1.25, (e) 1.5,
and (f) 2.0 h. The R features are retained for up to 1 h annealing, and
films annealed for 1.25 h or more have β1 characteristics. Spectrum f
is less intense due to partial sublimation of the film.
intensity shoulder at about 690 nm. Samples annealed for longer
times (d-f) show characteristics of the β1 phase, with distinct
peaks at 650 and 710 nm. There is some evidence that the
relative intensities of the two bands in the β1 phase spectrum
are not the same. The broad higher wavelength Q-band (710
nm) becomes slightly more intense with prolonged annealing
with respect to the equally broad, lower wavelength Q-band
(650 nm). A similar phenomenon has been observed by Loutfy14
and has been explained in terms of the size of the crystallites,
with larger crystals having more intense bands at higher
wavelength. This assumption will be confirmed by the AFM
analysis presented in this paper.
Resonance Raman spectra were also recorded for the films
after different annealing times. Here, the focused laser meant
that a 1 µm2 area of the sample was measured and spectra were
recorded from 8 to 10 different points of the surface. The Raman
spectra presented in Figure 3 show a representative spectrum
for each sample. Typical spectra of the pure β1 and R phase are
shown as a reference in (a) and (b), respectively. The regions
that allow for distinction between the two phases are shaded in
gray. In the 600-800 cm-1 region, corresponding to the
vibrations of the macrocycle,15 the high-energy peak at 791 cm-1
is more intense than the low-energy one at 677 cm-1 for the β1
phase and this intensity ratio is reversed in the R phase. The
transitions around 1500 cm-1 are present as a doublet in the R
phase and a triplet in the β phase and correspond to vibrations
of the isoindole modified by the macrocycle. After annealing
for 0.75 h, the Raman spectra showed that the film was still R
across the whole surface (c). Annealing for 1 h leads to a mixture
of the R and β1 phase coexisting on the surface (d,e). This
observation shows the advantage of a microscopic probe such
as Raman over the “bulk” film measurement techniques (XRD
and electronic absorption spectroscopy), which were not sensi-
tive to the onset of β1 phase formation. The ratio of R phase
spectra to β1 phase spectra after 1 h annealing is approximately
7126 J. Phys. Chem. B, Vol. 104, No. 30, 2000
Figure 3. Resonance Raman spectra of 2330 Å H2Pc films acquired
with a 632.8 nm laser source. (a) and (b) are reference spectra for β1
and R films, respectively. Different annealing times are shown: (c)
0.75 h, (d) 1.0 h, R phase, (e) 1.0 h, β1 phase, (f) 1.25 h, (g) 1.5 h, and
(h) 2.0 h. The ratio of R (d) to β1 (e) for the film annealed for 1 h is
approximately 5:2.
Figure 4. AFM images of 2330 Å thick H2Pc films as a function of
annealing time: (a) no anneal, (b) 1.0 h, R phase, (c) 1.0 h, β1 phase
(minor component), (d) 1.25 h and (e) 2.0 h.
5:2, indicating that the surface is still predominantly R phase,
as previously observed. Annealing for 1.25, 1.5, and 2 h (f-h)
leads to spectra characteristic of the β1 phase only with the
appearance of a new peak at 1525 cm-1, the intensity of which
increases with annealing time.
The morphology of the samples annealed for different times
was assessed using AFM (Figure 4). A film grown at room
Heutz et al.
Figure 5. Nomarski micrographs of (a) an R H2Pc film and films
annealed for (b) 1.0, (c) 1.25, and (d) 2.0 h. The film thickness was
2330 Å.
temperature with no annealing is shown as a reference in (a)
and displays the high density of spherical islands that character-
izes the R phase.10 The first changes become apparent after
annealing for 0.75 h. The underlying surface morphology is
similar to that seen for growth at room temperature, but closer
inspection reveals some elongation of the spheres and the
presence of several larger islands on the surface, with a typical
diameter of 0.2-0.3 µm. Elongation of the R spheres becomes
more pronounced after annealing for 1 h, (b). This elongation
prior to transformation has been reported in a previous electron
microscopy study of CuPc films on muscovite.14 Larger islands
are also present on the surface, although these have not increased
in size and number (number density of islands = 4 µm-1). A
small proportion of the sample displays regions covered in
oriented slender crystallites (c). These areas are at least 49 µm,2
the typical area of an AFM image, and are characteristic of a
pure β1 phase film.10 The organized growth of the β1 phase
starts therefore after 1 h annealing, consistent with the Raman
spectra shown in Figure 3. After 1.25 h annealing the surface
is completely covered with the long thin crystals of the β1 phase.
The crystallites are parallel to each other over large areas, and
a boundary between two domains of different orientations can
be seen in (d). Annealing for longer times leads to no appreciable
change in the surface morphology until after 2 h (e). At this
point, the appearance of smooth areas between remaining islands
of β1 crystals indicates that the β1 phase crystals have grown
together and there only remain a few well-defined thin β1
crystallites, mostly arranged in columns. However, the domain
boundaries are still present and there are some features
reminiscent of the oriented crystallites in the smooth areas,
indicating that these have been formed by the merging of the
slender β1 crystallites.
Nucleation and growth of the β1 phase with prolonged
annealing can also be seen morphologically on a larger scale
using optical interference microscopy, as shown in Figure 5.
The first appearance of distinctive features occurs after annealing
for 1 h (b), where isolated islands are seen superimposed on
the smooth background that characterizes the R phase (a).10
These islands are thought to be nucleation sites of domains of
β1 phase crystals, corresponding to the areas that have β1
characteristics in Raman (Figure 3e) and that display oriented
slender crystallites in AFM (Figure 4c). Annealing for 1.25 h
results in complete coverage of the surface with the irregular
Polymorphism in Phthalocyanine Thin Films
Figure 6. Mean crystallite size, as obtained by AFM, as a function of
annealing time for 2330 Å thick H2Pc films. The R spheres and islands
become slightly larger with annealing time, but the effect is particularly
pronounced for the β1 crystallites, which grow from 0.10 to 0.51 µm2
when the annealing time is increased from 1.0 to 2.0 h.
shaped domains of the β1 phase (c). It has been verified by a
large scale AFM analysis that the domains correspond to regions
where the crystallites have a similar orientation. The boundary
seen by AFM (Figure 4d,e) corresponds to a separation between
two zones of different contrast in the optical micrograph. The
main characteristics of the Nomarski images are retained with
increased annealing time (d).
The sizes of the crystallites measured by AFM and of the
domains detected on the Nomarski micrographs have been
analyzed to obtain quantitative information concerning the R-β1
transition. Images were taken at four to five different areas of
the sample, and all the crystallites or domains present were
measured to ensure a statistical and representative picture of
the total sample. Figure 6 shows the evolution of the mean size
of the main features appearing in AFM images: (i) the R phase
crystallites, (ii) the ill-defined islands that appear during the
transition (Figure 4c), and (iii) the slender β1 crystallites. The
elongation of the R spheres prior to the transition is accompanied
by an increase in mean size from 0.015 to 0.022 µm2. The β1
crystallites undergo a clear linear increase in size from 0.10 to
0.51 µm2. This confirms the earlier observation that the ratio
of the two Q-bands in the electronic absorption spectra change
as a function of annealing time due to the growth of the crystals
(Figure 2). It is likely that the size of the crystallites will continue
to increase until sublimation reduces the film thickness to a level
where gaps between the crystallites will appear.
Closer analysis of the size evolution for the β1 phase can be
made by evaluating the shape of the crystals. We define a shape
parameter S, which is the length/width ratio of the crystallites.
S is plotted as a function of annealing time in Figure 7 and it
is clear that the crystallites become progressively more elon-
gated. This elongation has also been noted for R crystallites.
Since the lattice vector b is the common vector that lies parallel
to the substrate for both phases of H2Pc, it can be concluded
that the crystals, either R or β1, grow along their b axis.
A quantitative size analysis can also be made using the
Nomarski micrographs. Figure 8 shows the evolution of the
domains as a function of annealing time. The mean size of the
domains increases until an annealing time of between 1.25 and
1.5 h, at which point the size saturates at approximately 100
µm2.
The different domains observed have been shown to be
regions where the β1 crystals are oriented in one particular
direction. It is improbable that the boundaries between two
regions where the crystals are oriented differently would break
J. Phys. Chem. B, Vol. 104, No. 30, 2000 7127
Figure 7. The shape parameter, S, corresponding to the length/width
ratio of the β1 crystallites, as a function of annealing time for 2330 Å
thick H2Pc films. The crystallites become more elongated and grow
along their b axis. The solid line is simply a guide to the eye.
Figure 8. Mean size of the domains observed by Nomarski microscopy
as a function of annealing time for 2330 Å thick H2Pc films. The domain
size increases and saturates at about 100 µm2 after 1.25-1.5 h
annealing. The solid line is simply a guide to the eye.
down to allow for the merging of the domains, and hence the
saturation of the domain size is to be expected. The Nomarski
image presented in Figure 5b indicates that nucleation occurs
at many sites. As these domains grow in size, their final and
finite size is inversely related to the number of nucleation sites
that can be achieved before boundaries are formed between the
domains. The finite number of nucleation sites can be obtained
by evaluating the number of domains in a totally β1 sample,
and this number should remain constant after complete coverage.
Here, the number of sites are 1.2 ( 0.3 µm-1.
It is apparent that when the crystallites and hence the domain
boundaries have all merged, a totally smooth β1 film is produced.
A high thickness for the film initially grown at room temperature
is therefore required to compensate for the progressive sublima-
tion of material during the annealing transformation.
A qualitative analysis of the influence of the film thickness
on the R f β1 transformation was carried out by studying the
surface morphology. It is first important to note that there is a
film thickness constraint on the R f β1 phase transition. It is
not possible to affect the transformation on films that are thinner
than 560 Å, either by growth at an elevated substrate temper-
ature, or by annealing. Ashida et al.16 suggested that complete
transformation of films below a certain thickness did not occur
because there was not enough material present on the surface
to ensure a continuous film during the transition. An alternative
explanation is that below a certain film thickness, and therefore
below a certain R phase crystal size, the R phase is more stable
than the β1 phase, leading to the transformation being energeti-
cally unfavorable; the figure quoted for the point at which the
stability of the two polymorphs is equal is 2 × 104 molecules.8
If the R phase crystals are assumed to be spherical, this
corresponds to a crystal radius of 177 Å, or a diameter of 345
Å. This is the theoretical sphere diameter below which the R
7128 J. Phys. Chem. B, Vol. 104, No. 30, 2000
Figure 9. AFM images of H2Pc films annealed for 2 h at 325 °C, for
different film thicknesses: (a) 560, (b) 990, and (c) 4880 Å. Partial
transformation with discrete domains of R and β1 phases is observed
for the thinnest film. The crystallites are more ordered for thicker films.
phase will be more stable than the β1. This compares well with
the observed film thickness of 560 Å, below which the
transformation does not appear to occur. For films less than
560 Å, sublimation of material occurs rather than transformation
for equivalent annealing conditions.
The effects of film thickness are also apparent in the electronic
absorption spectra. Samples with a film thickness greater than
940 Å are characteristic of the β1 phase whereas thinner films
give a weak signal that is mainly β1 but still shows traces of R.
AFM images of the annealed films (2 h) at different
thicknesses is presented in Figure 9. The thinner films (<660
Å) show two distinct regions having morphological character-
istics of the β1 and the R phase, respectively (a). There are gaps
between the two phases, consistent with previous observations
that the R f β1 transition is inhibited by the lack of material
below a critical film thickness.12 Figure 9b shows the morphol-
ogy of a 940 Å film. The surface is completely covered in
elongated crystallites that are parallel to each other over a short
range and many boundaries are present. An AFM image of a
2330 Å film was shown in Figure 4e and displays the same
characteristics, with additional merged domains. The thickest
film (Figure 9c) differs from the other two β1 samples in that
all the crystallites are oriented over the 49 µm2 range of the
AFM image. It appears that the higher thickness facilitates
parallel orientation of the crystallites. It is likely that the cross
section of the crystallites is square, so that a thicker sample is
formed by stacks of crystallites, and only the top crystallites
are imaged by AFM. If the transformation is initiated at the
glass/H2Pc interface, i.e., at the hottest point, the successive
stacks will have opportunity to reorganize and be parallel at
the top, as seen by AFM. The crystal size is smaller because of
the reduced thermal energy that reaches the top layer to induce
the growth of the crystal along the b axis when compared to
the thinner films. This also explains the absence of smooth areas
on the thick sample.
Figure 10 shows the effect of film thickness on the larger
scale morphology of the β1 phase. For the thinnest film for
which it is possible to induce the R f β1 transformation, the
result is isolated areas of fern-like morphology (a). There are
large areas of nontransformed material between the β1 phase
islands, and there is also space between the individual strands
of the fern-like islands. When the starting film is slightly thicker,
Heutz et al.
Figure 10. Nomarski micrographs of H2Pc films annealed for 2 h at
325 °C, for different film thicknesses: (a) 560, (b) 990, and (c) 4880
Å. The thinnest film shows nucleation of the β1 phase and a fern-like
morphology. Increasing thickness leads to an increase in the domain
size.
the β1 islands are larger, but they are still isolated from one
another (b). This correlates well with the AFM results, which
showed discrete domains of R and β1 phase H2Pc. Figure 10c
shows a sample that has the features typical of all films above
a critical thickness where the transformation is complete, i.e.,
940 Å. The surface is covered entirely by domains of aligned
β1 phase crystals. On close inspection this thicker film can be
seen to exhibit the same fern-like fine structure as the thinner
films, but there is no interlying space between the individual
strands. It can be seen without any quantitative analysis that
the size of the domains increases with film thickness for a given
annealing time and temperature. This is a direct consequence
of the higher degree of alignment observed of the crystallites
for the thickest film.
The above observations suggest three regimes of behavior
for films of different thickness. The extreme case is for thin
films, i.e., less than 560 Å. In this case there is not enough
material to facilitate any transformation from the R phase to
the β1. This is consistent with the suggestion that particles of
the size found in these films are more stable in the R phase
than in β1. For film thicknesses between 560 and 940 Å, only
partial transformation of the film occurs, indicating that the film
is thick enough to allow transformation, but there is not enough
material on the surface to ensure continuity of the film during
transformation. Clearly, the β1 phase grows at the expense of
the R phase directly in contact with it. The transformation occurs
via discrete nucleations, since the remaining R areas coexist
and do not intermix with completely transformed β1 phase
regions. It is also likely that since the transformation is very
close to the sublimation point, the regions that have not been
transformed are thin enough to be in the regime where the R
phase is more stable than the β1. For film thicknesses above
940 Å, both the size of the R phase crystallites and the thickness
of the film (and hence its continuity) allow complete transfor-
mation of the film.
4. Conclusions
This study elucidates the mechanism of the R f β1 phase
transformation as a consequence of annealing H2Pc films.
Preliminary elongation of the spherical R crystallites and
appearance of rough areas where the crystallites have grown
much larger are observed. Nucleation of the β1 phase occurs at
discrete centers across the film and appears as domains of
oriented slender β1 crystallites. These precursor domains grow
until they cover the entire area of the sample. At this point, the
size of the domains saturates because boundaries are found,
Polymorphism in Phthalocyanine Thin Films
while the individual crystallites continue to grow until they
finally merge.
The thickness of the film plays an important role and three
regimes are observed for films of different thickness. The
extreme case is for thin films, i.e., less than 560 Å. The R f
β1 transformation is inhibited since the R phase is supposed to
be the most stable for reduced thickness, and sublimation occurs
without any transformation. For films between 560 and 940 Å
only partial transformation of the film occurs, indicating that
the film is thick enough to allow the transition, but there is not
enough material on the surface to ensure continuity of the film
during transformation. Where continuity of the film is not
preserved, transformation cannot continue and the resultant film
is a mixture of the R and β1 phases. For films above 940 Å,
both the size of the R phase crystallites and the thickness of
the film (and hence its continuity) allow complete transformation
of the film.
Both the alignment of the crystallites and the domain size
increase with film thickness. This configuration should allow
the formation of smooth films if the annealing process is
prolonged for more than 2 h. Such films where the transport
properties of a highly crystalline film could be combined with
the mechanical advantages of a smooth surface are potentially
attractive for many electronic and optoelectronic device ap-
plications. The morphology of the β1 film is thermally stable
up to 320 °C and smooth β1 layers could therefore be preferred
to films grown at room temperature.
Acknowledgment. We thank Professor W. Griffiths for the
provision of the Raman spectrometer and Dr R. Cloots
J. Phys. Chem. B, Vol. 104, No. 30, 2000 7129
(University of Liège, Belgium) for the X-ray diffraction
measurements. S.H. thanks the Department of Chemistry,
Imperial College, for a postgraduate teaching assistantship.
S.M.B. is grateful to the Engineering and Physical Sciences
Research Council (EPSRC), U.K., for the provision of a Ph.D.
studentship. This work was supported by the EPSRC, U.K.
References and Notes
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