ISSN 1063-7834, Physics of the Solid State, 2007, Vol. 49, No. 2, pp. 272–277. © Pleiades Publishing, Ltd.

, 2007.
Original Russian Text © V.L. Berkovits, A.V. Ziminov, A.G. Kazanskiœ, A.G. Kolos’ko, S.M. Ramsh, E.I. Terukov, A.V. Fenukhin, V.P. Ulin, T.A. Yurre, J.P. Kleider, 2007, published
in Fizika Tverdogo Tela, 2007, Vol. 49, No. 2, pp. 262–266.

OPTICAL
PROPERTIES

Influence of the Molecular Structure of Copper Phthalocyanines

on Their Ordering in Thin Films and Photoluminescence
and Absorption Spectra
V. L. Berkovitsa, A. V. Ziminovb, A. G. Kazanskiœc, A. G. Kolos’koa, S. M. Ramshd,
E. I. Terukova, A. V. Fenukhinc, V. P. Ulina, T. A. Yurreb, and J. P. Kleiderd
a Ioffe
Physicotechnical Institute, Russian Academy of Sciences,
Politekhnicheskaya ul. 26, St. Petersburg, 194021 Russia
e-mail: vladimir.berkovits@mail.ioffe.ru
b St. Petersburg Technological Institute (Technical University),
Moskovskiœ pr. 26, St. Petersburg, 198013 Russia
c Moscow State University, Leninskie gory, Moscow, 119992 Russia
d Laboratoire de Génie Électrique de Paris (CNRS UMR 8507), Ecole Superieure d’Electricite,
Universites Paris VI et XI, France
Received April 6, 2006

Abstract—Thin films consisting of copper phthalocyanine (CuPc) molecules and copper phthalocyanine
molecular complexes with different structures on glass and glass-ceramic substrates are studied using reflec-
tance anisotropy, photoluminescence, and photoconductivity (constant photocurrent method) spectroscopies. It
is established that, in the studied films, the CuPc molecules and CuPc molecules containing peripheral phthal-
imide substituents are located in planes virtually parallel to the surface of the substrate. In thin films consisting
of µ-peroxo dimer complexes, the angle between the CuPc molecular planes and the surface of the substrate is
close to 90°. The thin films formed by CuPc molecules containing peripheral phthalimide substituents are char-
acterized by the highest luminescence intensity in the range of ~1.12 eV and the lowest absorption intensity in
the range of energies less than the band gap. These properties are explained by the lower concentration of non-
radiative recombination centers in the film.
PACS numbers: 68.47.Pe, 73.61.Wp
DOI: 10.1134/S1063783407020151

1. INTRODUCTION optoelectronics. Planar molecules of metal phthalocya-

A burst of activity in the study of molecular organic
materials that possess semiconductor properties in the
solid state has been observed over the last decade.
Films prepared from these materials have already been
used in optical and electronic instruments, data record-
ing devices, displays, and solar energy converters [1].
This allows us to speak of the appearance of a new sci-
entific and technical direction—molecular organic
electronics. In order to develop this new direction, thor-
ough investigations are required into the optical and
physical properties of thin films prepared from organic
compounds because these properties substantially
depend both on the structure of organic molecules and
on their ordering in the film.
In this work, we investigated the structural features
and optical properties of thin films consisting of copper
phthalocyanine (CuPc) molecules with peripheral
groups of different types. Among organic semiconduc-
tors, metal phthalocyanine (MPc) complexes have the
highest carrier mobility and, consequently, can be con-
sidered promising materials for use in electronics and
nines are high-symmetry π-electron systems with a
strong electron delocalization [2]. The quantum effi-
ciency of the molecular photoluminescence in the red
visible and near-infrared ranges is greater than or equal
to 0.5.
2. SAMPLES AND EXPERIMENTAL
TECHNIQUES
The initial copper phthalocyanine complexes CuPc
were prepared by template synthesis (at 180°–190° for
2 h) upon melting of phthalonitride with copper ace-
tate, followed by sequential purification with boiling
distilled water and organic solvents. The purity was
controlled using silica gel thin-layer chromatography.
Experiments were also performed with modifications
of the initial copper phthalocyanine complex, which
were prepared by the introduction of peripheral
(phthalimide) substituents into phthalocyanine and
through the formation of µ-peroxo dimer complexes
with the CuPc–O–O–CuPc bond. The copper phthalo-
cyanine tetraphthalimide CuPc(CH2phti)4 was synthe-

272
 INFLUENCE OF THE MOLECULAR STRUCTURE 273

(a)

N N N

N Cu N

N N N

(b)

N N N O

N Cu N H2C N

N N N O
n

(c)

N N
N N Cu N
O N N
N N O
N Cu N N
OH2 N N

Fig. 1. Structures of the initial molecules: (a) copper phthalocyanine CuPc, (b) copper phthalocyanine with peripheral substituents
CuPc(CH2phti)4, and (c) copper phthalocyanine with axial substituents (H2OCuPcO)2.

sized by the Mannich reaction upon interaction of cop-
per phthalocyanine with phthalimide and formalin in
the presence of sulfuric acid. The dimeric µ-peroxo
copper phthalocyanine (H2OCuPcO)2 was prepared by
oxidizing copper phthalocyanine with nitric acid. The
structures of the initial molecules are shown in Fig. 1.
Films of thickness d ≈ 0.65 µm were produced
through the deposition of the aforementioned copper
phthalocyanine complexes onto substrates prepared
from glass-ceramics and silica glass. Samples 1, 2, and
3 were obtained in the form of films formed by the
CuPc, CuPc(CH2phti)4, and (H2OCuPcO)2 molecules,
respectively.
The structural features of the CuPc films were inves-
tigated using optical reflectance anisotropy spectros-
copy. Moreover, we studied the photoluminescence
spectra and the spectral dependences of the absorption
coefficient α in the visual and near-infrared ranges by
measuring the photoconductivity with the constant
photocurrent method.

PHYSICS OF THE SOLID STATE Vol. 49 No. 2 2007

274
4 multiplier over the entire spectral range (1.5–5.5 eV)
∆R/R, %
2 Reflectance anisotropy spectroscopy has been
0
300 400 500 600
Wavelength, nm
Fig. 2. Reflectance anisotropy spectra of (a) CuPc (sample 1),
(b) CuPc(CH2phti)4 (sample 2), and (c) (H2OCuPcO)2
(sample 3) films. Horizontal lines in the initial range of each
spectrum indicate zero signal.
2 β coincide with the anisotropy axes in the plane of the
b
PL intensity, arb. units
a
1 3. EXPERIMENTAL RESULTS
c AND DISCUSSION
0 anisotropy spectra of all the samples contain specific
1.0 1.2 1.4
Wavelength, µm
Fig. 3. Photoluminescence spectra of (a) CuPc (sample 1),
(b) CuPc(CH2phti)4 (sample 2), and (c) (H2OCuPcO)2
(sample 3) films.
For normally incident light, the reflectance anisot-
ropy spectrum is a spectral dependence of the quantity
[3]
∆R/R = 2 ( R α – R β )/ ( R α + R β ),
where Rα and Rβ are the reflectivities of linearly polar-
ized light along the orthogonal directions α and β in the
plane of the sample surface, respectively. In a setup
used for recording the reflectance anisotropy spectra
[4], the linear polarization of light incident on a sample
is modulated between the α and β directions at a fre-
quency of 100 kHz with the use of a photoelastic mod-
ulator. If the CuPc film at the light absorption depth has
an anisotropy of optical properties along the α and β
directions, the intensity modulation in reflected light
arises at the same frequency. Reflected light is recorded
by a photomultiplier with subsequent processing of the
BERKOVITS et al.
signal by a synchronous detector. A special electronic
a circuit maintains a constant photocurrent of the photo-
b
under investigation and, thus, provides an anisotropy
signal ∆R/R at the output of the synchronous detector.
c widely used in investigations into the optical properties
of surfaces of semiconductor and metal crystals. In
these experiments, the surface is oriented so that the
surface axes coincide with the orthogonal directions α
and β. Since the directions of the anisotropy axes for
CuPc films deposited onto amorphous glass surfaces
are not known a priori, it becomes necessary to study
700 the azimuthal dependence of the anisotropy effect. If
the anisotropy axes lying in the plane of the film surface
make an angle F with respect to the orthogonal direc-
tions α and β, the anisotropy signal can be written in the
form [5]
∆R/R = ∆R/R max cos ( 2F ). (2)
It is clear that the anisotropy signal reaches a maxi-
mum in the case where the orthogonal directions α and
sample surface. In all the experiments performed, the
plane of the film surface was oriented so that the anisot-
ropy signal ∆R/R would be maximum.
It is found that all the studied samples (1–3) of the
CuPc films exhibit characteristic reflectance anisotropy
spectra, which are shown in Fig. 2. The reflectance
1.6 features located in the ranges that correspond to the so-
called Q absorption bands (600–700 nm) and the Soret
band (250–450 nm) for copper phthalocyanine [6]. As
a rule, these absorption bands are assigned to the elec-
tronic transitions between the doubly degenerate levels
of the HOMO and LUMO orbitals, which are formed
by the system of conjugated π-bonds of the central ring
in the CuPc molecules.
For molecular films, the nonzero anisotropy signal
∆R/R can be due to the anisotropy of molecules them-
selves and/or the anisotropy of the structure of the
(1) molecular film. The CuPc molecules have a planar
symmetry. In the simplest case, the reflectance anisot-
ropy signal can arise from the CuPc film if the constit-
uent molecules are equally tilted with respect to the
substrate plane. It is known that compact layers formed
upon deposition of CuPc molecules onto glass sub-
strates consist of linear associates (stacks) composed of
uniaxially aligned molecules [7]. Hence, the tilt angle
the molecular planes in stacks make with the plane of
the substrate surface can be considered the main factor
responsible for the nonzero reflectance anisotropy sig-
nal. The reflectance anisotropy spectra of samples 1 and
2 (Fig. 2, curves a, b) exhibit similar features, which,
however, somewhat differ in intensity. As was noted
PHYSICS OF THE SOLID STATE Vol. 49 No. 2 2007
 INFLUENCE OF THE MOLECULAR STRUCTURE
above, the optical properties of the CuPc and
CuPc(CH2phti)4 films in the range under investigation
are determined by the electronic transitions in the cen-
tral rings of these molecules, which have the same
structure. Therefore, the similarity of curves a and c
depicted in Fig. 2 indicates that the associates forming
the films of these molecules have similar structures.
The observed difference between the intensities of the
reflectance anisotropy signals in the spectra (Fig. 2,
curves a, b) is most likely associated with the insignif-
icant differences in the thickness of film samples 1 and
2 [5].
The intensities of the features observed in the reflec-
tance anisotropy spectrum of sample 3 (Fig. 2, curve c)
are severalfold higher than the intensities of the corre-
sponding features in the spectra of film samples 1 and
2. This difference suggests that the structures of these
films differ significantly. Indeed, the joining of the
CuPc molecules in pairs by peroxo bridges (Fig. 1c)
should lead to a radical change both in the packing of
molecules in associates and in their coordination with
respect to the substrate. The formation of linear associ-
ates from uniaxially aligned copper phthalocyanine
molecules is governed by the intermolecular interac-
tions between the macrocycles of the neighboring mol-
ecules. In the case of dimer complexes, these associates
cannot be formed because of the repulsive Coulomb
interaction between similar groupings. The formation
of a structure composed of close-packed layers of
dimer molecules alternating in a hexagonal order
(ABAB) in the film becomes more energetically favor-
able. The centers of the molecules in adjacent rows
appear to be shifted with respect to each other by a dis-
tance equal to the molecular radius. The arrangement of
the molecular layers with respect to the plane of the
substrate surface is dictated by the minimization of the
energy for the substrate–layer interface. Oxygen atoms
that are involved in the structure of SiO4 tetrahedral
groupings and bear effective negative charges are
located at the surface of the glass substrate. The cores
of the (H2OCuPcO)2 molecules are negatively charged,
whereas the hydrocarbon terminal groups of the mole-
cules are positively charged. Consequently, the wetting
conditions turn out to be optimum when the peripheral
groups are in contact with the glass surface, i.e., for the
vertical arrangement of the layers formed by dimer
molecules. Initially, the molecular axes in the substrate
plane are randomly oriented and the reflectance anisot-
ropy signal is absent. The growth of molecular layers in
the film can be accompanied by the formation a domain
structure containing macroscopic regions with a pre-
ferred orientation of the molecular axes, i.e., film
regions that serve as a polarizing medium in the course
of the interaction with light. It should be noted that the
amplitude of the reflectance anisotropy signal for the
perfect domain ordering should approach unity. The
observed amplitude (≈0.14–0.16) indicates that
domains are weakly ordered in the regions under inves-
tigation.
PHYSICS OF THE SOLID STATE Vol. 49 No. 2 2007
275
100
a
10–1
αη/αη1.8 eV
b
c
10–2
10–3
0.8 1.2 1.6 2.0
Light energy, eV
Fig. 4. Spectral dependences of the product αη in terms of
relative units for (a) CuPc (sample 1), (b) CuPc(CH2phti)4
(sample 2), and (c) (H2OCuPcO)2 (sample 3) films accord-
ing to the data obtained by the constant photocurrent
method.
Figure 3 shows the photoluminescence spectra of
samples 1–3 in the near-infrared range. As can be seen
from Fig. 3, these spectra have a similar structure with
a clear maximum at a wavelength λ ≈ 1.11 µm
(1.12 eV). The location of this maximum in the spectra
of the CuPc films is close to that of the phosphores-
cence maximum (λ ~ 1.075 µm) observed in the spectra
of copper phthalocyanine solutions in α-chloronaph-
thalene [8]. According to Vincett et al. [8], this maxi-
mum is attributed to the transition from the excited trip-
let state T1 to the ground state S0 of the molecule. It can
also be seen from Fig. 3 that, like the reflectance anisot-
ropy spectra, the photoluminescence intensity, in par-
ticular, the intensity of the principal maximum at a
wavelength of 1.11 µm, depends on the structure of the
molecules forming the films under investigation. The
maximum luminescence intensity is observed in the
spectrum of sample 2.
The spectral dependences of the absorption coeffi-
cient α for organic semiconductors, as a rule, are
obtained by measuring the optical transmission spectra
[9]. However, the use of this technique is very compli-
cated for thin films of organic semiconductors in the
range of small absorption coefficients α satisfying the
inequality αd < 1. At the same time, owing to the high
photoconductivity of phthalocyanines, the spectral
dependences of the absorption coefficient α can be
determined by photoelectric techniques, specifically by
the constant photocurrent method [10], which has been
used to advantage in studying such dependences for
amorphous semiconductors. Since the internal quantum
efficiency η depends on the energy of photons incident
on the sample, the constant photocurrent method makes
276 BERKOVITS et al.
it possible to measure the spectral dependence of the
product αη.
In order to measure the photoconductivity, alumi-
num contacts 4 mm long were evaporated onto the film
surface. The distance between the contacts was equal to
0.5 mm. The measurements were performed at room
temperature under vacuum at a residual pressure of
10−3 Pa in an electric field with a strength of 200 V/cm.
Figure 4 shows the spectral dependences of the product
αη in terms of the relative units (αη)/(αη)1.8 eV for
the samples under investigation. It can be seen from
Fig. 4 that the dependence of the product αη on hν in
the energy range of the absorption edge (1.4–1.6 eV) is
similar to an exponential curve. This dependence can
be associated with the exponential distribution of local-
ized states in metal phthalocyanines [11]. The energy
corresponding to the slope of the dependence of the
product αη on hν in the spectral range under consider-
ation is minimum for sample 2 and amounts to
≈53 meV. According to Naito et al. [11], these localized
states are attributed to concentration fluctuations of
–
charged ions, in particular, MPc+ and O 2 ions, which
are responsible for the fluctuations of the electrostatic
potential in the bulk of the film.
In the energy range hν < 1.4 eV, the spectral depen-
dences of the product αη exhibit three local maxima at
photon energies of 1.12, 1.21, and 1.36 eV. The posi-
tions of these maxima for the films under investigation
are close to those observed in the absorption spectra of
thick (10–30 µm) single-crystal flakes of copper phtha-
locyanine [12] and in the photoconductivity spectra of
copper phthalocyanine in the near-infrared range [13,
14]. The intense absorption maximum located in the
photon energy range 1.12–1.14 eV is assigned to the
transition from the ground state S0 to the excited triplet
state T1. In this case, it is assumed that the forbidden-
ness of the transition is removed as a result of the spin–
orbit interaction owing to the presence of the heavy
central atom. The above interpretation of the maximum
in the photoconductivity spectra obtained by the con-
stant photocurrent method is confirmed by the coinci-
dence of its energy position (1.12 eV) with the position
of the most intense photoluminescence maximum,
which, as was noted above, should be attributed to the
T1 S0 transition.
A comparison of the photoluminescence and
absorption spectra shown in Figs. 3 and 4 demonstrates
that these spectra correlate with each other. Among the
samples under investigation, the maximum photolumi-
nescence intensity and the minimum absorption in the
range of energies less than the band gap of copper phth-
alocyanine is observed for sample 2. The high photolu-
minescence intensity revealed for sample 2 indicates
that the concentration of nonradiative recombination
centers in this film is lower than that in the other sam-
ples. In turn, a decrease in the concentration of nonra-
diative recombination centers leads to a decrease in the
relative intensity of the absorption maximum at the
PHYSICS OF THE SOLID STATE
photon energy hν = 1.12 eV in the photoconductivity
spectra. Since the photoconductivity of the films is
measured by the constant photocurrent method, the
observed decrease in the concentration of nonradiative
recombination centers can lead to a decrease in the rate
of dissociation of Frenkel excitons generated upon opti-
cal excitation of the molecules. This should be accom-
panied by a decrease in the relative photoconductivity
corresponding to the S0 T1 transition.
The low concentration of nonradiative recombina-
tion centers in sample 2 is in agreement with the photo-
conductivities measured in the samples under illumina-
tion with a photon energy of 1.95 eV. The photoconduc-
tivity of sample 2 at room temperature is one order of
magnitude higher than that of samples 1 and 3. The
luminescence intensity is minimum for sample 3. This
result can be explained by the presence of intracomplex
centers of electron nonradiative recombination at deep
levels associated with the oxygen atoms.
4. CONCLUSIONS
Thus, thin films of copper phthalocyanines with dif-
ferent substituents were investigated using reflectance
anisotropy, photoluminescence, and photoconductivity
(constant photocurrent method) spectroscopies. The
analysis of the reflectance anisotropy spectra of the
copper phthalocyanine films uniquely demonstrated
that the structural characteristics of the films depend on
the axial and peripheral substituents in the CuPc mole-
cules. It was established that the CuPc and
CuPc(CH2phti)4 molecules in the films are arranged in
planes aligned almost parallel to the surface of the sub-
strate. In the films consisting of (H2OCuPcO)2 mole-
cules, the angle between the molecular planes and the
surface of the substrate is close to 90°. Among all the
samples under investigation, the film formed by
CuPc(CH2phti)4 molecules is characterized by the
highest luminescence intensity in the range of ≈1.12 eV
and the lowest absorption in the range of energies less
than the band gap. These properties can be associated
with the lower concentration of nonradiative recombi-
nation centers in the film.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research, project no. 05-03-32823.
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Translated by O. Borovik-Romanova