ISSN 1063-7826, Semiconductors, 2008, Vol. 42, No. 3, pp. 321–324. © Pleiades Publishing, Ltd., 2008.

Original Russian Text © I.A. Belogorokhov, Yu.V. Ryabchikov, E.V. Tikhonov, V.E. Pushkarev, M.O. Breusova, L.G. Tomilova, D.R. Khokhlov, 2008, published in Fizika i Tekhnika
Poluprovodnikov, 2008, Vol. 42, No. 3, pp. 327–330.

AMORPHOUS, VITREOUS, POROUS, ORGANIC,

AND MICROCRYSTALLINE SEMICONDUCTORS;
SEMICONDUCTOR COMPOSITES

Photoluminescence in Semiconductor Structures Based

on Butyl-Substituted Erbium Phthalocyanine Complexes
I. A. Belogorokhov^, Yu. V. Ryabchikov, E. V. Tikhonov, V. E. Pushkarev,
M. O. Breusova, L. G. Tomilova, and D. R. Khokhlov
Moscow State University, Moscow, 119899 Russia
^e-mail: [email protected]
Submitted July 3, 2007; accepted for publication August 21, 2007

Abstract—The study is concerned with the luminescence properties of ensembles of semiconductor structures
containing organic phthalocyanine molecules with erbium ions as complexing agents. The photoluminescence
spectra of the structures of the type of erbium monophthalocyanine, bisphthalocyanine, and triphthalocyanine
are recorded. The photoluminescence peaks are detected at the wavelengths 888, 760, and 708 nm (and photon
energies 1.4, 1.6, and 1.75 eV) corresponding to electronic transitions within the organic complexes. It is found
that, when a metal complexing agent is introduced into the molecular structure of the ligand, the 708 nm lumi-
nescence peak becomes unobservable. It is shown that, in the bisphthalocyanine samples, the photolumines-
cence signal corresponding to transitions from the 4F9/2 level of erbium ions is enhanced.
PACS numbers: 78.55.Kz
DOI: 10.1134/S1063782608030147

1. INTRODUCTION can show two distinguishable photoluminescence (PL)

peaks in the range between 900 and 1100 nm.
Organic semiconductor structures find expanding
applications in the problems of present-day microelec- Current achievements in the chemistry of phthalo-
tronics [1]. In particular, it is known that structures cyanines make it possible to synthesize three-dimen-
composed of large protein molecules feature a rather sional-structured organic molecules, in which one com-
high mobility of electrons [2]. The basic advantage of plexing atom is bound with two organic ligands [11].
organic materials is the simplicity of their production The purpose of this study is to obtain and analyze the
from the derivatives of organic compounds widely spectral dependences of the PL signal from semicon-
occurring in nature. The technologies of synthesizing ductor structures based on erbium monophthalocya-
organic molecules do not require large expenditures of nine, bisphthalocyanine, and triphthalocyanine in the
energy or complex instrumentations, such as are used, e.g., visible spectral region.
in molecular beam epitaxy, gas phase epitaxy, hydride epi-
taxy, photolithography, or anisotropic chemical etching 2. EXPERIMENTAL
[3, 4]. It should be also noted that many organic struc-
tures exhibiting semiconductor properties occur in Molecular structures based on free ligands (metal-
nature in a ready form [5]. For example, the structures free monophthalocyanine) with butyl peripheral substi-
of magnesium porphyrinates reveal themselves as chlo- tutes were produced by boiling dibutylphthalodinitrile
rophyll molecules in the cells of any plants, and eryth- in n-pentanol in the presence of metal sodium [12]. The
rocytes in blood corpuscles of mammals are the com- butyl-substituted structures of erbium monophthalocy-
pound of porphyrin with an iron atom. anine and lutetium monophthalocyanine were synthe-
sized in argon atmosphere in 3–4 h by boiling stoichio-
Phthalocyanine is a synthetic analogue of porphy- metric amounts of metal-free phthalocyanine ligands
rin. The basic feature of phthalocyanines is their stabil- and the corresponding rare-earth acetates in ortho-
ity to thermal decomposition [2]. dichlorobenzene (DCB) in the presence of 1.8-diazabi-
To the advantages of organic structures can be added cyclo[5,4,0]undecene-7 (DBU). The sandwich-like
their selective optical properties that can be varied by structures of butyl-substituted erbium bisphthalocya-
modifying the structure of molecules during synthesis nine and triphthalocyanine were produced in cetyl alco-
[6, 7]. In [8–10], it was shown that phthalocyanine mol- hol [13].
ecules exhibit three peaks of absorption of optical radi- The prepared molecular complexes were deposited
ation in the visible and ultraviolet spectral regions and on quartz substrates by centrifuging (spin-coating). The

321
322 BELOGOROKHOV et al.

PL intensity, arb. units PL intensity, arb. units

200 Transmittance, arb. units
80
1 1
150 2
60

100
40
2
3
50
20
4
0
600 700 800 900 1000 1100 0
Wavelength, nm 600 700 800 900 1000 1100
Wavelength, nm
Fig. 1. The photoluminescence spectrum of butyl-substi-
tuted monophthalocyanine, as (symbols) observed experi- Fig. 2. Spectra of (1) the photoluminescence and (2) trans-
mentally and (1) fitted with (2–4) three Lorentzian con- mittance of semiconductor structures based on metal-free
tours. butyl-substituted monophthalocyanine.

thickness of the sample produced in such manner was observed at the wavelength 708 nm can be due to exci-
50 µm. tonic transitions from one molecular orbital to another
The PL signal of phthalocyanine molecules was inside the molecule itself, similar to the PL at interband
excited by radiation of a nitrogen laser operating at the transitions in crystalline semiconductors. In order to
wavelength λ = 337 nm with the pulse duration 10 ns. gain a deeper insight into the origin of the high-energy
The PL spectra were recorded using a monochromator peak at 1.75 eV (708 nm), we carried out a comparative
equipped with a cooled CCD cell. analysis of the spectral dependences of the transmit-
tance and PL intensity in butyl-substituted monophtha-
To record the transmittance spectra, we used a Hita-
locyanine samples. The experimental results are shown
chi-330 spectrophotometer. The wavelength resolution
in Fig. 2. For convenient comparison, the PL spectra and
was 1 nm.
the transmittance spectra are shown together (Fig. 2).
The drastic decrease in the transmitted intensity in
3. RESULTS AND DISCUSSION
the short-wavelength part of the spectra of butyl-substi-
The PL spectrum of the structures composed of free tuted monophthalocyanine complexes corresponds to
ligands (metal-free monophthalocyanine) is repre- the electronic transitions between the highest occupied
sented by a broad band with three distinguishable peaks molecular orbital (HOMO) b1 and the lowest unoccu-
at the wavelengths 888, 760, and 708 nm corresponding pied molecular orbital (LUMO) e3 of the phthalocya-
to the photon energies 1.4, 1.6, and 1.75 eV (Fig. 1). nine ligand, in which the orbitals b1 and e3 are predom-
Approximation of the experimental curve with three inantly localized at the α-isoindole carbon atoms [15].
Lorentzian bands allows us to establish that the peak at In publications, this absorption line is referred to as the
880 nm makes the major contribution to the observed Q band; its spectral position in monophthalocyanine
PL band in the red region, whereas the PL peak at molecules corresponds to 690 nm [8, 15]. In the spectra
760 nm is maximal in spectral intensity. Pakhomov et al. of the structures under study, the transmitted intensity
[14] recorded the PL spectra that consisted of two peaks steadily decreases even starting from 850 nm.
at 980 and 1100 nm. It was also shown that, in phthalo-
cyanine molecular structures deposited on sapphire The decrease in the transmittance in the spectral
substrates, structural and compositional variations in range from 850 to 620 nm suggests that the absorption
the samples are liable to influence the spectral position of electromagnetic radiation may involve contributions
of the PL peaks. In the PL spectra recorded in this of two processes, specifically, the formation of molec-
study, the intermediate-intensity peak at 888 nm can be ular excitons in the first singlet state and the transitions
between the HOMOs and LUMOs. The transitions
attributed to the molecular luminescence ( S '1 –S0) or to between the HOMOs and LUMOs are responsible for
the formation of the excimer state [14]. the PL peak around 706 nm. From the relationship
The peak at 760 nm may appear due to emission between the PL signal intensities, we can conclude that the
from the first singlet exciton state [14]. The PL peak major contribution to the absorption of electromagnetic

SEMICONDUCTORS Vol. 42 No. 3 2008

 PHOTOLUMINESCENCE IN SEMICONDUCTOR STRUCTURES 323

PL intensity, arb. units PL intensity, arb. units

1 250
300
200

200 150 2
2
100 3
100
1
50

0
0
600 700 800 900 1000 1100
700 800 900 Wavelength, nm
Wavelength, nm
Fig. 4. Photoluminescence spectra of semiconductor struc-
Fig. 3. Photoluminescence spectra of the metal-free tures based on butyl-substituted phthalocyanine complexes.
monophthalocyanine sample at the temperatures T = (1) 4 Curves 1, 2, and 3 refer to metal-free monophthalocyanine,
and (2) 300 K. Dashed and dotted curves show the Lorent- erbium monophthalocyanine, and lutetium monophthalocy-
zian components obtained by decomposing spectra 1 and 2, anine, respectively.
respectively; solid curve refers to the sums of the Lorentzian
components.
When studying the sandwich-like structures of
radiation in the visible wavelength region is made by the bisphthalocyanine and triphthalocyanine instead of the
exciton states formed in phthalocyanine molecules. planar monophthalocyanine structure, we observe dra-
matic degradation of the PL signals corresponding to
As temperature is decreased to 4 K, the PL signal the exciton states of the molecules as such (Fig. 5).
intensities at the wavelengths 708 and 760 nm increase From the spectral dependences of the PL intensity
by factors of 2.4 and 1.5, respectively (Fig. 3). In this (Fig. 5), it can be seen that the intensities of the peaks
case, the PL peak corresponding to the exciton states at 888 and 760 nm (1.4 and 1.6 eV) become, corre-
slightly shifts, from 760 nm at T = 300 K to 752 nm at spondingly, 1.8 and 2.24 times lower (Fig. 5, curve 2).
liquid-helium temperature; at the same time, the spec- However, the intensity of the peak produced by elec-
tral position of the PL peak corresponding to transitions tronic transitions between the energy levels of erbium
between the molecular orbitals remains unchanged. ions (1.87 eV) becomes 1.4 times higher.
A noticeable shift to shorter wavelengths is observed
for the long-wavelength peak characterizing the exci-
mer state; with decreasing temperature, the signal PL intensity, arb. units
intensity at 850 nm becomes twice as high. It should
also be noted that, with decreasing temperature in the 250
cell with the sample, the PL signal intensity corre- 1
sponding to the short-wavelength peaks remains virtu- 200
ally unchanged.
When erbium ions or lutecium ions as complexing 150
agents are incorporated into phthalocyanine molecules,
an extra peak at 660 nm (1.87 eV) appears in the 2
100
PL spectra (Fig. 4); this peak corresponds to transitions
from the 4F9/2 level in lanthanide ions [16]. The 3
50
PL spectra of the lutecium monophthalocyanine struc-
tures also exhibit an extra peak observable at 606 nm
(2.04 eV). The lack of extrema in the high-energy 0
region of the PL spectra of metal-free phthalocyanine 600 750 900 1050
allows us to relate the high-energy PL lines exactly to Wavelength, nm
the lanthanide atoms. It should be noted that the line
corresponding to the HOMO LUMO transitions is Fig. 5. Photoluminescence spectra of semiconductor struc-
tures based on butyl-substituted phthalocyanine complexes
lacking in the PL spectra of the compounds containing containing erbium. Curves 1, 2, and 3 refer to monophthalocy-
complexing agents. anine, bisphthalocyanine, and triphthalocyanine, respectively.

SEMICONDUCTORS Vol. 42 No. 3 2008

324 BELOGOROKHOV et al.

In the erbium triphthalocyanine samples, we ACKNOWLEDGMENTS

observe all three peaks, at 1.4, 1.6, and 1.87 eV, with the This study was supported in part by the Russian
identical intensities. However, in such complex sand- Foundation for Basic Research, project nos. 06-02-
wich-like structures as triphthalocyanine, the magni- 18555, 05-03-33202, and 07-02-01406.
tudes of intensities of the PL peaks are 3, 4, and 5 times
lower than those in the PL spectra of the planar
monophthalocyanine structure. REFERENCES
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nal at 706 nm. Translated by É. Smorgonskaya

SEMICONDUCTORS Vol. 42 No. 3 2008