Journal of Molecular Structure 1193 (2019) 365e372

Contents lists available at ScienceDirect

Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Doping of molecular materials based on ferrocene and the study of

their properties as organic semiconductors for their application in
optoelectronic devices

nchez Vergara a, *, Vincent Medel a, Citlalli Rios b, Roberto Salcedo b
M.E. Sa
a
Universidad Ana
huac M
exico. Avenida Universidad Ana
huac 46, Col. Lomas Ana

huac, Huixquilucan 52786, Estado de M
exico, Mexico
b
Instituto de Investigaciones en Materiales, Universidad Nacional Auto
noma de M

n, 04510,
exico, Circuito Exterior S/n, Ciudad Universitaria, Coyoaca
Ciudad de M
exico, Mexico

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

Article history: The present study refers to the chemical doping of ferrocene materials from the reaction with 2,6-
Received 16 December 2018 Dihydroxyanthraquinone and 2,6-Diaminoanthraquinone. Thin films of the doped molecular materials
Received in revised form were prepared by vacuum evaporation and the morphology and structure of films were studied using
12 May 2019
SEM, EDS and IR spectroscopy. Theoretical calculations were carried out by means Gaussian16 software
Accepted 14 May 2019
Available online 18 May 2019
and all the involved species were geometrically optimized. The IR spectrum, the HOMO-LUMO energy
and the bandgaps from these calculations were achieved. The theoretical and experimental IR spectra
were compared in order to verify the presence of the main functional groups of the molecular materials.
Keywords:
Ferrocenes
The theoretical bandgap of each film was also compared with that obtained by UVevis spectroscopy,
DFT calculations showing similar results in the range of 2e2.9 eV. These bandgap values place the synthesized materials
Thin films within the so-called organic semiconductors. Additionally from the calculations of HOMO-LUMO and
Bandgap bandgap results, it has been suggested that the synthesized materials can be used as a semiconductor p-
Semiconductor behavior type. The films were evaluated in their p-type semiconductor behavior by means of unipolar devices. In
the material synthesized from ferrocene and 2,6-Dihydroxyanthraquinone a virtually ohmic I-V ratio was
obtained, while the compound constituted by 2,6-Diaminoanthraquinone behaved as an insulator. In
order to improve the p-type behavior of the synthesized semiconductors, unipolar devices were given a
hole-injecting layer between the anode and the synthesized materials: glass/ITO/CuPc/synthesized
material/Ag. Its I-V electrical behavior was evaluated by the effect of influencing electromagnetic radi-
ation in the range of the electromagnetic spectrum between the IR and the UV passing through the
visible spectrum. The results for both devices have shown that the one manufactured from ferrocene and
2,6-Dihydroxyanthraquinone exhibited a behavior similar to that of a Schottky diode, while the one
prepared from ferrocene and 2,6-Diaminoanthraquinone behaves like a resistor.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction because of its great potential in the application of organic semi-

The success of microelectronics is based on the important ad-
vances in the fabrication of silicon-based integrated circuits.
However, a number of physical, ambient and economic factors,
which threaten the continued scaling down of silicon semi-
conductor devices, have motivated research into electronic systems
based on other technologies [1]. Within the new technologies,
organic microelectronics is considered a promising research field
* Corresponding author.

nchez Vergara).
E-mail address: elena.sanchez@anahuac.mx (M.E. Sa
conductors as an alternative to the traditional inorganic semi-
conductors like silicon. The advantages afforded by the organic
semiconductors over their inorganic counterparts comprise large
availability, easy processing and good compatibility with a wide
range of substrates. Additionally, since organic materials can be
easily tuned to improve their electrical, optical, electrochemical
and morphological properties, their potential applicability is rein-
forced. In this regard, the search for new organic semiconductors
for optoelectronic applications has become an appealing goal for
the microelectronic field. Within the family of organic materials,
the organometallic compounds, containing at least one metal-to-

https://doi.org/10.1016/j.molstruc.2019.05.053
0022-2860/© 2019 Elsevier B.V. All rights reserved.
366
nchez Vergara et al. / Journal of Molecular Structure 1193 (2019) 365e372
M.E. Sa
carbon bond in which the carbon is part of an organic group, are a
very important class of dopants; ferrocene is included within this
family. Ferrocene has drawn much attention in the contemporary
organometallic research due to its important physical and chemical
properties as well as technological usefulness [2]. The appearance
of ferrocene in the middle of the 20th century meant a significant
revolution in the field of organometallic chemistry and is now
providing applications in areas as varied and sometimes initially
unexpected as optical and redox devices, sensing, catalysis,
including asymmetric and enantioselective catalysis, and medicine.
In the field of optoelectronic devices, ferrocene is one of the most
widely used organometallic molecules in functional materials for
sensors [3] solar cells [4] magnets [5] and so on. The utility of
ferrocene and its derivatives is, in part, because it shows stable
redox behavior with respect to chemical and physical environ-
ments, which is therefore useful for sensors and dye sensitized
solar cells. The neutral ferrocenyl species is diamagnetic, whilst the
cationic form has a magnetic moment, which has been widely used
as a magnetic source in molecular magnetism. One of the most
well-known compounds is a ferromagnet, the complex of deca-
methylferrocene with tetracyanoethylene, also known as Dicyclo-
pentadienyliron (Fc). This is the earliest and best known of the so-
called sandwich compounds; these compounds are constituted by
transition metals in which two organic ring systems are bonded
symmetrically to the metal atom. Its molecular formula is (C5H5)2Fe
and was first prepared in 1951 by the reaction of sodium cyclo-
pentadienide with iron(II) chloride. Chemically, Fc behaves like
benzene and other aromatic compounds in that it undergoes sub-
stitution reactions. The removal of one electron from the molecule
raises the iron atom to the next-higher oxidation state (i.e., from þ2
to þ3), leading to the formation of salts containing the blue ferri-
cinium cation, (C5H5)2Feþ1. Fc groups and its derivatives have been
the focus of research for years due to their unique redox charac-
teristics and pi-conjugated system, which could readily offer su-
perb electron-transfer ability. This behavior in the Fc makes it stand
out over other organic semiconductors however the main disad-
vantage with respect to inorganic semiconductors is the low cur-
rent density they generate due to its reduced number of charge-
carriers. This disadvantage can be reduced by the chemical
doping of Fc which can contribute to the creation of charge-carriers
and it can be accomplished by means of either a mixture of the
organic semiconductor with strongly electron-donor molecules or
with electron-acceptor molecules that ease the electronic transfer
between the semiconductor and the dopant when they are very
close to each other [6]. The molecules of 2,6-
Dihydroxyanthraquinone and 2,6-Diaminoanthraquinone can pre-
sent a “ribbon” arrangement that encompasses the organometallic
compound [7e12]. Even in these structures, hydrogen bonds can
also be formed towards the organometallic compound [7,9,12];
water molecules are involved in a network of hydrogen bonds with
the compound, in such a way that both semiconductor and dopant
form successive layers throughout the structure of the material. In
these anisotropic molecular materials, preferential directions are
induced to carry the charge through the formation of energy bands
due to the p orbitals of the molecules and the partial occupation of
the bands in which the Fermi level is located. The partial occupation
of the bands is caused by the ability to yield or accept electrons with
a low energy cost by the semiconductor and dopant molecules that
make up the molecular material.
The main goal of this study is the determination of the electronic
effect which is a particularity of the molecular materials doped
from Fc with 2,6-Dihydroxyanthraquinone and 2,6-
Diaminoanthraquinone and the transcendence of these materials
as organic semiconductors. Thus, we report the electrical behavior
of molecular material films prepared through vacuum deposition.
Evaporation at high vacuum is a technique that, due to the thermal
gradient between the temperature of the substrate used for the
deposit, and the temperature of the semiconductor in a gaseous
state, generates films of a heterogeneous morphology. However,
the ability of organic semiconductors to form thin films of low cost
and large contact surface makes them suitable for the manufacture
of electronic devices [13]. Based upon the current-voltage (I-V)
evaluation on unipolar devices of each molecular material doped,
new unipolar devices were manufactured introducing a hole-
injecting layer in order to complement the results on the possible
use of these materials as organic semiconductors. In optoelec-
tronics design a key element is the transparent conductor electrode
[14], due to its optical and electrical properties; thus ITO
(In2O3$(SnO2)x) is used as the transparent electrode [15]. ITO acts
as an anode or hole injector, with Fermi level (4.7 eV) near to the
energy of HOMO orbitals of organic semiconductor [16], whereas
silver electrodes acting as cathode or electron injector (4.2 eV),
were deposited. The above will modify the electronic structure of
the molecular materials. The frontier molecular orbitals of the
ferrocene complex were theoretically studied because the impor-
tant electronic interchange of the whole system strongly depends
on these functions. The results match well with those obtained by
the experimental procedure.
2. Experimental
1,10 -Dimethylferrocene, 2,6-Dihydroxyanthraquinone and 2,6-
Diaminoanthraquinone were used in this study to obtain organo-
metallic semiconductor; they were purchased from Sigma-Aldrich
and required no further purification. Two molecular materials
were chemically doped by a simple reaction in absolute methanol
between C12H14Fe, C14H8O4 and C14H10N2O2 in a conventionally
heated reactor Monowave 50 with pressure sensor. Briefly, 2.4 mg
(0.01 mmol) of C14H8O4 or 3.2 mg (0.01 mmol) of C14H10N2O2 were
added to 21.4 mg (0.1 mmol) of C12H14Fe and then dissolved in 6 ml
of absolute methanol. Keep in reflux at 15 bar for 30 min and the
materials S1 and S2 respectively were then filtered, purified from
1:1 methanol-water and dried in vacuum. These materials are
insoluble in organic solvents such as methanol, ethanol, dichloro-
methane, acetonitrile and acetone. The above in order to avoid their
solubility and chemical degradation, which are the main problems
that organic semiconductors present in front of inorganic semi-
conductors such as silicon [1,6,13].
Molecular materials S1 and S2 were subsequently deposited
using the high vacuum evaporation technique. Thanks to their
thermal stability, the powdered materials were heated at 573 K in
order to produce their phase change, which was initially carried out
in the gaseous state. Finally, the molecular materials were depos-
ited in the form of thin film upon the contact with substrates, which
were at room temperature and vacuum of 1  106 Torr. Substrates
used were indium tin oxide (ITO) coated glass slides, high resistivity
monocrystalline n-type silicon wafers (c-Si) and Corning glass. The
substrates were previously submitted to a sonication cleaning
process with different solvents and were dried under vacuum. An
IR spectroscopy was carried out in order to verify the vibrational
modes of the organic radicals that integrate the molecular material.
The IR analysis was carried out using a Nicolet iS5-FT in KBr pellet
and the film deposited on the silicon wafers. For EDS in silicon
substrate Bruker microanalysis system was coupled to a SEM. A
ZEISS EVO LS 10 scanning electron microscope (SEM) was used to
analyze the thin films supported on glass substrate. The X-ray
diffraction analysis was performed in glass substrates with the q-2q
technique using a Bragg-Brentano Geometry with a Bruker, D8
Avance diffractometer and working with CuK-a (l ¼ 0.15405 nm)
radiation. The films on glass substrates were used also to determine

nchez Vergara et al. / Journal of Molecular Structure 1193 (2019) 365e372
M.E. Sa
the optical absorption of the films with a Unicam spectrophotom-
eter, model UV300, in the wavelength range of 200e1100 nm. In
order to estimate individually the charge carrying properties of the
synthesized materials, unipolar devices were manufactured. The
film of the material to be evaluated was placed between the ITO
that acted as the anode and the Ag as the cathode. The electrical
evaluation was also performed with reverse polarity. Later, glass/
ITO/CuPc/S1 or S2/Ag device was fabricated by deposition process,
under the same conditions of temperature and pressure. The cop-
per phthalocyanine (CuPc) film was deposited as a hole-injecting
layer (HIL) between the anode and the synthesized materials in
order to reduce the injection barriers and improve the performance
of S1 and S2. Electric measurements were performed by using the
wires method, in which the electric current is passed through the
end wires, and measures the potential difference between the
central wires. All the I-V measurements were performed employing
a programmable voltage source Keithley 4200-SCS-PK1 auto-
ranging pico-ammeter. A Next Robotix sensing station with light-
ing controller circuits acted as a solar simulator that emits elec-
tromagnetic radiation between the UV an IR wavelength interval.
3. Theoretical methods
All calculations were carried out by applying a DFT method
based on the combination of Becke's gradient corrections [17] for
exchange and Perdew-Wang's for correlation [18]. This is the
scheme for the B3PW91 method which is included in the
Gaussian16 [19] package. The calculations were performed using
the 6-31G** basis set. Frequency calculations were carried out at
the same level of theory in order to confirm that the optimized
structures were at a minimum of the potential surfaces.
4. Results and discussion
IR spectroscopy was carried out in order to characterize the
main functional groups in materials, the first with Fc and 2,6-
Dihydroxyanthraquinone (S1) and the second with Fc and 2,6-
Diaminoanthraquinone (S2). Fig. 1 shows the structure optimized
for each of them, in the case of S1 the hydroxyanthraquinone
molecule, by means of a hydrogen atom of its OH- group, is directly
linked to the Fc when displacing a methyl group of the organo-
metallic compound ring. In S2 a similar situation is observed,
although in this case the doping is through one of the amino groups
of aminoanthraquinone. The above was verified by the IR spec-
troscopy of both materials, Fig. 2 compares the experimental and
the simulated infrared spectra of S1 and S2 films. The IR spectra of
Fc are relatively simple with only a few transition peaks caused by
vibrations which lead to the formation of induced dipole moments
due to the absence of permanent dipole moments in Fc [20]. Fig. 2
shows for the experimental and simulated IR measurements, in the
400-3700 cm-1: the peak around 470 cm-1 corresponding to the
stretching mode of FeCp (Cp ¼ cyclopentadienyl), signals in 848
and 864 cm-1 corresponding to the different modes of stretching
CH, the peak in 1035 cm-1 of the bending CCH and the peak in
Fig. 1. Optimized molecular structures of the molecular materials.
367
Fig. 2. Comparison of IR (a) experimental and (b) simulated spectra of S1 and S2
materials.
1477 cm-1 of the assimilable stretching CC: Cp, in the CCH plane.
The characteristic signals of the anthraquinone derivatives are also
present in 1606 and 1327 cm-1 for the anthraquinone group C]O
and CO respectively of S1 and 1606 cm-1 and 3395-3403 cm-1 for
the anthraquinone group C]O and NH respectively in S2. Finally,
the signal concerning the group OH- in S1 is observed between
3100 and 3350 cm-1. To further understand the spectra, a more
detailed analysis is presented in Table 1. The good agreement be-
tween the experimental IR spectrum and those obtained theoreti-
cally indicates that the calculations yield a good approach to the
experimental study. Then the optimized structures of Fig. 1 will be
used in the subsequent evaluation of the optoelectronic properties
of the films.
EDS studies were carried out on the films over silicon substrate.
In Fig. 3 it is observed the presence of different atoms in the films of
the molecular materials. The presence of the iron is correspondent
to the Fc molecule, whereas carbon can be an indicator of the
presence of both the molecule itself and anthraquinone derivatives.
Furthermore oxygen indicates the existence of anthraquinone de-
rivatives, in all the cases oxygen corresponds to the one found in
the C]O group of the central ring of all the dopant substituents.
Finally, the presence of nitrogen in the molecular material S2 is
confirmed by the appearance of the band assigned to the NH2 vi-
bration mode, which corresponds to the diaminoanthraquinone.
The study of the morphology of films S1 and S2 is relevant
because it is related to its electrical properties. To analyze the
morphology of the film structures, SEM was performed in glass
substrates and from the images in Fig. 4 it is clear that the surface
morphology is different. Although in both cases a homogeneous
base is observed, it is interesting to highlight that in the S1 film
irregular particles with preferentially elongated form are found on
the surface, while in the film S2 it is observed that the particles are
round shape and are not found as conglomerates on some regions
of the film as in S1, but are homogeneously distributed along the
entire surface. It is important to mention that due to the distribu-
tion of particles, the film S2 is expected to show the best conditions
for the transport of electrical charges with respect to the film S1.
The presence of the particles on the films S1 and S2 can be
explained as the deposition of the films took place in two stages:
initially, the molecular material were deposited directly over the
substrate at room temperature, forming the homogeneous layer. In
the second stage, the compound came in contact with the layer
previously deposited, that was at a higher temperature than room
temperature. Thanks to the decrease in the thermal gradient during
this deposition, additional nuclei slowly grew, forming particles of a
considerable size. The heterogeneity of the films can affect the
charge transportation throughout the sandwich structure. How-
ever, this type of morphology has been used successfully in the
evaluation of the electrical behavior of compounds derived from
Fcs [22,23]. This is because although the morphology is heteroge-
neous, the internal structure of the material retains a certain order
368
nchez Vergara et al. / Journal of Molecular Structure 1193 (2019) 365e372
M.E. Sa
Table 1
Experimental and calculated IR frequencies and their assignment for S1 and S2 materials.
S1 n (cm-1) experimental S1 n (cm-1) simulated S2 n (cm-1) experimental
473 479 477
844, 865 834, 886 848, 864
1039 1036 1036
1477 1478 1477
1327, 1606 1315, 1600 e e
e e 1606, 3395-3403
Fig. 3. EDS spectrum for films in silicon substrate.
that can be verified by XRD in the films of S1 and S2 (Fig. 5). The X-
ray diffraction patterns of the semiconductors films present well
defined diffraction peaks, so it can be said that the samples are
polycrystalline. The S2 film has higher crystallinity and according to
SEM it also has greater homogeneity than S1, so is expected it
shows the best conditions for the transport of electrical charges
with respect to the film S1.
The absorption of radiation is the principle of the operation of
optoelectronic devices, in this sense the study of the spectroscopic
properties of doped semiconductors is important to facilitate the
application of these materials in this field. Then UVevis spectros-
copy was performed in order to analyze the different electronic
transitions taking place between the ground state and excited state
of both molecular materials and films as a consequence of the ra-
diation absorption of distinct wavelengths, the results are shown in
the electronic spectrum of Fig. 6. It is evident that the S1 and S2
films have different absorptive properties, the main differences
observed in the absorption spectra between the molecular mate-
rials are properly appreciated within the 250e650 nm interval.
According to B. Hu et al. [22], Hsung et al. [24] and J. Xiang et al. [25]
the absorption spectra of the films show different bands: the most
energetic corresponds to an intense band around 250 for S1 and
300 nm for S2, and they are associated with transitions p-p*. The
presence of a weaker band around 360 nm for S2 is associated with
metal-to-ligand charge transfer (MLCT) [24,25]. Finally, for S1 it is
possible to discern a band of low intensity, around 530 nm, corre-
sponding to d-d transitions [24]. From the absorption spectra it is
suggested that the electronic density of the energy states that
Fig. 4. Microphotograph of (a) S1 and (b) S2 in glass substrate at 500x
S2 n (cm-1) simulated Assignment Referencea
463 n FeCp 470
814, 876 Asymmetric g CH (2 CH upward, 848, 864
2 CH downward)
1033 d CCH 1035
1485 Asymmetric n CC: Cp, 1477
in plane CCH
n C]O, n CO 1327, 1606
1605 n C]O, n NH2 1606, 3395-3403
participates in the charge traffic is responsible of the bands that
appear mainly on the Fc skeleton; however, the effect of the
anthraquinone derivative is what determines the optical properties
of the molecular material. The replacement of the NH2 of the dia-
minoanthraquinone in S2 by the OH- of the dihydroxyan-
thraquinone in S1, generates a shift of the bands of the absorption
spectrum towards greater wavelengths as a result of the electronic
effect that the anthraquinone derivative exerts on the Fc backbone.
Electronic transitions are important in the behavior of semi-
conductors because a parameter that provides very useful infor-
mation to quantify the properties of organic semiconductors is the
energy difference between the HOMO and LUMO orbitals, that is,
the HOMO-LUMO gap. The gap value can be obtained assuming the
approximation that the first electronic transition from the ground
state S0 to the excited state S1 usually corresponds to the promotion
of an electron from the HOMO to the LUMO of the excited material.
Using UVevis spectroscopy, the value of the optical HOMO-LUMO
gap (Eopt) can be estimated for thin films, this number is attrib-
uted to the lowest energy transition that takes place by absorption
of a photon. Different methods are used to calculate the Eopt, among
them the most commonly used is the extrapolation of the linear
section of the skirt of the lowest energy band of the absorption
spectrum to the cutoff point with the abscissa axis. Therefore the
wavelength value, Eopt is obtained from the following equation:
hc
Eopt ðeVÞ ¼
l nm
where h is the Planck constant, c the speed of light in vacuum and l
the wavelength. The Eopt values estimated from the absorption
spectra are shown in Table 2, S1 presents the smallest HOMO-
LUMO gap. These Eopt values are close to those obtained experi-
mentally for compounds with Fc in their structure, for example Hu
et al. obtained 2.1, 2.35 and 2.61eV for carbazole derivatives with
ferrocene groups [22] and Singla et al. they obtained values be-
tween 1.872 y 2.046eV for isomers of ferrocenebenzo[1,2-b:4,5-b’]
difuran-2,6-(3H, 7H)-dione [21]. Additionally the bandgap for
organic semiconductors is generally found between 1.5 and 4.0 EV

nchez Vergara et al. / Journal of Molecular Structure 1193 (2019) 365e372
M.E. Sa
Fig. 5. DRX spectrum for S1 and S2 films.
Fig. 6. Absorption spectra for S1 y S2 films.
[16], so the two synthesized materials are good targets to be
deposited as semiconductor films within optoelectronic devices,
because their Eopt is found within this range. However is necessary
to consider that the separation of energy levels HOMO and LUMO
also depends on structural factors of the material, such as the
alternation in bond length, nature of the films, presence of impu-
rities resulting from the synthesis process and degree of stacking of
the electron donor and acceptor molecules [16]. Due to the above,
the theoretical bandgap (Eg) that does not consider external effects
to the semiconductor molecules was calculated and compared with
that obtained by UVevis spectroscopy. The results are shown in
Table 2, in which a difference of 0.75 eV is observed for S1 film
while the bandgap values obtained for S2 are practically the same.
The variation between the bandgap for S1 can be explained due to
the presence of oxygen from the dihydroxyanthraquinone that not
only serves as a bridge for the Fc, but also attracts the electrons,
decreasing the bandgap with respect to the theoretically calculated
value. Apparently an electronic transfer is carried out from the
HOMO of the Fc to the LUMO of the dihydroxyanthraquinone that
will ionize, transforming into a strong oxidized radical anion and
representing a formal charge embedded in the Fc. For this reason,
the bandgap of S1 is lower than that obtained by UVevis
Table 2
Bandgap and Optical HOMO-LUMO spacing.
Sample Eopt (eV) Eteo (eV) HOMO
S1 2.0 2.75 0.202 au
5.497 eV
S2 2.9 2.88 0.212 au
5.769 eV
369
spectroscopy for the semiconductor S2, where apparently the
amine group does not attract electrons as strongly. When
comparing the Eteo values obtained with those reported by other
authors, it is observed that they are in the same interval: Xiang et al.
obtained values between 1.74 and 3.33eV for non-conjugated
ferrocene-containing copolymers [25] and Hao et al. obtained
2.18eV for functional polyimides bearing pendent ferrocene group
[4]. Even the values obtained are smaller than those reported by
Chuhmanov et al. 3.41 and 4.54eV for Tris(perfluoroalkyl)germy-
lethynyl derivatives of biphenyl containing ferrocenyl donor [5] and
for Singla et al. values between 2.866 and 3.450eV for isomers of
ferrocenebenzo[1,2-b:4,5-b’]difuran-2,6-(3H, 7H)-dione [21].
DFT calculations were used not only to obtain the theoretical
bandgap, but also to examine the border molecular orbitals HOMOs
and LUMOs, as these determine the optoelectronic properties of the
semiconductors. The energy value of the quantum levels directly
involved in electronic transfer processes has fundamental impor-
tance in the design and fabrication of optoelectronic devices.
Theoretical calculations by means a DFT method were carried out in
order to get a reliable scheme of the frontier molecular orbitals
region. These functions are shown in Fig. 7 for both compounds, the
behavior is similar, in both cases the HOMO is mainly localized on
the ferrocene fragment whereas LUMO is a function of the
anthraquinone moiety. In this sense it is expected to have a
considerable and constant electronic flux from ferrocene to the
lateral substituent through the aromatic rings of both sections and
this direction should be reinforced by the inductive effect of the
substituent. The shape of the frontier molecular orbitals should be
highlighted because the design of a particular optoelectronic device
involves weak electronic interactions among the different parts of a
molecular model, thus the qualitative information yielded by these
shapes allows the prediction of the electronic interaction. Moreover
an arrangement which involves the whole aromatic framework as
the one described in Fig. 7 enables to propose these molecules as
the main parts in such a device. The dihydroxyanthraquinone and
the diaminoanthraquinone will act as dopants in the Fc that will be
either p-type or hole transporter and an electronic transfer will be
carried out from the HOMO of the Fc to the LUMO of the dopant, as
a result the energy gap will give place to a some kind of electrical
conduction in the device. The calculated values for the energies of
the HOMO and LUMO orbitals in S1 and S2 are show in Table 2 and a
remarkable similarity is observed among them and those reported
in the literature [5,21,25].
Another useful result is the electrostatic potential mapped onto
LUMO
0.101 au
2.748 eV
0.106 au
Fig. 7. Frontier molecular orbitals for both systems: (a) molecule with oxygen bridge
2.884 eV
S1 and (b) molecule with nitrogen bridge S2.
370
nchez Vergara et al. / Journal of Molecular Structure 1193 (2019) 365e372
M.E. Sa

the total electronic density which is shown in Fig. 8a/b for both
molecules. They show their active zones in which a reaction can be
carried out, the important points to consider are the carbonyl ox-
ygen atoms and the terminal nitrogen atoms which generate the
main negative and positive charge densities in both cases. However
the polarization is very different, the analog which contains an
oxygen bridge, S1 (see Fig. 8a) has practically a value of zero for the
dipole moment, meanwhile the one with nitrogen on the bridge S2
(Fig. 8b) has a net value of 5 Db for the dipole moment, the larger
the dipole moment the better the electronic delocalization, there-
fore the compound with nitrogen bridge S2 should be a better
semiconductor agent. Nevertheless, it is important to consider that
both its optical and theoretical bandgap are greater than those
presented by S1, so it is essential to evaluate the electrical behavior
of each material. For this purposes, unipolar devices were manu-
factured to estimate the contribution of each of the materials S1
and S2, since according to the previous results, they can behave as
p-type semiconductors. The evaluation of the behavior of semi-
conductors S1 and S2 obtaining the electrical I-V measurements
that can be related to the parameters that quantify the flow of
electrical current through the device. Fig. 8c/d shows I-V curves for Fig. 9. (a) Device structure, (b) Representation of the charge generation process
the thin films of both materials under normal lighting conditions. responsible for the electric current in S2 and I-V behavior for (c) S1 and (d) S2 devices.
According to the curves of Fig. 8c/d, when the polarity is changed to
the devices, the behavior remains the same. In the case of the S1
out as a result of the electronic transfer process between the CuPc
film, it is observed a relationship that can be considered as directly
and S1 and S2 layers. Finally, the charges are stored in the elec-
proportional between the applied voltage and the current that
trodes. The ITO used for hole-injection has a Fermi level close to the
flows, the curve can be analyzed with the ohmic model. On the
energy of the HOMO orbital of the CuPc HIL as well as to that of the
other hand and contrary to what was expected from the calculation
HOMO orbital of S1 and S2 p-semiconductor films. On the other
of electronic density, the film S2 behaves as an insulator with a
hand, the energy of the LUMO orbital of these materials is very high
resistance of around 102 U with the device at its OFF-state [1].
compared to the Fermi level of Ag used as a cathode. The evaluation
Perhaps it is the morphology of the film of molecular material that
of the electrical behavior was measured by changing the polarity of
is directly in contact with the electrode the responsible for the lack
the device and the results obtained are presented in Fig. 9c/d. In
of response in this device. Due to the above, it is necessary to
Fig. 9c for the device manufactured from S1 it is observed that there
introduce a hole-injecting layer in each device, in order to help p-
is no perfect symmetry when exchanging the polarity in the device,
type semiconductors S1 and S2 to increase the transport of charges.
whereas when the voltage is applied in direct mode (forward bias)
Based on previous results as well as those obtained for the
the polarity of the applied external voltage source coincides with
bandgap and the HOMO and LUMO orbitals, new unipolar devices
the polarity of the electrode. In this case, the anode corresponds to
were produced. As shown in Fig. 9a, S1 and S2 act as p-type
the positive polarity electrode, that is, the injection of electrons
semiconductors or hole transporters, whereas ITO and silver were
from the electrode, or the extraction of holes towards the electrode,
chosen as electrodes and CuPc as a HIL between the anode and the
the potential gradient is accentuated, and the shortage zone nar-
films S1 and S2 [6,16,26e28]. According to the calculations made
rows and increases the current intensity that circulates. If the
for the HOMO and LUMO of each semiconductor, Fig. 9b shows the
connection is made applying a reverse polarity voltage (reverse
way in which these devices would be expected to operate: initially,
bias) the current will be lower. The fact that the measured current is
when the electromagnetic radiation affects the device, the ab-
greater when a voltage of a certain polarity is applied, and that the
sorption of light is carried out onto the CuPc film. Then, generated
current is almost zero when the reverse polarity is applied, is called
holes migrate to the interfacial region of the S1 or S2 semi-
rectification. This asymmetry in the current magnitude presented
conductor film. As a next step, a charge separation process is carried
in Fig. 8c, which depends on the polarity of the applied external

Fig. 8. Electrostatic potential mapped on the electronic density for (a) S1 and (b) S2 molecules. I-V curves for (c) S1 and (d) S2 films.

nchez Vergara et al. / Journal of Molecular Structure 1193 (2019) 365e372
M.E. Sa
voltage is similar to the Schottky contact, which indicates that the
manufactured device can be used as a Schottky Diode [6]. Under
low voltage (0 Ve0.1 V), the I-V curve 8c is linear and can be fitted
with an ohmic behavior. The material is insulating and the device is
at its OFF-state. When the voltage exceeds the Schottky barrier
(0.1 V), holes are injected from the ITO and the CuPc into the S1 film.
The existence of traps in S1 can lead to an accumulation of space
charges and a redistribution of the electric field. Thus, the ohmic
current changes to the space-charge limited current [1]. It is
important to note that the effect of electromagnetic radiation on
the operation of the device is practically null, whereas when
measurements are taken in the dark, a small increase in the electric
current transported along the device is observed. On the other
hand, in the device manufactured from S2 (see Fig. 9d), a behavior
completely different from that obtained with S1 is observed.
Apparently, the effect of the anthraquinone derivative on the Fc
skeleton drastically changes the electrical behavior towards that of
a resistor [6]. The molecular material S2 has virtually zero capacity
to carry electrical charges between 0 V and 0.03 V, whilst between
0.03 V and 0.2 V the behavior changes to ohmic. However, as of
0.2 V its behavior becomes that of an insulator with a resistance of
about 10U. In this case, the polarity of the device is completely
symmetrical, so there is no rectification of the current: when the
polarity of the applied voltage is inverted through the electrodes,
the current intensities have the same magnitude. The above results
indicate that the transport properties of the doped molecular ma-
terials directly depend on the anthraquinone derivative used.
Although the presence of CuPc as a HIL does influence the process
of injection of charges in the devices, the similarity of the energies
in the HOMOs of the molecular materials seem to show a certain
relationship between the charge carrying properties and the mo-
lecular structure of the doped organic semiconductors. The struc-
ture of these semiconductors, leads to a difference on the
surrounding of each molecule integrated in the solid. This poly-
crystalline structure modifies the electronic conformation of the
organic semiconductor, that is, it alters the energy of the orbitals of
its molecules [29e31]. The organic semiconductors will present a
distribution of energies that can lead to the generation of energy
levels located between the LUMO and the HOMO; these levels can
contribute to the transport of charges. It is important to consider
that the current transported in the device is three orders of
magnitude greater in the device S2 with respect to the device S1.
The S2 film is more homogeneous and more crystalline than the
film S1. The value of 0.02 A in curve I-V for S2 is similar to those
obtained in memory devices based on functional polyimides
bonded to a ferrocene group [4] and superior to that obtained in
Organic Field-Effect Transistors manufactured with o-Carborane,
Ferrocene, and Phthalocyanine [3,4]. However, the comparison of
electrical parameters is not always valid as it depends on the type of
device and its structure.
5. Conclusions
Two molecular materials were doped from the reaction between
ferrocene and the derivatives of anthraquinone: 2,6-
Dihydroxyanthraquinone (S1) and 2,6-Diaminoanthraquinone
(S2). The previously synthesized Fc-based molecular materials
were theoretically studied and it was found that in the case of S1
the hydroxyanthraquinone molecule is directly linked to the Fc by
means of an H atom from its OH- group when displacing a methyl
group of the organometallic compound ring. While in the S2 mo-
lecular material a similar situation is observed, although in this case
the synthesis was carried out through one of the amino groups of
aminoanthraquinone. The experimental and the simulated infrared
spectra show that the theoretical calculations provide very good
371
coincidence between the calculated and experimental band posi-
tions. In order to evaluate the semiconductor behavior of the syn-
thesized molecular materials, they were deposited as thin films.
The theoretical bandgap of each film was also compared with that
obtained by UVevis spectroscopy, showing similar results in the
range of 2e2.9 eV. These values of bandgap place the synthesized
materials within the organic semiconductors range. Additionally
from the calculations of HOMO-LUMO, it is suggested that syn-
thesized materials can be used as a semiconductor p-type. Unipolar
devices were made with these films; each one was electrically
characterized, first in an isolated manner and later through the
introduction of CuPc used as HIL in the devices. Based on the results
obtained from the I-V analysis in the devices, it seems possible to
use the semiconductor S1 as a component of Schottky diodes, while
semiconductor S2 behaves like a resistor.
Acknowledgements
M.E. S

anchez-Vergara acknowledges the financial support from
Anahuac Me
xico University, Project number NNAIASEVM16070616.
M.E. S

anchez-Vergara and Vincent Medel want to thank to Aline
Herna
ndez Garcia, for the SEM and EDS measurements. Citlalli Rios
and Roberto Salcedo want to thank to Adriana Tejeda, Maria Teresa
V
azquez, Oralia Jime
nez, Alberto Lo
pez, Cain Gonza

lez and Ale-
jandro Pompa for technical help, besides they acknowledges the
financial support of DGAPA-UNAM, project number PAPIIT
IN203816.
References
[1] Q.D. Ling, D.J. Liaw, E. Yeow-Hwee Teo, C. Zhu, D.S.H. Chan, E.T. Kang,
K.G. Neoh, Polymer memories, Bistable electrical switching and device per-
formance, Polymer 48 (18) (2007) 5182e5201, 24, https://doi.org/10.1016/j.
polymer.2007.06.025.
[2] A. Thader, B. Mallik, Observation of persistent photoconductivity at room
temperature in ferrocene-doped poly(methyl methacrylate) thin films con-
taining chloroform molecules, Solid State Commun. 121 (2e3) (2002)
159e164. https://doi.org/10.1016/S0038-1098(01)00459-8.
[3] H. Akutsu, R. Hashimoto, J. Yamada, S. Nakatsuji, S.S. Turner, Y. Nakazawa,
Structure and properties of a BEDT-TTF-based organic conductor with a
ferrocene-based magnetic anion octamethylferrocenedisulfonate, Eur. J. Inorg.
Chem. 27 (2018) 3249e3252, 2018, https://doi.org/10.1002/ejic.201800482.
[4] R. Hao, N. Jia, G. Tian, S. Qi, L. Shi, X. Wang, D. Wu, Flash memory effects and
devices based on functional polyimides bearing pendent ferrocene group,
Mater. Des. 139 (5) (2018) 298e303. https://doi.org/10.1016/j.matdes.2017.
11.020.
[5] E.P. Chuhmanov, N.L. Ermolaev, B.N. Plakhutin, S.K. Ignatov, Tris(per-
fluoroalkyl)germylethynyl derivatives of biphenyl containing ferrocenyl
donor group: structure, spectra, and photoinduced intramolecular electron
transfer, Computational and Theoretical Chemistry 1123 (2018) 50e60.
https://doi.org/10.1016/j.comptc.2017.11.007.
[6] M. Ma
s-Montoya, Synthesis of New Heteroarene Systems and Study of Their
Properties as Organic Semiconductors for Their Application in Molecular
Electronics, Master’s Thesis, Faculty of Chemistry, University of Murcia,
Murcia, Spain, 2015.
[7] M.E. S
anchez-Vergara, J. Go
mez-Lara, R.A. Toscano, S. Herna
ndez-Ortega,
Diaqua tetrabenzo (b,f,j,n) {1,5,9,13} tetraazacyclohexadecine copper (II) and
nickel (II) bisanthraflavates; crystal and molecular structure, J. Chem. Crys-
tallogr. 28 (11) (1998) 825e830. https://doi.org/10.1023/A:1021879804444.
[8] M.E. S
anchez Vergara, J. Go
mez Lara, A. Ortíz Rebollo, V. García Montalvo,
Synthesis, characterization and evaluation of electrical properties of
[Cu(TAABLn)] compounds, J. Coord. Chem. 54 (2001) 441e454. https://doi.org/
10.1080/00958970108022655.
[9] M.E. S


anchez-Vergara, A. Ortiz, Cecilio Alvarez-Toledano,

J.R. Alvarez, Prepa-
ration and characterization of molecular-material thin films containing diaqua
tetrabenzo (b,f,j,n) {1,5,9,13} tetraazacyclohexadecine copper (II) and nickel
(II) bisanthraflavates, Thin Solid Films 488 (1e2) (2005) 34e39. https://doi.
org/10.1016/j.tsf.2005.04.087.

nchez Vergara, A. Ortiz Rebollo, J.R. Alvarez Bada, M. Rivera, Molecular
[10] M.E. Sa
materials derived from MPc (M ¼ Fe, Pb, Co) and 1, 8-dihydroxyantraquinone
thin films: formation, electrical and optical properties, J. Phys. Chem. Solids 69
(1) (2008) 1e7. https://doi.org/10.1016/j.jpcs.2007.07.084.
[11] O.G. Morales-Saavedra, M.E. Sa
nchez-Vergara, A.A. Rodríguez-Rosales,
R. Ortega-Martínez, A. Ortiz-Rebollo, B.A. Frontana-Uribe, V. García-Montalvo,
Synthesis and electrical, spectroscopic and nonlinear optical properties of
372
nchez Vergara et al. / Journal of Molecular Structure 1193 (2019) 365e372
M.E. Sa
cobalt molecular materials obtained from PcCo(CN)L (L ¼ ethylenediamine,
1,4-diaminebutane, 1,12-diaminododecane and 2,6-diamineanthraquinone),
Mater. Chem. Phys. 123 (2e3) (2010) 776e785. https://doi.org/10.1016/j.
matchemphys.2010.05.059.
[12] M.E. Sa
nchez-Vergara, O.G. Morales-Saavedra, A.A. Rodríguez-Rosales,


J.R. Alvarez Bada, Electrosynthesis and characterization of [Cu(Taab)(-
H2O)2](L)2 non-crystalline thin films, J. Non-Cryst. Solids 357 (15) (2011)
2780e2786. https://doi.org/10.1016/j.matchemphys.2010.05.059.
[13] F.C. Krebs, Fabrication and processing of polymer solar cells: a review of
printing and coating techniques, Sol. Energy Mater. Sol. Cells 93 (4) (2009)
394e412. https://doi.org/10.1016/j.solmat.2008.10.004.
[14] M. Socol, N. Preda, O. Rasoga, C. Breazu, I. Stavarache, F. Stanculescu, G. Socol,
F. Gherendi, V. Grumezescu, G. Popescu-Pelin, M. Girtan, N. Stefan, Flexible
heterostructures based on metal phthalocyanines thin fils obtainde by MAPLE,
Appl. Surf. Sci. 374 (2016) 403e410. https://doi.org/10.1016/j.apsusc.2015.10.
166.
[15] R. Ponce Ortiz, reportOrganic Semiconductors Based on Oligotiofenes Tetra-
cyanesubstitutes: Spectroscopic, Electrochemical and Theoretical Study
(Doctoral Thesis). University of Ma
laga, Espan~ a.
[16] G. García-Moreno, Pi-conjugated Organic Semiconductor Based on Thiophene.
A Theoretical Study, Doctoral Thesis, University of Jae
n Faculty of Experi-
mental Science, Spain, 2012.
[17] A.D. Becke, Density-functional exchange-energy approximation with correct
asymptotic behavior, Phys. Rev. 38 (1988) 3098e3100. https://doi.org/10.
1103/PhysRevA.38.3098.
[18] J.P. Perdew, Y. Wang, Accurate and simple analytic representation of the
electron-gas correlation energy, Phys. Rev. B 45 (1992) 13244e13249. https://
doi.org/10.1103/PhysRevB.45.13244.
[19] A. 03, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb,
J.R. Cheeseman, G. Scalmani, V. Barone, G.A. Petersson, H. Nakatsuji, X. Li,
M. Caricato, A.V. Marenich, J. Bloino, B.G. Janesko, R. Gomperts, B. Mennucci,
H.P. Hratchian, J.V. Ortiz, A.F. Izmaylov, J.L. Sonnenberg, D. Williams-Young,
F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson,
D. Ranasinghe, V.G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada,
M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, T. Vreven, K. Throssell, J.A. Montgomery Jr., J.E. Peralta,
F. Ogliaro, M.J. Bearpark, J.J. Heyd, E.N. Brothers, K.N. Kudin, V.N. Staroverov,
T.A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A.P. Rendell, J.C. Burant,
S.S. Iyengar, J. Tomasi, M. Cossi, J.M. Millam, M. Klene, C. Adamo, R. Cammi,
J.W. Ochterski, R.L. Martin, K. Morokuma, O. Farkas, J.B. Foresman, D.J. Fox,
Gaussian 16, Revision, Gaussian, Inc., Wallingford CT, 2016.
[20] N. Mohammadi, A. Ganesan, C.T. Chantler, F. Wang, Differentiation of ferro-
cene D5d and D5h conformers using IR spectroscopy, J. Organomet. Chem. 713
(2012) 51e59. https://doi.org/10.1016/j.jorganchem.2012.04.009.
[21] P. Singla, N. Van Steerteghem, N. Kaur, A.Z. Ashar, P. Kaur, K. Clays,
K.S. Narayan, K. Singh, Multifunctional geometrical isomers of ferrocenebenzo
[1,2-b:4,5-b’]difuran-2,6-(3H,7H)-dione adducts: second-order nonlinear op-
tical behaviour and charge transport in thin film OFET devices, J. Mater. Chem.
C. 5 (2017) 697e708, https://doi.org/10.1039/C6TC03876J.
[22] B. Hu, X. Zhang, B. Tian, Y. Qi, X. Lai, L. Jin, Synthesis, electrochemical and
spectroelectrochemical properties of carbazole derivatives with ferrocene
groups, J. Electroanal. Chem. 788 (2017) 29e37. https://doi.org/10.1016/j.
jelechem.2017.01.046.
[23] S. Wang, Z. Xu, T. Wang, T. Xiao, X.Y. Hu, Y.Z. Shen, L. Wang, Warm/cool-tone
switchable thermochromic material for smart windows by orthogonally
integrating properties of pillar[6]arene and ferrocene, Nat. Commun. 9 (1737)
(2018) 1e19, https://doi.org/10.1038/s41467-018-03827-3.
[24] R.P. Hsung, C.E.D. Chidsey, L.R. Sita, Organomet. Synthesis and characteriza-
tion of unsymmetric ferrocene-terminated phenylethynyl oligomers Cp2Fe-
[C.tplbond.C-C6H4]n-X, (X ¼ SH, SMe, SOMe, and SO2Me), Organometallics
14 (10) (1995) 4808e4815. https://doi.org/10.1021/om00010a0491995.
[25] J. Xiang, X. Li, Y. Ma, Q. Zhao, C.L. Ho, W.Y. Wong, Efficient flash memory
devices based on non-conjugated ferrocene-containing copolymers, J. Mater.
Chem. C. 6 (2018) 11348e11355, https://doi.org/10.1039/c8tc03140a.
[26] J. Zhang, P. Gu, G. Long, R. Ganguly, Y. Li, N. Aranti, H. Yamadac, Q. Zhang,
Switching charge-transfer characteristics from ptype to n-type through mo-
lecular “doping” (cocrystallization), Chem. Sci. 7 (2016) 3851e3856. https://
doi.org/10.1039/C5SC04954G.
[27] H. Zhao, Z. He, X. Zhang, Z. Zhang, A. Diyaf, A.N.H. Lind, C. Liang, J.I.B. Wilson,
A preliminary investigation into hybrid photovoltaic cells with organic
phthalocyanines and amorphous silicon heterojunction, J. Phys. D Appl. Phys.
48 (2015) 19. https://doi.org/10.1088/0022-3727/48/19/195102.
[28] N. Touka, H. Benelmadjat, B. Boudine, O. Halimi, M. Sebais, Copper phthalo-
cyanine nanocrystals embedded into polymer host: preparation and struc-
tural characterization, J. Assoc. Arab Univ. Basic Appl. Sci. 13 (2012) 52e56, 1,
https://doi.org/10.1016/j.jaubas.2012.03.002.
[29] H. Ba€ssler, Charge transport in disordered organic photoconductors a Monte
Carlo simulation study, Phys. Status Solidi B 175 (1993) 15e56. https://doi.
org/10.1002/pssb.2221750102.
[30] L.G. Kaake, P.F. Barbara, X.Y. Zhu, Intrinsic charge trapping in organic and
polymeric semiconductors: a physical chemistry perspective, J. Phys. Chem.
Lett. 1 (2010) 628e635, https://doi.org/10.1021/jz9002857.
[31] I. Nar, A. Atsay, A. Altındal, E. Hamuryudan, o-Carborane, ferrocene, and
phthalocyanine triad for high-mobility organic field-effect Transistors, Inorg.
Chem. 57 (4) (2018) 2199e2208, https://doi.org/10.1021/
acs.inorgchem.7b03097.