Journal of Luminescence 180 (2016) 31–37

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Full Length Article

Triplet exciplex electroluminescence from two columnar liquid crystal

perylene derivatives
Juliana Eccher a,n, Ana Cláudia Batista Almeida b, Thiago Cazati b, Heinz von Seggern c,
Harald Bock d, Ivan H. Bechtold a,n
a
Departamento de Física, Universidade Federal de Santa Catarina
UFSC, 88040-900 Florianópolis, SC, Brazil
b
Departamento de Física, Universidade Federal de Ouro Preto – UFOP, 35400-000 Ouro Preto, MG, Brazil
c
Department of Electronic Materials, Institute of Materials Science, Technical University of Darmstadt, Alarich-Weiss Strasse 2, D-64287 Darmstadt, Germany
d
Centre de Recherche Paul Pascal, Université de Bordeaux & CNRS, 115 Avenue Schweitzer, 33600 Pessac, France

art ic l e i nf o a b s t r a c t

Article history: Double layers and mixed single layers of two electronically complementary columnar liquid crystals show
Received 11 February 2016 enhanced performances in light emitting diodes compared to devices made from single layers of only one
Received in revised form of the materials. A shift from green to red electroluminescence is observed between single-material and
26 July 2016
two-material devices, assigned as resulting from triplet exciplexes in the electroluminescence of the two-
Accepted 2 August 2016
Available online 8 August 2016
material films, whereas singlet exciplex states contribute to the photoluminescence of the mixture and
double layer films.
Keywords: & 2016 Elsevier B.V. All rights reserved.
Columnar liquid crystals
Photoluminescence
Electroluminescence
Diode devices

1. Introduction In ColLC materials, where disk-like molecules self-assemble in

columnar stacks, an improved charge transport along the π-
Organic charge-transport materials are the object of intense stacking direction can be exploited in optoelectronic devices [8].
scientific activity because of their potential application in organic In the here considered ColLCs a planar polycyclic π-electron-rich
electronics. Columnar liquid crystals (ColLCs) have been con- molecular core is surrounded by insulating aliphatic side chains.
sidered an attractive alternative to amorphous or polycrystalline Thus the charge transport in such materials is prone to be highly
materials as active layers in optoelectronic devices [1]. Their anisotropic occurring preferentially via hopping from one mole-
main advantage is the possibility to control molecular organiza- cule to another in stack direction. It has been reported that the
tion to improve optical and electrical responses as well as easy mobility along the columns can be several orders of magnitude
film processing. Perylene liquid crystalline derivatives have been higher than perpendicular to that direction. Therefore, the col-
intensively studied for these purposes due to their absorption umns have been described as “molecular wires” [9,10]. The
potential of ColLCs has been demonstrated successfully in devices
and emission in the visible light spectrum, long-range ordered
such as organic photovoltaic cells (OPVs) [11–14], organic light-
π-aggregates in columnar superstructures and high electron
emitting diodes (OLEDs) [15–18] and organic field-effect transis-
mobility [2,3]. Perylene-diimide (PDI) derivatives with pro-
tors (OFETs) [19,20].
nounced n-type semiconducting character are among the mate-
In particular, ColLCs have been used to form mixtures in OPV
rials most used in organic solar cells as an efficient alternative to
systems with good performance [21]. In a recent report, a ColLC
fullerene derivatives [4,5]. ColLCs allow controlling the structural has been used as additive to a conventional binary P3HT:PCBM
order in the bulk and at the interfaces, from molecular to mac- blend resulting in a twentyfold increase in the mean current of the
roscopic distances. Because of their liquid-like property they film [22]. Seguy et al. showed that double-layer OLEDs formed by
have the ability to self repair structural defects such as grain two sequential ColLC layers are an interesting option for such a
boundaries [6,7]. Furthermore, they can be easily processed both device [16].
from solution as well as by thermal evaporation. The development of n-type organic semiconductors is still a
challenge in comparison to extensively investigated p-type organic
n
Corresponding authors.
semiconductors [23]. In this respect perylene diimide materials are
E-mail addresses: juliana.eccher@ufsc.br (J. Eccher), an important class of n-type semiconductors due to their relatively
ivan.bechtold@ufsc.br (I.H. Bechtold). high electron affinity and strong visible-light absorption,

http://dx.doi.org/10.1016/j.jlumin.2016.08.012
0022-2313/& 2016 Elsevier B.V. All rights reserved.
32 J. Eccher et al. / Journal of Luminescence 180 (2016) 31–37

combined with good photochemical and thermal stability [8]. Due Optical textures of the ColLC 1 sandwiched between two glass slides
to the strong π–π intermolecular interactions of the perylene were obtained from an Olympus BX50 polarizing optical micro-
cores, high electron mobility values have been reported [24–27]. scope (POM) in transmission mode, equipped with a Mettler Toledo
In the present study, the photophysical and electrical prop- FP-82 hot stage to control the temperature. The images were
erties of an electron-rich perylene tetraester that presents a recorded with a CCD camera coupled to the optical microscope.
columnar mesophase at room temperature were investigated. In The temperature dependent X-ray diffraction (XRD) measure-
addition, an electron-deficient room temperature columnar ments were performed with an X’Pert PRO (PANalytical) dif-
benzoperylene diimide was used to produce double layer and fractometer with CuKα radiation (λ ¼1.5418 Å) equipped with an
mixed structures. Due to the less pronounced electron with- X’Celerator detector. An amount of 1 was deposited on a glass
drawing effect of ester groups compared to imide substituents, substrate and heated to the isotropic liquid phase. The diffracted
such materials are shown to transport both positive and nega- radiation was collected in continuous mode from 2° to 30° (2θ
tive charges, and thus function in single layer devices [16]. The angle) at specific temperatures during the cooling down to room
electrical response of the combined systems applied in diode temperature. The temperature was controlled with a TCU2000-
devices was superior to devices fabricated by individual mate- Temperature Control Unit (Anton Paar).
rials, as well as, the green electroluminescence of the OLED Cyclic voltammetry (CV) was performed in a three electrode
turned to red. Time-resolved fluorescence measurements sug- cell, with a platinum disc working electrode, a platinum wire
gest significant contributions of exciplex emission in the solid counter electrode and an Ag þ /AgCl reference electrode. The
state of the combined systems. compound 1 was dissolved in acetonitrile supplemented with
0.1 M tetrabutylammonium hexafluorophosphate and degassed by
purging with nitrogen gas before each measurement. The vol-
2. Experimental details tammogram was recorded at a scan rate of 100 mV s
1 and the
potentials were corrected with respect to the ferrocene/ferroce-
2.1. Materials nium (Fc/Fc þ ) redox couple used as internal standard. From the CV
measurements only the LUMO (lowest unoccupied molecular
The synthesis of the ColLCs investigated here, namely (3,9 orbital) energy level was determined. Thus, using the LUMO level
(10)-bis(2-methoxyethoxycarbonyl)-4,10(9)-bis(2-(2-methox- obtained from the CV and the optical band gap determined from
yethoxy)ethoxycarbonyl)perylene) 1 and benzo[ghi]perylene- the absorption spectrum, the HOMO (highest occupied molecular
1,2,4,5,10,11-hexacarboxylic-1,2-bis(2-ethylhexyl)ester-4,5:10,11- orbital) energy level was estimated.
bis(undec-4-yl)imide 2, has been published elsewhere [28,29]. The absorbance spectra in solution using CHCl3 (chloroform)
The complete chemical and physical characterization of the dii- and in spin-coated films were collected with an Ocean Optics
mide 2 has also been published elsewhere including its behavior USB4000 spectrophotometer. For the photoluminescence (PL)
as a semiconducting layer in electronic devices [30,31]. measurements in solution and in films a Hitachi fluorescence

2.2. Characterization methods spectrophotometer (Model F-7000) was used and the samples
were excited at the wavelength of maximal absorption.
Phase transitions and enthalpies of 1 have been evaluated by The diodes were produced by solution processing of com-
differential scanning calorimetry (DSC) using a TA Q2000 module. pounds 1 and 2 individually and by mixing of the two materials in
For the heating and cooling cycles a rate of 10 °C min
1 was used double layer and mixture (wt:wt%) structures, respectively. Indium
with a nitrogen flow of 50 mL min
1. The thermal stability of 1 was tin oxide (ITO) coated glass plates with a sheet resistance of about
analyzed with a Shimadzu thermogravimetric analyzer TGA-50. □
15 Ω/ were used as conductive substrates. A thin layer of PEDOT:
 J. Eccher et al. / Journal of Luminescence 180 (2016) 31–37 33

PSS [poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)] exponentials using the FluoFits software. The plots of weighted
was deposited by spin coating at 3000 rpm during 30 s, followed residuals and reduced chi-square (χ2) were used to accurately
by annealing at 110 °C for 5 min. In all cases the organic semi- determine the quality of the fittings during the analysis procedure.
conductor layers were deposited by spin-coating at 2000 rpm
during 30 s from solutions in CHCl3 at a concentration of
50 mg/mL. In the case of the double layer devices, the films were 3. Results and discussion
produced by successive depositions using an orthogonal solvent
for the second layer. The more polar semiconductor 1 was The thermal stability of 1 was evaluated by thermogravimetric
deposited first from a solution in CHCl3, followed by deposition of analysis (TGA) under a nitrogen atmosphere where the decom-
the less polar semiconductor 2 from a solution in n-heptane, a position sets at temperature exceeding 350 °C. Differential scan-
solvent that does not dissolve the previously deposited layer 1. For ning calorimetry (DSC) showed a mesophase between
25 °C and
the mixture, equal weights of both materials were dissolved in 148 °C as can be seen in Fig. S1 of the Supporting Information. By
CHCl3. The thickness of the spin-coated films was probed with a polarized optical microscopy (POM) and X-ray diffraction (XRD),
Dektak 8000 profilometer. Top electrodes were deposited by suc- the mesophase was found to be hexagonal columnar (Colh), with a
cessive vacuum depositions (10
7 mbar) of Ca (50 nm) and Al lattice constant a ¼18.8 Å and a mean distance of 3.5 Å between
(100 nm) both at a rate of 2 Å/s. The active area of the diode was adjacent molecules inside the columns, which is consistent with
10 mm2. The current density-voltage ( J/V) and the luminance- the π–π interaction distance. A periodic intracolumnar packing is
voltage (L/V) characteristics were measured at room temperature fundamental for an efficient overlap of the π-orbitals and therefore
using a HP Semiconductor Parameter Analyzer (Model 4145A). for a good charge transport as can be suspected from Fig. S2 in the
Time-resolved fluorescence decay curves were recorded using supporting information.
the technique of time-correlated single photon counting [32] with The LUMO of 1 was determined by cyclic voltammetry to be at
a FluoTime 200 (PicoQuant). Excitation was provided using a
3.56 eV as can be seen in Fig. S3 in the supporting information.
401 nm pulsed diode laser with repetition rates varying from The optical band gap energy (Eg) of 1 was determined from the
5.0 to 20 MHz. Fluorescence was collected perpendicular to exci- absorption edge of the π–πn transition [33] to be 2.26 eV, allowing
tation and passed through a polarizer set at the magic angle. The the estimation of the HOMO level to be
5.82 eV. These values are
detection system consisted of a monochromator and a multi- comparable to already published ones for similar perylene ester
channel bases photomultiplier (Hamamatsu R3809U-50). Life- derivatives [16,27,34,35]. The HOMO and LUMO energy levels of
times were obtained by fitting of the fluorescence decays to a compound 2 were found to be
3.65 eV and
6.11 eV, respec-
convolution of the instrument response function and a sum of tively, in an earlier publication [30].

1.2
b 1.2

476 nm 492 nm 523 nm

1.0 466 nm 472 nm 1.0
Normalized Absorbance

Normalized Intensity

0.8 1 0.8
1
2
2
0.6 Mixture 0.6 Mixture

0.4 0.4

0.2 0.2

0.0 0.0
360 380 400 420 440 460 480 500 520 460 480 500 520 540 560 580 600 620
Wavelength (nm) Wavelength (nm)

1.2 1.2
580 nm
445 nm 502 nm 560 nm 587 nm
1.0 1.0 547 nm 593 nm
Normalized Absorbance

Normalized Intensity

1
0.8 2 0.8
1
Double layer 2
0.6 Mixture 0.6 Double layer
476 nm Mixture
0.4 0.4

0.2 0.2

0.0 0.0
350 400 450 500 550 600 500 550 600 650 700 750
Wavelength (nm) Wavelength (nm)

Fig. 1. Absorbance spectra and PL spectra of 1 and 2 for the individual and mixed molecules in chloroform solution (a, b) compared to spin-coated solid films (c, d) of the
same materials, mixture and double layer.
34 J. Eccher et al. / Journal of Luminescence 180 (2016) 31–37

The well-defined vibronic bands which can be seen in the fluorescence decay of the mixture in solution at 523 nm is bi-
absorption and emission spectra in solution in Fig. 1a and b, exponential, showing two lifetimes (4.4 ns and 2.4 ns) very similar
respectively, are typical for materials based on a perylene core or to those observed individually for monomeric 1 and 2, indicating
on closely related benzo[ghi]perylenes [35–38]. The emission that the individual emissive properties are preserved at the
spectra in solution (see Fig. 1b) are mirror images of the absorption investigated concentration. It is important to emphasize that
spectra with a Stokes shift of 20 nm for 1 and 10 nm for 2 due to charge or energy transfer processes between the molecules would
transitions from the ground state (S0) to the vibronic levels of the necessarily lead to additional longer lifetimes, as it was observed
excited state (S1). The absorbance and PL of the 1:1 mixture of in films (see below). The larger amplitude of the first long-living
compounds 1 and 2 in solution preserves the vibronic character- exponential component (A1) compared to the second one (A2),
istics of both compounds. However, the lower energy decays of 1 reveals that the major contribution for fluorescence at 523 nm is
and 2 dominate the PL spectra of the mixture. due to the emission of compound 1 (Fig. 1b). In part, it is asso-
In solution, the fluorescence quantum yields of 1 and 2 are ΦFL/1 ciated to the lower fluorescence quantum yield of compound 2
¼ 64% and ΦFL/2 ¼55% as determined using Coumarin 6 as reference (ΦFL/2 ¼ 55% and ΦFL/1 ¼ 64%).
(ΦFL ¼80% in ethanol) with excitation at 444 nm. The best fitting of fluorescence decay of the spin-coated film of
In the solid state the main absorption peak of 1 shows a red- 1 showed three lifetimes, where the longer excited state lifetime of
shift of 30 nm compared to the solution as can be seen in Fig. 1c. 6.0 ns was slightly longer than observed for 1 in CHCl3, while the
This red-shift indicates π-stacking in the solid state [39,40]. In shorter lifetimes of 0.64 ns and 0.14 ns were much shorter than
addition, the absorption spectrum in the solid film is broader and that of the monomer emission in solution. The shorter excited
consequently the vibronic bands are less defined, indicating an state lifetimes in spin-coated films indicate aggregations of the
agglomeration of a varying number of molecules in the solid state. molecules driven by π–π interactions [46]. Aggregated formation
The vibronic structure of the film absorption spectrum of 1 has been observed previously for perylene derivatives in highly
(Fig. 1c) is partially preserved in the PL spectrum (Fig. 1d). How- concentrated solutions and solid films [44,47]. In addition, the
ever, for 2 the intensity of the 0–0 absorption band decreases shortest lifetime dominates the fluorescence of 1 in the film
while the intensity of the 0–1 band increases from solution to film. (Table 1) as can be seen from its amplitude (86.5%). Two distinctive
This intensity inversion suggests the formation of H-aggregates, emission lifetimes were sufficient to describe the spin-coated film
leading to excimer fluorescence [41]. The emission of 2 is centered of 2. The shorter excited lifetime of 0.9 ns might also be attributed
at 547 nm (Fig. 1d), with a red-shift and a loss of the vibronic to emission of aggregates, while the longer lifetime of 42.0 ns
structure compared to the solution emission resulting from π–π might be attributed to emission from excimers. The lifetimes of
intermolecular interactions due to molecular aggregation typical excimer emission are usually longer than those of the monomer
of excimer fluorescence [35,37,40]. single states [41,48]. Excimer formation was observed previously
The film absorbance spectra of the double layer and of the for perylene molecules at highly concentrated solutions driven by
mixture are quite similar, presenting the same main bands around the covalent interaction between excited π–π stacked molecules
445 and 476 nm characteristic of 2 with a pronounced shoulder at [49,50]. As discussed above, the inversion of the 0-0 and 0-1
502 nm which coincides with the main absorption peak of 1 absorption bands accompanied with non-vibronic red shifted
(Fig. 1c). The maximum of the emission band of the double layer fluorescence emission of 2 in the film corroborates with excimer
and of the mixture at 580 nm and 587 nm, respectively, are posi- formation. The major contribution (87%) to the fluorescence of
tioned between the emission bands of the individual materials 1 compound 2 comes from the excimer emission and only around
and 2. The energy associated to these maxima is 2.14 eV and 13% from aggregation of molecules.
2.11 eV, being in good agreement with the difference between the The excited state lifetimes for the mixture solid film are very
HOMO of 1 and the LUMO of 2, i.e., 2.17 eV. This suggests that the similar to those of the double layer film. However, the best fitting
emission is coming from exciplex states in the combined systems of fluorescence decay for these films revealed three distinct life-
[42]. It is known that in mixtures composed by an electron donor times varying between 30.6 ns and 0.39 ns, where it is possible to
and acceptor, the formation of the excited bimolecular states by identify the individual contribution of the monomeric emission of
charge transfer between the molecules of the donor and acceptor compound 1 (around 4.3 ns). The shorter excited lifetimes around
species is highly favored [43]. 0.40 ns dominate the emission and are also attributed to emission
The excited state lifetimes of 1 and 2 in chloroform solution of aggregates species. The difference observed for the longer life-
and in spin-coated films both excited at 401 nm are listed in times (around 30 ns) in comparison to the individual molecules
Table 1. Mono-exponential emission lifetimes of 4.3 and 2.6 ns indicate the existence of new emitting species as a result of the
were observed in solution, and these lifetimes are typical for interaction of both materials, and suggest the formation of exci-
monomeric emission of perylene derivatives [44,45]. The plex states, which are characterized by their longer lifetimes [42].

Table 1
Emission maxima, excited state lifetimes and their relative amplitudes of single materials, mixture and double layer in CHCl3 solutions and spin-coated films at room
temperature.

Compound λmáxa (nm) τ1 (ns) A1 (%) τ2 (ns) A2 (%) τ3 (ns) A3 (%) χ2

1b 492.0 4.3 7 0.3 100.0 – – – – 0.990

2b 476.0 2.6 7 0.2 100.0 – – – – 0.982
Mixturec 523.0 4.4 7 0.1 93.87 2.4 7 0.6 6.13 – – 0.995
1 593.0 6.0 7 0.2 1.67 0.647 0.03 11.87 0.147 0.04 86.46 0.998
2 547.0 42.0 7 0.3 86.99 0.9 7 0.5 13.01 – – 1.035
Mixturec 587.0 30.4 7 0.4 26.31 4.4 7 0.3 27.75 0.447 0.09 45.94 1.013
Double layer 580.0 30.6 7 0.4 17.13 4.2 7 0.3 20.20 0.39 70.05 62.67 0.996

a
All fluorescence decays were measured at maxima of the emission intensities (λmax) using 401 nm excitation.
b
0.17 g/L.
c
Mixture (1:1 by weight). The comparison of fluorescence decays in solution and in films is shown in Fig. S4 in the Supporting Information.
 J. Eccher et al. / Journal of Luminescence 180 (2016) 31–37 35

a 1 -6
b 1
10 10 10
1 1
0
10 -7

Current Density (mA/cm2)

10 10
0
Current Density (mA/cm2)
Experimental
-1
10 -8 Theoretical
10 -1
10

Luminance (a.u.)
-2
10
-9 μ0= 9.50 x 10-10 cm2/V.s SCLC
-3
10 -2 trap-limited
10 -3 1/2
10 γ = 5.75 x 10 (cm/V)
-10
10
-4 10
-3
10
-5 -11
VΩ
10 10
-4 Ohmic
-6 10
10
-20 -15 -10 -5 0 5 10 15 20 1 10
Voltage (V)
Voltage (V)

c 1 -6
d 1
10 10 10
Double layer Double layer
0 -7
10 10

Current Density (mA/cm2)

0
10
Current Density (mA/cm2)

Experimental
-1
-8
10 Theoretical
10 -1
10
-9 μ0= 9.82 x 10-9 cm2/V.s
-2 10 SCLC
10 1/2
γ = 6.45 x 10-3 (cm/V)
Luminance (a.u.)

10
-2 trap-limited
-10
-3 10
10
-11
10
-3 VΩ
-4 10
10
-12
10 -4
Ohmic
-5 10
10
-40 -30 -20 -10 0 10 20 30 40 1 10
Voltage (V)
Voltage (V)

e 1 10
-6 f 1
10 Mixture 10 Mixture
Current Density (mA/cm2)

0
10 10
-7
10
0 Experimental
Current Density (mA/cm2)

-1
Theoretical
10 10
-1

10
-8 μ0= 8.15 x 10-9 cm2/V.s
Luminance (a.u.)

-2
10 1/2 SCLC
10
-2
γ = 6.28 x 10-3 (cm/V) trap-limited
-3 -9
10 10
-3
10
-4
10 -10
10 10
-4
-5
10
-11 10
-5 Ohmic
10
-6 10
-25 -20 -15 -10 -5 0 5 10 15 20 25 1 10
Voltage (V) Voltage (V)

Fig. 2. J–V (black) and L–V (blue) characteristics of spin-coated films in a diode structure of (a, b) compound 1, (c, d) a double layer of 1 and 2 and (e, f) a mixture of 1 and 2.
The graphs on the right resemble the J–V characteristics from the left plotted in a log–log plot for a separation in an Ohmic and an SCLC regime. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

Table 2 The device structure utilized for the electrical characterization

Fitting values obtained for m0 and γ parameters, luminance and Vturn-on of the
of 1 alone and in combinations with 2 was ITO/PEDOT:PSS
devices.
(45 nm)/ColLC/Ca (50 nm)/Al (100 nm). The thicknesses of the
Active l0 (10
9 cm2/ γ (10
3 (cm/ l (10
6 cm2/ Luminance Vturn-on ColLC films were about 200 nm for a single layer of 1, 600 nm for
Layer V s) V)1/2) V s)a (cd/m2)b (V) the double layer and 315 nm for the solid mixed film.
1 0.95 5.70 0.14 2.4 (13.3 V) 2.6
The electrical measurements were performed at room tem-
2c 0.98 4.45 0.12 – 15.0 perature in a controlled N2 atmosphere. Fig. 2a, c and e show the
Double 9.82 6.45 2.64 6.5 (40.0 V) 6.6 current-density/voltage ( J–V) and luminance/voltage (L-V) char-
layer
Mixture 8.15 6.28 2.54 8.6 (21.0 V) 2.6
acteristics of 1, of the double layer and of the mixture device,
respectively. The J–V curves show weak diode-like behavior with
a,b 5 c
Calculated for electric field strength of 6.67  10 V/cm. Values extracted from rectification ratios lower than two orders of magnitude. Taking
Ref. [30], where the luminance was not determined due to low intensity.
into account the energy diagram of the devices (see Fig. S5 in the
36 J. Eccher et al. / Journal of Luminescence 180 (2016) 31–37

Supporting Information ), the LUMO energy levels of compounds 1 639 nm

and 2 match satisfactory with the work functions of the Ca elec-
564 nm 648 nm
trode (  2.9 eV), favoring an Ohmic contact at the cathode for both
materials. This means that an electron reservoir will be formed at
the cathodes. As can be seen from the Ohmic regime of the J–V 1

Normalized EL
characteristics the electrons from this reservoir do not seem to be 2
mobile for small voltages as one would expect from the absence of Double layer
an injection barrier for electrons between Ca and the LUMO levels Mixture
of 1 and 2. However, a much larger barrier has to be overcome for
the injection of holes from PEDOT into the organic materials which
amounts to 0.62 eV for 1 and 0.91 eV for 2.
Fig. 2b, d and f display the log-log plots of the J–V character-
istics, where two conduction regimes can be observed. At low
voltages the device shows an Ohmic behavior where J p V n with
n ¼ 1 followed by a space-charge-limited-current (SCLC) regime at
higher voltages. The two regimes are separated by the critical 400 500 600 700 800 900
voltage V Ω defined as the voltage where the Ohmic current is Wavelength (nm)
exceeded by the SCLC, which in a trap-free material would
increase quadratically with the applied voltage. For the present Fig. 3. EL spectra for monolayer (1 and 2), double layer and mixture devices.

results, however, this is not the case. The reason has been shown
to be related to the existence of traps leading to an J–V char- higher than the single material devices. In addition, the mixture
acteristics with J p V n with n 4 2. device is brighter than the double layer followed by the device of
In the Fig. 2b and d, V Ω ¼ 2:4 V for 1 and V Ω ¼ 6.6 V for the 1 (see Table 2).
double layer. Whereas for the device containing the mixture this Fig. 3 shows the EL spectra for the single-material, double layer
value is not as clearly detectable since two changes of slope can and mixture devices. The emission maxima of both single-material
be observed, which may indicate two injection processes. The devices coincide at 564 nm, while a red-shift of 75 nm and 84 nm
threshold voltages V Ω separating the two conduction regimes appears for the double layer and the mixture devices, respectively.
agree for 1 and double layer very well with the turn-on voltage This red-shift represents a change in the emission color from
for the luminescence. Considering the existence of the charge green to red and may be related to exciplex emission coming from
reservoir for electrons at the cathode and assuming absence of the interfaces of materials 1 and 2. Moreover, in devices formed by
an electron transport in all devices for low voltages, V Ω repre- the combination of two materials, the accumulation of charges at
sents the onset of hole injection. This indicates that the voltage interfaces between organic layers is expected and favorable for
where injection of both charge carrier types becomes dominant recombination. Due to the initial condition of separated charge
corresponds to the voltage needed for exciton formation, carriers, spin statistics favor the formation of triplet excited states
recombination and consequently for light emission. This for the charge carrier recombination process. Thus, it can be
increased value of V Ω is owed the larger thickness of the double expected that triplet exciplexes, which tend to be of lower energy
layer device compared to 1 and the mixture. Taking the thick- and thus of longer emission wavelengths than singlet exciplexes,
ness into account one observes that the critical field strength dominate the light emission [43]. The PL for the double layer and
EΩ ¼ V Ω =d for 1 as well as the double layer is with mixture films as taken from Fig. 1 is at distinctively shorter
EΩ ¼ 1:1  105 V/cm almost comparable. wavelengths than the EL as displayed in Fig. 3. Therefore the PL is
In order to determine the field dependence of the charge car- dominated by singlet exciplex states, while triplet exciplexes seem
rier mobility a model, described in an earlier publication from the to dominate the emission under electrical excitation. However, in
present authors of this article, [30] was used with an electric field the EL spectra of the combined systems, a low intensity emission
pffiffi
dependent mobility of the form μðEÞ ¼ μ0 eγ E as suggested by band is present at the position of the individual emissions of
Bässler [51]. In this model the traps distribution is implicitly compounds 1 and 2, which indicates that a minor degree of
included in the mobility through m0 and γ which can be obtained recombination is occurring on the individual molecules.
from fitting the currents in the SCLC regimes of the J–V curves. The
fits for each case are shown as red solid lines in Fig. 2b, d and f.
Table 2 presents the m0 and γ values obtained from the fits, which 4. Conclusions
were used to determine the maximum mobility for the monolayer
1 and the combined devices (mobilities as a function of the applied In solution, the photoluminescence from a mesogenic perylene
voltage are shown in Fig. S6 in the Supporting Information). As tetraester and from a mesogenic benzoperylene diimide is mainly
POM of the films showed a texture characteristic of planar orien- due to monomeric species. However, in the solid columnar liquid
tation (see supporting information), with the majority of the crystalline state, the formation of molecular aggregates driven by
columnar domains oriented parallel to the surface, this low π-π interactions dominates the fluorescence emission from single-
mobility is likely due to charge transport perpendicular to the π- material films of the tetraester 1, while excimers were found to
stacking direction. Such anisotropy of the mobility in columnar dominate the fluorescence of films made of the diimide 2. The
mesophases is known from the literature [52–54]. mixture of both materials in solution clearly displays the char-
Considering the electrical performance of the three devices of acteristic times of the emission of the individual materials, while
Fig. 2 at the largest common field strength, which results from exciplex states formed at the interface of both materials contribute
the double layer device, the field strength can be calculated to be to the photoluminescence of mixture and double layer films of the
E ¼ 40V =600 nm ¼ 6:67  105 V=cm: For the single layer device 1 two materials together.
this field corresponds to a voltage of 13.3 V and 21.0 V for the LEDs based on a mixture or a double layer of both mesogens
mixture device. For this electric field the devices of the combined show higher charge mobilities and luminances than LEDs based on
materials exhibited mobility values one order of magnitude each of the individual materials alone, resulting in a change of
 J. Eccher et al. / Journal of Luminescence 180 (2016) 31–37 37

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