Appl. Phys.

A 83, 115121 (2006)

Applied Physics A

DOI: 10.1007/s00339-005-3467-y

Materials Science & Processing

c.b. lee
a. uddinu
c.c. teo

Effect of polar dopant on energetic

and positional disorders
in tris(8-hydroxyquinolinato) aluminum (Alq3)
School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798,
Singapore

a conjugated bridge [5, 6]. The lowest unoccupied molecular

orbital (LUMO) and the highest occupied molecular orbital
(HOMO) energy level of DCM are located at 3.2 and 5.4 eV,
ABSTRACT The influence of polar dopant on the charge carrespectively which is well coupled within the energy band gap
rier transport in amorphous tris (8-hydroxyquinolinato) aluof Alq3 . In fact, DCM is acting as a recombination center in
minum (Alq3 ) was studied by time-of-flight measurement. The
Alq
3 because of its low potential barrier and good fluores4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4Hcent
efficiency [7]. In these two material systems the energy
pyran (DCM) was doped into Alq3 with various concentration
of
the
excitation is transferred from the host material (donor)
from 0.5 to 24 wt. %. The electron mobility was reduced by
about one order by DCM doping in Alq3 . The electric-field to the dopant (acceptor) material through the efficient Forster
dependence electron mobility in Alq3 :DCMfilms separated resonant energy transfer or charge transfer processes [8, 9].
intotwo discrete regions of critical fields E c . The value The doping concentration directly influences the color and
of E c ranged from 360 to 405 (V/cm)1/2 depending on the the efficiency of the emission of OLEDs devices [2, 6]. HowDCM concentration in Alq3 films. The energetic disorder in ever, the dye-dope organic molecules, especially with polar
Alq3 :DCM films increased from 0.01 eV to 0.09 eV with DCM molecular structure, may also affect the carrier transport propdoping concentration. The positional disorder in Alq3 :DCM erties in doped film due to dipole effects on surrounding host
films also increased from 0.3 to 6.5 with DCM doping con- molecules. The dopant dipoles will locally modify the polarcentration up to 24 wt. %. These results indicated the strong ization energy due to its effects on the local field of localized
Coulombic and dipoledipole interactions between DCM and carriers.
Alq3 molecules. The interactions between randomly located
The interaction between randomly located and oriented
DCM molecules, Alq3 dipoles and oriented dipoles are the
dipoles
is one of the major causes of energetic disorder in the
major caused of positional disorder.
doped film. When the structure of the dye-dope molecules is
PACS 73.50.-h; 73.61.Ph; 71.20.Rv
different from the guest molecules, an additional local modification of the polarization energy appears due to a static distortion of the structure. The polar dopants enhance the dipolar
1
Introduction
disorder, and decrease the carrier mobility in the film [11].
The localization of charge carriers due to the increased of
Normally, the active region of organic light emit- positional and energetic disorders in doped layers [12, 13] is
ting diodes (OLEDs) is obtained in the mixtures of molecules, directly influenced by the transport of carriers. The increase of
polymers and dye-doped organic materials [1, 2]. Sometimes positional disorder also rises with the energetic disorder due to
the active layer is doped with dye material in order to increase the interaction of doped molecules.
the emission intensity, select the emission color, provide both
There are only a few reports on the role of polar dopants
good charge transporter and reduce unwanted self-absorption on charge carrier transport in host materials [6, 14]. For this
effects. Tris-(8-hydroxyquinolinato)-aluminum (Alq3 ) is one study, DCM and Alq3 were chosen as the dye dopant and
of the chelate metal complexes and has been intensively used host materials respectively. We analyzed the carrier mobilin vacuum-deposition thin films as light emitters in OLEDs. ity in Alq3 :DCM amorphous films with various doping conThe Alq3 is one of the most stable and efficient electrolumi- centrations from the time-of-flight (TOF) measurement. The
nescence (EL) emitter. The laser dye, 4-(diacynomethylene)- carrier mobility in DCM doped films was only in agreement


2-methyl-6-(p-dimethylaminostyryl)-4H-pyan (DCM) is one with the PooleFrenkel (PF) model of 1,2 exp(1,2 E 1,2 )
of the most commonly used red emitters in color OLEDs and at two different ranges of square root fields, where 1 and

has been intensely investigated [14]. The DCM is a very 2 were indicated before and after the critical field E c .

1/2
efficient arylidene laser dye with a dimethylamino electron The values of E c shifted from 360 to 405 (V/cm) with
donor group linked to two cyano electron acceptor groups by DCM concentration. The energetic disorder in the bulk film
increased from 0.013 eV (in pure Alq3 film) to 0.09 eV with
DCM doping concentration up to 24 wt. %. The positional
u Fax: +65-6790-9081, E-mail: ashraf@ntu.edu.sg
Received: 9 June 2005/Accepted: 21 November 2005
Published online: 13 January 2006 Springer-Verlag 2005

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Applied Physics A Materials Science & Processing

disorder increased from 0.3 to 6.5 with DCM concentration

up
to 24 wt. % in Alq3 :DCM films before the critical field
Ec.
2

Experimental

Highly pure (99.9%) Alq3 and DCM were purchased from Aldrich-Sigma for this experiment. The molecular structures of Alq3 and DCM are shown in Fig. 1a. The
Alq3 film doped with DCM concentration ranged from 0.5
to 24 wt. % on pre-patterned indium-tin-oxide (ITO) coated
glass substrates for the carrier transport measurements. The
device structure was ITO/Alq3 :DCM/Al as shown in Fig. 1b.
We also prepared an ITO/Alq3 /Al device for a standard reference. The ITO substrates were cleaned by a series of sonication in chemical and deionized water baths, followed by
drying and exposure to UV/ozone, and dipping in nitric acid
for 3 min. Subsequently, ITO substrates were loaded into a
thermal evaporator chamber, and the doped films Alq3 :DCM
were deposited by vacuum sublimation at 106 Torr. The deposition rate was chosen as 1.5 /s for the best quality of
layer [15]. The Alq3 and DCM were co-evaporated. The thickness of films was monitored by a crystal oscillator and measured by an Alpha-Step profiler for further confirmation. The
film thickness was 0.8 m. Sample preparation was completed by the deposition of a 100 nm thick aluminum (Al)
layer. We prepared 10 samples at a time on glass substrate,
each with an active area of 32 mm2 .
The carrier mobility was measured by the photo-induced
TOF method. The sample was attached vertically to precisely controlled heater plate. A NG-YAG laser ( = 355 nm)
with a 5 ns pulse width was used as the excitation source
for the generation of carriers. The sample was exposed to
laser light through the ITO electrode. The ITO electrode was
biased negatively with respect to the Al electrode. The negligible dark current was found under the bias condition indicating that ITO and Al act as non-injecting electrodes for
electron or hole. The photocurrent was recorded in the sin-

gle shot regime. The intensity of the laser was kept sufficiently low to avoid space charge effects. The response time
of the circuit was kept well below the transit time. The resistor chosen for this TOF method was 1 k. The voltage
drop across the resistor produced by the photocurrent was
measured with a Gage-Scope (Professional) oscilloscope with
a frequency of 10 MHz. The measurement was considered
invalid if the duration of the photocurrent was shorter than
ten times that of the system time constant (= RC , where
R was the series resistance and C was the sample capacitance). All ten samples on the same substrate exhibited similar
TOF traces.
3

Figure 2 shows the transient photocurrent in pure

Alq3 and Alq3 :DCM films for different DCM concentrations.
The TOF transient in both films can be regarded as dispersive

The typical transient photocurrent curves, (a) in pure Alq3 film,

(b) in Alq3 :DCM films for various concentrations. The inset in 2a shows the
two lines crossed at the point indicated as flight time . The dotted lines in
(a) and (b) are the simulated curves fitted with experimental data at RT
FIGURE 2

(a) The molecular structure of materials Alq3 and DCM.

(b) The device structure was ITO/Alq3 :DCM/Al for TOF measurement. The
film thickness of Alq3 :DCM was about 0.8 m
FIGURE 1

Results and discussion

LEE et al.

Effect of polar dopant on energetic and positional disorders in tris (8-hydroxyquinolinato) aluminum (Alq3 )

transport. The inset in Fig. 2a shows the two lines crossed at

a point which indicated the flight time of carriers [16, 17].
We used the carriers average mobility model [18, 19] to simulate TOF photocurrent instead of using the well-known mobil2
ity relation: = (Vd) , where V is the applied voltage, is the
flight time and d is the sample thickness. The applied model
for our study was modified from [18], by assuming the carriers
hopping velocity v is a Gaussian function across the Alq3 bulk
film. The photocurrent was depended on the carriers average
drift velocity and density. The modified photocurrent is defined as:
 
q
t
i(t) = exp
d

   d/t
 

t
t
v fv (v, t) dv d
,
exp
(1)

where the charge velocity distribution

(v v0 )2
 
exp

2
02
2 t0
2
t

f v (v, t) =

and q(x, t) = q0
02
t

 x/t
0

(2)

f(v, t) dv,

where and v0 are the variance and the mean for Gaussian distribution function, respectively, d is the sample thickness, is the carrier drift time, q is the total amount of charge
reached the electrode and t is the photocurrent measurement
time. By fitting the simulated photocurrent to the experimental data four constant parameters, , 0 , 0 and q , were estimated. The estimated values of four constant parameters
in pure Alq3 were found as = 5.97 0.5 s, 0 = 0.09
0.03 m/s, 0 = 0.099 0.001 cm/s and q0 = 538 25 pC. In
terms of physical meaning, 0 is giving the width of the velocity distribution of carriers and 0 is the mean diffusion velocity of carriers in the film.
The average velocity v can be defined as [19]
 
dt
v f(v, t) dv
v = 0 0
.
(3)
0 dt 0 f(v, t) dv
The integration in the numerator is the carrier hopping velocity v weighted by the Gaussian distribution function fv (v, t)
within the time dt . The denominator is the probability of finding a carrier with a hopping velocity v. It is the total number
of carriers with hopping velocity in the system. The average
mobility  was then calculated from the relation:
 = v /E ,

(4)

where E is the applied electric field. Figure 2a and b show the

fitted curve of the simulated photocurrent (dot line) from (1)
to the observed curve (hollow circle) from the TOF measurements in pure Alq3 and Alq3 :DCM films with various DCM
doping concentration respectively.

117

The electron mobility in each doped film was estimated.

The measured photocurrents indicated that the heavily doped
(12 and 24 wt. %) films had lower conductivity than lightly
doped film. This may be due to the increase in trapping of carriers in heavily doped bulk films. We summarized the field
dependence electron mobility at various temperatures in pure
Alq3 and Alq3 :DCM films for various DCM doping concentrations in Fig. 3af. The carrier mobility in both the pure
and doped films increased with temperature. This is in contrast to the carrier transport in inorganic semiconductors such
as Si where the carrier mobility decreases with temperature
due to the increase of phonon scattering. The mechanism of
carrier transport in organic films is by phonon assisted hopping. The local potential barrier of carrier trapping is modified with temperature due to the increased lattice vibrations.
The thermal energy helps the trap carriers to escape and hop
more easily over the local potential barriers. Figure 3a shows
the field dependence electron mobility in pure Alq3 , which
closely follows
  the PooleFrenkel (PF) model of mobility
exp E , where is a constant at a fixed temperature [20, 21]. The field dependence electron mobility wasseparated into two discrete regions of square root field ( E ),
which is indicated by an arrow in each curve as shown in
Fig. 3b to f. This discrete region phenomenon was observed
even in lightly doped 0.5 wt. % Alq3 :DCM film. The carrier mobility in the doped film is only in agreement with the
PF model at two different ranges of square root fields. The
electron mobility characteristic in doped films
into two
 discrete regions can be defined as 1,2 exp 1,2 E 1,2 . Here,
we have indicated
1 and 2 for before and after the criti
cal point of E c .
The electron mobility in doped films increased faster after E c . We observed the values of 2 > 1 .
This
phenomenon is not reported elsewhere. The values of
E c were shifted to the higher field with DCM concentration in Alq3 :DCM films and saturated at DCM concentration
3wt. %. The results are summarized in Fig. 4. The values
of E c were changed from 360 to 405 (V/cm2 )1/2 with DCM
doping
concentration up to 24 wt. %. The saturated values of

E c are attributed to the maximum polarity effect of DCM on

Alq3 molecules when the biasing field is parallel to the orientation of the dipole in the films [11].
The electric field and temperature dependence carrier mobility in Alq3 :DCM bulk films can be described by the empirical equation [12, 13, 22]:
 

 
2 2
(E, T ) = exp
exp E ,
(5)
3kT
where T is the absolute temperature, k is the Boltzmann constant,
 is2the high
 temperature limit of the mobility, and
= C kT
2 ; where C is a temperature and field independent constant related to the inter-site distance, is the
energetic disorder of the film, and is a temperature independent parameter related to positional disorder. The electron

mobility in doped-Alq3 films depend exponentially on E at

a fixed temperature according to (5). The constant parameters value was obtained by fitting the simulated curve from
(5) with experimental results. The parameters value is also depended on the nature of the charge-transporting material and
the polarity of the organic material. The charge carrier trans-

118

Applied Physics A Materials Science & Processing

The plot of electron mobility versus E at various

3 film, (b)(f) in Alq3 :DCM films for various concentrations.
temperatures (a) in pure Alq
The arrow marks in each figure shows the critical electric field E c of electron mobility. The E c increased as the DCM concentration increased in Alq3
FIGURE 3

port in disorder molecular solids is changed with field and

temperature due to the local (random) modifications of the
polarization energy. For this model we have assumed (i) the
distributions of intersite distances and site energies are Gaussian, (ii) the process is incoherent. The condition (i) defines
the shape of the density-of-states (DOS) function [13, 22],



Ntot
( m )2
N() =
exp
,
(2 2 )1/2
2 2

(6)

where Ntot is the total DOS, m is the energy of the maximum

distribution and is the energetic disorder. The width of the

LEE et al.

Effect of polar dopant on energetic and positional disorders in tris (8-hydroxyquinolinato) aluminum (Alq3 )

119

The plot of critical

electric field E c versus DCM concentrations in Alq3 bulk films. The E c was saturated at the higher concentrations
of DCM 12 wt. % in Alq3
FIGURE 4

DOS is assumed as a superposition of van der Waals vdW and

dipolar dip components. Then
2
2
2 = vdW
+ dip

(7)

with the dipolar component related to the permanent dipole

moment of the species (m ) and its concentration, where
dip =

Kx b m
,
a02

(8)

where K and b are constants, is the relative electric permittivity of the medium and a0 is the inter-site distance and x is
the mole fraction. We applied this approach to calculate the
electron mobility in Alq3 :DCM bulk films and estimated the
energetic and positional disorders in films.
Figure 5a shows the zero-field mobility ln (E = 0, T )
vs. (1/T 2 ) plot for pure Alq3 bulk film as derived from (5).
The linear curve was extrapolated for each temperature and
revealed the linear dependence as predicted in (5). We also
plotted the zero-field mobility (E = 0, T ) vs. (1/T 2 ) curve
for each DCM doping concentration in Alq3 film. From the
slope of (E = 0, T ) vs. (1/T 2 ) plot, the energetic disorder
was estimated for each DCM concentration in Alq3 film. The
results were summarized in Fig. 5b. The energetic disorder
was estimated as 1 and
2 corresponding to two discrete linear lines separated by E c in each doped film. The energetic
disorder 1 (> 2 ) is higher in each doped
film. The
energetic
disorder 2 was considerably reduced at E > E c due to
the lower influenced of DCM molecules polarity and van der
Waals interaction in the films. The higher DCM concentration
in Alq3 :DCM films showed higher energetic disorder compared to lightly doped films. The energetic disorder 1 was
increased from 0.013 eV (in pure Alq3 film) to 0.09 eV with
DCM doping concentration up to 24 wt. %. Similar observations were also made in [11]. The energetic disorder has lower
influence on charge carrier mobility at the higher electric field
in amorphous film. The DCM molecules have a tendency to

(a) The zero field mobility vs. 1/T 2 in pure Alq3 film. The energetic disorder was estimated from this zero
field mobility plot. (b) The plot
of energetic disorders before and after the E c in Alq3 :DCM for various
concentrations
FIGURE 5

aggravate the molecular structural asymmetry due to their

strong dipolar interactions between themselves [6]. In highly
doped films (such as 12 and 24 wt. %) the DCM molecules
may arrange themselves in an anti-parallel manner due to the
strong attraction between molecules at reduced distances. The
DCM molecules also have a strong interaction with surrounding Alq3 molecules due to the phenoxide donor and a pyridyl
acceptor in the quinolate ligands of Alq3 as shown in Fig. 1a.
These interactions raise the positional and energetic disorders in the doped films. We believe that the dipole orientation
should dominate the geometric disorder than the fluctuation in
intermolecular separation. At the higher field, Alq3 and DCM
molecules may be polarized and well aligned with each other,
and may reduce the effect of dipolar contribution in the DOS
function. The energetic disorder will mainly depend on van
der Waals component. Thats why we observed the higher
electron mobility (2> 1 ) when the bias field was greater
than the critical field E c .
2
Figure 6a shows the plot of as a function of ( kT
) for
1 wt. % DCM doped in Alq3 before and after the critical field.

120

Applied Physics A Materials Science & Processing

2
The has a linear relationship with ( kT
) . The constant C
was estimated from the slope of the linear curve. The
linear
line was extrapolated to obtain the positional disorder, . We
2
plotted as a function of ( kT
) curves for each DCM doping
film
to
estimate
the
constant
C and positional disorder,

. Figure 6b shows the results of
positional disorder
for different
DCM
concentrations.
The
was
assigned
to
1 and


for
two
regions
of
the
field.
The
values
of
were
found
2
1

to be higher than 2 . The positional disorder in doped films
related to the geometric disorders associated with randomness both 
in dipole orientations and intermolecular separations. The 1 values were changed from 0.3 to 6.5 with DCM
doping concentration up to 24 wt. % in Alq3 . The Coulombic interaction between the randomly distributed polar DCM
and Alq3 molecules was responsible for the increased positional disorder with doping concentration. This also leads to

a broadening of the effective

 density of states distribution.
The positional disorder 2 values were changed from 0.3
to 1.9 with DCM doping concentration up to 24 wt. %. The
positional disorders were saturated at the higher doping concentration of DCM. The increase of positional disorder gives
the energetic disorder due to the positional molecular dependence potential energy of interaction. This has been proven
from the above result of the energetic disorder (van der Waals
and dipoledipole) , which had a higher estimate as (i) the doping
concentration of DCM increased,
and (ii) when the bias field
is lower than the critical field E c .
It was recognized that the dipoledipole interaction between randomly located and oriented dipoles is one of the major causes of positional and energetic disorders in doped films.
The random distribution of DCM dopant molecules Coulombically interact with carriers localized in intrinsic hopping
sites. The DCM molecule has higher dipolar interactions due
to the existence of donor-like dimethylamine, and acceptorlike dicyanomethylene. The Alq3 molecule also shows the
dipole characteristic where a phenoxide donor and a pyridyl
acceptor formed the quinolate ligands. The higher densities of
randomly distributed DCM molecules interact either via attraction or repulsion among dimethylamine or dicyanomethylene with phenoxide or pyridyl of Alq3 molecules. The degree of interaction strongly depends on the density and the
polarity of DCM molecules. The intermolecular interaction
forces stretch molecular bonds and shift charge distribution on
molecules, which effectively broadens the DOS distribution.
In addition to the broad DOS distribution, disordered DCM
doped films probably have deeper localized states originating
from chemical and structural defects. These deeper localized
states are normally located well below the intrinsic DOS distribution, which is often referred to as deep traps. These deep
traps strongly influence the charge transport characteristics in
the doped Alq3 film.
The energy of the localized states is affected by the nearest
dopant molecules. The total density of deep localized states is
increased with increasing dopant concentration. The increase
of DCM concentration in Alq3 bulk films induces the additional deep traps and broadens the deep tail of the DOS. The
change of DOS distribution by doping was affected by the
electron carrier hopping mobility in Alq3 :DCM films.
4

(a) An example of the plot of corresponding vs.

(/kT)2 in
Alq3 :DCM (1 wt. %) film. The constant C and position disorder
were estimated from these
plots. (b) The plot of positional disorders before and after
the critical field E c in Alq3 :DCM films for various concentrations
FIGURE 6

Conclusions

We investigated the electron mobility in DCM

doped Alq3 bulk film by TOF measurements. We used the
carriers average mobility model to simulate the TOF photocurrent. The electron mobility was reduced with DCM
doping concentration in Alq3 films. The field dependence
electron mobility was separated
into two discrete
regions of

a critical electric-field E c . The values of E c was shifted

to the higher values with DCM concentration and saturated.
The similar trend was also observed for the positional and energetic disorders in DCM doped films. The energetic disorder
was increased from 0.013 eV to 0.09 eV with DCM concentration up to 24 wt. % in Alq3 . The positional disorder was also
changed from 0.3 to 6.5 with the same DCM concentration.
The results indicated strong Coulombic and dipoledipole interactions between DCM and Alq3 molecules. It was realized

LEE et al.

Effect of polar dopant on energetic and positional disorders in tris (8-hydroxyquinolinato) aluminum (Alq3 )

that the dipoledipole interaction between randomly located

and oriented dipoles is one of the major causes of energy disorder in organic materials. The DOS distribution was broaden
with DCM doping concentration in Alq3 .
ACKNOWLEDGEMENTS The authors would like to thank the
polymer lab technicians at MSE/NTU for their support. One of the authors
(C.B. Lee) would like to thank NTU for his financial support. We are also
grateful to all of our group members for useful discussions and suggestions
in this work.

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