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Structure of pentacenehetracene
on glass substrate
superlattices
deposited
greased by acetone and set on a holder mounted on a turntable, which was rotated so that the substrate would face
the two evaporators alternatively. Prior to the sample
placement in front of the evaporators, the deposition rate
was monitored by a quartz oscillator attached to the turntable. The typical deposition rate was 0.16 rim/s for tetracene (source temperature= 120 C) and 0.02 rim/s for
pentacene ( 140 C). Throughout the deposition, the temperatures of the cells were kept constant.
Let us hereafter designate the structure of the samples
by P(n)/T( n) XN, where n (n) denotes the number of
pentacene (tetracene) molecular layers within a period and
N is the number of periods. We arbitrarily set n = n, and
various samples with 14>n>0.7 were prepared. To ease
comparison between samples, the total number of molecular layers (2nN) was chosen to be nearly constant. For
reference purposes, we also made two bulk samples consisting of a single thick layer of pentacene (thickness
d=320 nm) and tetracene (d=430 nm), respectively.
X-ray diffraction measurements were carried out at
room temperature using an x-ray diffractometer (Rigaku
RAD-B) operated with Cu Ka radiation. Figure 1 shows
the diffraction patterns of the reference samples, both of
which clearly display the first-order peak (at 26= 5.7 and
7.14 for pentacene and tetracene, respectively) as well as
higher-order peaks. The sharpness of these peaks indicates
the highly ordered structure of these samples. The interplanar spacing obtained from the peak positions are 1.54
and 1.21 nm for pentacene and tetracene, respectively. We
assumed that these spacings remain unchanged in SL and
estimated the n and n of each SL sample from the experimental growth rate and the growth time.
Diffraction patterns for various SL samples are presented in Fig. 2. Compared to bulk samples, the peaks are
broadened and higher-order structures (28> 10) are
weaker, reflecting increased disorder. A salient feature is
the splitting of the first-order peak for n>3 with larger
splitting for larger n. P(3)/T(3)
X 50, for instance, displays two subpeaks (28=6.46 and 6.78), whereas four
subpeaks are seen in P(7)/T(7)
x20 (at 28=5.86, 6.22,
6.7, and 7.14, respectively). Note the nearly equal subpeak spacing (~0.4) for the latter. As for P( 14)/T( 14)
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z
.t:
(a) pcntacene
11
(a)
-z
.s
1
d
2
5
2
2
E
P( 14)/T( 14)x10
L
2e (degree)
28 (dcgrce)
FIG. 1. X-ray diffraction patterns at room temperature for the bulk
(a) pentacene and (b) tetracene samples deposited on glass used for
reference.
28 (degree)
FIG. 2. X-ray diffraction patterns of pentacene/tetracene SL samples at
room temperature.
28 (degree)
FIG. 3. Calculated structure factors for (a) P( 14)/T(
P(7)/T(7)
x20.
To make our discussion more quantitative, the structure factors S(e) of these SLs were calculated and compared with the diffraction patterns. In the calculation (1)
we took into account carbon atoms only, (2) each pentacene or tetracene layer was assumed to be a perfect crystal
with its atomic arrangement identical to that of the u-b
molecular plane reported in the literature,7 and (3) the
interlayer spacings were set equal to the experimental values obtained above.
Figure 3 presents the calculated results. Overall agreement between the calculation and the experiment is good.
(It should be noted that our calculation does not take into
account atomic form factors. Their inclusion would suppress higher-order peaks, bringing the calculation closer to
the experiment.) The S( 0) for P( 14)/T( 14) x 10 exhibits
two main first-order (28 < 8) peaks (at 8 equal to the bulk
pentacene and tetracene values) plus subpeaks resulting
from the superlattice period, in agreement with the experiment. For P(7)/T(7)
X20, the superlattice period modulates S( 0) more strongly and, therefore, the simple classification of the peaks into bulklike main peaks and SL
subpeaks is not very meaningful, again consistent with the
experiment. A closer inspection, however, reveals that the
calculated S( 0) almost vanishes at 28==6 (halfway between the two bulk values) but the diffraction pattern does
not. This discrepancy may be explained by structural disorder. The S(0) generally relies on the subtle interplay
between the two bulk periods and the SL period. Thus
S( f3) would be particularly sensitive to disorder if 8 is at
the middle of the two bulk peaks where all the three periods are equally important. The calculated peak spacings
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Appl. Phys. Lett., Vol. 63, No. 23, 6 December 1993
203.199.213.130 On: Tue, 24 Mar 2015 11:25:53
500
GO0
700
800
900
Wavelength (nm)
FIG. 4. Photoluminescence spectra of pentacene/tetracene SL as well as
reference pentacene and tetracene samples taken at 77 K.
Photoluminescence (PL) measurements of the samples are also performed at 77 K, using a chopped Ar+ laser
beam at wavelength 514.5 nm. At this wavelength, absorption occurs predominantly in tetracene since pentacene is
nearly transparent in this regime. Figure 4 presents the
obtained spectra for various n. One immediately sees that
there is an abrupt change in spectrum at n = 3: For n>3 the
spectrum is essentially that of tetracene, whereas for n < 3
radiative recombination takes place in pentacene (meaning
that the initial excitation in tetracene is transferred to pentacene where radiative recombination took place). That
PL and x-ray diffraction exhibit a crossover behavior at
exactly the same n value is a strong indication that they
have the same structural origin. This seems quite likely,
since energy transfer between scenes is mainly through
dipoledipole
interaction, which is orders of magnitude
stronger within a layer than between layers,* and should be
strongly dependent on whether pentacene and tetracene
molecules are found in the same layer (intermixing).
In conclusion, a combined x-ray diffraction and PL
study was conducted on pentacene/tetracene SLs deposited on a glass substrate. The result shows that a welldefined SL structure is achieved for n>3, whereas the samples with n < 3 exhibit no SL period, indicating the
complete intermixing of pentacene and tetracene.
The authors would like to thank Dr. M. KuwataGonokami, Dr. T. Matsusue, and Dr. K. Uchiyama for
many useful discussions.