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6 -
COOH-modified tip.
on NH,-region
- 4 -
Y 2
Q) 2 -
0 .
0 -
toward the surface
tip moves
away from the surface -
1 1 . 1 , . , , I
0 100 200 300 400
Distance [nm]
8 I ' I ' I ' I ' I
6- on CH,-region
COOH-modified tip.
-? 4 -
= ! -
2 -
toward the surface
T 2-
9 0-
away from the surface
-2 1
0 100 200 300 400
Distance [nm]
Fig. 5. a) Force-distance curve taken on an NH, region. b) Force-distance
curve taken on a CH, region. Both of the measurements (a and h) were made
with the same cantilever; although the absolute scale is arbitrary, the relative
sizeof both curves is correctly represented.
tion at different pH-values demonstrate that the same fea-
tures can be obtained compared to experiments in air.
To conclude, wehave provided confirmation that chemical
modification of the SFM tip can beused for chemical imaging.
The preparation of the chemical FM-sensor can be achieved
by chemisorbing molecules with functional groups on the tip.
The attached functional groups determine the chemical
interaction of the tip with the substrate surface. A wide range
of these groups with different chemical properties can be
attached leading to a large flexibility in choosing the proper
tip. Work following these lines is underway in our labora-
Making use of the specific tip-sample interaction, an
identification and selection of the specific chemical sub-
stances even on a molecular scale can be achieved. The limits
of the lateral resolution are expected to be comparable to the
resolution of a conventional SFM. This methodology might
bepromising for molecular identification in chemistry, biol-
ogy but also for applications on technical surfaces, especially
for systems where there would be little or no contrast by
standard SFM.
Received: J anuary 12, 1995
Final vesion: March 2, 1995
[I] G. Binnig, H. Rohrer, C. Gerber, E. Weibel, Phys. Rev. Lett. 1982, 4Y,
[2] J. Frommer, Angew. Chem. Znt. Ed. Engl. 1992,3f, 1298 -1328.
[3] U. Dammer (Ed.), Scanning 1993, 15, 257-264.
[4] J. A. Stroscio, P. M. Feenstra, A. P. Fein, J. Vuc. Sri. Techno/. 1987, A5,
[5] S. Akari, K. Friemelt, K. Glockler, M. C. Lux-Steiner, E. Bucher, K.
Dransfeld, Appl. Phys. 1993, A57, 221 -223.
[6] C. M. Mate, G. M. McClelland, R. Erlandson, S. Chiang, Phys. Rev. Lett.
1987,59, 1942-1945.
[7] L. A. Wenzler, T. Han. R. S. Bryner, T. P. Beehe, Rev. Sci. 1~7sfvum. 1994,
65, 85 -88.
[XI S. Akari, E. W. van der Vegte, P. C. M. Grim, G. F. Belder, V. Koustos, G.
ten Brinke, G. Hadziioannou, App/ . Phys. Leu. 1994, 65, 1915-1917.
[9] L. F. Chi, M. Anders. H. Fuchs, R. R. J ohnston, H. Ringsdorf, Science
1993, 25Y, 213-216.
[lo] N. A. Burnham, R. J. Colton, J. Vuc. Sci. Techno/. 1989, A7, 2906-2913.
[I l l E. -L. Florin, V. T. Moy, H. E. Gauh, Science 1994, 264, 415-417.
[I21 C. D. Frisbie, L. F. Rozsnyai, A. Noy. M. Wrighton, C. M. Lieher, Science
[I31 R. G. Nuzzo, A. L. Allara, J. Am. Chem. Soc. 1983, 105,4481-4483.
[I41 H. Keller, W. Schrepp, H. Fuchs, T/7in SolidFilms 1992, Zi Oj Zi i , 799-802.
[I51 R. Singhvi, A. Kumar, G. P. Lopez, G. N. Stephanopoulos, D. I. C .
Wang, G. M. Whitesides, D. E. Ingher, Science 1994, 264, 696--698. J. L.
Wilbur, A. Kumar, E. Kim, G. M. Whitesides, Adv. Muter. 1994, 6, 600-
[I 61 The commercial electronics used for our experiments (TMX 2000) cannot
he used for the recording of force- distance curves with the 0.3 N/m
cantilever as the preamplifier is driven into saturation. The poor sensitivity
of the rigid cantilever might he a reason for the absence of hysteresis in
Fig. 5b.
57 - 59.
1994,265,2071 -2074.
Efficient Two Layer LEDs on a Polymer Blend
By Jiirn Pomrnerehne, Horst Vestweber, Werner Gun,
Ruiner E: Muhrt, Heinz Bassler,* Michael Porsch
and Jorg Daub
There is much current interest in the development of effi-
cient organic light emitting diodes (LEDs) with tunable emis-
sion color.[' - 31 Our approach has been based upon the use
of polymer blends as the active component, advantages be-
ing their processibility combined with a broad range of avail-
able chrornophore~.[~] Recently, wereported LEDs fabricated
with poly-phenylphenylenevinylene (PPPV) and tristilben-
amine (TSA) derivatives doped into various polymeric hosts.
It turned out that incorporating, e.g. PPPV, into a polymeric
binder enhances the quantum efficiency c~nsiderably.[~] Al-
though not directly participating in charge transport a polar
matrix can have a positive effect on LED performance by
giving rise to an enhancement of the cell current via a reduc-
tion of the energy barrier for charge injection.r61
[*I Prof. H. Bassler, Dr. J. Pommerehne, Dr. H. Vestweber, Dr. W Guss,
Dr. R. F. Mahrt
Fachhereiche Physikalische Chemie
und Zentrumfur Materialwissenschaften
Philipps-Universitit Marhurg
Postfach, D-35032 Marhurg (Germany)
Dr. M. Porsch, Prof. J. Daub
Institut fur Organische Chemie, Universitat Regenshurg
D-93053 Regenshurg (Germany)
L**] We are indebted to Prof. W. Heitz, Dr. A. Greiner, and R. Sander for
material synthesis and continuous advice. This work has been supported
by the Bundesministeriumfur Forschung und Technologie.
Adv Muter 1995, 7, No 6 VCH V2rlugsgese/lsehuft mhH, 0-69469 Weinham. I Y Y S 0935-9648/95/0606-055~ $ 5 00i 2510 553
It has been ~hown[ ~- ~] that insertion of a cathodic block-
ing layer for hole discharge raises the LED efficiency. The
fabrication of two-layer structures is easy if the bottom layer
of the device is insoluble as is the standard precursor PPV.
Otherwise deposition of the second layer may cause material
interpenetration. In this communication we report on the
successful preparation of efficient two-layer polymer-blend
LED structures produced using the spin coating technique
and a combination of mutually incompatible solvents["] for
the materials under consideration.
A circa 100 nm thick layer of approximately 20 YO tristilbe-
neamine or a derivative thereof dissolved in polysulfone
(PSu) was deposited onto a commercial I T0 layer ("Bal-
tacron") via spin coating using chloroform as solvent (the
chemical structures of the active materials are shown in
Fig. 1). Subsequently, a second layer, also about 100 nm
Tn(stilbene)amine, TSA
Tn( 4-methoxystilbene)amine, MSA
2-(4-hiphenyl)-5-(4-t-hutylphenyl)- 1.3,4-oxadiazol, PBD
I 0 I
Polysulfone, PSu
Fig. 1. Chemical structures of thecompounds
thick, of 2-(4-biphenyl)-5-(4-t-butylphenyl)-l,3,4-oxadiazole
(PBD) dispersed in polystyrene was deposited from cyclo-
hexane solution. Due to the incornpatability of the polar
polysulfone and the apolar cyclohexane no interfacial mix-
ing occurs during the spin coating process. An aluminum
cathode completed the sandwich structure which had an ac-
tive area of 0.13 cm2.
The LEDs were characterized on the basis of theirj(E)
characteristics, their emission spectra as well as the emission
intensity as a function of cell current. To estimate the en-
ergetic location of charge transporting states the oxidation
and reduction potentials of MSA and PBD were measured
by cyclic voltammetry. These experiments were carried out
using an Amel 5000 electrochemical system interfaced to a
personal computer. A three-electrode configuration con-
tained in an undivided cell consisting of a platinum disc as
working electrode, a platinum plate as counter electrode and
an AgCl coated silver wire as "pseudo" reference electrode.
All potentials are referenced against ferrocene/ferrocenium
(FOC) as internal standard. Acetonitrile (for the measurement
of PBD) or dichloromethane (for TSA) served as solvents.
Tetra-n-butylammoniumhexafluorophosphate (TBAHFP)
was used as supporting electrolyte.
The oxidation and reduction potentials of PBD have been
determined as +1.49 V and - 2.41 V vs. FOC.["] Under the
premise that the energy level of ferrocene/ferrocenium is
4.8 eV below the vacuum level,"21 the HOMO and LUMO
levels must be located at c - 6.3 eV and c - 2.4 eV, respec-
tively, below vacuum. The HOMO-LUMO gap is 3.9 eV,
i.e. 0.2eV bigger than the energy of the onset of optical
absorption (S,+S, 0-0 energy). One should notice that ow-
ing to the improved ion stabilization in a polar solvent
voltammetry underestimates the HOMO/LUMO gap of a
chromophore embedded in a solid matrix below the glass
transition temperature where dipolar relaxation is arrested.
The data, therefore, confirms the motiv that the binding
energy of an excited state relative to that of a radical anion/
cation pair E,,, >0.2 eV in accord with previous work sug-
gesting that E,,, be about 0.4 eV.[13]
The oxidation potential of TSA is 0.32 V, hence the
HOMO should be at z - 5.1 eV below vacuum. The reduc-
tion potential turned out to be beyond the instrumental limit
(- 2.5 V), consistent with optical absorption that locates the
S,+S, (0-0 transition) at 2.9 V. Adopting the above result
that the voltammetrically determined HOMO/LUMO gap
exceeds the optical gap by 0.2 eV one would expect the re-
duction potential to be -2.8 V and, concomitantly the elec-
tron transporting level to be located at - 2.0 eV below vacu-
um. From the above value of E,, (TSA) one would expect the
energy barrier for hole injection from I T0 to be c0.3 eV
(assuming q (ITO) =4.8 eV). This is close to the value
x+ =0.2-0.25 eV inferred from Fowler-Nordheim plots of
j ( E) curves for TSA-like systems in various polymeric
binders.[61 Note that charge transporting levels of molecules
embedded in random matrices are always inhomogeneously
broadened, variation being typicaly 0.1 eV, implying that
energy barriers for injection from a metallic or semimetallic
electrode into tail states are lowered relative to an ordered
counterpart structure.
The energy level structure for a TSAjPBD double layer
that follows from cyclic voltammetry is shown in Figure 2.
On this basis it can be predicted that the transport of holes
from TSA to PBD is impeded by a 1.2 eV energy barrier, the
barrier for (reverse) electron flow being c 0.4 eV only. Fur-
thermore, electron injection from A1 (possibly through an
interfacial A1,03 layer) should be facilitated, although holes
552 0 VCH Verlagsgerellschaft mbH, 0-69469 Wecnheim 1995 O935-9648/95/O606-0552 $5 O O i 2510 Adv Mater 1995, 7, NO 6
- 2 . 0
- 2. 4
- 4. 8
- 4 . 2
El eV
vacuum level
- 6
Fig. 2. Energy level structure for an ITOITSA(PSu)lPBD(PS)IAl assembly as
determined by cyclic voltammetry.
should remain the majority carriers. Hence, a space-charge
layer should be established at the internal interface that re-
duces the electric field at the anode. This is supported by
comparing j ( E) curves for an ITOITSA(PSu)(Al and an
ITO(TSA(PSu)PBDIAl device (Fig. 3). The latter is shifted
towards higher fields equivalent to a reduction of the field at
I T0 by a factor of 0.8. In order to maintain a given voltage
drop across the cell this implies an increase of the field inside
the PBD layer by a factor of 1.2.
L I I 1
0.20 0.40 0.60 0.80
1 /E /* 1 0-6 crnV-'
Fig. 3. j ( E) curves for a single-layer LED and a double-layer LED plotted on
a Igj vs. E- scale.
A change of the field across the interface by AF =0.4 F
corresponds to an internal positive charge density (per unit
area) as shown in Equation 1, where for F =lo6 Vcm-' and
E =3, N , =6.6 x 10" charges cm-' is obtained.
Introducing an internal blockade against mono-molecular
(non-radiative) loss of majority carriers by discharge at the
cathode should increase the quantum efficiency of the LED.
In fact, Figure 4 bears out an increase of the light intensity
of the double layer by up to three orders of magnitude as
compared to single-layer devices. On an absolute scale the
quantum efficiency achieved with a TSA(PSu)/PBD cell was
about 1.3 %, which to the best of our knowledge is the
highest efficiency of an LED operating with aluminum as
cathode material.
1 o - ~
I O - ~ 1 0 - ~ l o-*
c ur r ent / A
Fig. 4. Relative electroluminescence intensities as a function of the cell current
for various LEDs. The results for the TSAjPBD systemare equivalent to an
external quantum yield of 1. 3%.
The enhancement of the LED quantum efficiency by a
blocking layer for majority carriers is readily understood in
terms of carrier recombination kinetics. Unless injection as
well as transport of holes and electrons is exactly balanced
the probability that a minority carrier i.e. an electron, in the
present system, will recombine with a hole rather than get
discharged at the anode is given by Equation2, where
k,,, =yn, is the rate constant for recombination, n, the
volume concentration of holes and y the (bimolecular) re-
combination coefficient.
Since z,, =d/pF is the carrier transit time, d the sample
thickness and p the electron mobility, i.e. is a measure of
the rate of monomolecular recombination of minority carri-
ers, Equation 2 can be rewritten as shown in Equation 3.
Unless the cell current is space-charge limited (in which
case n,,,,, =3~~,,F/2ed['~'), pF/yn+d >>1. Since in the
strong scattering limit, equivalent to Langevin recombina-
tion yip =e/sE,, E being the dielectric constant,
Equation 4 holds.
Adv. Mater. 1995, 7, No. 6 (0 VCH Verlagsgesellschaft mbH, 0-69469 Wemheim, 1995 0U35-9648195l0606-0553 $5.00+ ,2510 553
In the absence of a carrier blocking layer, n+ equals the
stationary charge density n, =j/(epE).[l6I For d =
cmZ/Vs andj =l o-' Acm-', n, =6 x lo1' cm-3 and
P,,,x0.03 is obtained. In the case of an interfacial space
charge n + =N +d, N , being given by Equation 1 and pF/
yn, d =FlAFyielding P,,, % 0.3. It is obvious that build-up
of an interfacial space charge increases the probability that
an injected minority carrier will find a countercharge to re-
combine with. Recombination occurs inside the TSA and
MSA layers, respectively as evidenced by the electrolumines-
cence spectra shown in Figure 5.
1 .o
. 0. 8
\ 0. 6
0. 2
0. 0
I 1 I
400 500 600 700
wavel engt h/ nm
Fig 5 Electroluminescence spectra of rSA/PBD and TSA/PSu
The observed increase of the LED efficiency by a PBD
blocking layer exceeds the factor estimated on the above
basis indicating that such a layer also has a favorable effect
on other efficiency controlling factors. Since the reduction
potential of PBD is zz 0.4 eV less than that of TSA electron
injection is facilitated. Furthermore, the recombination zone
is spatially isolated from the cathode thus eliminating excit-
ed-state quenching by the metal.[7, ' ' 9 '*I
The above analysis, though crude, indicates that the LED
efficiency should scale inversely with the mobility of the ma-
jority carriers as long as the majority current is injection-
rather than space-charge limited, because the stationary
concentration of recombinations centers scales inversely
with their transport velocity. This provides an explanation of
why in single-layer cells the efficiency increases upon dilu-
ti ~n. [ ~] The concomitant decrease of the diffusivity of the
generated excited state will also be of advantage because
quenching by non-fluorescent impurities becomes less effi-
ci ~nt.['~]
Received: J anuary 9, 1995
Final version: March 1, 1995
[I ] C. W Tang, S. A. van Slyke, Appl. Phys. Lett. 1987, 5f, 913.
[2] C. Adachi, T. Tsutsui, S. Saito, Jpn. J. Appl. Phys. 1989, 55, 1489.
[3] P. L. Burn, A. B. Holmes, A. Kraft, D. D. C. Bradley, A. R. Brown, R. H.
[4] H. Vestweber, A. Greiner, U. Lemmer, R. F. Mahrt, R. Richert, W. Heitz,
Friend, W. Symer, h'uture 1992, 356, 47.
H. Bissler, A d i ~. Mo m. 1992, 4, 661.
[5] H. Vestweber. J. Oberski, A. Greiner, W. Heitz, R. F. Mahrt, H. Bdssler,
Adv. Matar. Opt. Electron. 1993, 2, 191.
[6] H. Vestweber, R. Sander, A. Greiner, R. F. Mahrt, H. Bassler, Synth. Met.
1994, 64, 141.
[7] A. R. Brown, J. H. Burroughes, N. Greenham, R. H. Friend, D. D. C.
Bradley, P. L. Burn, A. Kraft, A. B. Holmes, Appl. Phys. Lett. 1992, 61,
[S] D. D. C. Bradley, Synth. Met. 1993, 54, 401.
[9] C. Zhang, S. Hoger, K. Pakbaz, F. Wudl, A. J. Heeger, J. Electron. Mater.
1994, 23. 453.
[lo] I. D. Parker, Q. Pei, M. Marrocco, Appl. Phys. Lef t . 1994, 65, 1272.
[l l ] To provide additional proof for the reversibility of the formation of the
radical ions investigations by UV/vis/NIR spectroelectrochemistry were
undertaken. Both, the formation of the radical anion of PBD and the
formation of the radical cation of TSA display sharp isosbestic points and
absorption signals at 309, 517, and 1105 nmfor PBD and 225,460,1115,
131 5 nmfor TSA, . UV/vis/NIR spectroelectrochemical measurements
were carried out with a Perkin Elmer Lambda 9 spectrophotometer. Po-
tentials wereadjusted by an AMEL 550 potentiostat. The construction of
the thin-layer cell is described in J. Salbeck, I. Aurbach. J. Daub, Dechema
Monographien, Vol. 112, p. 177, VCH, Weinheim1988. J. Salbeck, Anal.
Chem. 1993, 65, 2169.
[12] This estimate is calculated on the basis of a rather crude approximation
neglecting solvent effects using the standard electrode potential (E') for the
normal hydrogen electrode (NHE) at about -4.6 eV (A. J. Bard, L. R.
Faulkner, Electrochemicul Methud~y - Fundamentals and Applications, Wi-
ley, New York, p. 634) on the zero vacuumlevel scale and a valueof 0.2 V
vs. NHE for the potential of FOC (in acetonitrile, see: H.-M. Koepp, H.
Wendt, H. Strehlow, 2. Electruchem. 1960, 64, 483.
[13] R. Kersting. I J . Lemmer, M. Deussen, H. J. Bakker, R. F. Mahrt, H. Kurz,
V. I. Arkhipov, H. Bassler, E. 0. Gobel, Phq's. Rev. Lelr. 1994, 73, 1440.
[14] W. Helfrich, in Physics and ChemistrjJ of t he Orgunic Solid Stute. Vol. 111
(Eds: M. M. Labes, A. Weissberger) Interscience Publ., New York 1967,
[I51 M. Silver, M. Sharma, J. Clzem. Phys. 1967, 46. 692.
[I61 A. R. Brown, N. C. Greenham, J. H. Burroughes, D. D. C. Bradley, R. H.
Friend, P. L. Burn, A. Krdft, A. B. Holmes, Chem. Phjs. Lett. 1992,200,
[17] K. H. Drexhage, J. Lumin. 1970, f/2, 693.
[IS] H. Kruczewskd, H. Bassler, 1 Lumin. 1977, /5, 261.
[I91 U. Lemmer, R. F. Mahrt, Y Wada, A. Greiner, H. Bassler, E. 0. Gobel,
Appl. Phys. Lett. 1993, 62, 2728.
Rectifying Properties and Photoconductivity
of Tetraruthenated Nickel Porphyrin Films""
By Koiti Araki, Lucio Angnes, and Henrique E. Toma*
Porphyrin films constitute an exciting area of research
because of their electronic, photochemical and chemical
properties. Recently, Malinski and Taha,"] successfully em-
ployed carbon fiber microelectrodes modified with the poly-
tetrakis(3-methoxy-4-hydroxyphenyl)porphynate nickel(@
complex to monitor the NO produced by a single cell.
Here, we report the properties and characterization of
films of the polymetallated porphyrin ( I) obtained by attach-
ing four Ru(bpy),CIQ complexes (bpy =2,2'-bipyridine) to
the peripheral pyridyl residues of the meso-tetra(4-pyr-
idy1)porphynate nickel(@ complex (NiTPyP) . This modified
porphyrin has been isolated as [NiTPyP{ Ru(bpy),CI},-
(TFMS), (TFMS =trifluoromethanesulfonate anion). It
[*I H. E. Toma, Prof. K. Araki, L. Angnes
Inbtituto de Quimica, Universidade de Sao Paulo
Caixa Postal 26077, CEP 05599-970, Sao Paulo, SP (Brazil)
[**I Financial support fromPADCT, CNPq and FAPESP is gratefully ac-
554 c ) VCH Verlayygesellschuft mhH D-6Y46Y Wemherm, f9Y5 OY35-Y64B/Y5/O606-0554 $ 5 O0+ 25/0 Adv Mater 1995, 7. No 6