Volume 69, number 3 CHEhfICAL PHYSICS LEmERS 1 February 1980

NONRADIATIVE DECAY OF EXCITED MOLECULES NEAR A METAL SURFACE

I. POCKRAND, A. BRILLANTE *
Experimentalphyslk III, Unwerszt~t Diisseldorf.
D-4000 Diisseldorf I, FRG

and

D. M6BIUS
Abtetlung Molekularer Systemaufbau. Max-Planck-Institut jiir Btophynkalische Chemie.
D-3100 Giittmgen-Ntkolausberg. FRG

Received 31 October 1979

Nonradlatwe energy transfer from evated dye molecules near a metal surface to plasmon surface polaritons has been
mvrstlgated expenmentally. By usmg the Langmwr-Blodgett techmque, the molecule-metal separation was varied and
the cohplmg eftklency measured with the mverse attenuated-total-reflection technique. For an orient&on of the trz&
tlon dipole moment of the dye parallel to a silver surface. and nonresonant interaction, maximum energy transfer to pIas-
mon surface polantons was observed for a molecule-silver spacing of about 18 nm. Reducing the spacing results in a mono-
tome decrease of the couphng efficiency: this decay channel becomes unimportant and eventuaBy vanishes if the mole-
cule is placed very close to the metal surface. The experimental results are discussed in connection with theoretical pre-
dlctlons and the surface-enhanced Raman scattenng observed for some adsorbates at metal surfaces.

1. Introduction Drexhage et al. [3-l l] determined the dependence

The fate of an excitedknolecule adjacent to a met-
al surface depends substantially upon the different
efficiency of competing radiative and nonradiative
decay channels. Energy transfer to the metal intro-
duces various new decay mechanisms according to
the states of the metal whch accept the energy. When
the molecule is adsorbed or located very close to the
metal (within a few tens of MI) new phenomena may
occur such as surface-enhanced Rarnan scattering [ 21
or *thepostulated cooperatwe effects analogous to
superradiance [2] _Quantitative understanding of
these phenomena requires knowledge of the relative
efficiency of the various competing radiative and
nonradiative energy transfer processes as a fimction
of the metal-molecule separation.
In a series of elegant experiments Kuhn and
l Permanentaddress: Laboratorio Spettroswpia
CNR, 40126 Bologna, Italy.
of the lifetime T of an excited molecule fluorescing
near a metal surface on the metal-molecule spacing
d. For large d an oscillating variation of r was ob-
served and interpreted as an interference effect which
arises from the superposition of the directly emitted
field of the molecule and that reflected at the metal
surface [ 121. For very small distances (d s 30 nm)
the lifetime shortened rapidly. The experimental re-
sult could be explained by considering the metal as
absorbing species located in the near field of the ex-
cited molecule. In this case nonradiative energy transfer
of the excitation eneigy of the molecule to the metaI
is responsible for the observed behaviour [3--5,7] _
To our knowledge no experimental evidence con-
cerning this mechanism has yet been reported which
elucidates the nature of the states of the metal that
accept the energy. Very recently it was shown 113,
141 that plasmon surface polaritons (PSI%) at a metaE
Molecolare surface may act as an effkiznt energy acceptor_ The
experiments however do not provide information on

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Volume 69, number 3 CHLhIICAL PHYSICS LETTERS 1 February 1980

the dependence of this effect on the distance between

the excited molecule and the metal surface. Therefore
the relative eftlclency of dye-sensitized PSP excitation
compared to other energy acceptmg processes in the
metal is stdl not known.
Theoretlcally, excited molecules in front of a met-
al have been treated by representmg the molecule as
a dipole antenna (see e.g. the review by Chance et al.
[15] ; quantum theory calculations [12,16] give sim-
liar results). Although the experimental observations
of Kuhn and Dretiage et al. could be described quan-
Utatively with this theory. the actual contnbution
and the discnmination of the various energy transfer
processes causing the decrease of 7 at small metal-
molecule separation has not been completely elabo-
rated_ Some theoretical interpretations [IS-l81 em-
phasize the Importance of couphng to PSPs if this Fig 1. Experrmental arrangement, layer system, and molec-
process is resonant (fluorescence frequency wFL ular structure, absorptron and fluorescence spectrum of the
dye For clarity, the scattermg angles 13. BFL and f3o are given
equal to the asymptotic PSP frequency wFsp for
only at one side of the film normal, although ail phenomena
large u avevectors). Recent calculations [ 131 showed are symmetrrcal m the observatron plane wth respect to the
that also for nonresonant couphng (oFL < w~ssp as normal.
m refs. [3-l I]) this decay channel dominates for a
rather large metal-molecule spacing of the order of a
few tens of nm, dependmg on the actual configuration at a definite distance from the surface of a sliver film
The couphng efficiency however drops to zero near by using the Langmuir-Blodgett monolayer tech-
the surface. nique [20] _The molecules were excited by incident
Persson pointed out [ 191 that a third decay chan- hght. Subsequent energy transfer to PSPs has been
nel, excitation of electron-hole pairs m the metal, detected by coupling the PSPs to radiative fields with
may become important for metal-molecule spacmgs mverse ATR (attenuated total reflection [21]) tech-
d 5 10 nm (m addition to the usual resistance damp- mque. The layer system, the dye properties, and the
ing, i.e. convers:on of electromc currents m the metal, experimental arrangement are sketched m fig. 1.
mduced by the near field of the molecule, into heat, A sliver film of 55 nm thickness was vacuum-
and the coupling to PSPs). His calculations showed evaporated @ = 10m5 Torr, evaporation rate = 1
that resistance damping and electron-hole pair ex- rim/s)) onto a quartz slide and then coated with the
citation are the dominant processes for nonresonant monolayer assembly (fig. 1, bottom left). The dye
coupling and very small d. Only for the resonant case molecules have been deposited on fatty acid layers
may energy transfer to PSPs successfully compete each 2.68 nm ttick with 0,2,4,6, and 8 layers be-
with these decay mechanisms. tween the sliver surface and the dye molecule gvmg
We have studied one of the decay mechamsms, a spacing from about 2 68 run to 24.12 nm in steps
energy transfer to PsPs, and present m this paper the of 5.36 nm. Afterwards the system was completed
first experimental mvestigation of nonresonant cou- by depositing an appropnate number of further fatty
pling of excited molecules to plasmon surface polan- acid layers to yield the same total fdm thickness of
tons as a function of the metal-molecule separation twelve layers for every system. A system with three
d. fatty acid layers on top of the dye for every region
(dashed line in the layer system, fig. 1) has also been
2. Experiment investigated.
The molecular structure of the dye cation is given
in our experiment dye molecules have been placed m fig. 1, bottom right (we used the dye 5,6,5,6-

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Volume 69, number 3 CHEMICAL PHYSICS LETTERS
tetrachloro-I ,ldioctadecyl-3,3diethyl-benzimidazolo-
carbocyanin-p-toluenesulfonate). In monolayers the
transitron dipole moment of this dye is oriented par-
allel to the layer plane (i.e. parallel to the silver sur-
face) and the molecules are arranged by forming J ag-
gregates [22]. This causes the pronounced relatively
narrow absorption peak at 584 MI, whereas monomer
(dlmer) absorption is responsrble for the structure at
the short wavelength side (fig. 1, top right). The fluo-
rescence of the dye peaks at h,, = 595 run, a quan-
tum yield of about 0.08 was estimated_
The coated slide was brought into optical contact
with the base of a quartz half-cyhnder by usmg an
index-matchmg flurd (fig. 1, top left). Monochromat-
ic, polarized light of an Ar- or Kr-ion laser was direct-
ed perpendicularly onto the layer system. The polari-
zation of the hght was defied with respect to the
plane of observation. Photo decomposition of the
dye set an upper limrt to the mcident hght mtensity
of about 20 ,~\V/mm~.
Because of the finite thickness of the silver film,
nonradiatlve plasmon surface polaritons excited at
the Ag-monolayer interface couple to propagating
waves m the quartz half-cylinder and create a cone
of scattered hght whose angular dlstnbutron in the
observatron plane has been measured with a photo-
multipher (angular resolution = 0.3). The cone angle
1s related unequivocally to the wavelength of the PSP
by the dispersion relation [21]. Therefore l?SPs of
different wavelength are detected at different scatter-
mg angles. It should be noted that the efficiency of
this coupling depends on the parameters of the layer
system, especially on the sdve; thrckness [23] . Most
of the PSP energy IS dissipated in the metal for our
evpenmental condltrons. Only about 20% is radiated
mto the quartz half-cylinder, this fractron being in-
dependent of the dye-srlver spacmg. Therefore the
measured scattered hght mtensity is proportional to
the dye-PSP couphng efficiency.
A filter could be placed in front of the detector
to dlscnminate scattered light of different frequency.
3. Results and discussion
Frg. 2 shows the measured scattered mtensity 1s~
as a function of the scattering angle 0 (increasing 8
from right to left) for a dye-Ag spacing of d = 18.76
1 February 1980
- SCATTERING bNGLEB(dcg)
Fig. 2. Measured angular dependence of scattered Ii&t for
lncldent h&t polarized perpendicular to the observatron
plane (s-p0talZit10n).
run and three wavelen,& $-, of the exciting light as
mdicated. A pronounced peak, which shifts to greater
0 with decreasing 7t,,, accompanied by a small m&xi-
mum at tiFL Z=49.5) whose position is independent
of X0, has been observed. These spectra have been
taken without any filter in front of the detector using
s-polarized exciting light of about 12 pW/mm2. Sim-
ilar curves have been measured for p-polarized inci-
dent light. In this case the intensrty of the main peak
was even larger and the small maximum at 8FL =
49.5 was hardly detectable as a weakly pronounced
shoulder at the low-angle side of the dominating max-
rmum.
The observations are explained by recalling that
the scattered hght intensity in our arrangement is
caused by three processes:
(i) via roughness scattered light penetrating the
thin silver film (no participation of PSI%),
(ii) via roughness excited PSPs at the Ag-mono-
layer interface which couple to propagating waves in
the quartz half-cylinder, and
(iii) excitation of PSPs at the Ag-monolayer inter-
face by nonradiative energy transfer from excited dye
molecules and subsequent coupling of the PsFs to
radiative fields in the quartz half-cylinder-
Volume 69. number 3 CHEhlICAL PHYSICS LE-l-rERS 1 February 1980

The angular dependence of the light due to (i) is

determmed by the roughness spectrum of the layer
system. It peaks in the forward direction (0 = 0) and
decreases with Increasing 8, thus leading only to a
weakly varymg background tntensrty for the region
of interesting scattenng angles in our experiment
1241 . Process (Ii) describes elastic excrtation of PSPS
with wavelength ho (energy hw, and complex wave- d=1636m

vector kEsp)_ Coupling to radrative fields in the half-

cylinder is governed by Re(kF& = (21~/h~&, sin 80
and an intense peak IS observed at (IO [2 I] (frp is the
refractive index of the half-cyhnder, Re means the
real part of the following quantity). Because of the
drspersron of PSPs [k& = k&P(foo)] e. increases
with increasmg fro, and therefore with decreasmg
X, for PSPs evcrted vra roughness_ Process (ri) IS most
promment for p-polarized incident hght, because
PsPs are p-polan7ed surface waves. Energy transfer
of excited dye molecules (in) creates plasmon sur-
face polaritons wrth X,,, the fluorescence wavelength,
independent of ho. Therefore this process is de;&ed
as a peak at constant OPL a 49~5~ due to Re(kpSp) =
(2s/XFL)np sin 8 FL (fig. 2). Since we are only in-
terested in the latter process the experrment has been
optimized in the followmg way. Only s-polanzed in-
cident light with ho = 457.9 nm has been used, re-
sulting m a large angular separation of the scattenng
maxrma due to (ir) and (iu). In addition, a cut-off
filter was placed in front of the detector to decrease
the scattered light due to processes (I) and (ii) (cut-
off wavelength 500 run).
Fig. 3 shows actual scans obtained wrth thrs op-
timized arrangement_ The nonradiative decay of ex-
cited dye molecules into plasmon surface potaritons
is now detected as a pronounced maximum at %FL
(the background increasing with B is due to msuffi-
ctent operatron of the cut-off filter). The most stnking
experimental resuh is the dramatic decrease of the
efficiency of this process when the dye-metal spacmg
is reduced from 18.76 nm to 2.68 nm it almost com-
pletely vanishes when the dye is placed very close to
the surface.
In fig. 4 this dependence IS drsplayed in detad. The
fraction of nonradiatlve energy transfer that results
in PSP excitation peaks for a dye-sdver spacmg of
about 18 nm, drops continuously with decreasmg
separation and also becomes less efficrent when the
dye molecule is placed further away. The results are
Ftg. 3. Actual scans obtamed usmg s-polarized lncrdentllgbt
(A0 = 457.9 nm) for two dye-sdver spacmgs as mdxated A
cut-off filter (cut-off wavelength 500 nm) has been placed
III front of the detector.
summarized by plottmg the scattered intensity IFL
agamst the dye-stlver spacrng d (mset fig. 4; fulI
cucles: directly from measured curves, open circles-
corrected for standing wave effects, see below).
Care has to be taken when assigning this behaviour
to the energy transfer process exchrsively. Actually
a complicated process has been investigated which
might be divided into three steps: (I) excitation of
the dye, (2) energy transfer to PSPs, and (3) coupling
to radiative fields in the quartz half-cyhnder. The
third step is independent of the dye-metal spacing
as outlined above. However, the first step - excita-
tion of the dye molecules - does depend on d al-
though the excitmg light intensity has been kept con-
stant for ail measurements. This is due to the well
known formation of standing waves in front of a
mirror. The experimental results (full circles in fig. 4,
inset) have been corrected by calculating the inten-
sity dtstribution of the incident light, assuming ex-
citation of the dye proportional to the intensity, and
calibrating with respect to the tntensity for the largest

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Volume 69, number 3 CHEMICAL PHYSICS LETTERS

Fig. 4. Distance dependence of dye-PSP coupling (same experimental conditions as for fig. 3). The inset shows the effkiency of
the nonradiative energy transfer process by plotting the area under the p&c (f& versus the distanced. Full circles: directly
from measurements; open circtes: corrected for standinp. wave effects (see text). The dashed curve shows schematically the life-
time of an excited moieeule as a function ofd.

spacing d (open circles in fig. 4, inset). Although the Summarizing our experimental results we show~l!
peak energy transfer efficiency is shifted to some- that nonradiative energy transfer of ezcited mob-
what smaller spacing the general behaviour of the cules to plasmon surface polaritons strongiy depends
dependence on d remains unchanged_ on the metal-molecuIe separation_ For an orienta-
Standing wave effects can be avoided when ex- tion of the transition dipole moment parallel to a
citing the dye by the evanescent fields of plasmon silver surface and nonresonant coupling, it peaks at
surface polaritons ]13,14] _ Corresponding prelim- rather large separations (about 18 run), drops to zero
inary measurements yieIded similar results as those with decreasing spacing, and decreases also when the
presented in Bg. 4. molecuie is at distances larger than 18 run. The rate .
Finally we discuss the infhrence of the second in- constant of PSP excitation via energy transfer can be
terface in the layer system, the fatty acid-airbound- considered as approximately independent of the
ary. It was shown experimentally and theoretically metal-molecule separation d as long as d is small
[ 15 ] that the dye-air spacing influences the lifetime compared to the extension of the PSP, i.e. ford e h.
of an excited molecule in front of a metal and there- Then, the PSP emission efficiency must have nearly
fore might also affect the nonradiative energy trans- the same distance dependence as the lifetime of an
fer to PSPs. Since, for the results presented so far, excited molecule in front of a mirror (see inset of
this spacing varies with the dye-metal separation, a fig. 4, dashed line). The rate of PSP excitation via
second system with constant dye-air spacing (see energy transfer, according to Weber and Eagen [231,
fig. 1) has been investigated. A slight shift of the peak decreases exponentially with increasing d, and at
energy transfer to PSPs has been observed, but the d=lSnmitis 1/2oftherateatd=2nm.Thisshows
strong decrease of the coupling efficiency was con- the small influence of this rate OR the distance de-
firmed by these measurements.
Volume 69, number 3 CHEMICAL PHI SlCS LETTERS
pendence of the PSP emrssion efficiency in the range
of our expenments.
Our results m&t also be interestmg in connection
with the interpretatron of surface enhanced Raman
scattenng [ 1 ] _ Drfferent mechanisms have been sug-
gested to explam the grant Increase of the Raman
cross sectron observed for some molecules adsorbed
at srlver (and orher metal) surfaces_ Some of them
emphasrze the rmportance of the partrcipation
plasmon surface polaritons whrch couple to an elec-
tronic transrtron of the adsorbed molecule [16,25,
26]_ This Interaction is assumed to cause a broaden-
ing and a shift of the transrtion. Hence for the ad-
sorbed molecule, resonance Raman scattering usmg
visible Incident light may be possrble even rf the free
molecule shows only normal Raman scattermg. Al-
though we are aware of the problem involved m ex-
trapolatmg our results to metal-molecule spacmgs
of atomrc drmensrons, we believe that our observa-
tions make this hypothesis unhkely and farour in-
stead other models (e.g. models which emphasize the
interactron of the molecule with electron-hole
in the metal [ 1,19,27] )_ Only for resonant molecule-
I5P coupling may thrs process contnbute consider-
ably to the enhancement of the Raman cross section.
In conclusron, we mention some extensrons of
tlus work. As monolayer deposrtion techruques allow
defied onentatron and separation of the molecule
with respect to a metal surface for a great vanety of
dyes, drfferent aspects oi the interaction with the
collectrve excitations of the metal may be studied.
Some problems of interest are the dependence
the onentation of the dipole transitron moment on
the fluorescence wavelength X0 (approachmg
nant coupling to TSR), and on the metal propertres.
Correspondmg expenments are m progress.
Acknowledgement
We thank Professor A. Otto, Universitit Diissel-
dorf, and Professor H. Kuhn, Max-Planck-Institut
fur Biophysrkalrsche Chemre, Giittingen, for fruitful
discusslons, Mrs. G. Debuch for the careful prepara-
tion of the monolayer assembhes, and Dr. R. Steiger,
504
1 February 1980
Cuba-Gergy-Photochemre, Marly, Swrtzerland, for
supplymg the dye.
References
[I] J. Bdlmann, G. Kovacs and A. Otto, Surface Scl 92
(1980) 153, and references therein.
121 H hlorawltz. IBhi J. Res Develou. 23 (19791 517.
of
i31 H Kuhn, Pure Appl Chem 11 (i965) 345, .
D hI2ibius, Theses. Marburg (1965). unpubhshed
141 K H. Drexhage, hl Fleck. F_P SchHfer and W. Sperlmg,
Ber. Bunsenges. Physik. Chem. 70 (1966) 1179
151 K H. Drexhage, H. Kuhn and F P. SchZfer. Ber. Bunsenges.
Physrk. Chem. 72 (1968) 329.
161 K.H Drexhage, Optrsche Untersuchungen an neuartrgen
monomolekularen Farbstoffschrchten, Habrbtatrons-
schnft, Marburg (1966), unpubhshed.
I71 H. Bucher, K.H. Drexhage, hIi. Fleck, H. Kuhn, D.
hliibius. F.P. Schsfer, J. Sondermann. W. Sperlmg, P.
Ttllmann and J. Wregand, hlol. Cryst. 2 (1967) 199.
K H Dreuhage, J. Lurrunescence l/2 (1970) 693.
K H Drexhage. SCI. Am 222 (1970) 108.
K H Tews. Ann. Physik (Leipzrg) 29 (1973) 97.
pans K H. Drexhage. m: Progress m optrcs. Vol. 12, ed. E.
Wolf (North-Holland. Amsterdam, 1974) p. 165.
H Kuhn, J Chem. Phys 53 (1970) 101.
W H. Weber and CF. Eagen, Opt. Letters 4 (1979) 236.
R-E. Benner, R. Dornhaus and R K. Chang, Opt. Com-
mun. 30 (1979) 115.
R.R. Chance, A. Prock and R Sdbey, Advan Chem.
Phys 37 (1978) 1, and references therein
hI.R Phdpott, J. Chem Phys. 62 (1975) 1812.
H. hlorawrtz and hI R. Philpott, Phys Rev. BlO (1974)
4863.
G S Agarual, Phys Rev Al2 (1975) 1475.
on B NJ. Persson, J. Phys. C 11 (1978) 4251.
H. Kuhn, D. hIGbius and H. Biicher, in: Techniques of
chemtstry, Vol. 1. Physrcal methods of chemistry, Part
reso- 2B, eds A. Werssberger and B-W. Rossiter (Wiley-
Intersrence, New York, 1972) ch. 7.
1211 H. Raether, in: Physics of thm films. Vol. 9 (Acadenuc
Press, New York, 1977) p 145.
[2J H. Biicher and H. Kuhn, Chem Phys Letters 6 (1970)
183.
t231 1. Pockrand. Surface Ser. 72 (1978) 577.
v41 J. Bodesherm and A. Otto, Surface SCI. 45 (1974) 441.
t= I S. Efnma and H. Metru, 1. Chem Phys. 70 (1979)
1939; to be publrshed.
WI R.M. Hexter and h1.G Albrecht, Spectrochun. Acta
35A (1979) 233.
1271 E. Burstem, YJ. Chen, C.Y. Chen, S. Lundqvrst and
E. Tosattr. Sohd State Commun. 29 (1979) 567.