Vacuum 87 (2013) 21e25

Contents lists available at SciVerse ScienceDirect

Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Study of swift heavy ion irradiation effect on Rhodamine 6G dye for dye sensitize
solar cell application
Hemant Kr. Singh a, Shruti Aggarwal a, *, D.C. Agrawal b, Pawan Kulria b, S.K. Tripathi c, D.K. Avasthi b
a

University School of Basic and Applied Science, Guru Gobind Singh Indraprastha University (GGSIPU), Sector-16C, Dwarka, New Delhi, India
Inter University Accelerator Center, Post Box-10502, New Delhi, India
c
Dept. of Physics, CAS, Panjab University, Chandigarh, India
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 26 December 2011
Received in revised form
3 July 2012
Accepted 5 July 2012

The Rhodamine 6G (R6G) dye sample synthesized by thermal evaporation method is irradiated by
120 MeV Ag9 ions at different uences from 1  1011 ion/cm2 to 3  1012 ion/cm2. These samples are
characterized by X-ray diffraction (XRD), ultravioletevisible (UVeVis) absorption spectroscopy and
photo-conductivity measurements. In XRD, it is observed that amorphous nature of dye lms increases
with uence and hence aggregates of dye molecules spread homogeneously on the substrate after
irradiation .The absorption spectroscopy and photoconductivity results show maximum absorption and
minimum photoresistivity at lowest uence. The properties of the dye lms such as increase in amorphous nature, increase in absorption peak area and marginal increase in photoconductivity are favorable
for Dye-sensitize solar cell (DSSC) applications.
2012 Elsevier Ltd. All rights reserved.

Keywords:
Dye-sensitize solar cell
Rhodamine 6G dye
Swift heavy ion
Photosensitizers

1. Introduction
Dye is one of the main constituent of anode and used as photosensitizer in Dye-sensitize solar cell (DSSC) application. When solar
radiation is incident on dye, it provides electron for the outer circuit
of the cell. The sensitization of the dye increases with increase in
absorption spectrum which in turn increases the efciency of
solar cell.
Aggregations happen generally during the deposition of the
organic lms on the substrate. More recently, dyes have become the
subject of great interest with focus on the phenomenon of molecular aggregation [1e4]. The Rhodamine 6G (R6G) dye has a high
tendency to form H-type nonluminescent dimer sandwich-like
aggregates with parallel aligned molecular axes [2,4e6]. Another
conguration of R6G molecules with head-to tail aligned dipole
moments (J-type dimers) is also observed in the presence of an
additional external potential. H-type R6G dimers are associated
with a remarkable blue-shift and J-type R6G dimmers are characterized by a red-shift in the optical absorption band and in the
luminescence band with respect to that in R6G monomers [2e4,6].
R6G is a dye from the xanthene family having a molecular
structure as shown in Fig. 1. R6G had been used extensively as
a sensor [7], nonlinear optical material [8] and photosensitizer [9].

* Corresponding author.
E-mail address: shruti.al@gmail.com (S. Aggarwal).
0042-207X/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.vacuum.2012.07.002

In DSSC Photosensitizers basically absorb solar radiations and

provide charge for wide band gap materials like ZnO or TiO2 etc
that functions as charge transporter and separator. Organic dyes
have several advantages as photosensitizers for DSSCs like: (1)
Larger absorption coefcients than metal-complex photosensitizers; (2) variety in their structures provides possibilities for
molecular design, e.g., the introduction of substituents, and thus
allows for easy control of their absorption spectra; (3) cheap
because they do not contain noble metals like ruthenium. This
reduces the overall cost of the cell production. Their extensive
wavelength coverage and tunability coupled with a high uorescence yield have contributed to their widespread use. Injection of
charge from dye to wide band gap materials takes place through
coupling. If the coupling is strong between dye and wide band gap
materials then injection is fast and recombinations are reduced.
Swift heavy ion (SHI) irradiation is known for modication of
materials and is attractive tool for device applications. SHI irradiation of organic materials results in the chemical changes and in the
modication of band-gap, which in turn affect the structural,
optical and electrical properties. Therefore, there is a possibility of
tailoring the optical and electrical (especially photo-conductivity)
properties of the dye lm.
Our long term objective is to study the effect of SHI irradiation
on photoanode of DSSC to investigate the possibility of improvement in the efciency and stability of its components for extraterrestrial applications. The photoanode of DSSC has three
components namely transparent conducting oxides (TCOs), wide

22

H.Kr. Singh et al. / Vacuum 87 (2013) 21e25

metallic sample holder. The lms were annealed at 373 K for 1 h in

vacuum of about 103 mbar and the dark and photoconductivity
measurements were carried out for pristine and irradiated samples
of R6G. The photocurrent (Iph) was obtained after subtracting the
dark current from the current measured in the presence of light.
3. Results and discussion
3.1. Structural characteristics

Fig. 1. Structural formula for R6G dye.

band gap oxide semiconductor materials (OSMs) like ZnO or TiO2

and photosensitized materials like dye. The goal of the present
work is to study the effect of SHI irradiation on dye and to see its
effects in terms of its photoconductivity.
2. Experimental details
Thin lms of R6G, with thickness 200 nm, on Corning 7059 glass
substrates were prepared by the thermal evaporation technique at
room temperature and base pressure of w2  105 mbar using
a molybdenum boat keeping deposition rate of w2.5 A s1 as reported by Tripathi et al. [10]. R6G lm were irradiated by
120 MeV Ag9 at four different uences starting from
1  1011 ion/cm2 to 3  1012 ion/cm2 in a vacuum chamber
w106 mbar in material science beam line at IUAC, New Delhi,
India. The structures of pristine and irradiated R6G were determined through X-ray diffraction (XRD) technique using Bruker D8
advanced diffractometer. The angle of the incidence of X-ray beam
of wavelength 1.5405 is 2 in a 2q range from 20 to 60 . The
absorbance spectra of the pristine and irradiated lms were
recorded at normal incidence at room temperature in the spectral
range 400e800 nm by using a spectrograph model no UV-3300.
Pre-deposited thick indium electrodes on Corning 7059 glass
substrates were used for the electrical contacts. A planar geometry
of the lm was used for electrical measurements. The lms were
kept in the deposition chamber in the dark for 24 h before
mounting them in the metallic sample holder to attain thermodynamic equilibrium [11].
To carry out the electrical characterizations on these thin lms,
a specially designed metallic (stainless steel) sample holder, fabricated in laboratory is used. Keitheley 224 Programmable set up
provides the desired voltage. For measuring the current, a digital
Pico ammeter (DPM-111) with an accuracy of 1 pA is used. The
sample holder is connected to a rotary vacuum pump [ British
Thomson Houston Ltd., Type BC2410 ] to maintain a vacuum
w103 mbar throughout the measurements. The photo and dark
conductivities of the thin lms have been measured using indium
as electrode by thermal vapor deposition on corning 7059 glass
substrates. The electrical conductivity of the lms deposited under
the optimum deposition conditions is measured at different
temperatures ranging from 40 to 100  C. The light is shined through
the glass window by using a commercial Tungsten lamp of 150 W as
a photo excitation source to carry out the photoconductivity
measurements. To cut off the IR part of the light, water in transparent petridish is kept in between the glass window and Tungsten
source, while taking reading in the presence of light. The intensity
of light is measured using a digital luxmeter (TES-1332). Before
measuring photoconductivity of the sample, it is kept in dark till it
attains equilibrium.
The electrical conductivity of the pristine and irradiated R6G
lms were studied by mounting them in a specially designed

The XRD of the pristine sample of R6G thin lm is shown in

Fig. 2 and is similar to the result reported by Tripathi et al. [10]. In
the present case, the diffraction pattern exhibited a little peak with
very low intensity around 2q 23 , indicating the amorphous
structure of the evaporated R6G lm. The peak diminishes with SHI
irradiation and at higher uence 3  1012 ion/cm2, it completely
vanishes. This shows that the lm becomes complete amorphous
after irradiation. This is a favorable result from DSSC point of view
as amorphous structure of dye spreads homogeneously on oxide
surface and results in enhancing the light harvesting effect (LHE) of
photo-sensitive material.
3.2. Optical characteristics
Optical properties of pristine and irradiated R6G were studied
by recording the absorbance spectra of the lm as shown in Fig. 3.
Generally absorption band peak dominant in between 400 and
700 nm wavelength region along with one little peak around
350 nm and drastic rising around 300 nm is observed. In this
observation it is obvious that absorption band of R6G dye lm
becomes narrower due to red shifting and blue shifting of the
spectrum with increasing uence. The maximum absorbance area
is observed at a uence of 1011 ion/cm2 as shown in Fig. 4. Band tail
of the absorption spectra becomes sharper as uence increases.
Red shift and blue shift with uence is may be due to basic
operations such as translation and rotation occurring between
cofacial dimers. When translation is applied keeping plane parallel
to each other complex (dimer), only blue shift is observed because
of selection rule and when simultaneously rotation is applied to
each other, red shift is also observed [12]. In other reports, it is
reported that red shift and blue shift of absorption band of dye
molecules is due to formation of J-type and H-type dimers. R6G dye

Fig. 2. XRD of pristine and SHI irradiated lm of R6G dye.

H.Kr. Singh et al. / Vacuum 87 (2013) 21e25

23

energetic ions pass through the lm, a considerable amount of

electronic energy is transferred by collision with the electron of the
target material, resulting in transient high local energy densities
along the ion path. The dissipation of the transferred energy occurs
by collisions with other electrons or by electronephonon coupling.
The electronephonon coupling generates a localized heating of the
atomic system in the ion track. This process is equivalent to
a transient thermal process during some picoseconds. The
temperature shows a radial gradient, assumed of Gaussian type,
around the ion path, which cools down always from the track as
reported by Kastner et al. and Kumar et al. in the case of Fullerene
[14e16]. However, less intense heating in tracks halos with much
larger radii is responsible for the improvement of the R6G lm at
low uence. The annealing phenomenon is expected to vanish with
the increase in ion uence as the damaged core starts to take over.
Increased absorption area signies increased light harvesting effect
(LHE) which may in turn increase the efciency of DSSC.
3.3. Electrical characteristics
Fig. 3. UVeVis spectra of pristine and irradiated lm of R6G dye lm.

has a high tendency to form H-type nonluminescent dimer

sandwich-like aggregates with parallel aligned molecular axes as
already reported by some groups [2,4e6]. Another conguration of
R6G molecules with head-to tail aligned dipole moments (J-type
dimers) was normally observed in the presence of an additional
external potential as in the case by SHI irradiation. H-type R6G
dimers are associated with a remarkable blue shift and J-type R6G
dimmers are characterized by a red-shift in the optical absorption
band and in the luminescence band with respect to that in R6G
monomers [2e4,6]. In another report, V.N. Rai [13] has also reported that blue shift in R6G absorption spectra of dye is due to Htype dimers formation. Hence these reports (experimental observations) verify the above theoretical explanations of red shift and
blue shift given by Cornil et al. [12].
Band tail gets sharper with uence because of domination of
aggregates formation rather than amorphous nature of the dye
molecules on the band spectra. However relevant absorption band
region of R6G dye that contributes to charge carrier generation in
DSSC lies in the wavelength range of 400e700 nm (Visible range).
Improvement of the lm or annealing effectat low uence can
be understood in terms of ionesolid interaction. When the

Fig. 4. Absorbance area verses uence graph for R6G dye lm.

The charge-transport properties critically depend on the degree

of ordering of the chains in the solid state as well as on the density
of chemical and structural defects [17e19]. This dependence
explains why the experimental characterization of the transport
properties in organic thin lms or crystals has led to results that
vary with sample quality.
At the microscopic level, one of the key parameters for transport
in organic conjugated materials is the interchain transfer integral,
that expresses the ease of transfer of a charge between two interacting chains. The transfer integral associated with a given electronic level is related to the energetic splitting of that level when
going from an isolated chain to a system of interacting chains. In
organic semiconductors, the splitting of the highest occupied
molecular orbital (HOMO)/lowest unoccupied molecular orbital
(LUMO) level resulting from the interaction of adjacent chains
along given directions yields the transfer integral to be used for the
description of hole (electron) transport in these directions. For
simple cosine-shaped bands, the higher the HOMO (LUMO) bandwidth, the higher the expected hole (electron) mobility.
It turns out that, at low temperature, the charge transport in
a number of organic crystals and highly organized thin lms can be
described in a band-like regime similar to that in inorganic semiconductors [20]. In that case, the total widths and shapes of the
valence and conduction bands formed by the interaction of the
HOMO and LUMO levels of the conjugated chains, respectively,
determine the hole and electron mobilities. In a tight-binding
model, the total bandwidth of a one-dimensional innite stack is
simply equal to four times the transfer integral between neighbors
[21]; by extension, the total width can be expressed for any
molecular packing from the amplitude of the transfer integrals
between the various interacting units. When temperature
increases, the effective bandwidths are progressively reduced by
phonon-scattering processes; this result translates into a decrease
in charge mobilities leading to a high temperature regime where
the charge carriers get localized over single chains and transport
operates by a thermally activated hopping mechanism [20,22]. At
the microscopic level, the charge transport mechanism can then be
described as involving an electron transfer from a charged oligomer
to an adjacent neutral oligomer. Bredas et al. [23] has nicely
explained this parameter in his charge transport study of the
organic semiconductor material.
In the disordered organic semiconductors, where the charge
carrier transport takes place by hopping between localized states
and carriers are scattered at every step. Hopping is assisted by
phonons and the mobility increases with temperature, although

24

H.Kr. Singh et al. / Vacuum 87 (2013) 21e25

Table 1
Photo-conductivity measurement at different uence and temperature.
S. no

Samples types (ion/cm2)

1.
2.
3.
4.

Pristine
1.0  1011
1.0  1012
3.0  1012

Photo-conductivity sph (ohm-cm)1

At 40  C
6.25
7.50
1.25
2.50






109
109
109
109

At 46  C
6.88
1.12
1.87
4.36






109
108
109
109

At 52  C
1.00
1.37
1.87
4.36






108
108
109
109

At 58  C
1.37
2.43
5.00
8.13






108
108
109
109

At 64  C
2.82
3.34
6.88
1.00






108
108
109
108

At 70  C
4.26
4.76
1.50
2.75






108
108
108
108

typically it remains very low overall (m  1 cm2 V1 S1). The

boundary between band transport and hopping is dened by
materials having RT mobilities of the order of 1 cm2 V1 S1
[24e26]. Thin lms of highly ordered organic semiconductors, such
as several members of the acene series including pentacene, have
RT mobilities in this intermediate range [26,27]. In some cases
temperature independent mobility has been observed, even in
polycrystalline thin lms of pentacene. This observation was used
to argue that a simple thermally activated hopping mechanism can
be excluded as a transport mechanism in high quality polycrystalline thin lms of pentacene despite of the fact that in some
samples containing a large concentration of traps related to structural defects and chemical impurities the mobility increases with
temperature [26]. Trapping at the grain boundaries in polycrystalline lms of pentacene and the dependence of trap
concentration on the lm deposition conditions has been suggested
as the main cause of the observed variability of the temperature
dependence of mobility [28].
In present case, thin lm of R6G dye is taken which is very
similar to other disordered organic material like pentacene. This
lm is irradiated by 120 MeV Ag9 ion at 3 different uences and its
phoconductivity has been measured. The values of photoconductivities sph for pristine and irradiated sample of the R6G
dye were measured to be 6.25  109 (ohm-cm)1 for pristine and
2.5  109 (ohm-cm)1 for higher uence 3.0  1012 ion/cm2 at
room temperature 40  C (w313 K). Details of photo-conductivities
are given in Table 1 with uence at different temperature started
from 40  C to 70  C. It is very clear from the Table 1 that photoconductivity of pristine and irradiated samples increases as we
increase the temperature. It is observed that 1  1011 ion/cm2 uence irradiated sample has the highest value of photoconductivity
in the irradiated lms.

The photoresistivity of R6G dye with uence at different

temperatures is shown in Fig. 5. The photoresistivity measurement
shows that it is minimum for a uence of 1011 ion/cm2 at all
temperatures. It may be due to increase of conduction states during
SHI irradiation at lower uence. Further increase in photoresistivity
at higher uences is may be due to unfavorable cross linking and
chain scissoring. This trend supports the optical results presented
in section 3.2 wherein absorbance rst increases at lower uence
and then starts decreasing at higher uences.
To see the variation on resistivity of dye with temperature, its
temperature is varied from 40 to 70  C. Photo-resistivity decreases
with increasing temperature at all uences, is similar behavior to
that of organic semiconductors. At higher temperature (70  C),
effect of uence on photoresistivity is weakened and the curve
becomes attened. Eventhough we can not rule out the possibility
of defects (structural defects) because lm becomes more amorphous after SHI irradiation as it is revealed in XRD measurements.
Since conductivity of the all irradiated sample increases with
temperature which might be possible only for including increasing
trap states in the material which causes hopping [29]. Increasing
nature of photoconductivity is mainly due to increase of trap state
concentrations due to structural defects. Structural defects are
mainly created by SHI irradiation which causes more electron
concentration by trap states as temperature increases and reaches
high where hoping mechanism starts to happen [23,27,29].
Arhinious plot lnsph versus 1000/T is plotted as shown in Fig. 6.
In this plot it is seen that slope of the graph rst decreases for
1.0  1011 ion/cm2 uence and after that it is increased for further
higher uences in comparison to the pristine sample. Slope is
directly proportional to activation energy Ea and increase and
decrease of Ea is justied by the photoconductivity response
respectively.

Fig. 5. Variation of photo-conductivity with uences: whole uence with inset around
1.0  1011 ion/cm2.

Fig. 6. Arhinious plot lnsph versus 1000/T for R6G sample at different uen.

H.Kr. Singh et al. / Vacuum 87 (2013) 21e25

4. Conclusion
The long term perspective of ongoingstudy is to see the effect of
SHI irradiation on different components of photoanode and to
investigate the possibility of improvement in stability and efciency of DSSC. In the present work effect of SHI on photosensitizer
(R6G dye) is discussed. R6G lm becomes more amorphous with
irradiation in comparison to pristine sample and therefore lm
would spread homogeneously on the substrate. It is also observed
that the absorbance spectra and photo-conductivity of the dye lm
has good co-relation with each other at lower uences. Since lm
growth is not optimized therefore optimized lm growth and
optimized uence for the lm is required. In conclusion, SHI irradiations on R6G lm at lower uence are more advantageous in
comparison to higher uence.
Acknowledgments
Authors SA and HKS are thankful to IUAC New Delhi for
providing us project # 43314 under UFUP scheme. One of the
author HKS also appreciate the support of Miss. Mamta Garg (PU,
Chandigarh) for this work.
References
[1] Bujdak J, Iyi N, Sasai R. J Phys Chem B 2004;108:4470.
[2] Sasai R, Fujita T, Iyi N, Itoh H, Takagi K. Langmuir 2002;18:6578.
[3] Kikteva T, Star D, Zhao Z, Baislev TL, Leach GW. J Phys Chem B 1999;103:1124.

25

[4] Martinez V, Lopez Arbeola F, Banuelos T, Arbeola Lopez T, LopezArbeola I.

J Phys Chem B 2004;108:20030. Martinez V, Lopez Arbeola F, Banuelos T,
Arbeola Lopez T and Lopez Arbeola I J. Phys. Chem. B2005; 109 :7443.
[5] Sasai R, Iyi N, Fujita T, Arbeloa FL, Martinez VM, Takagi K, et al. Langmuir 2004;
20:4715.
[6] Del Monte F, Levy D. J Phys Chem 1998;102:8036.
[7] Boutin P, Mugnier J, Valeur B. J Fluoresc 1997;7:215.
[8] Rao SV, Naga Srinivas NKM, Rao DN. Chem Phys Lett 2002;361:439.
[9] Prakash RS. J Mater Sci Mater Electron 2002;13:735.
[10] Tripathi SK, Monga Alka, Saini GSS. Smart Mater Struct 2009;18:125012.
[11] Abkowitz M, Foley GMT, Markovics JM, Pulumbo AC. Optical effects in
amorphous semiconductors. AIP Conf Proc 1984;120:117e24.
[12] Cornil J, dos Santos DA, Crispin X, Silbey R, Brdas JL. J Am Chem Soc 1998;
120:1289e99.
[13] Rai VN. Appl Opt 1988;27(13):2776e80.
[14] Kastner J, Kuzmany H, Palmetshofer L. Appl Phys Lett 1994;65:543.
[15] Kumar A, Avasthi DK, Tripathi A, Singh F, Pivin JC. J Appl Phys 2007;101:014308.
[16] Kumar Amit, Avasthi DK, Pivin JC, Koinkar PM. Appl Phys Lett 2008;92:221904.
[17] Laquindanum JG, Katz HE, Lovinger AJ, Dodabalapur A. Chem Mater 1996;8:
2542e4.
[18] Gundlach DJ, Lin YY, Jackson TN, Nelson SF, Schlom DG. IEEE Electron Device
Lett 1997;18:87e9.
[19] Fichou D. J Mat Chem 2000;10:571e88.
[20] Schn JH, Kloc C, Batlogg B. Phys Rev Lett 2001;86:3843e6.
[21] Haddon RC, Siegriest T, Fleming RM, Bridenbaugh PM, Laudise RA. J Mater
Chem 1995;5:1719e24.
[22] Horowitz G, Hajlaoui R, Bourguiga R, Hajlaoui M. Synt Met 1999;101:401e4.
[23] Bredas JL, Calbert JP, da Silva Filho DA, Cornil J. PNAS 2002;99(9):5804e9.
[24] Pope M, Swenberg CE. Electronic processes in organic crystals and polymers.
2nd ed. Oxford: Oxford University Press; 1999. p. 337e40.
[25] Horowitz G. Adv Mater 1998;10:3.
[26] Nelson SF, Lin Y-Y, Gundlach DJ, Jackson TN. Appl Phys Lett 1998;72:1854.
[27] Dimitrakopoulos C, Purushothaman S, Kymissis J, Callegari A, Shaw JM.
Science 1999;283:822.
[28] Schn JH, Kloc C, Batlogg B. Org Electron 2000;1:57.
[29 ] Arkhipov VI, Reynaert J, Jin YD, Heremans P, Emelianova EV, Adriaenssens GJ,
et al. Synth Metals 2003;138:209e12.