Vol. 6, No.

1, April 2003

FORENSIC DO CUME NT EXAMINATION/Inks and Raman Scattering: 29-07-01-06/0304

SURFACE ENHANCED RESONANCE RAMAN SCATTERING
(SERRS) SPECTROSCOPY— STUDY ON INKS 1
Raman spectroscopy without sample prep that provides rapid, real-time analysis in an office environment.
by N. Jaufmann2,3
REFERENCES: Jaufmann, N., "Surface Enhanced Resonance Raman picture of the behaviour under a certain setting of illumination and
Scattering (SERRS) Spectroscopy — Study On Inks.," The certain filter conditions.
International Journal of Forensic Document Examiners, Vol. 6, No. 1,
2003, pp. 1-7.

ABSTRACT: Surface Enhanced Resonance Raman Scattering (SERRS)

spectroscopy can overcome many of the limitations of conventional
Raman spectroscopy in ink analysis, specifically dominant fluorescence
and weak Raman signals. The use of Raman spectroscopy in forensic
examinations is increasing. However there are certain samples that are not
readily suited to conventional Raman spectroscopy. These mostly include
fluorescent materials or samples with intrinsically weak scattering
cross-sections. Examples of this type commonly seen in forensic document
examination are pen inks that are fluorescent in the near infrared and toner
samples that show only weak Raman signals. In this study we show how,
with the SERRS technique, we could obtain detailed spectra from ink
samples that were weak Raman scatterers or exhibited dominant levels of
fluorescence when analyzed previously. Further to this, it was possible to
differentiate samples based on their SERRS spectra that could not be
otherwise discriminated with conventional infrared techniques (e.g. VSC).
Inks analyzed for this study were as follows: Blue Ball Point Pen Inks,
Black Ball Point Pen Inks, Blue Fluid Inks, Black Fluid Inks, Red Fluid
Inks, Green Fluid Inks, and Inkjet Printer Inks.

KEYWORDS: SERRS, Raman, inks, inkjet.

INTRODUCTION

The forensic investigation of inks is a theme, that, although very old,

has lost nothing of it’s importance. Very often it deals about comparison
of inks and the proof of equality and/or inequality. Thereby mainly two
different test methods are in use: optic excitation with document test
equipment and chemical analysis, e.g. using Chromatography.
Very often chemical investigation excludes already through the
regulation, not to destroy the document. Through costly sample
preparation and the time needed , Chromatography does not fulfil the
demands for a fast test of a document in the lab - routine.
Document examination, e.g. with a Video Spectral Comparator (Figure
1) based on optic excitation and visual examination, is here clearly
considered as the winner. Using an optic - and most of all non-destructive
- method, radiation processes are triggered by suitable combinations of
light and filters, which are recorded with a camera, sensitive in Near-IR.
All ingredients of an ink, involved in the radiation process are procured
with the characterisation of the ink.
If excitation of two inks – especially, when on the same document –
causes different photo physical behaviour, we are able to state, that these
inks are different (Figure 2). Any image given by such a system can of
course be sufficient to proof alterations but can only be a momentary
1
Presented at the GFS Annual Meeting in Bingen, June 2001.
2
Foster+Freeman Europe GmbH, Ravensburger Strasse 6, 88410 Bad Figure 1: Document test equipment foster + Freeman VSC-2000/HR
Wurzach, Germany. (top) and VSC-4C (bottom)
3
Supported by Emma Wagner and Simon Clement, Foster and Freeman
Ltd, 25 Swan Lane, Evesham, WR114PE.

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The International Journal of Forensic Document Examiners

What is the Raman effect?

If we look to the collision of a photon and a molecule, e.g. of an
ink, we can basically recognize three different effects. These effects
are absorption, refection and Fluorescence (Figure 4). With absorption,
the photon is disappearing in the molecule and transfers it’s complete
energy into the molecule. With reflection the photon is re-bounced
from the molecule, looses energy, but emits light with more or less the
wavelength of the excitation.
With fluorescence the photon penetrates into the molecule and
causes the molecule to emit another photo n. That fluorescence photon
usually has a wavelength different from the excitation.

Figure 2: Differentiation between two inks via IR Luminescence.

A big step forward for the examination of inks, which are very similar
in the Near-IR, is spectrometric measurement. In a spectrometric graph
(Figure 3) even very fine differences are to be seen much more clearly than
by optical view to a camera picture. If no difference is to be seen over a
wide range of excitation wavelength, this does not necessarily mean, that
the inks are the same. It just states, that the ingredients, influencing the
radiation process behave in the same way. Equality of inks is therefore
very difficult to proof by means of common document examination
equipment. Chemical analysis is here superior.

Figure 4: Fluorescence Effect.

The Raman effect (Figure 5) basically is similar, but is based on

appearance of no reflection and no fluorescence. The photon hitting
the molecule, is rebounced and scattered. Due to the collision, the
photon looses energy and re-appears as Raman scattered photon with
considerably lower energy and longer wavelength. Raman radiation is
up to 10 million times smaller than the excitation.

Figure 3: Spectrographic Representation of the luminescence behavior of

two different inks.

Raman Spectroscopy
In the recent past, Raman spectroscopy is considered as being very
useful for characterising of more complicated formulated material. This
technology offers as well document examiners a easy to use and versatile
method to examine inks. Although Indian scientist Dr. Raman discovered
already in 1928 the effect, named Raman effect, only since the recent past
commercial-available and cost-effective components are available, to use
Raman spectroscopy in a commercial way. Figure 5: The Raman Effect

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In practice Raman scattered photons are not only shifted to one
wavelength, but to a special pattern of shifts.A set of Raman shifts gives
a Raman spectrum as seen in Figure 6. The small wavelength shifts are
related to the vibrational energy levels of the material and are highly
characteristic of its chemical constitution. The spectra are capable of
providing good material ‘fingerprints’.
Figure 6: Raman Spectrogram.
Raman Spectrometer
In the last two years Foster + Freeman raised the challenge to develop
a Raman Spectroscope (Figure 7), which is specially dedicated for forensic
routine case-work. The requirements for a system like this were:
• No sample preparation required;
• No dark room facility necessary;
• Non-destructive measurement;
• Rapid analysis;
• Easy to use – short start-up phase;
• PC-controlled - Windows TM NT software;
• Bench top configuration; and,
• Clear graphical representation of the results.
Figure 7: Foram 685-2 Raman Spectroscope.
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Vol. 6, No.1, April 2003
The result is the Foram 685-2, a Raman machine, which is from
development on dedicated to the needs of forensic applications. The
three basic components of a Raman machine are a source of
monochromatic light, a wavelength dispersing device and a detector.
For monochromatic light, the modern laser is ideal and one of the
reasons why Raman is now available technique (Figure 8).
Figure 8: General structure Foram 685-2 Raman Spectroscopy.
The actual machine (Figure 9) uses a stabilised diode laser, which
guides it’s beam via a microscope objective to the questioned
document. The reflected scattered light, which includes the scattered
Raman emissions, is lead through an optical system to a set of filters.
This filter system uses also interference and coloured glass filters to
remove scattered laser light and separates the Raman scatter. Via a
defraction grating the Raman light is spectrographically separated and
finally guided to a CCD-detector-array. To reduce noise, the detector
is thermoelectrically cooled.
Figure 9: Focusing of the laser beam through camera picture.
3
The International Journal of Forensic Document Examiners

In addition to these essential components, a small camera has been

installed to allow viewing of the sample area to enable the operator to
align the laser spot and to ensure that the beam is focussed on to sample
surface.
As soon as the sample area is displayed on screen (Figure 10) and the
laser beam is focused, the intelligent software enables the user to release
a measurement by a simple click on a button. The result is displayed as a
spectrum graph already. The graph shows the intensity of the received
Raman light in co-relation to the shift in wavelength (Raman shift or
wavenumber) The expression wavenumber equals 1/ wavelength [cm]. The
wavenumber is measured in cm –1. The spectral resolution of that machine
is 7 cm –1.

Figure 11: Raman Spectrogram of various toners.

Figure 10: Raman Spectrogram of an ink.

As well as a basic shell programme to run the machine and record the
spectra, there will be filters for removing noise and background
fluorescence, algorithms, to carry out spectral comparisons and archive
facilities to allow search and match operations (Figure 10).
Initial research work started with different wavelengths of laser light.
A wavelength of 785nm has the advantage of not inducing fluorescence,
which masks the Raman signal, but at this wavelength the Raman effect is
less efficient. 532nm produces more Raman signal but also more
fluorescence. Like most design, there is always a trade-off. The
wavelength of 685nm, which is used now, appeared to be the best
compromise between both behaviors and gave best results for document
applications. Figure 12: Raman Spectrogram of various ball point inks.
Due to non-destructive test method, an extremely rapid analysis and
very easy use Foram 685-2 completes the range of document test
equipment. The system does not put worth on offering very high resolution for the forensic application, we have not necessarily the need of unique
or extremely accurate quantitative data over a wide spectral range. In Raman emissions. If e.g. looking for non-equality of two questioned
general forensic examination of documents, the examiner needs to see inks, which don’t show big differences under IR, one ink gives a
significant differences, if a claim of forgery is to be made. Very small reproducible typical Raman spectrum and the other gives a
differences can often be attributed to ‘natural’ causes - variations in age or reproducible fluorescence covered graph, this in enough.
storage conditions or variability in ink density or contamination, which We are at least able to distinguish these two inks and state that
would have little significance if any. The reduction in specification has they are not the same. Anyway a satisfying number of samples gave
enabled Foster + Freeman to significantly reduce the cost of the clear Raman spectra. Here Raman spectroscopy is superior to IR
instrument. technology because of the resolution and superior to chemical analysis
A row of measurements on various inks (Figure 11) and toners because of rapid, easy and non-destructive methods.
(Figure 12) showed, that unfortunately not all inks give Raman peaks as Influenced by our experience from working with the Foram 685-2,
wished. Quite a number of inks gave graphs, where the Raman effect is some changes were made to the equipment, opening the possibility to
covered by a flourescent curve, regardless of the choosen wavelength. But use it for other forensic applications as well. Good results were

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 Vol. 6, No.1, April 2003

received with car paints, textile fibres, pharmaceuticals and drugs.

The Foram 685-2 Raman Spectroscope shall not be regarded as a
system, which lights up a red light for “falsified” or a green light for
“genuine”. Still the expertise and knowledge of a document expert, able
to consider all circumstances of a document and results of different
methods to interpret a spectrum, is needed. Raman spectroscopy shall not
be regarded as a competitor technology to existing IR examination or
chemical analysis. Raman Spectroscopy should rather be considered a
additional building block when putting together the Puzzles of document
evidence .

Surface Enhanced Raman Spectroscopy (SERRS)

However there are certain samples that are not readily suited to
conventional Raman spectroscopy. These mostly include fluorescent
materials or samples with intrinsically weak scattering cross-sections.
Examples of this type commonly seen in forensic document examination
are pen inks that are fluorescent in the near infrared and toner samples that
show only weak Raman signals.
A recent article by White et al [1], has demonstrated that these
limitations can largely be overcome using the technique of SERRS.
Raman signals are enhanced through resonance effects [2] and by SERRS
[3]. The resonance enhancement would be expected through most of the
visible spectrum, as the dye components of inks tend to have broad
absorption bands in this spectral region, however the increase in Raman
signal will be accompanied by a corresponding increase in the
fluorescence yield. The surface enhancement is achieved through use of
a colloidal silver aggregate. Not only are the Raman signals further
enhanced, but the presence of colloidal silver largely quenches the
fluorescence.
For SERRS to be effective, relevant sample molecules must either be
bound to or held in close proximity to the silver colloid. This is achieved
here through the use of an aggregating agent, poly-L-lysine. Results
Methods and Materials Figure 14 below shows examples of the conventional Raman
spectrum from a fluorescent ink sample.
All measurements were made using a Foram 685-2 Raman Spectral
Comparator (Foster and Freeman Ltd., UK). The laser wavelength was
685 nm. The measurements were taken on the lowest power setting ( ~ 0.5
mW ). A colloidal silver solution and poly-L-ysine aggregating agent were
used for the SERRS measurements.
The aggregating agent was applied to a small portion of the ink sample
using a micro pipette and then allowed to dry (approximately one minute).
The colloidal silver was then applied to the same portion of ink using a
different pipette and allowed to dry. Typically an area of 1 mm2 or less
was treated in this way.
The SERRS technique is considered non-destructive as no sample is
removed from the document, and there is only a microscopic effect to the
sample surface.
Figure 13 shows the image of pen stroke after the silver colloid
treatment. The two vertical lines are pencil marks between which the Figure 14: Fluorescent ink sample.
sample has been treated. The pen stroke outside the two pencil marks has
not been treated. The fluorescence emitted is many, many times more intense than
Data acquisition times were typically less than 1 second, with spectra any Raman signal, saturating the sensitive Raman detector and
averaged over several readings. masking the Raman signal.
Inks analysed for this study were as follows: Figure 15 shows an example of a typical SERRS spectrum from an
ink sample.
• Blue Ball Point Pen Inks The application of the SERRS techniques quenches the
• Black Ball Point Pen Inks fluorescence and enhances the Raman signal of the dye components of
• Blue Fluid Inks the ink. Fluorescent inks with different dye components may give
• Black Fluid Inks similar results when viewed under the VSC, or with normal Raman
• Red Fluid Inks spectroscopy. However, when SERRS is used, these inks may be
• Green Fluid Inks discriminated as they display peaks at different wavenumbers in their

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The International Journal of Forensic Document Examiners

SERRS spectra. Graphical Representation of the Results

The Raman and SERRS spectra of each ink were compared to every
other ink of the same colour and type. The discriminating power for
Raman, SERRS and Raman and SERRS combined was then calculated for Blue Ball Point — 325 pairs
each sample group. These are detailed in Table 1below.

Figure 15: SERRS spectrum.

Black Ball Point — 325 pairs

Table 1: Discriminating power for Raman, SERRS and Raman and

SERRS combined calculated for the sample group.

Blue Fluid Ink — 1953 pairs

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 Vol. 6, No.1, April 2003

Black Fluid Ink — 1770 pairs. Conclusions

It has been shown that SERRS spectroscopy dramatically enhances
the usefulness of Raman based techniques. Samples which are either
inherently IR fluorescent or weak Raman scatterers may now yield
quality spectra which can be used for discrimination. It is likely that
SERRS spectroscopy will have wider applications in many aspects of
Forensic Science, especially in questioned document examination

References
[1]. White, P.C., Rodger, C., Rutherford, V., Finnon, Y., Smith,
W.E., and Fitzgerald, M., “Surface Enhnaced Resonance Raman
Scattering (SERRS) Spectroscopy. A Powerful Technique For
The Forensic Analysis of Colourants?”, SPIE, Vol. 3576, Nov.
1998.

[2]. Demtroder, W., Laser Spectroscopy, 2nd Edition, Springer.

Green Fluid Ink — 630 pairs.
[3]. Pelletier, M. J., Analytical Application of Raman Spectroscopy,
1st Edition, Blackwell Science Ltd.

Red Fluid Ink — 1128 pairs.

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