A New Era in Affordable
Raman Spectroscopy
This article overviews several recent advancements in Raman
components that are enabling high analytical performance in
low-cost Raman instruments.
Tony Lam
R
aman spectroscopy is an ideal
tool for chemical analysis due to
its unique advantages over other
analytical techniques. It is a nondestruc-
tive and noncontacting method of
obtaining the fingerprint spectrum of
materials, requiring no special sample
preparation. Raman can analyze sam-
ples via sample plastic bags, glass vials,
and in aqueous solution. It does not
require a large amount of a sample to do
analysis; the sample can be as small as
1–2 µm across. A short amount of meas-
uring time, normally a few seconds, is
required to obtain a Raman spectrum.
Thus, it can be used to monitor chemi-
cal reactions in real time.
Despite the fact that Raman spec-
troscopy has so many advantages, it still
is not in widespread use. The main rea-
son is the high cost typically associated
with Raman analyzer systems.
Currently, a high-resolution and high
signal-to-noise ratio Raman analyzer
can be priced from $40,000 and above.
On the other hand, there is a market
need for low-cost Raman analyzer sys-
tems as general laboratory tools.
However, those systems usually are
Tony Lam is a senior system engineer at EnWave Optronics (Irvine, CA). He can be
reached at: tlam@enwaveopt.com.
30 Raman Technology For Today’s Spectroscopists
equipped with low-resolution, low-
power visible lasers, and low signal-to-
noise ratios, which is not adequate
enough to perform any high perform-
ance chemical analysis. Therefore, bet-
ter-resolution and lower-cost Raman
systems are key to increasing and
enabling greater acceptance and usage
of Raman spectroscopy.
This article presents a few key
advancements in Raman components
that will enable low costs and high per-
formance. It also establishes the figure
of merit to identify and characterize
Raman systems in terms of high resolu-
tion and low cost. Finally, Raman appli-
cations and sample Raman spectra in
pharmaceutical, petrochemical process-
ing, and plastic recycling applications
will be presented.
Modern Raman Systems
A typical laboratory Raman analyzer
system consists of four major compo-
nents: the excitation source, the collec-
tion device, the spectrograph, and the
post-processing software. The excita-
tion source must be strong enough to
generate sufficient Raman signals, and
June 2004
Raman Components Raman Components

monochromatic light to Recent developments in 14

provide clean and uncom- 3.0 diode laser wavelength stabi-
785 nm, > 300 mW E
plicated spectra. A laser lization and linewidth nar-
< 1 cm-1 Linewdith
typically is used as the exci- D F rowing have been very dra- 12
tation source because it can 2.5 matic. Current wavelength

Cost in US dollars (x104)

provide a coherent beam of stabilization designs include
monochromatic light with A C Littrow with traditional 10 C A

Figure of merit
high intensity. The collec- 2.0 gratings, Littmann with tra-
tion device is the fiber- ditional gratings, fiber Bragg
optic probe. It collects the gratings, volume Bragg grat- 8
B
scattered photons, filters 1.5 ings, distributed feedback
out the Rayleigh scattering, lasers (DFBs), distributed
6
and sends the Raman sig- Bragg reflector lasers
nals to the spectrograph. 1.0
E (DBRs), and master oscilla-
D
The spectrograph then sep- tor power amplifier lasers 4
arates the Raman signals by (MOPAs). Some designs B
their wavelengths and also integrate a bandpass fil-
0.5
transfers them to the light 1996 1998 2000 2002 2004 ter or amplified sponta- 2
detector, which records the neous emission (ASE) 1.0 1.2 1.4 1.6 1.8 2.0
Year
intensity of the accumulat- reduction technique to Cost in US dollars (x10 4 )
ed photons at its own Figure 1. Cost survey of diode-based Raman spectroscopy remove the unwanted ASE Figure 2. Comparison of diode-based Raman laser
wavelength. These record- lasers (A, B, C, D, E, and F are different Raman spec- interference that often is sources on the current market (figure of merit =
troscopy laser manufacturers).
ed data then are passed to seen in a high-power diode power/linewidth).
the postprocessing soft- laser. All these lasers should
ware to display as a Raman spectrum. For any high resolution (<6 cm-1) at least provide 150 mW in optical Due to the recent development of a
Several types of lasers can be used as Raman system, the laser linewidth (ide- power, a stabilized center wavelength silicon CCD camera, the CCD sensor has
the excitation source for Raman spec- ally <1 cm-1) of the excitation source within a tenth of a wavenumber, and a replaced the single channel detector,
troscopy. They are Ar+ ion (488.0 and plays a key role. Also, to avoid fluores- spectral linewidth of less than 1 cm-1 for photomultiplier tube (PMT) and ava-
514.5 nm), Kr+ ion (530.9 and 647.1 cence interference, NIR wavelengths are a high-resolution Raman system. A laser lanche photodiodes (APD), as a multi-
nm), He:Ne (632.8 nm), Nd:YAG (1064 preferred. Thus, diode lasers emitting at linewidth (~3–4 cm-1) close to the spec- channel photon detector in the spectro-
nm), and diode (630 and 980 nm) 785 nm (NIR) generally have been rec- trometer’s resolution is not ideal because graph. It can detect radiation from 400
lasers (1). Due to recent advancements ognized as the industry standard in the the system’s overall spectral profile or to 1100 nm (2). In addition, the CCD
in diode laser technology, it is the best past few years because of their coverage response will be the convolution of the sensor will reduce integration time
candidate to be utilized in low-cost, of nearly 3000-cm-1 useful spectra two responses (laser linewidth and spec- because it allows spectrum multiplexing.
portable Raman analyzer systems when based upon a silicon charged- trometer’s resolution). Thus, any laser A typical integration time of the CCD
because of its relatively low cost, com- coupled device (CCD) detector. spectral profile changes due to tempera- spectrograph is less than 30 s.
pact size, high reliability (>10,000-h Unfortunately, without any frequency ture, current, or any other nonlinearities A general laboratory Raman probe is
lifetime), and near-infrared (NIR) stabilization and linewidth narrowing, will affect the overall system spectral composed of two fibers. The excitation
emission wavelength for fluorescence these diode lasers cannot be used in a profile and cause inaccuracies in chemo- fiber is used to deliver the excitation
reduction. A typical diode laser used in high-resolution Raman system because metric prediction. Figure 1 depicts a cost source to a sample. The collection fiber
a modern Raman analyzer system is a of their free running spectral linewidth survey over the past eight years for wave- is used to collect Raman signals and
high power laser diode (>300 mW), of ~25 cm-1 and unstable center wave- length-stabilized, 785-nm, 300-mW, 1- deliver it to the spectrograph.
with wavelengths ranging from 630 to length that causes random shifts in cm-1 linewidth Raman spectroscopy Normally, the bandpass filter and
980 nm. Raman spectra. laser systems on the market. band-reject filter are integrated into

32 Raman Technology For Today’s Spectroscopists June 2004 June 2004 Raman Technology For Today’s Spectroscopists 33
Raman Components Raman Components

the fiber-optic probe head of laser sources is compared

to remove the laser 3.5 because the laser still is the
Rayleigh scattering, silica major cost component for a
Raman interference from 3.0 D Raman system. The figure of
the fiber, and ASE from the merit of the laser is defined
laser excitation source. 2.5 as the laser power inversed
The data collected from proportionally with the laser

Figure of merit (x105)

the spectrograph then are 2.0 linewidth:
sent to the software. The Figure of merit =
software then converts the 1.5 E power/linewidth [1]
data into the Raman spec- Using Equation 1, the
trum and displays it on an 1.0 figures of merit of lasers
x–y chart. The x axis of the (A–E) are calculated and
chart is the wavenumber, 0.5 A mapped in Figure 2.
while the y axis is the inten- Observing the figure-of-
sity of the spectrum. 0.0 C B merit chart (Figure 2), the
laser excitation sources are
Resolution of Raman 1 2 3 4 5 6 divided into three groups.
Systems Cost in US dollars (x104) One group is the high per-
Three basic bandpass filters Figure 3. Comparison of laboratory Raman systems on formance and high cost Figure 4. Raman spectra of OTC medicines.
are used in a typical Raman the current market (figure of merit = [coverage x group, including A and C
measuring system to deter- power]/[resolution]). laser sources. The second group is the Raman spectroscopy applications that
mine the overall Raman low-performance and low-cost group, determine which Raman systems should
spectrum quality (that is, resolution). For most Raman applications in including B and D laser sources. The be used, but for most of the applications,
These three bandpass filters are: laser solid and liquid samples, a system reso- last group, E laser sources, is the high a Raman system that has a 6-cm-1 spec-
linewidth bandpass, spectrometer band- lution of 6 cm-1 or less is sufficient. performance and low cost group. tral resolution is sufficient (1).
pass, and sample bandpass (natural Unfortunately, any high-resolution The figure of merit of the Raman
linewidth) filters. (<6 cm-1) Raman system usually is system is defined as the product of the Applications of Affordable
Ideally, a laser linewidth bandpass highly priced primarily because of the spectral range (coverage) and the laser Raman Systems
filter should be much less than the high cost of the high power power divided by the system resolution: With high-resolution and low-cost
spectrometer bandpass filter. In this (>300 mW), wavelength-stabilized, Figure of merit = (coverage x Raman systems, many Raman spec-
case, the spectrometer will be the only and linewidth narrowed (<1 cm-1) power)/(resolution) [2] troscopy applications in chemical
factor in determining the Raman sys- Raman spectroscopy laser. Using Equation 2, the figures of analysis become feasible. To name a few,
tem’s bandpass filter. If the bandpass merit of Raman systems (A–E) are cal- Raman spectroscopy is useful in drug
filters of the two (that is, laser and Costs of Raman Systems culated and mapped in Figure 3. identification for the pharmaceutical
spectrometer) are close, the system’s To compare the cost of different Raman Observing the figure-of-merit chart industry, the control of octane level in
bandpass filter will be a convolutional systems currently on the market, a figure of the Raman system (Figure 3), the A gasoline, and the classification of plastic
bandpass filter of the two components. of merit is adopted as a way to normal- and E Raman systems are considered to in the plastic recycling industry. To
Generally, a spectrometer bandpass fil- ize different features and performances be the medium-performance and low- demonstrate the feasibility of using a
ter’s profile is much more stable than for a fair comparison. The higher the fig- cost systems. The B and C systems are low-cost Raman instrument in these
the laser bandpass filter profile, thus a ure of merit, the better the system’s per- considered to be low-performance and applications, the HRC-10 Raman ana-
much narrower laser linewidth band- formance. This section of the article high-cost systems. The D system is con- lyzer with less than 6-cm-1 system reso-
pass filter is preferred and could make compares the costs of the laser sources sidered a high-end system, high per- lution, manufactured by EnWave
a system much more stable. and the overall Raman systems. The cost formance versus high cost. It is the Optronics, was chosen to collect Raman

34 Raman Technology For Today’s Spectroscopists June 2004 June 2004 Raman Technology For Today’s Spectroscopists 35
Raman Components Raman Components

spectra of some over-the- lene (PP, 5); polystyrene

counter medicines, unlead- (PS, 6); and “other,”
ed isooctane levels of labeled as 7 (5). In the
Chevron gasoline, and plastics industry, Raman
some plastic samples. spectroscopy systems find
Pharmaceutical. One of application in real-time
the advantages of the monitoring of polymer-
Raman system is its ability ization reactions to con-
to measure down to trol the processing time, in
50 cm-1 in spectral range quantitative composition-
compared to the mid-IR al analysis of polymer
system that can only reach melt streams, and in plas-
approximately 400 cm-1. tic identification for recy-
The feature is very attractive cling purposes. Figure 6
to the pharmaceutical shows an example of plas-
industry because most of tic Raman spectra.
the spectra of drug lattices
are below 200 cm-1 (3). Conclusion
Raman spectroscopy finds With the current
its application in lattice advancements in diode
vibration study for the char- Figure 5. Raman spectra of Chevron unleaded gasoline laser technology, Raman Figure 6. Raman spectra of polypropylene and
acterization of the solid with various isooctane levels. systems have been polystyrene plastics.
state of a drug and especial- improved on two fronts:
ly for the investigation of polymor- Environmental Protection Agency cost and resolution. Raman excitation Hennip, Chem. Educator, 2, 15–18
phism and amorphous systems. In addi- (EPA) (3), to reduce the levels of car- sources now can be made with a lower (2002).
tion, it finds application in analysis and bon monoxide in the air, the govern- cost. In addition, laser wavelength sta- 3. Ian R. Lewis and Howell G.M. Edwards,
quantification of drug blends, and in the ment entity requires the use of oxy- bilizing and linewidth narrowing have Eds., Handbook of Raman
examination of drug formulations and genate additives to the gasoline. The improved the resolution of Raman sys- Spectroscopy: From the Research
drug excipient incompatibilities. petroleum manufacturers have been tems. Consequently, these advance- Laboratory to the Process Line
Petrochemical. The gasoline pur- maintaining and monitoring the oxy- ments have eliminated the high costs (Marcel Dekker, New York, 2001).
chased from any local gas station has genate level accurately in the gasoline associated with the high-resolution 4. Susanne Brunsgaard Hansens, The
the methyl-tert-butyl ether (MTBE) during refinery process. Raman spec- system and brought this novel technol- Application of Raman Spectroscopy
(4) content added to improve the troscopy systems have been a favored ogy to every corner of life. It signifies a for Analysis of Multi-Component
octane number. The octane number is approach for qualitative identification new era in Raman spectroscopy. Systems (Department of Chemistry,
an experimentally determined proper- of oxygenate materials. Perhaps, within five years, it will find Technical University of Denmark,
ty of petroleum fuel that defines the Plastics. Plastics are used extensively itself within many potential applica- Denmark, 2000).
quality of engine antiknocking. Raman and vastly in many common materials. tions that have not been considered 5. “Resin Identification Codes,” American
spectroscopy can be used to identify Plastics consist of seven different kinds previously for chemical analysis. Plastics Council
the octane level within gasoline. An of polymers. They are polyethylene- (http://americanplasticscouncil.org;
example of the octane level in Chevron terephthalate (labeled as PET, and References accessed 4/29/04).
unleaded gasoline is shown in Figure 5. number 1 under recycling symbol); 1. Richard L. McCreery, Raman 6. “CHEM*3440 Raman Spectroscopy:
Also, Raman systems can be used to high density polyethylene (HDPE, 2); Spectroscopy for Chemical Analysis How it Works the Spectrum,”
measure oxygenate material in the polyvinyl chloride (PVC, 3); low densi- (John Wiley & Sons, New York, 2000). (http://www.chembio.uoguelph.ca;
gasoline. According to the U.S. ty polyethylene (LDPE, 4); polypropy- 2. Benjamin A. DeGraff and Mandy accessed 4/29/04). ■

36 Raman Technology For Today’s Spectroscopists June 2004 June 2004 Raman Technology For Today’s Spectroscopists 37