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Spectrometric Determination of the Refractive Index of Optical

Wave Guiding Materials Used in Lab-On-a-Chip Applications


ANDRES M. CARDENAS-VALENCIA,* JAY DLUTOWSKI, DAVID FRIES, and
LARRY LANGEBRAKE
University of South Florida, Marine Science College, Center for Ocean Technology, 140 Seventh Ave. S., St. Petersburg, Florida 33626

The design and optimization of light-based analytical devices often The knowledge of a material’s optical properties enables
require optical characterization of materials involved in their construc- modeling and potentially optimization of device performance.
tion. With the aim of benefiting lab-on-a-chip applications, a transmission For instance, the optical constants of a waveguide core and
spectrometric method for determining refractive indices, n, of transparent
cladding directly determine the numerical aperture of a wave-
solids is presented here. Angular dependence of the reflection coefficient
guiding fiber and dictate its transparency. In our work towards
between material–air interfaces constitutes the basis of the procedure.
Firstly, the method is studied via simulation, using a theoretical algorithm
the development of integrated wave-guides for conducting
that describes the light propagation through the sample slide, to assess the spectroscopic measurements on miniaturized systems, rather
potentially attainable accuracy. Simulations also serve to specify the than fiber integration,3,6 the index of refraction of optical
angles at which measurements should be taken. Secondly, a visible light materials as a function of frequency is required. Certain
source and an optical fiber spectrometer are used to perform measure- plastics’ refractive indices are known at specific wave-
ments on three commonly used materials in optical lab-on-a-chip devices. lengths.10,12 However, the method used for processing
A nonlinear regression subroutine fits experimental data to the proposed a material dictates the final optical properties.13 Varying the
theoretical model and is used to obtain n. Because the attainable precision curing time for polymerizing a resin, or applying additives and
using this method of refractive index determination is dictated by the
dyes, as well as mechanical and irradiation processes, are
uncertainty in the transmission measurements, the precision (with 95%
possibilities for inducing small changes in the polymeric
confidence) for mechanically rigid samples, namely glass and poly(methyl
methacrylate) (PMMA), is higher than those estimated for the elastomer structure that can be used to tailor their optical properties and
sample (in-house-molded poly(dimethylsiloxane) (PDMS)). At wave- hence their transmission characteristics.7,8,11,13
lengths with the highest signal-to-noise ratio for the spectrometer setup, Standard techniques for refractive index determination of
the estimated refractive indices were 1.43 6 0.05 (580 nm) for PDMS, 1.54 solid materials include the prism coupling method, ellipsom-
6 0.02 (546 nm) for glass, and 1.485 6 0.005 (656 nm) for PMMA. etry, and spectroscopic techniques.14–19 Reported accuracies of
Accurate refractive index estimations with an average precision equal to these techniques are 0.001 refractive index units (RIU) and
0.01 refractive index units (RIU) were obtained for PMMA and glass 0.005 RIU for prism coupling method and ellipsometry,
samples, and an average precision of 0.09 RIU for the PDMS molded slide respectively.17 These techniques can be elaborate (coupling
between 550 and 750 nm was obtained.
method), and sometimes expensive (especially ellipsometry). A
Index Headings: Refractive index; Optical materials; Plastics; Glasses; simple method for determining specific optical properties
Visible spectroscopy; Instrumental methods.
resulting from the preparation of a film under certain conditions
is desirable. Because of this, and due to the importance of the
refractive index, techniques to measure this variable continue
INTRODUCTION to be reported.14–21 Most standard methods, as well as other
The development of total analysis lab-on-a-chip systems has reports, use coherent monochromatic lasers. However, laser
experienced a fast growth during the last 30 years.1–6 In these sources are generally more expensive, require more laborious
applications, optical sensing techniques are preferred due to alignment, and the results are limited to the radiation
their minimally invasive nature, their virtually instantaneous wavelength provided by the laser. Infrared spectroscopy, which
response, and the large variety of low-cost, small light sources determines both real and imaginary optical constants, is also
and detectors available. Glasses and polymeric materials have quickly becoming a standard methodology,18,19 but optical
been extensively used to fabricate integrated micro-total constants in other ranges of the electromagnetic spectrum are
analysis systems. Due to the ease of processing, which allows also needed. Photometry has been utilized to obtain visible
for micro fabrication outside a clean-room environment, multi-wavelength refractive indices. Nussbaumer et al.17
glasses and polymers have been widely used to conform reported a method based on immersion refractometry that
micro-fluidic elements and/or to fabricate channels that host required an ultraviolet–visible (UV-Vis) spectrometer for
optical fibers.3–6 In some cases, glasses and plastics readily transmission measurements. The accuracy reported was better
lend themselves to fabrication of optically functional elements, than 0.01 RIU. Bass and Weidner15 and Bozlee et al.20 also
enabling their incorporation into sensing devices, facilitating used visible spectroscopy. However, their methods required
the fabrication of total lab-on-a-chip devices.7–9 The wide a powered sample, and, as in Nussbaumer et al.,17 they required
variety of transparent materials that can potentially be used for solvents of known refractive indices. Other works that compete
creating micro-optical devices has created the need for with standard instruments’ accuracy,21–23 although useful for
measurement systems that can optically characterize them. refractive index determinations, are, however, specific either in
the type of mathematical analyses, sample use, or required
transducers. A methodology for refractive index determination
Received 15 August 2005; accepted 9 January 2006.
* Author to whom correspondence should be sent. E-mail: cardenas@ based on reflection losses measured indirectly via transmission
marine.usf.edu was reported by Jung and Rhee.24 From forty-five indepen-

0003-7028/06/6003-0322$2.00/0
322 Volume 60, Number 3, 2006 Ó 2006 Society for Applied Spectroscopy APPLIED SPECTROSCOPY
dently measured angular observations of the polarized re- m ¼ n þ ik ð1Þ
flection components, refractive indices as well as sample
thickness were estimated. In a setup similar to the illustration in If the slide is transparent to electromagnetic radiation at a given
Fig. 1, the magnitude of reflection loss as a function of the wavelength k, then the absorption is equal to zero (k(k) ¼ 0)
incident angle, h (angle that is formed between the slide and the and reflection constitutes the only cause for the beam
beam) can be measured. We reported a pedagogical procedure attenuation.
Reflection coefficients depend not only on the value of the
that evidences the refractive index influence on visible
refractive index of the sample, n1, but also on that of the
transmitted light through transparent polymeric slides.25 Trans-
surrounding fluid (air), n0, and are quantified via Fresnel
mission measurements at four angles and various wavelengths
formulas.26 The parallel, R1p, and perpendicular, Rls, Fresnel
were reported. Refractive indices could then be obtained from
component formulae are given by Eq. 2:
transmission-versus-angle calibration curves. One of the 0   2 1=2 1
method’s advantages is that it does not require the availability
ðn1 =n0 Þ2 cosðhÞ þ ðn1 =n0 Þ2  sinðhÞ
of sample-inert solvents with proper indices of refraction. B C
Rlp ¼ @   2 1=2 A
In this paper, we study the described transmission method for 2 2
ðn1 =n0 Þ cosðhÞ þ ðn1 =n0 Þ  sinðhÞ
determining multi-wavelength n values (in the visible range).
Firstly, simulations serve as a guide to determine the potentially
attainable accuracy and for the experimental setup design. and
Secondly, transmission spectra at various angles are recorded 0   2 1=2 1
for materials common in the fabrication of lab-on-a-chip cosðhÞ  ðn1 =n0 Þ2  sinðhÞ
B C
devices: poly(dimethyl siloxane) (PDMS), poly(methyl meth- Rls ¼ @   2 1=2 A ð2Þ
2
acrylate) (PMMA), and glass slides. Multiple measurements at cosðhÞ þ ðn1 =n0 Þ  sinðhÞ
various angles improve the statistics of the estimated refractive
index. The measured light signals and the simulation algorithm For unpolarized light, the total reflection loss coefficient, Rl, is
are then used in a regression subroutine to determine the index given by
of refraction values of the slide. Proving the hypothesis that Rl ¼ 1=2ðR2lp þ R2ls Þ ð3Þ
measured transmitted signals are a sufficiently strong function
of the angle h, which allows for distinguishing the material
Strictly speaking, the light transmitted power, Tp, of a beam
refractive index, even when using incoherent light, and at what
through the slide is composed (when total internal reflection
degree, constitutes this work’s rationale. Reported experimental does not occur) of various contributions that take place due to
results illustrate the accuracy and precision, and replicated multiple reflections. In Jung and Rhee’s work, all the
measurement tests illustrate the method’s reproducibility. transmitted light contributions were captured by the detector
and were considered in the modeling to determine n.24 If only
PRINCIPLES AND MATHEMATICAL the ‘‘first-order’’ transmitted beam is detected, then
FORMULATION
Tp ¼ ð1  Rl Þ2 ð4Þ
Figure 1 illustrates the transmission setup used to obtain the
refractive indices. As the collimated beam passes through the The exponent arises from the fact that the beam encounters two
slide, it is attenuated due to absorption and reflection. The interfaces as it passes through the slide. Since our source and
angle h and the sample’s complex refractive index, m (or its detector are aligned (as shown in Fig. 1), the detector captures
components, the refractive and absorption indices, n and k, mainly the first-order transmitted light. Assuming, that the first-
respectively), determine the magnitude of this attenuation: order Fresnel loss is the only significant attenuation of the
incident beam, the transmitted Tp can be written as
Tp ¼ Cð1  Rl Þ2 ð5Þ

C is a constant that accounts for the beam’s refraction as it


passes through the slide, which can be calculated as shown in
the Appendix.

MATERIALS, EQUIPMENT, AND


MEASUREMENT PROTOCOL
Microscope glass slides (7.5 3 2.5 cm2, bought from Fisher
Scientific Co.), PMMA (acquired in 12 3 12 in.2 plates from
United States Plastic Corp. and cut into pieces of approximately
2.0 3 5.0 cm2), and PDMS prepared slides are used for the
measurements. PDMS slides were prepared by mixing silicone
curing agent with silicone elastomer base in a 1:10 ratio
(Sylgard 184, Dow Corning). Uncured resin was poured into
plastic molds, covered to prevent contamination, and allowed to
cure overnight, which also permits air bubbles to settle out. The
FIG. 1. Schematic of the used setup for determining refractive indices of resulting thin sheets are cut into samples (1 3 1 cm2). A PMMA
transparent solid slides. slide frame (with an aperture in the center) mounts the PDMS

APPLIED SPECTROSCOPY 323


flexible samples for taking the measurements. All slides are index, n, was determined by least squares best fitting
thoroughly dusted before the measurements. techniques. Figure 2 shows a flow diagram of the strategy
A USB 2000 fiber-optic spectrometer, two 400 lm core followed in this paper. The numerical implementation of the
diameter fiber-optic cables, a CUV-Var variable path-length proposed modeling has two uses: (1) it performs a theoretical
cuvette holder, and an LS1 tungsten lamp (Ocean Optics, analysis on factors that could potentially affect an experiment,
Dunedin, FL) were part of the measurement system. The and (2) it provides a first-principles interpretation algorithm for
mounting components (NCR, Fountain Valley, CA, except as the measurements performed. Figure 3 shows simulated
noted) were: Mounting base, BA2; Filter holder, FH2; 1-in. transmission curves as a function of the incidence angle and
post, TR1; Turntable, RSX1; Right angle bracket, AB90; and refractive index. Figure 3a is a direct theoretical simulation
a 1.5 diameter mounting post and a mounting post clamp (Thor with the set of equations 1–4 and A1–A4. In Figs. 3b and 3c,
Labs, Newton, NJ). The test fixture is assembled as described a normal distribution of randomly generated numbers, with
previously.25 A 1/16-in. aperture drilled into opaque plastic standard deviations of 0.01 and 0.02, respectively, and zero
was placed in the light path to prevent spectrometer saturation. mean for both cases (‘‘white noise’’), are added to the simulated
Optical bench leveling ensures that the beam passes through transmission to generate an ‘‘experimental-like’’ transmission.
the sample center directly over the rotation axis. The magnitude of the added uncertainty is within the typical
In fiber-optic spectrometers, the spectral transmission, often attainable precision for current charge-couple device (CCD)
called transmittance, is given by27 fiber-optic spectrometers.28 Note that the number of angles for
Isample ðkÞ  Idark ðkÞ which the transmission was experimentally simulated is
T ¼ 100 ð6Þ different for Fig. 3b and Fig. 3c, using seven and seventy
Ireference ðkÞ  Idark ðkÞ
equally spaced incident angle data points, respectively. The
where each I value represents the measured intensity at a given original set of data (Fig. 3) and the two ‘‘experimentally
wavelength. The dark, Idark(k) (taken with the room lighting simulated’’ sets of values were input into an optimization
off, and while no light is delivered to the collecting optical search using the algorithm (Eqs. 1–3 and A1–A3) as the
fiber), and reference, Ireference(k), spectra (transmission mea- interpretation model and n as the regressed parameter. The
sured in air) correct for ambient illumination conditions, regression was performed using a bounded simplex method in
allowing meaningful comparison between data sets. The a least squares sense. The search was limited to refractive index
sample measurement, Isample(k), is taken while the slide is values between 1 and 4. The regressed values are compared to
positioned in the beam path. At least five spectral transmission the real values in Fig. 3d. The correspondence between these
replicates were taken at each angle. values indicates that the software numerical double precision
does not add rounding errors to the estimation. The discrete
RESULTS AND DISCUSSION points are regressed values obtained for the two cases with
added error. Figure 3d shows that the regressed values for the
Simulation Results. Equations 1–4 and A1–A4, in the two considered cases appeared with a similar deviation from
Appendix, completely define the transmission of light in the actual value. Two estimators that can be used to quantify
transparent samples as shown in Fig. 2. The feasibility of using this deviation are
this set of nonlinear equations for estimation of refractive " # 
Mean sum of  X N 
indices is first evaluated via a set of simulated transmission  
¼ ðnregressed  nactual Þ =N  ð7Þ
spectra as case studies. Randomly generated white noise was absolute residuals  i¼1 
added to simulated transmission spectra, and the refractive
and " #
X
N
2
Mean RSSQ ¼ ðnregressed  nactual Þ =N ð8Þ
i¼1

Table I has been prepared using Eqs. 7 and 8 on the data


plotted in Fig. 3d.
Effects of Positioning and Number of Angular Measure-
ments. It has been shown via simulation (using the theoretical
route in Fig. 2) that it is possible to vary both the number of
angular experimental data and the detector precision to obtain
a similar precision (estimated via the RSSQ) in the refractive
index estimation. Increasing the number of measured angular
inputs, h, increases the correlation of the data, and may lead to
the conclusion that this effectively reduces the effects of other
experimental errors. Simulation results are used to test this
contention. Randomly chosen sequences of error with a normal
distribution and different standard deviation were added to
simulated transmission curves with different numbers of
equally spaced angles. The data was then regressed, and an
average residual sum was calculated. The mean absolute
residual sum (Eq. 7) was plotted as function of the number of
FIG. 2. Flow chart with the strategy followed for studying the spectrometric angles in Fig. 4, clearly showing the effect of the number of
method presented. angles on the determined accuracy of n.

324 Volume 60, Number 3, 2006


FIG. 3. (a) Simulated transmission as a function of refractive indices and incidence angle. (b) Experiment-like simulated transmission spectra; white noise added has
a standard deviation equal to 0.01. (c) Simulated experiment-like transmission spectra, white noise added has a standard deviation equal to 0.02. (d) Regressed
refractive indices as a function of the actual input value in the simulation.

The effect of the relative position of the angular measure-


ments on the accuracy of the index calculation is also
considered. It has been shown (Fig. 3) that the reflection
coefficient value, Rl, is a strong function of the input angle,
especially for the range 408 , h , 908, and is nearly constant
within the incidence angles of 08 , h , 408. Mean sum of
absolute residuals for randomly uniformly distributed errors
with different standard deviation for two different incident-
angular distributions were calculated. Figure 5 reveals that the
attainable precision in refractive index is nearly insensitive to
the incidence angle positions for the studied cases.
Effects of Imprecision in the Estimation of the Correc-
tion Factor C in Equation 5. The constant C (defined in the
Appendix) depends on both the lens radius and the sample

TABLE I. Comparison between estimated performances for determin-


ing refractive indices using a different number of angularly positioned
detectors and different white noise signals.

Case Figure 3b Figure 3c

Number of angles 7 70
Mean of the added error distribution .01 .02
Mean absolute sum of residuals 8.1 3 103 7.9 3 103 FIG. 4. Calculated mean sum of absolute residuals of determined refractive
RSSQ 1.2 3 104 1.1 3 104 indices as a function of the number of angular measurements for various
precisions in the transmission measurement.

APPLIED SPECTROSCOPY 325


FIG. 7. Transmission spectra as a function of wavelength taken at various
FIG. 5. Mean sum of absolute residuals of determined refractive indices as incidence angles for the glass slide sample.
a function of the number of the precision on the transmission measurement for
two angular distributions. Data for equally spaced angles, between 08 and 908,
are labeled with open circles. The data points illustrated as triangles encompass
five equally spaced angles (between 408 and 908) and one additional measurements. Points below 350 nm are not shown due to the
measurement at h ¼ 08. high noise content of that data. Error bars are shown at
arbitrary points and are two standard deviations in length.
thickness as well as on the refractive index of the sample. The These error bars constitute an estimate of the imprecision due
sample thickness can be obtained with inexpensive calipers that to the lack of repeatability of the spectral measurements. Notice
can resolve up to 25 lm (1 thousandth of an inch). The sample that in general the estimated error bars are smaller for data
thickness measurement uncertainty influences the refractive obtained within the wavelength ranges of 550 nm and 700 nm.
index determination as shown in Fig. 6a. Another aspect to The average values of these estimates calculated for all
consider is the radius diameter imprecision. To provide an idea obtained data points as a function of wavelength within the
of the effect of measuring a lens diameter value with an mentioned range have been calculated from the transmission
imprecision of 625 lm, Fig. 6b is presented. It is expected that curve taken at each angle (Table II). Notice that the magnitude
of the error bars is similar for the glass and PMMA slides
variation in the actual transmission signal due to small
(0.5% transmisttance), but they are, however, considerably
variations in this variable (and even small misalignments28)
higher in the PDMS sample (around 2.0% transmission). The
will be taken into account by the fact that a reference
larger imprecision in the spectral data is probably due to the
measurement (denominator in Eq. 6) is taken.
fact that the PDMS samples are molded in-house and that
PDMS is a flexible material. To obtain the transmission
EXPERIMENTAL RESULTS
measurements, the elastomer was mounted on a frame, and
Figures 7 through 9 depict experimental spectra for glass, even though care is taken to place the sample as flat as possible,
PMMA, and PDMS, respectively, taken at eight different it might be difficult to obtain a high degree of parallelism
incident angles. Equal angular spacing was used for the between the sample’s faces.

FIG. 6. (a) Calculated mean sum of refractive index residuals for an uncertainty of 25 lm as a function of the determined refractive index for various sample
thicknesses. (b) Calculated mean sum of refractive index residuals as a function of n for the same uncertainty in measuring the diameter of various projecting lenses
in a setup similar to that shown in Fig. 1.

326 Volume 60, Number 3, 2006


FIG. 8. Transmission spectra as a function of wavelength taken at various
incidence angles for the PMMA slide sample.
FIG. 9. Transmission spectra as a function of wavelength taken at various
incidence angles for the PDMS sample.
Figure 10 shows calculated refractive indices from the
transmission data for glass, PMMA, and PDMS over the compared with estimated refractive indices in Table III. Values
wavelength range of interest. The error bars presented in Fig. taken from Ref. 10 were reported with a precision of 1 3 104
10 constitute an estimate of experimental uncertainty of the RIU and are rounded to show two or three decimal places and
refractive index determination. This estimate is calculated as
are assumed accurate in order to calculate residuals for the
Tmax;min ðkÞ ¼ Tave ðkÞ62rTexp ðkÞ ð9Þ estimated refractive index values obtained. Table III shows that
the determined refractive index values were considerably
where Tmax,min represent the cases in which 2rTexp is added or higher in magnitude than those previously reported at the
subtracted to the average transmission spectra, Tave, to extremes of wavelength-span readings. At these extremes, the
represent data with a 95% confidence if experimental errors signal-to-noise ratio is lower in the fiber-optic spectrometer
are normally distributed. The transmission standard deviation, setup, as suggested by the raw intensity data versus wavelength
rTexp, is calculated from the experimental replicates. By in Fig. 11. The lowest residual values (0.004–0.005) occur
inputting the values Tmax and Tmin in the regression algorithm, between 656 nm and 700 nm. The mean residual value for
nmax(k) and nmin(k) are estimated. Since it was determined that
refractive index values reported in between the wavelengths of
no numerical error (up to the fourth decimal place) was
550 nm and 752 nm is less than 0.01 RIU (6.6% absolute
generated from the numerical regression algorithm, the values
average deviation), but it has been reported with two decimal
nmax(k) and nmin(k) constitute an estimate of the attainable
places, since the average precision in that frequency range
precision, which considers the experimental reproducibility of
the observed light signals. equals 0.01 RIU. Figure 11 suggests that by using a light

jErrorbarsðkÞj ¼ nmax ðkÞ  nmin ðkÞ ð10Þ

Estimated values of the index of refraction are in agreement


with published results, proving the hypothesis that Eq. 5 can be
used as an interpretation algorithm of the described measure-
ments. The value estimated for PDMS, 1.43 6 0.05 at 580 nm,
agrees with published values.12 The regressed value of 1.54 6
0.02 for the soda lime commercial glass slide differs by 0.02
RIU from the reported value known at 546.07 nm.29 Only
information on the refractive index of PMMA as a function of
wavelength was found.10 These literature reported values are

TABLE II. Average uncertainty of transmission data (%) obtained from


five replicated measurements of each angular spectrum for the three
samples studied.

Angle, degrees 0 40 45 50 55 60 65 75 Average

Glass 0.2 0.5 0.5 0.5 0.5 0.5 0.5 0.4 0.5
PMMA 0.6 0.5 0.4 0.4 0.4 0.4 0.5 0.6 0.5
PDMS 0.8 2.0 1.0 1.0 1.0 2.0 2.0 3.0 2.0 FIG. 10. Refractive indices as function of wavelength for the materials
considered here. See the text for a description of the error-bar calculation.

APPLIED SPECTROSCOPY 327


FIG. 11. (a) Residual values and absolute deviation for refractive index
estimation as a function of wavelength obtained for PMMA. (b) Intensity FIG. 12. Schematic illustrating the beam refraction as it passes through the
spectra showing the relative counts as a function of wavelength to illustrate the sample slide, evidencing the need for a correction factor due to refraction of the
relative magnitude of signal-to-noise ratio with the light source/spectrometer beam.
utilized herein.
applications. The method can only be used in materials that
source and a spectrometer system that provides better light can be formed into slide shapes with parallel faces that can be
detection limits and wider wavelength range, the refractive held in the beam’s path. As this is an intrinsic limitation of the
index determination can be further enhanced. Another error method, it is also worth mentioning that most optical materials
source could be compositional differences between commercial used for lab-on-a-chip development are routinely molded, cast,
PMMA relative to that used in the reference.10 The precision of or cut into thin plates, making the method ideal for such
the method depends on the wavelength (as reproducibility in applications.
spectrometers normally does). Calculated average precisions ACKNOWLEDGMENTS
(between 550 and 750 nm) were 0.02 for the glass, 0.01 for
Dr. Cardenas acknowledges financial support from Consejo Nac. de Ciencia
PMMA, and 0.09 for PDMS. The higher imprecision found for y Technologia, Univ. of South Florida (through Dr. Garcia-Rubio), and Univ.
PDMS is attributed to the fact that the samples were molded, of Guadalajara for the completion of his doctoral studies.
and even though care was taken in the casting and mounting
process, the results were influenced by the flexible nature of the
material. The previously discussed uncertainty in the trans- 1. K. Huikko, R. Kostiainen, and T. Kotiaho, Eur. J. Pharm. Sci. 20, 149
(2003).
mission spectra for the PDMS sample suggests that the 2. S. Metz, R. Holzer, and P. Renaud, Lab on a Chip 1, 29 (2001).
reported method is demanding with respect to the planarity 3. M. Janowiak, A. M. Cardenas-Valencia, M. Hall, and D. P. Fries, Meas.
and parallelism of the faces of the measured samples. Sci. Technol. 16, 729 (2005).
4. D. C. Duffy, J. C. MacDonald, J. A. Schueller, and G. M. Whitesides,
Anal. Chem. 70, 4974 (1998).
CONCLUSION 5. P. K. Dasgupta, I. Y. Eom, K. J. Morris, and J. Li, Anal. Chim. Acta 500,
A relatively simple spectrometric technique for determining 337 (2003).
6. A. M. Cardenas-Valencia, D. P. Fries, X. Ding, H. Broadbent, and L.
refractive indices as a function of wavelength via the described Langebrake, 2004 Proceedings of the Micro-total Analysis Systems
interpretation model and low-cost optical components was Conference (Sweden, 2004), vol. 1, p. 114.
presented. Uncertainty in the transmission spectral measure- 7. R. Horváth, L. R. Lindvold, and N. B. Larsen, Micromech. Microeng. 13,
ments limits the attainable precision of the measured refractive 419 (2003).
indices with the presented method. Average refractive index 8. X. M. Zhao, S. P. Smith, M. Prentiss, and G. M. Whitesides, Conference
Proceedings - Lasers & Electro-Optics Society Annual Meeting-CLEO,
values estimated from eight angular measurements and vol. 11 (IEEE, Piscataway, NJ, 1997).
comparison with previously reported values10 suggest accura- 9. K. Hosokawa, K. Hanada, and R. Maeda, J. Micromech. Microeng. 12, 1
cies down to 0.005 RIU (for PMMA). Even though other (2002).
methods have been reported to provide better precision and 10. N. G. Sultanova, I. D. Nikolov, and C. D. Ivanov, Opt. Quantum Electron.
accuracy than the presented methodology, the described 35, 21 (2003).
11. K. Hoshino and I. Shimoyama, J. Micromech. Microeng. 13, 149 (2003).
approach allows one to report accurate refractive indices with 12. J. Brandrup and E. Immergut, Eds., Polymer Handbook (Wiley
a precision of at least 0.01 RIU, attractive for various Interscience, New York, 1989).

TABLE III. Comparison between refractive index values for PMMA, obtained with the method described herein, and those reported previously by
Sultanova et al.10

Wavelength nm 436 486 546 588 633 656 703 752

Estimated herein 1.71 6 0.08 1.66 6 0.06 1.57 6 0.03 1.50 6 0.02 1.48 6 0.01 1.485 6 0.005 1.49 6 0.02 1.50 6 0.03
Previously reported 1.50 1.50 1.49 1.49 1.49 1.489 1.49 1.49

328 Volume 60, Number 3, 2006


13. B. Schnyder, T. Lippert, R. Kötz, A. Wokaun, V. M. Graubner, and O. APPENDIX
Nuyken, Surf. Sci. 532, 1067 (2003).
14. I. L. Morris and T. E. Jenkins, J. Phys. E: Sci. Instrum. 22, 27 (1989). The light beam refracts upon entering the slide. The refraction
15. J. D. Bass and D. J. Weidner, Rev. Sci. Instrum. 55, 1569 (1984). angle h 0 is related to h (Fig. 1) by
16. A. R. Reisinger, H. B. Morris, and K. L. Lawley, Opt. Eng. 20, 111 (1981). h i
17. R. J. Nussbaumer, M. Halter, T. Tervoort, W. R. Caseri, and P. Smith, J. h 0 ¼ sin1 ðnair =nÞsinðhÞ ðA1Þ
Mater. Sci. 40, 575 (2005).
18. C.-P. E. Varsamis, Appl. Spectrosc. 56, 1107 (2002).
19. D. S. Moore, S. D. McGrane, and D. J. Funk, Appl. Spectrosc. 58, 491 The beam refraction reduces the amount of light received by
(2004). the optical detector. It can be proven that the center-to-center
20. B. J. Bozlee, G. J. Exharos, A. E. Jimenez, and S. L. van Swam, J. Chem.
Educ. 79, 619 (2002).
distances between the detector and beam projection is30
21. Y. Ding, Z. Q. Cao, and Q. S. Shen, Opt. Quantum Electron. 36, 489 dcc ¼ t sinðh  h 0 Þ=cosðh 0 Þ ðA2Þ
(2004).
22. L. A. Ageev, V. K. Miloslavskii, O. V. Tyutyunnik, and Kh. I. El’ashkhab,
Zh. Prikl. Spektrosk. 68, 270 (2001).
The cross-sectional area overlapping the beam projection and
23. Y. R. Wang, X. M. Qu, L. Z. Cai, and B. M. Ma, J. Mod. Opt. 46, 1369 the collection lens is twice the segment between the line that
(1999). crosses the intersections of the circles (shaded intersection in
24. C. Jung and B. K. Rhee, Appl. Opt. 41, 3861 (2002). Fig. 12). One of the segment’s areas can be written as
25. J. Dlutowski, A. M. Cardenas-Valencia, D. P. Fries, and L. Langebrake, J. a function of the center-to-center distance and the radius of the
Chem. Educ., paper in press (2005).
26. G. R. Fowles, Introduction to Modern Optics (Dover Publications, New
collecting lenses, r, in front of the detector:
h i qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
York, 1975), 2nd ed., pp. 43, 44.
27. Operating Manual and User’s Guide: S2000 Fiber Optic Spectrometers Aseg ¼ r a cos ðdcc=2Þ=r  ðdcc=2Þ r 2  ðdcc=2Þ2 ðA3Þ
2
and Accessories (Ocean Optics, Inc., Dunedin, FL, 2000).
28. A. M. Cardenas-Valencia, R. H. Byrne, and E. T. Steimle, Sens. Actuators,
B, paper in press (2005). The correction factor is then given by the intersected area and
29. E. Hauck, Fisher Brand Scientific, private communication (October 27, the original area of the beam reference when no sample is in
2004). between the delivering fiber and the detector.
30. F. W. Sears and M. W. Zemansky, Fisica Universitaria, Pearson Education
de Mexico S.A. de C. V. (1999). C ¼ 2Aseg =pr 2 ðA4Þ

APPLIED SPECTROSCOPY 329

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