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