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Polarized Light Spectroscopies
Polarized Light Spectroscopies
Polarized Light Spectroscopies
Polarized Light Spectroscopies
By Professor Robert W. Collins Apr 29 2011
Robert W. Collins, Center for Photovoltaics Innovation and Commercialization and
Department of Physics and Astronomy, University of Toledo, Toledo OH 43606
Corresponding author: rcollin8@utnet.utoledo.edu
Introduction
Thin film and multilayered materials having thicknesses on the nano to microscale (0.5
nm 5 μm) are critical components for numerous technologies. Substrates on which
these materials are fabricated can range in size from a few mm2 for specialized single
crystals designed for lattice matching and exceptional single crystalline quality in thin
film form, to m2 for glass plates designed for low cost production of amorphous,
nanocrystalline, or polycrystalline thin films.
Increases in the functionality of films and multilayers have led to a growing demand for
probes of their thicknesses and other key properties, applicable at all technology
development stages [1]. Polarized light spectroscopies, encompassing ellipsometry and
polarimetry performed in reflection, serve as noninvasive optical probes of films and
multilayers (see Fig. 1) [26]. Through the additional measurement of phase shift
difference, polarized light spectroscopies achieve significant advantage over
reflectometry.
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Figure 1. Optical configurations are shown for (a) ellipsometry, and (b,c) polarimetry. Instruments include: (a)
rotatingpolarizer spectroscopic ellipsometer; (b) single rotatingcompensator polarimeter for Stokes vector
spectroscopy, and (c) dual rotatingcompensator polarimeter for Mueller matrix spectroscopy.
All configurations incorporate a detection system consisting of a spectrograph and photodiode array for high
speed spectroscopy. Ref.: R.W. Collins, I. An, J. Li, and J.A. Zapien, “Multichannel ellipsometry”, in: H.G. Tompkins
and E.A. Irene, (eds.), Handbook of Ellipsometry, (William Andrew, Norwich NY, 2005), p. 481.
Reflectometry exploits the change in real irradiance I upon reflection; however, the
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technique of ellipsometry exploits the change in a complex polarization state parameter ξ,
which includes both a relative amplitude |ξ| and a phase difference δ: ξ = |ξ|exp(iδ) [2].
Thus, the irradiance change upon reflection is characterized by the reflectance R = Ir/Ii ,
the ratio of the reflected (r) to incident (i) beam irradiances, whereas the polarization
state change is described analogously, but as a complex number ρ = ξr/ξi = (|ξr|/|
ξi|)exp{i(δr δi)}.
Thus, ellipsometry provides two angles, a ratio of the relative amplitudes defined
(historically) by ψ = tan1 (|ξr|/|ξi|), and a shift (upon reflection) in the phase differences.
Δ = δr δi [2]. Ellipsometry is less sensitive to the surface defects and macroscopic
roughness that may scatter power out of the optical beam because, ultimately, it is based
on the measurement of the shape (not the size) of the polarization ellipse, characterized
by tilt and ellipticity angles (Q, χ). The ellipsometry angle Δ also exhibits extraordinary
sensitivity to film thickness. High precision ellipsometers can detect the formation of
hundredths of a monolayer, while characterizing the complex dielectric function of thin
films at the monolayer level [7].
Ellipsometry Measurement
The simplest ellipsometry measurement is that of a bare isotropic substrate. If the
dielectric function εa of the ambient medium (typically air or vacuum) and the oblique
angle of incidence θi are known, then (ψ, Δ) provide directly the real and imaginary parts
(ε1s, ε2s) of the complex dielectric function of the substrate for the given optical
wavelength λ of measurement [2]. This capability provides the unique opportunity for
spectroscopic ellipsometry to measure directly the wavelength or photon energy (ħω)
dependence of the complex dielectric function εs. Thus, spectroscopic ellipsometry of
substrates or opaque thin films enables development of a database of material dielectric
functions [8] that can then be applied to assist in the analysis of ellipsometry data on
single thin films and multilayers.
The next step in the progression of ellipsometric measurement involves determination of
the thickness d and the real and imaginary parts of the complex dielectric function (ε1f,
ε2f) of a single unknown ideal, isotropic thin film on a known isotropic substrate. Because
there are three unknowns in a single photon energy problem and only two data values
(ψ, Δ), multiple measurements are required [2]. Because spectroscopic ellipsometry is
powerful in its own right, this same multiple measurement approach is also most
desirable for solving the single film data analysis problem. Although there is always one
more unknown parameter, d, than measured (ψ, Δ) values, it is still possible to solve the
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single film problem using a single pair of (ψ, Δ) spectra [9]; however, even greater
success results from analyzing multiple spectra at different θi [10].
Features in the dielectric function (ε1, ε2) of a substrate or thin film can be described by
lineshape parameters, including amplitudes An, energies En, and broadenings Γn ,which
provide information on physical characteristics [11,12]. For example, An reflects material
density; En reflects composition, strain, and material temperature; and Γn reflects defect
density or grain size, and ordering. In many cases, such information cannot be
determined directly and must be established through correlations with direct
measurements. If εf can be expressed accurately as an analytical function of lineshape
parameters, then the single film analysis problem can be reduced to leastsquares
regression determination of only ħωindependent parameters. The validity of the best
fit model for (ε1f, ε2f) is evaluated using the mean square error [13].
A single thin film on a substrate can rarely be modeled adequately assuming a single
layer between the semiinfinite ambient and substrate. Film surfaces and interfaces are
microscopically rough to some degree with possible film/substrate interdiffusion, as well.
In fact, microscopic roughness, i.e., roughness having an inplane scale much smaller
than the light wavelength, can be incorporated into the optical model as one or more
layers. The complex dielectric functions of these layers are modeled as effective media of
the underlying and overlying materials. The Bruggeman approximation has been applied
most widely for determining ε for microscopic mixtures based on the dielectric functions
and volume fraction of the components [14,15]. Consequently, roughness regions can be
incorporated into least squares regression through the addition of ħωindependent
thickness parameters [13].
Polarimetry Measurement
The presence of a variety of nonidealities in thin films motivates spectroscopic
polarimetry, the measurement of the fourcomponent Stokes vector of the optical beam
before (Si) and after (Sr) oblique reflection [16]. This vector describes not only the
polarization ellipse shape (Q, χ), but also the irradiance I and degree of polarization p. I
and p can provide information on macroscopic roughness, whose inplane scale is on the
order of the wavelength and scatters irradiance out of the beam, as well as on non
uniformities that lead to a distribution of properties over the probed area typically 0.1
1 cm2. By expanding polarimetry to the measurement of the sample's 4x4 Mueller matrix
MS , anisotropic systems can be characterized including thicknesses and principal axis
complex dielectric functions of substrates and films [13,16].
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Outlook
From research to manufacturing, there exists a critical need to perform polarization
spectroscopies at high speed from milliseconds to seconds (see Fig. 1). For example in
research, such measurements performed in situ and in real time during thin film growth at
a single spot on the substrate surface can provide critical information on the development
of optimum processes (see Fig. 2). For evaluating the uniformity of optimum processes
and transitioning to full scale manufacturing, ex situ mapping spectroscopies are critical,
in which case measurements are performed on a grid over the full surface area of the
film/substrate (see Fig. 3). Finally, online single point or mapping polarization
spectroscopies can be applied to monitor production output.High speed requires
integration of detector arrays into the instruments, and these challenges are compounded
by the need to extract spectra in the Stokes vector of the beam or the Mueller matrix of
the sample in many applications [1719]. In fact, these challenges have defined the
current directions in instrumentation development [20].
Figure 2. Results are shown for (a) the effective layer thickness and (b) the real and imaginary parts of the dielectric function from a
leastsquares regression analysis of spectroscopic ellipsometry data collected during the growth of a ptype amorphous silicon (aSi:H)
layer component of an aSi:H nip solar cell on a polymer substrate in a rolltoroll plasma deposition system. The effective thickness is
respectively, which are all determined in the analysis, and fs and fi are the player volume fractions in the surface and interface
roughness layers. The dielectric function is deduced as an analytical formula (CodyLorentz expression) which provides the band gap of
the player material at the deposition temperature (108°C). Ref.: L.R. Dahal, Z. Huang, D. Attygalle, M.N. Sestak, C. Salupo, S. Marsillac,
and R.W. Collins, "Application of real time spectroscopic ellipsometry for analysis of rolltoroll fabrication of Si:H solar cells on polymer
substrates", 35th IEEE Photovoltaics Specialists Conference, June 2025, 2010, Honolulu, HI, (IEEE, Piscataway NJ, 2010) p. 631.
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Figure 3. (a) A map of the bulk layer thickness determined by ex situ spectroscopic ellipsometry at high speed is shown for a CdS thin
film deposited on top of a NSGPilkington TEC15 SnO2:F coated glass panel. The mapped area is 35 cm x 80 cm. The two plots (top
and right) show the CdS thickness variations along the X and Y axes. The experimental (y, D) spectra and best fit results for the two
indicated points are shown in (b). Experimental and best fit spectra at positions (X = 2.0, Y = 0) and (X = 21.8, Y = 0) show the effect of
differences in the CdS thickness; confidence limits and mean square errors are also given.
Ref.: Z. Huang, J. Chen, M. N. Sestak, D. Attygalle, L.R. Dahal, M.R. Mapes, D.A. Strickler, K.R. Kormanyos, C. Salupo, and R. W.
Collins, "Optical mapping of large area thin film solar cells", 35th IEEE Photovoltaics Specialists Conference, June 2025, 2010,
Honolulu, HI, (IEEE, Piscataway NJ, 2010) p. 1678.
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References
[1] I. P. Herman, Optical Diagnostics for Thin Film Processing, (Academic, New York,
1995).
[2] R. M. A. Azzam and N. M. Bashara, Ellipsometry and Polarized Light, (NorthHolland,
Amsterdam, 1977).
[3] H.G. Tompkins, A User’s Guide to Ellipsometry, (Academic, New York, 1992).
[4] H. Fujiwara, Spectroscopic Ellipsometry: Principles and Applications, (John Wiley &
Sons, West Sussex UK, 2007).
[5] H.G. Tompkins and E.A. Irene, (eds.), Handbook of Ellipsometry, (William Andrew,
Norwich NY, 2005).
[6] Five conferences on spectroscopic ellipsometry and polarimetry have been held. The
proceedings of these conferences provide snapshops of this rapidly evolving field:
(a) A. C. Boccara, C. Pickering, and J. Rivory, (eds.), Proceedings of
the First International Conference on Spectroscopic Ellipsometry,
(Elsevier, Amsterdam, 1993); also published as Thin Solid Films 233
234 (1993);
(b) R. W. Collins, D. E. Aspnes, and E. A. Irene, (eds.), Proceedings of
the Second International Conference on Spectroscopic Ellipsometry,
(Elsevier, Amsterdam, 1998); also published as Thin Solid Films 313
314 (1998);
(c) M. Fried, J. Humlicek, and K. Hingerl, (eds.), Proceedings of the
Third International Conference on Spectroscopic Ellipsometry,
(Elsevier, Amsterdam, 2003);
(d) H. Arwin, U. Beck, and M. Schubert, (eds.), Proceedings of the
Fourth International Conference on Spectroscopic Ellipsometry,
(WileyVCH, Weinheim Germany, 2007);
(e) H.G. Tompkins et al., (eds.), Proceedings of the Fifth International
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Conference on Spectroscopic Ellipsometry, (Elsevier, Amsterdam,
2011, in press).
[7] D.E. Aspnes and A.A. Studna, “High precision scanning ellipsometer”, Appl. Opt. 14,
220 (1975).
[8] Handbooks tabulate the ħωdependence of the optical properties of solids. Data are
presented in terms of the real and imaginary parts of the complex dielectric function (ε1,
ε2), or the index of refraction and extinction coefficient (n, k). The two pairs are related
according to ε1 = n2 k2 and ε2 = 2nk. See, for example:
(a) E.D. Palik, Handbook of Optical Constants of Solids, (Academic, New York 1985); (b)
E.D. Palik, Handbook of Optical Constants of Solids II, (Academic, New York, 1991).
[9] D.E. Aspnes, “Spectroscopic ellipsometry”, in: B.O. Seraphin (ed.), Optical Properties
of Solids: New Developments, (NorthHolland, Amsterdam, 1976) p. 799.
[10] J.A. Woollam, B. Johs, C.M. Herzinger, J.N. Hilfiker, R. Synowicki, and C. Bungay,
“Overview of variable angle spectroscopic ellipsometry (VASE), Parts I and II”, Proc. Soc.
PhotoOpt. Instrum. Eng. Crit. Rev. 72, 3 (1999).
[11] F. Wooten, Optical Properties of Solids (Academic, New York, 1972).
[12] R.W. Collins and A.S. Ferlauto, “Optical physics of materials”, in: H.G. Tompkins and
E.A. Irene, (eds.), Handbook of Ellipsometry, (William Andrew, Norwich NY, 2005), p. 93.
[13] G.E. Jellison, Jr., “Data analysis for spectroscopic ellipsometry”, in: H.G. Tompkins
and E.A. Irene, (eds.), Handbook of Ellipsometry, (William Andrew, Norwich NY, 2005), p.
237.
[14] D.E. Aspnes, “Optical properties of thin films”, Thin Solid Films 89, 249 (1982).
[15] H. Fujiwara, J. Koh, P.I. Rovira, and R.W. Collins, “Assessment of effectivemedium
theories in the analysis of nucleation and microscopic surface roughness evolution for
semiconductor thin films”, Phys. Rev. B 61, 10832 (2000).
[16] P. S. Hauge, “Recent developments in instrumentation in ellipsometry”, Surf. Sci. 96,
108 (1980).
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[17] I. An, Y.M. Li, H.V. Nguyen, and R.W. Collins, “Spectroscopic ellipsometry on the
millisecond time scale for realtime investigations of thin film and surface phenomena”,
Rev. Sci. Instrum. 63, 3842 (1992).
[18] J. Lee, P.I. Rovira, I. An, and R.W. Collins, “Rotating compensator multichannel
ellipsometry: applications for real time Stokes vector spectroscopy of thin film growth”,
Rev. Sci. Instrum. 69, 1800 (1998).
[19] J. Lee, J. Koh, and R. W. Collins, "Dual rotatingcompensator multichannel
ellipsometer: instrument development for highspeed Mueller matrix spectroscopy of
surfaces and thin films", Rev. Sci. Instrum. 72, 1742 (2001).
[20] R.W. Collins, I. An, J. Li, and J.A. Zapien, “Multichannel ellipsometry”, in: H.G.
Tompkins and E.A. Irene, (eds.), Handbook of Ellipsometry, (William Andrew, Norwich
NY, 2005), p. 481.
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