Measurement of the Lorenz-Mie Scattering of a Single Particle:

Polystyrene Latex
DAVID T. PHILLIPS, 1 P H I L I P J. WYATT, A~D R I C H A R D M. B E R K M A N

Science Spectrum, Inc., Santa Barbara, California 93105

Received June 11, 1970; accepted June 12, 1970

The differential intensity of polarized light scattered from a single polystyrene la-
tex sphere has been measured for the first time. Theoretical anMysis of the measured
intensities yielded values of the refractive index and size with relative errors of less
than 1%. This optical size determination is in significant disagreement with values
quoted by the manufacturer.

INTRODUCTION AND SUMMARY shadowing, sizes obtained in this way have

This article reports what we believe to be never been regarded as entirely satisfactory.
the first accurate measurement of the differ- Optical measurements using "monodisperse"
ential scattered intensity of light from a suspensions have disagreed (4) with electron
single mieroparticle. The radius and refrac- microscope results by about 5 %.
tive index of the particle were determined The scattering curves presented here are
with an error of less than 1%. The pioneering essentially identical to numerous other
efforts of Gueker and Egan (1) produced a curves obtained from individual particles of
rough measurement of differential scattered the same lot. However, the radius de-
intensity from a single sphere of dioctalph- termined from our measurements is ten
thalate in 1961. No similar measurements standard deviations from the radius quoted
since that time are known to us. by the manufacturer, whose value was pre-
The excellent agreement with theory of sumably determined by electron microscope
the present measurements demonstrates techniques.
that the optical scattering properties of any EXPERIMENTAL TECHNIQUE
spherically symmetric micropartiele can be
accurately measured by our instrument. By The light scattered by a single polystyrene
making similar measurements sequentially latex particle (Dow Chemical Run LS-1028-
on individual particles of a microparticle E with nominal diameter 1099 -4- 5.9 nm)
suspension, it is now also possible to de- was measured as a function of angle with the
termine size and composition distributions use of a Differential I I light-scattering pho-
accurately. tometer (Science Spectrum, Inc.).
Polystyrene latex particles with radii Single particles were introduced into the
200 to 2000 nm have become light-scatter- instrument by nebulizing a water suspen-
ing standards for a wide range of applications sion. This method of dispersing the particles
(2, 3). In the past, the size of individual par- leaves many of them charged and thus per-
ticles was determined from electron micro- mits their individual manipulation with elec-
graphs. Since preparation for the electron tric fields. This basic method is similar to
microscope Mways involves exposure to that used by Millikan (5) in his classic study
vacuum and, for example, may require metal of the electron charge.
A radial electric field similar to that de-
1 On leave from Department of Physics, Uni- scribed by Fletcher (6) kept theiparticles
versity of California, Santa Barbara, CMifornia. from drifting horizontally: The vertical posL
Journal of Colloid and Interface Science, Vol. 34, No. 1, September1970
159
160 PHILLIPS, WYATT, AND BEI~KMAN

LATEX

HORIZONTAL P O L A R I Z A T I O N

BACKGROUND

0° 25 ° 50 ° 75° lOB ° 125 ° 150 ° 175 °

O° 25" 50° 75" 100° 125° 150° 175°
SCATTERING ANGLE
SCATTERING ANGLE

FIG. 1. Differential scattered intensity of 514.5 FIG. 2. Same as Fig. 1, but for 514.5 nm hori-
nm vertically polarized light from a single poly- zontally polarized light. (Two traces.)
styrene latex sphere. (Two traces.)
1P21) and recorded as a function of angle on
tion of the particles was controlled by an an X-Y recorder.
electrooptieal serv0 system. The noise in the measured intensity, par-
The particle selected was held near the ticularly evident in Fig. 2, arose from defects
center of the light-scattering cell by manual of the laser optieN system. Variations in in-
control of the electrical fields until all other tensity were caused by slight particle motion
particles had been swept away. Control of through the striations of the beam.
the fields was then transferred to the servo The differential scattered intensities for
system, which allowed the particle to be held vertically and horizontally polarized incident
indefinitely. Single particles have been held light are shown, respectively, in Figs. 1 and
for severn hours without further attention 2. Corresponding theoretical computations
from the operator, although violent atmos- for a small range of radius and refractive
pheric disturbances such as sonic booms index variations about the "best fit" values
caused some particles to be lost. (600 4- 5 nm, and 1.59 4- 0.01, respectively)
The light source was a pulsed argon ion are shown in Figs. 3 through 6. The high
laser ( T R W Model 83-A) with multimode sensitivity of the scattering curve to small
plane polarized output at a wavelength of variations in the parameters is clear from
514.5 nm. A wavelength selector removed these figures. The " X ' s " correspond to se-
the other wavelengths present, but intro- lected data at extrema and inflection points
duced spatial variations (striations)in the from Figs. 1 and 2.
beam intensity. The laser beam was focused
to a region approximately 1 mm square. ANALYSIS
Scattered light was detected with an angular The scattering of radiation from a ho-
resolution of 2 ° by a photomultiplier (RCA mogeneous sphere has been understood
Jouvna~ of Colloid and Interface Science, V o l . 34, N o . 1, S e p t e m b e r 1970
 MEASUREMENT OF SINGLE PAI{TICLE SCATTERING 161

I/:: i i ¸

~: 80" 40' 50" 80 100' 120' 140" 150~ 180~ " 20"
L
40" 60" 80" 1~" 120" 140~ 160" 180"
SCAITERING ANGLE
SCATTERING ANGLE

FIG 3. Computer-generated differential scat- FI(I. 5. Computer-generated differential scat-

tered ii,tensities for 514.5 nm vertically polarized tered intensities for 514.5 nm vertically polarized
light scattered from a homogeneous 600 nm-radius light scattered from a homogeneous sphere of re-
sphere for refractive indices 1.58, 1.59, and 1.60. fractive index 1.59 for the three radii: 595,600, and
Some data points from Fig. 1 are shown. 605 nm. Some data points from Fig. 1 are shown.

o" 2ff 40- 6o" 80~ 1~" 1~o" 14o" 168" 18o"
O" 20" 40 ~ 60" 80" 180" 120" 140 ~ 16~" 180'
SCATIERING ANGLE
SCATTERING ANGLE
FIG. 6. Same as Fig. 5, but for horizontally
F~o. 4. Same as Fig. 3, but for horizontally polarized light. Some data points from Fig. 2 are
polarized light. Some data points from Fig. 2 are shown.
shown.
m a t h e m a t i c a l l y since t h e w o r k of C l e b s e h m i s t a k e n l y (9) a s c r i b e d to M i e (10). F o r a
(7) in 1861. L o r e n z (8) p r e s e n t e d t h e solu- c o n t e m p o r a r y t r e a t m e n t of light s c a t t e r i n g ,
t i o n of t h e s c a t t e r i n g p r o b l e m in its m o d e r n t h e r e a d e r is r e f e r r e d to t h e definitive t e x t b y
f o r m in 1890, t h o u g h t h e r e s u l t s are u s u a l l y K e r k e r (11).
Journal of Colloid and Interface Science, Vol. 34, No. l, September 1970
162 PHILLIPS, WYATT, AND BERKMAN

A high-speed computer (CDC 6400) scattered intensities of light from a ho-

generated and plotted the relative scattered mogeneous sphere, our calculations have
intensities as a function of particle size and shown no hint of ambiguity. As a result, we
refractive index over a range of values. The believe that our results represent a unique
refractive index variation was limited to the determination (to within experimental error)
physically reasonable range 1.2 to 2.0, and of the optical parameters of the single par-
the radius variation was restricted to the ticles we have examined.
range 350 to 700 nm. (Note that the number
of peaks obsel~ed for horizontally polarized ACKNOWLEDGMENT
light is approximately equal to 2~r/X.) The This work was supported by the U. S. Army
"best fit" parameters were obtained b y Medical Research and Development Command,
successive approximation. The theoretical Office of the Surgeon General.
curves were normalized to t h e experimental
values at the first maximum. Below a radius REFERENCES
of 500 n m it was impossible to obtain a 1. GUCKER, F. T., AND EGAN, J. J., ] . Colloid Sci.
sufficient number of peaks, irrespective of the 16, 68 (1961).
refractive index value assigned. At the manu- 2. KRATO~VlL,J. P., Anal. Chem. 36,4581% (1964).
facturer's quoted radius of 550 nm, no varia- 3. Y. RIM]~ERG, D. AND THOMAS, J. W . , fl: Colloid
tion of refractive index could force the theo- Interface Sei. 32,101 (1970).
retical curves to reflect extrema at the same 4. KaATOHVlL,J. P., ANn SMART, C., J. Colloid
Sci. 20,875 (1965).
positions as those measured. I t was only very
5. MILLIKAN,R. A., Phys. Rev. 32,349 (1911).
near to a radius of 600 n m that the theo- 6. FLETCHEn,H., Phys. Rev. 4,440 (1914).
retically predicted curve suddenly matched 7. CLEeSCH, A., J. Reine Angew Math. 61, 195
the experimental data. Since each theoreti- (1863).
cal curve was normalized at only one point, 8. LOnENZ, L. ¥., Vidensk. Selsk. Skrifter 6, 1
the remarkably good fit of the computer- (1890). (Translated into French 1896. Oeuv-
generated curve was further evidence that res Scientifiques de L. Lorenz, Librairie
the "best fit" parameters were unique. Lehmann, reprinted 1964, Johnson, New
The work b y Mireles (12) showed that the York.)
experimental procedures and deductions of 9. MIE, G., Ann. Physi]~ 25,377 (1908).
10. LOGAN,N., Proc. I E E E 53,733 (1965).
Farone and Xerker (13) on light scattering 11. KERKER, M., "The Scattering of Light and
from an infinite circular cylinder did indeed Other Electromagnetic Radiation." Aca-
result in a unique determination of the ra- demic Press, New York, 1969.
dius and refractive index of the cylinder. 12. MIRELES,R., J. Math. Phys. 45,179 (1966).
Though we know of no explicit mathematical 13. FARONE, W. A., AND KERKER, M., dr. Opt. Soc.
proof of the uniqueness of the differential Amer. 56,481 (1966).

Journa~ of Colloid and Interface Science, Vol. 34. No. 1, September 1970