Macromolecules 1998, 31, 9247-9252 9247

Small-Angle Neutron Scattering Studies on Thin Films of Isotopic

Polystyrene Blends

D. L. Ho and R. M. Briber*
Materials and Nuclear Engineering Department, 2100 Marie Mount Hall, University of Maryland,
College Park, Maryland 20742

R. L. Jones and S. K. Kumar

Department of Materials Science and Engineering, Pennsylvania State University,
University Park, Pennsylvania 16802

T. P. Russell
Department of Polymer Science and Engineering, University of Massachusetts,
Amherst, Massachusetts 01003
Received May 7, 1998; Revised Manuscript Received July 20, 1998
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ABSTRACT: Thin films of various thicknesses ranging from 100 µm down to 1390 Å of an isotopic
polystyrene blend were examined using small-angle neutron scattering. It was found that absolute
scattering data with reasonable signal-to-noise could be obtained from single films as thin as 1390 Å
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supported on single-crystal Si wafers by optimizing the neutron optics and by carefully eliminating
background arising from the substrate. The wave vector dependence of the neutron scattering from all
of the films examined could be described using the random phase approximation with the same Flory-
Huggins interaction parameter and RG values as found in the bulk. No dependence of the scattering on
film thickness was found. These results demonstrate that quantitative small-angle neutron scattering
measurements can be obtained from single ultrathin films of polymer mixtures.

Introduction I(0) and RG obtained suggest that the film is phase

In recent years small-angle neutron scattering (SANS) separated. Phase separation of the blend after anneal-
has been widely used to characterize the thermodynam- ing at 130 °C would indicate a large shift (∆TC ∼ 60
ics of polymer mixtures.1-3 These studies have gener- °C) in the upper critical solution temperature (UCST)
ally focused on bulk samples due to the limited neutron phase boundary due to finite size effects. In an optical
flux available at most sources. However, Russell et al.4 microscope study, Reich and Cohen6 have found that
have recently utilized SANS to qualitatively study the the lower critical solution temperature (LCST) phase
structure of films of block copolymers and polymer boundary for polystyrene and poly(vinyl methyl ether)
mixtures with thicknesses as small as 1000 Å. Block (PVME) blends was observed to begin to shift signifi-
copolymers of polystyrene (PSH) and deuterated poly- cantly for films as thick as 1 µm (i.e., ∆TC ∼ 5 °C)
(methyl methacrylate) (dPMMA) and homopolymer depending on the details of sample preparation. Sub-
blends of PSH and deuterated polystyrene (PSD) were stantially larger shifts were observed for thinner films
investigated in their experiments. All of the thin-film (∆TC ∼ 40 °C for ∼ 0.1 µm). The molecular weights used
samples were prepared by spin coating films onto silicon by Reich and Cohen were quite low (PS MW ) 36 000
single-crystal substrates. For the PSD (Mw ∼ 760 K g/mol and PVME MW ) 10 700 g/mol), indicating that
g/mol)/PSH (Mw ∼ 690 K g/mol) homopolymer blends finite size effects may be operative at film thicknesses
the experiments were performed on a ∼1700 Å thick 102 RG or greater.
thin film of a 50/50 mixture. SANS was measured for Recent theoretical calculations and simulations7-10
the as-spun film and after annealing at 130 °C for 15 have predicted that the miscibility of a polymer blend
h. The data for the as-spun film were fit to a Debye should be affected for film thicknesses less than the
scattering function which yielded a radius of gyration, contour length of the chain. A polystyrene chain with
RG ) 470 ( 50 Å, and I(0) ) 2000 ( 500 cm-1. For the a molecular weight of 105 g/mol has a contour length of
annealed film an RG ) 1900 ( 500 Å and I(0) ) 54 000 approximately 0.3 µm. These experimental and theo-
( 9000 cm-1 were obtained. These values correspond retical results indicate that finite size effects may be
to a Kuhn segment length of ∼56.5 Å and χ of ∼2.9 × found in films many times thicker than RG. The range
10-4. The calculated values in the bulk for this blend of differing results from both theory and experiments
(at 130 °C) are I(0) ) 2360 cm-1, RG ) 230 Å, χ ) 2.1 × where both stabilization and destabilization have been
10-4, and TC ) 67 °C based on the work by Londono et observed led to the conclusion that additional SANS
al.5 As discussed by Russell et al., the deviation from experiments on thin films of a model blend system (PSD/
the bulk values, particularly for RG of the as-spun film, PSH) were needed to gain insight into this important
could be due to the homopolymers being trapped in a issue. Prior to investigating the details of the phase
nonequilibrium conformation during the spinning pro- diagram and changes in TC for thin films, experimental
cess. For the annealed film the very large values for work was required to develop the SANS technique to
determine the limit of thickness for a single film where
* To whom correspondence should be addressed. I(0), RG, and χ could be determined quantitatively using
10.1021/ma980733s CCC: $15.00 © 1998 American Chemical Society
Published on Web 12/04/1998
9248 Ho et al. Macromolecules, Vol. 31, No. 26, 1998

Table 1. Characteristics of the Homopolymersa Table 2. Thickness Measurements (in Å)

PSD: Mw ) 289 000 Mw/Mn ) 1.04 nominal thickness ellipsometrya XRRb thickness used
PSH: Mw ) 284 000 Mw/Mn ) 1.05
1000 1390 ( 25 1430 1390
a PSD/PSH blend composition: 25/75 by weight. 2000 2340 ( 25 N/A 2340
4000 4270 ( 250 N/A 4270
7000 6960 ( 75 N/A 6960
current neutron sources. The ability to perform these 9000 9170 ( 30 N/A 9170
thin-film experiments in normal transmission scattering
a Errors reflect range in values determined by several measure-
geometry in a reasonable amount of time with a good
ments at different laboratories. b XRR: X-ray reflectivity.
signal-to-noise (S/N) ratio is based on the development
of a liquid hydrogen cold neutron source11 and the collimation aperture (1.91 cm) was used for all samples to
optimization of the collimation optics to maximize the increase the neutron flux on the sample (and hence the S/N
neutron flux on the sample. The experiments also ratio), except for the two thinnest films where a 1.59 cm
exploit the low absorption and (generally) negligible aperture was used due to defects on the edge of the Si wafers.
small-angle scattering of single-crystal silicon wafers for Using these collimation optics, the neutron flux on the sample
use as substrate materials. Although not discussed in was approximately 1.2 × 106 neutrons/(cm2 s). Due to the
this paper, grazing incidence small-angle scattering of small amount of scattering being measured, all experiments
neutrons has also been used for studying thin films and were performed with the sample chamber under vacuum (∼0.2
Torr). With air in the sample chamber the count rate of the
surfaces and is complementary to normal incidence
open beam (without any sample) would almost double, adding
scattering as it obtains information in the normal (z- greatly to the background signal and making the experiments
axis) direction along with in-plane structure in one significantly more difficult for the thinnest samples. The data
direction.12-15 collection times ranged from 2 h for the thickest sample to 10
In addition to testing the limits of SANS for the h for the thinnest. Transmission coefficients for all the thin-
quantitative study of thin polymer blend films, this work film samples were measured (and calculated) to be unity to
will also examine the results found by Russell et al., within experimental error.1,18
where significant effects of confinement were found even The scattered intensities were corrected for background and
when film thicknesses were L/RG ∼ 9. parasitic scattering using standard means.19 The data collec-
tion times for the blocked beam background and empty cell
Experimental Method and Data Analysis were comparable to that for the thinnest sample. The scat-
tering from the open beam, indistinguishable from that of a
The characteristics of the polystyrene homopolymers (ob- single clean Si wafer, was used as the empty cell for data
tained from Polymer Source, Inc.) used in these experiments reduction. The data were placed on an absolute level using a
are given in Table 1. Deuterated polystyrene (PSD)/protonated calibrated secondary standard and were circularly averaged
polystyrene (PSH) thin films of composition 25/75 PSD/PSH to yield the intensity, I, as a function of q where q ) (4π/λ)
by weight were spun from toluene solutions onto 2.3 cm sin(θ/2) (θ is the scattering angle).
diameter silicon (Si) wafers (∼0.02 cm thick). It should be The ability to perform these SANS experiments is dependent
noted that a 2.3 cm diameter polystyrene thin film which is on the Si wafer substrate being transparent to neutrons and
2000 Å thick corresponds to a sample mass of only about 100 not contributing significantly to the measured scattering. The
µg. Prior to spinning, the wafers were cleaned in chromerge Si(111) wafers used in this work (obtained from Semiconductor
at 80 °C for 3 h, etched using hydrofluoric (HF) acid, and Processing) were grown by the Czochralski (CZ) method. Si-
thoroughly rinsed with deionized water. The spin-coated films (111) wafers would not be suitable for experiments requiring
on the Si wafers were annealed at 120 °C in a vacuum stacking of multiple wafers using 6 Å wavelength neutrons
overnight and quenched to room temperature. PSD/PSH due to double diffraction, which would give rise to Bragg
blends are known to have a UCST phase diagram due to the diffraction and obscure the small-angle scattering region.
isotope effect.16 For the polymer molecular weights and Double diffraction can be avoided by increasing the neutron
compositions studied in this work, a spinodal temperature of wavelength to greater than the Bragg cutoff of 2d, where d111
-125 °C is estimated based on published values of the H/D ) 3.14 Å for Si (111); however, the incident neutron flux
segmental interaction parameter, χHD.5 It should be noted that decreases as λ4 for a reactor neutron source. As an alternative
the annealing temperature is more than 200 °C above the bulk to using (111) orientation wafers, a series of (100) wafers were
spinodal temperature, and hence the films should be deep tested as substrates. The lattice constant of Si (100) is d100 )
within the one-phase region of the phase diagram. The blend 5.43 Å, which should allow stacking of samples using 6 Å
studied in this work was specifically chosen to be far from the neutrons as the Bragg diffraction angle is significantly less
phase boundary to minimize complications arising from phase than 90° and should not cause problems with double diffraction
separation and/or shifts in TC, allowing the determination of in the forward direction. PSD/PSH films spun on the (100)
the limits of the SANS technique for single-phase blends. In orientation wafers exhibited scattering that is apparently
addition to the thin films, two bulk samples with thicknesses characteristic of a phase-separated blend. Figure 1 shows
of 109 and 129 µm were prepared by melt pressing at 160 °C, Zimm plots (I-1(q) versus q2) for ∼4000 Å thick films of PSD/
annealed at 120 °C, and quenched to room temperature prior PSH spin coated onto single Si(111) and Si(100) wafers. The
to the SANS measurements. SANS data from the (100) wafer show significantly enhanced
To generate absolute intensity SANS data from thin films, scattering with a negative intercept, suggesting that the blend
it is essential to obtain accurate measurements of the film is phase separated. On the other hand, the data from the
thickness. Ellipsometry and X-ray reflectivity (XRR) were mixture on the Si(111) wafer indicates that the system is single
used for this purpose. Table 2 shows the measured film phase. The origin of this discrepancy lies in the surface
thicknesses as well as the average values used for data roughness of the wafers. Video-enhanced differential interfer-
reduction. Samples will be denoted by their average thickness ence contrast (DIC) optical microscopy images (shown in
throughout the text of this paper. Figure 2a,b) and atomic force microscopy (AFM) images (shown
SANS experiments were performed at room temperature in Figure 3a,b) show that the surface of the Si(100) wafer is
using the 30 m NG3 and NG7 SANS instruments at the much rougher than that of the Si(111). (All wafers appeared
National Institute of Standards and Technology (NIST) Center highly polished to the eye.) The wavelength of the roughness
for Neutron Research (NCNR)17 with neutrons of wavelength is on the order of 1 µm while the peak-to-valley height is about
λ ) 6 Å, four guides, 10.8 m sample-to-detector distance, and 30 Å. AFM indicates that the roughness for the (111) wafer
wavelength resolution ∆λ/λ ) 0.22. Scattering was measured over a 1 µm wavelength is less than the noise level in the
over the q range from 0.007 to 0.06 Å-1. A large final image of (3 Å. Since the diffraction vector is oriented parallel
Macromolecules, Vol. 31, No. 26, 1998 Thin Films of Isotopic Polystyrene Blends 9249

Figure 1. SANS profiles from a smooth (111) Si wafer surface

and a rough (100) Si wafer surface. Inset: I-1/2(q) versus q2
for the residual data from the film on the rough Si(100) wafer
after the calculated single-phase scattering has been sub-
tracted.

to the surface, the neutron contrast between the Si and

mixture gives rise to scattering characterizing the lateral
correlations of the roughness. This scattering is sufficiently
large enough to dominate the scattering from the mixture. To
further explore the structure induced by the surface roughness,
the scattering for the single-phase blend was calculated using Figure 2. Optical micrographs of (a) a rough (100) Si wafer
the RPA and subtracted from the data for the 4000 Å film on surface and (b) a smooth (111) Si wafer surface. Both micro-
the rough (100) wafer. The remaining scattering data were graphs are on the same scale and were taken using differential
then plotted as I-1/2(q) versus q2 (Debye-Bueche analysis20). interference contrast optical microscopy.
The data are linear over a broad q range, and a correlation
length of 1050 Å was obtained (see inset, Figure 1). This Kn 1 1 2χ
) + - (1)
correlation length is relatively large (for a SANS measure- I(q) NavaφaPa(q) NbvbφbPb(q) v0
ment) but still smaller than the wavelength of the roughness
measured by AFM and optical microscopy (∼1 µm). It is not
possible to measure a 1 µm length scale directly by these SANS where Kn ) NA(ba/va - bb/vb)2 is the neutron contrast factor,
experiments since the scattering data would be at too small a NA is Avogadro’s number, vi is the specific volume, bi/vi is the
q value, and as such the measured correlation length probably scattering length density of species i, respectively, v0 ) (vavb)1/2
represents the tail of the roughness distribution. This rough- is the reference volume, and Pa(q) ) 2(exp(-X) - 1 + X)/X2 is
ness-induced scattering masks the scattering from the mixture, the Debye function with X ) RG2q2. Fits of eq 1 to the data
leading to the conclusion that smooth polished wafers with a provide a measure of χ/v0 and the statistical step length, l, and
roughness well below 30 Å are required for use as substrates allow calculation of the correlation length, ξ, I(0), and RG (RG
in this type of study. A second set of (100) orientation wafers ) Nl2/6). If eq 1 is expanded in the limit of small q and
grown by the CZ method were also examined as possible rearranged in Ornstein-Zernike format, the correlation length
substrates. These wafers were found to exhibit significant ξ can be calculated using ξ2 ) l2[36φaφb(χs - χ)]-1 where χs is
small-angle scattering above the open beam background. It the spinodal χ value (χs ) (1/Nava + 1/Nbvb)/2). In the analysis
has been reported by Livingston et al.21 that annealing CZ of the experimental data the following parameters were used
grown silicon single crystals leads to SiO2 precipitates due to from the literature:26-28 vPSD ) 100.5 cm3/mol, vPSH ) 99.8 cm3/
oxygen impurities introduced during crystal growth. Anneal- mol, and Kn ) 4.16 × 10-3 mol/cm4. Additionally, φPSD )
ing is often done to remove thermal donors generated in a CZ 0.2357, NPSD ) 2670, φPSH ) 0.7643, and NPSH ) 2601. For
grown crystal as the crystal cools from the growth tempera- comparison to the measured data the literature value of χ/v0
ture. Livingston et al. observed enhanced small-angle neutron ) 2.2 × 10-6 at 120 °C5,26 allows the calculation of I(0) ) 247
scattering from annealed crystals and were able to measure cm-1 for this blend.
RG ) 54 Å for the precipitates in a CZ grown Si single crystal
annealed at 750 °C for 72 h. Such excess background scat- Results and Discussion
tering from Si wafers can be eliminated by not annealing above Figure 4 shows the SANS I(q) data as a function of q
550 °C22 or by using float zone (FZ) grown crystals which
for all the PSD/PSH thin-film and bulk samples. The
should not develop SiO2 precipitates.
The SANS data from the polymer films were analyzed using data from all of the samples are virtually identical. As
the random phase approximation (RPA).23-25 The coherent expected, the S/N ratio decreases with decreasing film
scattering from a binary polymer mixture composed of chains thickness. The signal, S, includes both coherent and
of length Na and Nb with corresponding volume fractions, φa incoherent scattering from the sample, while the noise,
and φb, respectively, is N, arises from electronic noise and parasitic scattering.
9250 Ho et al. Macromolecules, Vol. 31, No. 26, 1998

Figure 4. Typical I(q) versus q SANS profiles of samples of

all thicknesses examined in this work.

Table 3. Detector Count Rates and Signal-to-Noise

Ratios
total detector count rateb
sample (counts/s) S/Nc
1390a 12 18
2340a 20 47
4270 38 36
6960 49 45
9170 62 46
bulk no. 1 3218 183
bulk no. 2 3797 199
EMP 28
EMPa 11
a Sample was run with 0.625 in. (1.59 cm) sample aperture.
b Total detector count rate (background not subtracted). c Nq ) 114
in eq 2 to calculate S/N.

Table 4. Results of RPA Fits

sample l (Å) χ/v0 (× 107) ξ (Å) I(0) (cm-1)
1390 6.4 ( 0.6 7 ( 15 81 ( 7 228 ( 38
2340 6.3 ( 0.4 6(6 79 ( 5 227 ( 20
4270 7.8 ( 0.3 4(6 98 ( 3 221 ( 14
6960 7.4 ( 0.2 14 ( 5 98 ( 3 249 ( 14
9170 7.4 ( 0.3 5(8 93 ( 4 224 ( 18
bulk no. 1 7.0 ( 0.2 7(5 89 ( 2 230 ( 12
bulk no. 2 6.9 ( 0.2 5(5 86 ( 2 225 ( 11

Parts a-d of Figure 5 show the plots of I(0), l, χ/v0, and

Figure 3. AFM images of (a) a rough (100) Si wafer surface ξ as a function of sample thickness, respectively. The
and (b) a smooth (111) Si wafer surface. Both images are on error bars were calculated using standard error propa-
the same scale. gation techniques and correspond to one standard
deviation.31 Within experimental error no dependence
The average S/N ratio at a particular value of the of I(0), l, χ/v0, and ξ on film thickness was found.
scattering vector for a circularly averaged I(q) versus q Therefore, no finite size effects were evident for the
data set can be estimated using eq 2 29,30 PSD/PSH blend, and the thermodynamic and structural

( )
properties are identical to the bulk values down to a
S Csam(t) - Cemp(t) 1/2
) (2) film thickness of 1390 Å. These results are in contra-
N Nq diction to the preliminary results on PSD/PSH pub-
lished by Russell et al. and the results on PS/PVME
where Csam(t) and Cemp(t) are the total detector counts presented by Reich and Cohen. The original work by
at the specific time t for the sample and empty cell, Russell et al. was on a significantly higher molecular
respectively, and Nq is the number of q intervals (Nq ) weight blend using Si(100) substrates and the data that
114 for all data sets). The S/N ratios of the samples may have contained contributions due to surface rough-
are given in Table 3. The S/N ratio decreases with film ness. In the work by Reich and Cohen on PS/PVME
thickness, and consequently, longer data acquisition thickness effects were observed for films as thick as 1
times are required for obtaining comparable quality µm, but the results varied depending on whether glass
scattering profiles. Nevertheless, even with the rela- or gold was used as a substrate. PS/PVME is also
tively low values of S/N shown for the thinnest film, complicated by surface and substrate wetting effects and
absolute intensities were obtained. the fact that PVME is hygroscopic. The results shown
A nonlinear least-squares fit of the RPA model (eq 1) here demonstrate that, by proper choice of neutron
to the data yields the parameters listed in Table 4. optics and substrate materials, quantitative SANS can
Macromolecules, Vol. 31, No. 26, 1998 Thin Films of Isotopic Polystyrene Blends 9251

Figure 5. Parameters obtained from RPA fits. Note that the bulk values are denoted in each figure by a straight line: (a) I(0)
versus sample thickness, (b) step length versus sample thickness, (c) χ/v0 versus sample thickness, and (d) correlation length
versus sample thickness.

be obtained from very thin polymer films and that It has been observed that the density of a polymer
changes in the characteristic properties for the model film thinner than the chain end-to-end distance de-
PSD/PSH blend used in this work are small. Although creases with decreasing film thickness.32-34 Orts et al.32
bulk scattering behavior was observed in this work for reported that a decrease in density of ultrathin poly-
the thinnest films, finite thickness effects may still be styrene films with decreasing film thickness was ob-
operative for systems close to the phase boundary. The served though the density variation could not be deter-
PSD/PSH system chosen in this work was specially mined quantitatively. The question arises as to whether
selected to be far from the phase boundary. Because of a change in density of the polystyrene as the film
this, the measured scattering will only be sensitive to thickness decreases would affect the results of the fit
large shifts in the phase diagram. The amount of this of the data reported in this work to the RPA equation
shift can be estimated by noting that for any tempera- ( eq 1). Varying the specific volumes of PSD and PSH
ture-dependent property, X (for example, I(0), ξ, ...), that from the literature values27,28 by (5% and refitting the
diverges at the spinodal, the scaling behavior is given data does not change the values of I(0), χ, ξ, and l
by significantly. (The relative changes in these parameters
are less than 1%.)
X ∝ [χS(L) - χ]y ∝ [1/TS(L) - 1/T]y (3) A final issue that needs to be addressed is the role of
surface segregation on the scattering obtained from thin
where the subscripts denote the values of T and χ at films of polymer blends. The preferential segregation
the spinodal for a film of thickness L, and y is the scaling of one component to an interface will cause a reduction
exponent for the property of interest. If a 20% change in the concentration of that component in the interior
in I(0) is taken as the minimum observable change of the film. This would cause a shift in the phase
within errors, then a 20 °C shift in the phase diagram separation temperature due to a composition change
would be required. Consequently, any changes less and, consequently, a change in the scattering. This
than this would not be observable. Sensitivity of the effect has no relation to shifts in the spinodal temper-
experiment to shifts in the phase diagram can be ature due to finite size effects. Past work of Kramer
enhanced by performing experiments closer to the and co-workers35 has suggested that the deuterated
spinodal point and will be the subject of future experi- component from an isotopic polystyrene mixture with
ments. equal chain length polymers would partition to the air
9252 Ho et al. Macromolecules, Vol. 31, No. 26, 1998

surface, since it has a lower surface free energy. The (2) Lovesey, S. W. Theory of Neutron Scattering from Condensed
situation at the Si interface is far less clear and is Matter; Oxford: New York, 1984.
(3) Feigin, L. A.; Svergun, D. I. Structure Analysis by Small-
affected by the nature of the Si surface, i.e., if it is the Angle X-Ray and Neutron Scattering; Plenum: New York,
native oxide or if it is passivated with HF.36 If it is 1987.
assumed that the segregation at both interfaces (air and (4) Russell, T. P.; Lambooy, P.; Barker, J. G.; Gallagher, P.;
substrate) is similar to that predicted at the air surface Satija, S. K.; Kellogg, G. J.; Mayes, A. M. Macromolecules
1995, 28, 787.
by the mean-field theory of Schmidt and Binder37 with (5) Londono, J. D.; Narten, A. H.; Wignall, G. D.; Honnell, K.
surface energy parameters from ref 35, the maximum G.; Hsieh, E. T.; Johnson, T. W.; Bates, F. S. Macromolecules
shift in the phase separation temperature can be 1994, 27, 2864.
estimated. The film was modeled by layers of homoge- (6) Reich, S.; Cohen, Y. J. Polym. Sci., Polym. Phys. Ed. 1981,
neous composition parallel to the film surface with 19, 1255.
(7) Kumar, S. K.; Tang, H.; Szleifer, I. Mol. Phys. 1994, 81, 867.
incremental changes in the composition between layers Tang, H.; Szleifer, I.; Kumar, S. K. J. Chem. Phys. 1994, 100,
used to approximate the composition profile normal to 5367.
the surface as predicted by Schmidt and Binder. The (8) Rouault, Y.; Baschnagel, J.; Binder, K. J. Stat. Phys. 1995,
scattering from each layer was assumed to be given by 80, 1009.
(9) Cifra, P.; Karasz, F. E.; Macknight, W. J. J. Polym. Sci., Part
eq 1, and the calculated scattering from each layer was B: Polym. Phys. 1992, 30, 1401.
summed incoherently. The scattering calculated by this (10) Flebbe, T.; Dunweg, B.; Binder, K. J. Phys. II 1996, 6, 667.
method was found to deviate less than 1% relative to (11) Wignall, G. D. In Encyclopedia of Polymer Science and
that calculated for a film exhibiting no surface segrega- Engineering; Mark, H., et al., Eds.; John Wiley & Sons: New
York, 1978; Vol. 10, p 121.
tion effects. Consequently, surface segregation effects (12) Zabel, H.; Robinson, I. K. Surface X-Ray and Neutron
cannot be considered significant in these studies. Scattering; Springer-Verlag: New York, 1992.
(13) Bienfait, M.; Gay, J. M. X-Ray and Neutron Scattering from
Conclusions Surfaces and Thin Films; Colloque De Physique: Paris, 1989.
(14) Baker, S. M.; Smith, G. S.; Pynn, R.; Butler, P. D.; Hayter,
In summary, it has been demonstrated that SANS can J. B.; Hamilton, W. A.; Magid, L. J. Rev. Sci. Instrum. 1994,
65, 412.
be performed to obtain quantitative intensities on single (15) Hamilton, W. A.; Butler, P. D.; Baker, S. M.; Smith, G. S.;
films of a PSD/PSH polymer blend film supported on a Hayter, J. B.; Magid, L. J.; Pynn, R. Phys. Rev. Lett. 1994,
Si wafer substrate down to a film thickness of 1390 Å. 72, 2219.
This work demonstrates the feasibility of experiments (16) Bates, F. S.; Wignall, G. D.; Koehler, W. C. Phys. Rev. Lett.
1985, 55, 2425.
on a new class of polymer sample with quantities of (17) Taylor, B. N., et al., Eds. J. Res. NIST 1993, 98, 31.
material as small as 100 µg. Analysis of the data has (18) MacGillavry, C. H.; Rieck, G. D. International Tables of
shown that the measured scattering is consistent with Crystallography; Kynoch Press: Birmingham, England, 1962;
the bulk, indicating that, for the molecular weights and Vol. III.
(19) Cold Neutron Research Facility at the National Institute of
composition examined in this paper, finite size effects Standards and Technology, NG3 and NG7 30-Meter SANS
on the thermodynamics of the mixture were not observ- Instruments Data Acquisition Manual, 1996.
able. In addition, surface segregation effects are not (20) Debye, P.; Bueche, A. M. J. Appl. Phys. 1949, 20, 518.
expected to alter the scattering significantly. Future (21) Livingston, F. M.; Messoloras, S.; Newman, R. C.; Pike, B.
C.; Stewart, R. J.; Binns, M. J.; Brown, W. P.; Wilkes, J. G.
studies are in progress to test the feasibility of stacking J. Phys. (Paris) 1984, C17, 6253.
of multiple films to extend the technique to thinner films (22) Schneider, J. R.; Goncalves, O. D.; Rollason, A. J.; Bonse, U.;
and on higher molecular weight mixtures to examine Lauer, J.; Zulehner, W. Nucl. Instrum. Methods 1988, B29,
finite size effects on the thermodynamics and chain 661.
conformation properties. (23) de Gennes, P. G. J. Phys. (Paris) 1970, 31, 235.
(24) Hadziioannou, G.; Stein, R. S. Macromolecules 1984, 17, 567.
(25) Warner, M.; Higgins, J. S.; Carter, A. J. Macromolecules 1983,
Acknowledgment. We acknowledge the support of 16, 1931.
the National Institute of Standards and Technology, (26) Hammouda, B.; Briber, R. M.; Bauer, B. J. Polymer 1992,
33, 1785.
U.S. Department of Commerce, and the National Sci- (27) Yang, H.; Shibayama, M.; Stein, R. S.; Shimizu, N.; Hash-
ence Foundation, through Agreement No. DMR-9423101, imoto, T. Macromolecules 1986, 19, 1667.
in providing the neutron research facilities used in this (28) Shibayama, M.; Yang, H.; Stein, R. S.; Han, C. C. Macro-
work. Financial support from the American Chemical molecules 1985, 18, 2179.
(29) Whalen, A. D. Detection of Signals in Noise; Academic: New
Society, Petroleum Research Fund [S.K.K.], the Na- York, 1971.
tional Science Foundation [CTS-9704907, S.K.K.], the (30) Papoulis, A. Signal Analysis; McGraw-Hill: New York, 1977.
Department of Energy, Office of Basic Energy Sciences (31) Bowker, A. H.; Lieberman, G. J. Engineering Statistics;
[DE-FG03-88ER45375, T.P.R.], and the Department of Prentice-Hall: Englewood Cliffs, NJ, 1972.
(32) Orts, W. J.; van Zanten, J. H.; Wu, W.-L.; Satija, S. K. Phys.
Commerce [7NANB7H0055, R.M.B., D.L.H.] is grate- Rev. Lett. 1993, 71, 867.
fully acknowledged. We thank Drs. Tania Slawecki and (33) Wu, W.-L.; van Zanten, J. H.; Orts, W. J. Macromolecules
Alamgir Karim at the NIST for their assistance during 1995, 28, 771.
these experiments and Mr. Lee Rockford at the Uni- (34) Reiter, G. Macromolecules 1994, 27, 3046.
(35) Jones, R. A. L.; Kramer, E. J.; Rafailovich, M. H.; Sokolov,
versity of Massachusetts for the AFM measurements. J.; Schwarz, S. A. Phys. Rev. Lett. 1988, 62, 2801.
(36) Hariharan, A.; Kumar, S. K.; Rafailovich, M. H.; Sokolov, J.;
References and Notes Schwarz, S.; Russell, T. P. J. Chem. Phys. 1993, 99, 656.
(37) Schmidt, I.; Binder, K. J. Phys. Paris, C3 1985, 46, 1631.
(1) Higgins, J. S.; Benoit, H. C. Polymers and Neutron Scattering;
Oxford: New York, 1994. MA980733S