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Determining the Molecular Weight of !

Petri Dish Derived Polystyrene through!
Thin Film Analysis

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Taicheng Song, Albert Tung, Arun Soni, and the rest of Group 5

ABSTRACT

Molecular weight is frequently determined by expensive and costly methods, such as Gel
Permeation Chromatography, that are often limited to certain size ranges. Approximating
molecular weight through an efficient and inexpensive process can allow scientists to understand
the properties of certain polymers as molecular weight is known to affect variables such as
temperature and viscosity. Here, we spin coat thin polystyrene films onto silicon wafers with
[1,0,0] orientation. The polystyrene from a standard petri dish is dissolved in toluene with
different concentrations resulting in different thicknesses of film. Optical contact angle
measurements and FTIR analysis were also taken of polystyrene to study its hydrophobic
properties and infrared spectrum. The thickness of the film was determined by an ellipsometer
which determined the average thickness of the polystyrene film on the silicon wafers. Our
experiment, at a concentration of 10 mg/mL, created a film of average thickness 450.4
Angstroms or 45.04 nanometers. Using our own polystyrene solution concentration versus
thickness, the concentration at 300 nm was extrapolated using the trend line for the linear plot
and calculated to be 50.79 mg/mL. The known relationship between polystyrene concentration to
molecular weight values at 300 nm allowed us to calculate that the unknown polystyrene had a
molecular weight of 156,040 daltons.

INTRODUCTION!
Molecular Weight
Molecular weight represents the sum of the mass of each atom in a
molecule. In polymers, it is known that molecular weight influences glass
temperature, bulk viscosity, the viscosity temperature coefficient, and
specific volume. Thus, knowing molecular weight is key to understanding
the properties of polystyrene.
One known method of evaluating molecular weight

Figure 1. Molecular Structure of Styrene

http://en.wikipedia.org/wiki/Polystyrene

is gel permeation chromatography, an expensive process with limited capabilities that can only
be used on soluble compounds. In this process, a specially polished expensive glass cuvette is
required and the beam has to be tightly focused to hit just a tiny region of a cell. Furthermore, the
mobile solvent, used to distribute the molecules according to size, is expensive.
Another method known as viscometry measures the viscosity and flow parameters of a
fluid but is very inaccurate as seen with results from a Colorado University study on the
molecular weight of cellulose acetate ranging from 0 to 34,900g/mol.
Polymer
The polymer being investigated is polystyrene obtained from a standard petri dish.
Polystyrene from petri dishes are usually formed by injection molding to create a hard and
durable plastic and typically sterilized in various manners, such as radiation. Though polystyrene
possesses many intrinsic and extrinsic qualities, the most important ones we take into
consideration are its melting point (about 100 degrees Celsius), its molecular weight, which is

being determined in this experiment, and its chemical makeup which consists of monomers of
styrene (C8H8).
Major Techniques Used
Spin Coating
Spin coating is a process used to create uniform thin films onto a flat surface by means of
spinner that spreads the material, usually a solution with a volatile solvent, by centrifugal force.
Spin speed, spin duration, viscosity and concentration of the solution all affect the thickness of
the final film.

Figure 2. Spin coating model derived by Emslie, Bonner, and Peck

Ellipsometry
Ellipsometry is an optical technique for investigating properties of thin films. It can be
used to present composition, roughness, thickness, crystalline nature, doping concentration,
electrical conductivity and other material properties. Generally, the measured stimulus is the
change in polarization as the incident radiation interacts with the material structure of interest.
Fourier Transform Infrared Spectroscopy
Fourier transform infrared spectroscopy (FTIR) is a technique which is used to obtain an
infrared spectrum of absorption or emission of a solid, liquid or gas. The machine collects data
and converts the raw data into an actual spectrum. This spectrum can be analyzed to determine
the property and identify of the material.

Compression Molding
Compression molding is the process in which pellets or pieces of a polymer are squeezed
and heated into a mold by a hydraulic press.
Optical Contact Angle Meter
Optical contact angle meter allowed an estimation of the hydrophobicity or hydrophilicity
of a material based on the angle a 5L drop of deionized water formed with the surface.
Purpose
This topic was researched to teach us how to process silicon wafer surfaces and
understand its differing crystal structures, spin-coat polymer thin films, measure thin film
thickness, and determine an unknown molecular weight. Each experiment conducted determined
the thickness of a thin film at a particular concentration and collectively, the whole experiment
was used to calculate the unknown molecular weight of the polystyrene in the petri dish. Our
concentration of 10mg/mL, in particular, formed a 450.4 angstrom layer of polystyrene on the
surface of the silicon wafer. Using this data point and other data points from other group
members, the calculated value for the molecular weight of polystyrene is 156,040 daltons.
METHODS AND MATERIALS
Silicon Wafer Preparation
Single crystalline silicon wafers with Miller
index of [1,0,0] orientation were cut into four
approximately 1cm x 1cm squares using a diamond
cutter and metal tweezers. Orientation of crystals in
the silicon wafers was verified using an Olympus

Figure 3. The various planes of silicon.

http://www.yale.edu/eas996/smart/lect_15.html

BH-2-UMA Optical Microscope at 500x magnification and images were taken.

Polymer Solution Creation
5.3 mg of virgin polystyrene from a standard petri dish was measured in a My Weigh
iBalance 211 with standard weigh paper. It was subsequently dissolved in 5.3 mL of toulene
from Sigma Aldrich that was measured using a measured pipet to achieve the desired
concentration of 10mg/mL; it remained under a Safeaire fume hood for about 3 hours.
Thin Film Spincoating
The solution was then pipetted spincoated using
Photo-Resis Spinner from Headway Research Inc. in
open air at 2500 revolutions per minute (rpm) for 45
seconds onto the reflective half of the silicon wafer,
attached to the spinner by double-sided tape. This
process was repeated 4-6 times per concentration with
concentrations ranging from 5 mg/mL to 25 mg/mL in 5
even intervals. The square silicon wafers with thin
film coating were put into a petri dish and the

Figure 4. Spincoating process.

http://www.smartcoater.com/spin-coatingtheory.html

thickness of the film was taken the next day.

Silicon Wafer Characterization
Pure silicon wafers with [1,0,0] orientation and silicon wafers with a polystyrene thin
film had their surfaces characterized by a CAM 200 Optical Contact Angle Meter to determine
its hydrophobicity and hydrophilicity. The silicon squares were placed in the center of the

platform and 5L deionized water was dropped on the silicon. The contact angle was obtained by
the software in the machine and analyzed.
Molding and Polymer Analysis with FTIR
Carver Model C hot press compressed several pieces of polystyrene from the petri dish
into a metal mold covered by non-stick, orange flame retardant Kapton paper and an additional
thin copper cylinder. The temperature was set to be 356F or 180C for two minutes and then
compressed at 6 psi for 5 minutes. The temperature of the sample was then reduced by blowing
pressurized air onto it and removing it from the mold with a razor blade. The sample was then
put into the Fourier Transform Infrared Spectroscopy: Thermo Scientific Nicolet 6700. The
machine displayed an infrared spectrum, which was then compared with the graph in a database
to determine what polymer it was.

Figure 5. This diagram illustrates how the FTIR works to obtain the
infrared spectrum of a sample.
http://sunedisonsemi.com/index.php?view=metrology

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Ellipsometer Testing
One silicon square was randomly selected from the petri dish to be tested by a Rudolph
Research Auto EL ellipsometer. The angle of incidence was 60 degree and 5 measurements of the
thickness of the thin film on the silicon square were taken. Three readings were obtained from
the ellipsometer because the ellipsometer reads the 0th, 1st and 2nd order. Qualitative analysis
using samples with known thicknesses were able to eliminate false values.

Figure 6. This diagram illustrates how the ellipsometer works to obtain

the thickness of the film on a sample
http://en.wikipedia.org/wiki/Ellipsometry#mediaviewer/

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RESULTS AND DISCUSSION

Silicon Wafer Images!

Figure 7. The left image is an image of [1,1,1] silicon and the right
image is an image of [1,0,0] silicon taken by an optical microscope

Microscope images of two different cleavages of single crystalline silicon show the difference
between [1,1,1] oriented silicon on the left and [1,0,0] oriented silicon on the right. The images
show the properties of silicon cleaved in different ways, but the different properties do not affect
the molecular weight of the polystyrene being analyzed.
Optical Contact Microscope

Figure 8. The above image is an image of a water drop on pure silicon

without any thin films.
Silicon Wafer Only

Silicon Wafer with Polystyrene Film

Trial 1

30.28 Left and 31.01 Right

85.34 Left and 84.39 Right

Trial 2

22.25 Left and 20.46 Right

83.72 Left and 83.45 Right

Table 1. The lower angle of the water droplets on only the silicon wafer indicates that the
silicon wafer is hydrophilic while the higher angle of the water droplets on the silicon wafer
indicates the hydrophobicity of polystyrene.

FTIR Data

Figure 9. The FTIR spectrum was compared to that of polystyrene

and found to be nearly an 80% match with few discrepancies.

A graph of absorbance vs. wavenumbers (cm-1) was obtained from the FTIR and comparison
with the standard spectrum from the Thermofisher spectrum library indicates that the
substance is polystyrene. Furthermore, peaks in the 2800-3000 range indicate aromatic and
aliphatic C-H stretch. Peaks in the 1400-1600 range are also indications of aromatic ring
stretching, characteristic of the benzene ring within the styrene monomer.

Data Table and Graphs

The data obtained from the ellipsometer was obtained and recorded below. Standard deviation
and other errors were calculated (Appendix A) and error analysis was conducted.

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5 mg/
mL

10 mg/
mL

15 mg/
mL

20 mg/
mL

25 mg/
mL

213

427

695

1058

1412

209

453

691

1059

1315

220

469

656

1026

1403

264

454

686

1033

1446

196

449

670

1051

1506

Standard Deviation

25.89

15.13

16.26

15.04

69.62

Average Thickness
(Angstroms)

220.4

450.4

679.6

1045.4

1416.4

Natural log (ln) thickness

5.40

6.11

6.52

6.95

7.26

0.11747

0.03358

0.02392

0.01439

0.04915

11.58

6.76

7.27

6.73

31.13

Mass (mg)

24

53

78

98

126

Error in Mass (mg)

Volume (mL)

5.20

5.30

5.20

5.0

5.00

Error in Volume (mL)

0.05

0.05

0.05

0.05

0.05

Error in concentration

0.04276

0.02109

0.01603

0.01429

0.01277

ln Error of thickness
Standard Deviation of the
Mean

Table 2. Ellipsometry data with instrumental error calculations.

The equation obtained from the graph of concentration on thickness of polystyrene film is
y = 1.1445x + 3.511 and the graph's axis minimum and maximum values have been altered to
show the distribution of error bars and the points near the linear regression as close as possible. A

R2 value of 0.9924 also indicates that the linear regression is a extremely close fit and accurately
represents the data, thus extrapolation is a viable technique to estimate what the concentration of
the solution would be to achieve a thickness of 300 nm.
The Effect of Concentration on Thickness of Polystyrene
Film

ln(thickness)

y = 1.1445x + 3.5111
R = 0.9924

7.25

6.5

5.75

1.5

2.5

3.5

ln(concentration)
Figure 10. The graph shows how different concentrations can affect thickness

Using the linear regression equation (calculations shown in Appendix A), the concentration was
determined to be 50.79 mg/mL and the molecular weight was calculated to be 156,040 Daltons.

Error Analysis
One error of the contact angle measurement is that because the silicon wafer was not
cleaned with nitrogen gas or acid so there is a very high chance that dust particles settled onto the
wafer or oils from fingertips before the drop of water was added and disrupted the results. Errors
involved with FTIR analysis are similar to that of the contact angle measurement as dust,
humidity and oils from the air and on the sample could affect the result. Furthermore, parallax in
reading the syringe could get a different value for the liquid, spin casting time differences could

create variations in thickness and presence of dirt on the silicon wafer could affect the film.
Human error could also result as different interpretations of analog values could create
discrepancies within the data.
CONCLUSION
In the experiment, confirmation of the type of single crystalline silicon being used was
examined through a optical microscope. The square crystals of the [1,0,0] silicon image prove
that it has the crystal planar structure it was believed to have. With the optical contact angle
meter, the hydrophobicity of polystyrene was observed as the water droplet on regular silicon
had anywhere from 20 to 30 angle while the water droplet on silicon coated with polystyrene
had between 80 and 90. The higher the contact angle, the more hydrophobic the material is and
polystyrene is known for being hydrophobic. Furthermore, FTIR readings, when compared to
other spectra, matched that of polystyrene, confirming the identity of the polymer. From the data
that we gathered and using extrapolation from known molecular weight, polystyrene was
determined to have a molecular weight of about 156,000 Daltons which is consistent with solid
polymers. Furthermore, understanding the molecular weight of polystyrene using a simple
extrapolation method is cheaper and is relatively simple compared to the methods discussed
previously, an important part of science. Using cleaner methods to handle samples would resolve
many of the errors discussed by improving the accuracy of our results and avoiding
contamination.

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APPENDIX A!
Standard Deviation
Standard Deviation was calculated by taking the square root of the
summation of the squared difference between values of thickness
and the average thickness, divided by 4 (1 less than the number of
samples: 5).
Standard Deviation of the Mean
Standard deviation of the mean is a value used to approximate
the accuracy to which another individual can obtain the same
results and calculated with this equation in which standard
deviateon is divided by the square root of the number of samples: 5.
Error of Thickness
The error of thickness was calculated using the propagation error thickness equation from the lab
protocol: dW=dx/X where X=thickness and dX=standard deviation of the thickness.
Error in Concentration!
Error in concentration was calculated by taking the square root of the sum of the squares of dA/A
and dB/B where dA and dB were the instrumental errors of mass and volume respectively and A
and B were the values of A and B respectively.

Calculation of Final Value

Regression equation from experiment, y = 1.1445x + 3.511, in which y was thickness in
angstroms and x was concentration was extrapolated to 3000 angstroms of which a concentration
of 50.79 mg/mL resulted.

The equation from known polystyrene concentration vs molecular weight at 3000 ,

log(concentration) = 3.378 - 0.322log(molecular mass), was calculated from the figure below
and the material was of a size 156,040 daltons.

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REFERENCES
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http://www.waters.com/waters/en_US/GPC---Gel-Permeation-Chromatography/nav.htm?
cid=10167568&locale=en_US
Levine, Shoemaker, Garland, & Nibler. (n.d.). Determination of the Molecular Weight of a
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Boulder website: http://chem.colorado.edu/chem4581_91/images/stories/
Sample_Lab_Report.pdf

Prapancham, B. (n.d.). Gel Permeation Chromatography [PowerPoint slides]. Retrieved July 9,

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Testing. Momentum Press