J.H. Teichroeb, J.A.

Forrest
Department of Physics, University of Waterloo, Canada

Introduction
Most interactions with solid material (including polymers) are through the surface, and not the bulk. Thin polymer films exhibit anomalous dynamics, including decreases in the glass transition temperature (where the polymer goes from being liquid-like to solid-like). Various theories put forth to explain polymer physics suggest a more mobile surface region. It is important to develop an understanding of the physical properties of polymer surfaces. Is the surface Tg the same as the bulk Tg? Use nanoparticle embedding to probe surface properties

Atomic Force Microscopy

Laser diode

Normalized 10 and 20nm Spheres at 105oC for Extended Time

1.2

Mirror

Apparent Height (nm)

Lens

1.0

Piezoelectric scanners Y
ile C a nt ve r

0.8

0.6

T ip Sample

Typical region used in study

20 nm spheres 10 nm spheres

0.4

Spheres are no longer embedding by 24 and 48 hours for T> Tg.

0.23 0.14

0.2

AFM Explorer

AFM basic schematic

Typical raw AFM image

0.0 0.01 0.1 1 10 100 1000

10000

Log(Time)

Atomic Force Microscopy (AFM) uses a cantilever with a sharp tip (<50nm diameter), to probe material surfaces. Non-contact mode Cantilever oscillates near resonant frequency. Surface force gradient alters resonance. Feedback circuits maintain a constant frequency
Cantilever
Piezo

Embedding of 20nm Au Spheres on PS

20

Apparent Height (nm)

18 16 14 12 10 8 6

T<Tg(bulk)

3.8 nm

Height of spheres on silicon do not change indicating embedding is not an artifact

Sample Preparation
Materials
Polystyrene (PS)
Mn: 214 000 Mw/Mn: 1.03 Tg =97 C. Glassy at room temperature.
H H

T>Tg(bulk)

378 368 363 358 363

K K K K K on bare Si

Embedding for T<Tg occurs within 50 minutes to depth of ~3.8 nm.

Sample

Non-contact mode

[ ]
C C H

Constant frequency gives constant height, which is recorded as the topography of the sample.
n

50

100 150 200 250 300 Time (minutes)

1100

Embedding of 10nm Au Spheres on PS

10

Apparent Height (nm)

AFM Heating Stage Monodisperse Gold nanospheres

Sizes used: Coefficient of Variation: Particles/ml: HAuCl4 concentration: 10, 20, 50nm < 10%, 15%, 20% respectively 5.7x1012, 7.0x1011, 4.5x1010 0.01%

3.5 nm

Height of spheres on silicon do not change indicating embedding is not an artifact

Precision alignment of AFM with sample Allows repeated measurement of identical positions

6
378 368 363 373 K K K K on Bare Si

Embedding for T<Tg occurs within 50 minutes to depth of ~3.5 nm.

Sample Preparation & Measurement

Spin-coat onto Silicon substrate Anneal film for 20h at 130oC

Results
Embedding of 10 nm Au Spheres on PS
9.0

40

80

120

160

200

Time (minutes)

Conclusions
T>Tg(bulk) Embedding occurs as expected. Embedding appears to follow some type of stretched exponential

Apparent height (nm)

PS in Toluene

8.5

8.0

Allow drop of colloidal gold nanospheres to dry

0 min.
Drop of Au colloid, diluted (1:50) with water, and allowed to dry on the sample Film thickness: 1800

7.5

7.0

6.5

Measure apparent height with AFM

6.0

5.5 0 50 100 150 200

10m scan

Annealing time (minutes)

Data over extended time suggests embedding until Au-PS contact angle reached. T<Tg(bulk) Clear evidence of particle embedding below bulk Tg. Particles do not continue to embed, but rather stop at a certain critical depth (3-4 nm beneath PS surface). Surface properties (critical depth and time to reach critical depth) do not depend on diameter of probe. Embedding is not due to colloidal coating. Surface does not act like bulk

4m scan

Essentially no Au particles

Dense Au particles Typical imaging region

15 min.

Gold nanospheres become embedded into surface at 7 degrees below the bulk Tg PS surface exhibits liquid behavior even when the bulk is solid

2m scan
Air cool to near room temperature

120 min.
Anneal at desired temperature for some time (eg. 5 min.)