Kit for PDMS Surface Modification

Aldrich Materials Science, in collaboration with Clemson University and the Pennsylvania State
University, has developed a Surface Modification Kit, which allows for durable hydrophilization
of various polydimethylsiloxane (PDMS) surfaces.
The procedure is based on technology developed by the group of Professor I. Luzinov (Clemson
University). It employs a macromolecular anchoring layer approach for grafting hydrophilic
polymer layers onto hydrophobic PDMS surfaces.
One of the possible applications for hydrophilic PDMS surfaces is microcontact printing. Figure
1 compares hydrophilic ink imprints, which have been created using untreated, oxygen plasma
treated and kit modified PDMS surfaces.

Untreated PDMS surface

Figure 1. Imprints of a hydrophilic electro ceramic ink on metal substrate created using
differently treated PDMS surfaces. (Courtesy of Professor Susan Trolier-McKinstry, the
Pennsylvania State University)

Technical facts and applications of this technology can be found in the following publications:
1. Zdyrko, B.; Klep, V.; Luzinov, I. Material Matters, 2008, 3(2), 44.
2. Nagata, S.H.; Ko, S.W.; Hong, E.; Randall, C.A.; Trolier-McKinstry, S. J. Am. Ceram. Soc., 2006, 89, 2816.
3. Nie, Z.; Kumacheva, E. Nature Materials, 2008, 7(4), 277.

Surface Modification Kit

Product No. 701912
Kit Components
Solution A (Glycidyl methacrylate based polymer) 10 mL
Solution B (Acrylamide/acrylic acid based polymer) 4 mL

Recommended Solvents (not included)

 Ethanol (Product No. 270741)
 2-Butanone (Product No. 34861)
 Water (Product No. 320072)

Figure 2. Schematic of the PDMS surface hydrophilization process.

Procedure

1. Pretreatment - PDMS surface should be activated using a low frequency air plasma treatment
for 1 minute (Recommended plasma cleaners: Product Nos. Z561673, Z561681, Z561657,
and Z561665).
2. Prerinsing - The plasma activated PDMS sample should be rinsed by washing with ethanol
(Product No. 270741) for at least 10 minutes. The rinsing procedure should be repeated 3
times. Then, the sample should be air-dried for at least 15 minutes. The water contact angle of
the resulting activated PDMS surface is expected to be between 25 and 40°.
3. First Modification Step - The surface of the horizontally positioned sample prepared in the
previous step should be covered with Solution A, typically ~1 mL per square inch of the
surface. The sample should be dried under ambient conditions for 20–30 minutes and
annealed at 110 °C under nitrogen or argon for 30 minutes.
4. Rinsing - The annealed sample should be rinsed three times with 2-Butanone (Product No.
34861) for 10 minutes each time. Then it should be air-dried for at least 30 minutes.
5. Polymer Grafting - 6 mL of ethanol must be added to the container containing Solution B. Stir
the mixture to homogeneity. The surface of the horizontally positioned sample prepared
previously should be treated by completely covering the area to be modified with the
 homogeneous solution, typically ~1 mL per square inch of the surface. The sample should be
dried under ambient conditions for 20–30 minutes, then annealed at 80 °C for 14 hours.
Finally, the unattached polymer should be removed from the sample by a thorough rinse with
water (Product No. 320072) and the sample air-dried at room temperature.

After treatment, water should effectively wet the surface as the water contact angle is expected to
be between 25 and 35°. The resulting PDMS surface should be wettable by hydrophilic inks and
appropriate for multiple printing applications.

https://www.sigmaaldrich.com/technical-documents/articles/materials-science/microelectronics-
nanoelectronics/pdms-surface-modification.html

Well-established approach to produce hydrophilic PDMS surfaces is to oxidize the polymer surface with
plasma or ultraviolet (UV) irradiation 23 . However, this effect is transient, and the hydrophobic nature of
PDMS returns several minutes after plasma or UV exposure because of the migration of the uncured
hydrophobic polymer chains to the surface. Methods to slow down or prevent this recovery from
occurring include keeping the surface in water immediately after treatment and removing uncured
polymers using solvent extraction 24,25 . However, the utility of these approaches for droplet microfluidics
has not been established, and it is likely that exposure of the surface to oil will negate these effects.
Another strategy to achieve surface modification is to coat substrates with polyvinyl alcohol (PVA; a
hydrophilic polymer). This strategy has primarily been used for non-PDMS surfaces, such as silica
capillaries for biopolymer separation and DNA sizing applications 26,27,28

Surface treatment

Surface treatment is a suitable tool for your purpose such a treatment adds surface energy to the
surface through increasing surface roughness and area. There are many tools such as ion beam
and reactive species of gas discharge plasma. Also thin film deposition of polar materials such as
oxides convert galss into hydrophilic material. Plasma polymerization adds a layer of plastic that
made it hydrophilic. Surface modification is highly required in such cases. For glass, clean it
thoroughly in piranha solution  @ 20 min. and clean in DI water, thereafter Heat it at 150 deg.
Cent. in oven for 30 min and treat in oxygen plasma for 30 sec and immediately coat by dip
method or spin coating. For Silicon an oxide layer is required for better adhesion.

I agree with @Pradip Kumar Dey. Basically you need a completely clean surface. And the
method mentioned by him is good. i would just like to add that the cleaning step with DI water
should be done properly and should involve 10 min sonication.
Another aspect you should pay attention to is that while cleaning the substrates should not get
scratched and at no point in the cleaning process you should touch the top of the surface (even
with forceps).
If you use the above method for cleaning it will even work for Si substrates, but of course it
would be better if you can oxidize the substrates (depends on the applications you are looking for
in the final stage). 
Surface modification also involves surface roughness.  The higher the surface roughness the
better chance of surface adherence particularly in dip/spin coating. Try it and you shall get better
adherence. Good luck.
Pre-treating the silicon surface or glass subtrate (with KOH for example) can help to attached
something on the surface. I agree also with the others, surface modification in the key to for
attaching something on a surface but it depends also on the functional groups of your coating
material (OH, H, COOH etc...). 

Possibly Oxygen plasma along with argon plasma could help you more than only oxygen
plasma. For glass: The surface should be cleaned by sonicating using a solution of acetone (10
min), solution mixtures of NH4OH : H2O2 : H2O (1 : 1 : 5, 30 min at 80 C), and  HCl : H2O2 :
H2O (1 : 1 : 6, 30 min at 80 C), followed by rinsing and drying.