The document outlines the progress and capabilities of a research and development group focused on printed molecular electronics, highlighting key technologies including low-cost manufacturing techniques and customized organic materials. It emphasizes the development of functionalized printed sensors for detecting biomarker proteins, especially for medical diagnostics, and discusses the integration of these technologies into printed systems-on-plastic. The document also points to ongoing efforts in creating specialized nanoscale sensors to achieve high sensitivity and selectivity for biomedical applications.

1. Printed Molecular Electronics
6th
May 09

2. 2
May 2009
Key Competencies
Post Silicon Technology (PST) is an R&D group leading the development
of a new technology paradigm focused on the combination of the following
key competencies:
Low-cost manufacturing technologies based on stamps, Soft and Nano-
Imprint lithography (down to 50nm), Ink-jet Printing and Surface
Functionalization as enabling techniques for printed organic and
molecular electronics
Design and modeling of printed organic electronic devices and circuits
Design, optimization and characterization of functional organic/hybrid
materials
Multi-scale and Multi-objective optimization – Neural Net (proprietary
algorithms)

3. 3
May 2009
Printed Molecular Electronics -Technology Platform
Mission:
Integrate organic molecules in and onto solid state devices as
functional units through a low-cost manufacturing technology and
pave the way to new profitable applications
Killer application
Functionalized printed sensors for the electrical detection of
biomarker proteins (i.e. cancer)
 Medical Diagnostics and Personalized Therapeutics
Strategic via: The Pharmaceutical/BioMed Industry

4. 4
May 2009
Key activities
Mix&matchMouldsforNILPrinteddemonstrator
Pharmaceutical/BioMed Industry

5. 5
May 2009
Printed Molecular Electronics: Some driving forces
Intrinsic potentiality
Assign the desired properties to functional molecules by specific design, modeling and
synthesis
Tailor the molecular structure to match processes issues
Potentially cost effective (10-13
-10-14
$† v.s. 10-9
$ per active elements @2014*)
Boost the performances of standard applications
Logics
- Intrinsic switching frequency >GHz
- Very low power consumption
– Memory (Both NV and DRAM possible)
- Retention time can be tuned ~ 1.5eV : 1015
s -108
s (20 C, 130 C)
-Read voltage ~ 0.15V, Write voltage ~ 0.3V (high frequency)
Pave the way to new profitable applications
Printed Functionalized Nano scale Sensors for the electrical detection of
chemicals and bio-molecules (Proteins, DNA, Cancer Bio-Markers….)
mEMS and Functionalized MEMS/NEMS
† not-including the silicon
*as per ITRS projection

6. 6
May 2009
TR&D Roadmaps
Vision: Ultra-low cost Printed System-on-Plastic, including
Printed Sensors for the electrical detection of chemicals/bio-
molecules
- Printed array of functionalized sensors (Demonstrated ~ 100nm)
- Test case: ssDNA-functionalized Si sensors (Demonstrated)
- 1st
plastic array planned by 2010
Printed RF-powered system (planned by 2010)
- New polymer composite materials and low-cost technology for
antenna and diodes
Printed Electro-wetting Micro-fluidic devices (planned by 2010)
- Printed Electro-wetting Technology as ultra low cost micro fluidic
solutions compatible with Printed Electronics.

7. 7
May 2009
Vision: Printed System-on-Plastic
Killer application
Early detection of disease biomarkers (i.e. proteins)
Energy scavenging from RF field to power on the System-on-Plastic
Pharmaceutical
BioMed Industry

8. 8
May 2009
The Process integration and expertise
Expertise & Achievements
• Provide the surface with suitable terminations (surface preparation)
• Graft of functional molecules by hydrosilation, silanization… (grafting+rinsing)
• A unique set of algorithms to extract quantitative indicators on reaction yields
• Integration of functional molecules into Si- X-bar devices  Hybrid Si-Mol-Si NV Memory
• Surface functionalization giving new properties antistiction, hydrophobic, corrosion resistance to
acid/basic or buffer bio-solution.
• Manufacture proprietary molds (with sub-µm features) to produce by printed devices
 Printed array of functionalized sensors
CH2 CH2RSi H CH2 CHR+
T <200°C
Si
R – functional group
Micro-wave enhanced Hyrdosilation
Strategy
Hydrogen-terminated Si surface can be functionalized by exposure to alkene-alkyne-
terminated molecules to form a chemically robust, environmentally stable, Si-C
30 min 60 min30 min 60 min30 min 60 min30 min 60 min

9. 9
May 2009
Si+4
Si+4
Si+3
Si+3
Si+2
Si+2
Si+1
Si+1
SiH3
SiH2SiH2
SiHSiH
Si-Si-
SiH3
SiH2
SiH
SiH3
SiH2
SiH
Chem. Phys. Characterization of Surface
AFM: 0.18 nm
H
O
+
HH
O
H
Si
H
O
+
H O
Si
H
Si
Si
H
Si
Si Si
SiSi
Si
Si
H
Si
Si
Si
H
Si
Si
H
H
Si
Si
Si Si
Si
Si
H
Si
Si
SiSi
Si
Si
H
O
Si
H
Si
H
Si
Si
Si
Si Si
H
Si
Si
H
Si
Si Si
Si
H
[100]
[111]
Development of proprietary strategy and
algorithms to fully quantify the results of
surface treatments in terms of surface
species
ATR-FTIR AR-XPS
Decomposition of surface species
(PST own algorithms)

10. 10
May 2009
Stability after 6 months
Native Oxide islands growth on defect sites
Highly robust/stability of the surface after grafting
Contact angles ~ 102 degree
 preserved after 6 months
Si-CSi-CSi-C
30 min 60 min30 min 60 min
AR-XPS decomposition by
proprietary algorithms giving evidence of Si-C

11. 11
May 2009
Poly-Si surface after grafting – some features
Data Physics Instruments OCA20 Method: sessile drop
CA: 33,8, Vs Si(100) CA: 36 CA: 103.1 Vs Si(100) CA: 106.7CA:80.4 Vs Si(100) CA: 76.4
Improved resistance versus harsh environment: aqueous NH4OH, KOH, HCl, HF
 unique possibility for silicon devices
High stability to thermal treatment. The contact angles decreases after 30min
annealing in air at 350 C (commercially-available)
It is possible to design molecule with the functionality to resist temperature as
high as 450 C If oxygen is removed from the atmosphere.
CA: 33,8 CA: 80,4 CA: 106,7
As received after HF+rinsing
after grafting of
1-octadecene

12. 12
May 2009
Examples of surface treatments 1/2
Ultra-hydrophobic self-cleaning surface  Particular suitable to handle with biological samples
179.8
102.8
Silicon
Ready to sense chemicals

13. 13
May 2009
Examples of anti-sticking 2/2
CA 142
High resolution molds for NIL
Down to 50nm
MEMS
Not treated devices exposed to water vapor Grafted surface

14. 14
May 2009
The very 1st
X-bar hybrid Si-organic-Si IC
Silicon host  for sense, address and control operations
Molecule guest  functionality
Xbar-device
Cross section
Q107
Q307
Feb08X-bar devices as
core element of
general-purpose
architecture.
Oxide tuned
on molecular length
scale

15. 15
May 2009
TEM analysis and IV
26.8 nm
Bottom electrode
Top electrode
oxide
27.1 nm
After HF
Pristine device
0.00E+00
5.00E-06
1.00E-05
1.50E-05
2.00E-05
2.50E-05
0.0
0.4
0.7
1.1
1.4
1.8
2.2
2.5
2.9
3.2
3.6
4.0
4.3
4.7
5.0
5.4
5.8
6.1
6.5
6.8
7.2
7.6
7.9
A
V
After grafting
27.1 nm
4.8 nm
ResultsResults
- The HF + CH3CN produces superior etching uniformity
- The TEM analysis give a gap of ~ 26.9 nm + molecules
completely filling the area.
The covalently-bonded molecules are responsible for
the NV memory effect (hysteretic)

16. 16
May 2009
A write-Read-Reset Cycle at room-
temperature in air
P-type
n-type
5.8nm
1.8nm
~ 20 nm
The tunnel junction is controlled by
grafted functional molecule in a
~50nm linear gap

17. 17
May 2009
4.8 nm devices with different area/perimeter ratio
-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6
-2.0x10
-5
-1.0x10
-5
0.0
1.0x10
-5
2.0x10
-5
3.0x10
-5
4.0x10
-5
5.0x10
-5
6.0x10
-5
7.0x10
-5
8.0x10
-5
-6 -5 -4 -3 -2 -1 0
-2.0x10
-5
-1.5x10
-5
-1.0x10
-5
-5.0x10
-6
0.0
Current/A
DC Bias /V
B, [0,+6], 1st Scan
B, [0,-6], 1st Scan
B, [0,+6], 4th Scan
B, [0,-6], 4th Scan
Device 1, Before Grafting
-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6
-1.0x10
-5
0.0
1.0x10
-5
2.0x10
-5
-6 -5 -4 -3 -2 -1 0
-1.5x10
-5
-1.0x10
-5
-5.0x10
-6
0.0
Device 1, After Grafting
Current/A
DC Bias /V
B, [0,+6], 1st Scan
B, [0,-6], 1st Scan
B, [0,+6], 4th Scan
B, [0,-6], 4th Scan
Before Grafting After Grafting
-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6
-1.0x10
-5
0.0
1.0x10
-5
2.0x10
-5
3.0x10
-5
4.0x10
-5
5.0x10
-5
6.0x10
-5
7.0x10
-5
8.0x10
-5
9.0x10
-5
1.0x10
-4
1.1x10
-4
1.2x10
-4
-6 -5 -4 -3 -2 -1 0
-5.0x10
-6
0.0
Device 2, Before Grafting
Current/A
DC Bias /V
B, [0,+6], 1st Scan
B, [0,-6], 1st Scan
B, [0,+6], 4th Scan
B, [0,-6], 4th Scan
-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6
-1.0x10
-5
0.0
1.0x10
-5
2.0x10
-5
3.0x10
-5
4.0x10
-5
5.0x10
-5
6.0x10
-5
-6 -5 -4 -3 -2 -1 0
-1.0x10
-5
-5.0x10
-6
0.0
Device 2, After Grafting
Current/A
DC Bias /V
B, [0,+6], 1st Scan
B, [0,-6], 1st Scan
B, [0,+6], 4th Scan
B, [0,-6], 4th Scan
~80% devices have showed a deep change in IV behavior
Device 1
Device 5
Before Grafting After Grafting

18. 18
May 2009
The main Challenges
Detect bio-markers diseases sensing their unique proteomic expression within others similar bio-
molecules in fluids/air. (<<ng/ml in early stages)
Basic Requirements for detection:
– Very high selectivity (capacity to give a response only to selected targets)
– Very high sensitivity (capacity to sense extremely low amount of targets)
– Parallel approach for protein/antibodies sets detection
Mission
Develop printed array of specialized nanoscale sensors to recognize selected antigen or other molecular
species (antibody fragments, globular proteins, cancer bio-markers....) by means of electrical detection
after specific interaction
Key features
– Extremely high sensitive << ng /ml
– Unique selective to specific targets by suitable functionalization
– Suitable for highly thought-put analysis
– Fast screening and cheap technology (plastic)
Electrical detection of bio-marker proteins by
nano-scale printed sensors

19. 19
May 2009
Process definition &
integration
Printed Array of Functionalized Nano-Sensors
Printed functionalized devices
Task1: Surface functionalization
Task 2: Printed Devices - sensors

20. 20
May 2009
Strategy:
Graft a carboxyl terminated molecule to gain access to the bio-cross linker chemistry
Grafting of a selected binary mixtures (a/b) characterized by:
– Molecule (a): terminal alkene, C atoms <10
(Molecular Spacer + insulating layer)
– Molecule (b): terminal alkene, C atoms >10 + a suitable reactive group
(Molecular linker to catch bio-molecules)
– Rinsing treatments
Immobilization of target bio-molecules on sensor for electrical sensing
Identification of a general-purpose strategy
for bio-functionalization of the Nano-devices
Sensors
C
O
H
(a) - insulator
(b) - linker
The strategy can be adapted to Antibodies, enzymes, DNA…
C
O
H C
O
H C
O
H
C
O
H

21. 21
May 2009
Conventional approaches
Antibodies
target
serum
Strategy for Proteins Immobilization
c
target
serum
Proteins
Strategy for Antibody Immobilization
Selective electrical detection by antibody-protein reaction
(1) (2)
Ad hoc
Molecules
Sensor
Sensor

22. 22
May 2009
General Structure of bio-hunter
A biological hunter is antibody-modified molecules with a
synthetic sequence of ssDNA
Strategy for bio-functionalization
– Primary amine groups (–NH2) on lysine sidechains and at the amino
terminus of each polypeptide chain.
– Sulfhydryl groups (–SH) can be generated by reducing disulfide
bonds in the hinge region.
Selective
Bio-Hunters
AGGATCCA -
CTGAACTA -
Complementary
DNA-functionalized
devices
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
NH
2
Targets
Device 1 Device 1
Self Recognition
Head Tail
linkage

23. 23
May 2009
Silicon bio-functionalization
Si-CSi-C
1
2
COOHCOOH
High-lights
Silicon and poly-silicon surface has been
functionalized by UME linker and modified
in terms of –COOH terminations
– AR-XPS:
- Stable functionalization of the Si surface
- Persistence of the C.A.s over 1 Month
under Lab condition
- The decomposition of the C 1s peak
 Si-C in both the samples
 Activation of carboxyl (- COOH)
– Microwave-assisted grafting showed
• Improved selectivity
• Reduced reaction time
• Improved yields and monolayer quality
CA: 72,4
after grafting of bio-linker precursor
Si-(CH2)12-COCH3
CA: 34
after bio-linker activation
Si-(CH2)12-COOH
hydrolisis

24. 24
May 2009
ss-DNA-functionalized Silicon surfaces
5 nm
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
C1s
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OCH3
CH2
O
OCH3
CH2
Methyl10undecenoate10-undecenoicacid
Hydrolysis
1.Boilingacidified
water
2.Microwave
200W/10’
O
OH
CH2
O
OH
CH2
N1s
Carboxylated Si surface  ssDNA-functionalized Si
– AR-XPS showed Si functionalized by ss-DNA when the EDC/NHS
strategy is applied to –COOH terminating Si surface
– When applied to Si-H surface:
- no N1s was detected on the Si surface
- the C1s spectra was noisy without components at higher B.E
- The Si2p showed significant oxidation
– When applied to –COCH3 Si surface:
- no N1s was detected on the Si surface
- the C1s spectra remains un-changed
– When applied to –COOH Si surface without NHS:
- no N1s was detected on the Si surface
- the C1s spectra remains un-changed
The strategy
Oligo-DNA: 5'–NH2–C6-AAAAAAAAAA-CgTgACATCATgCATg- 3‘

25. 25
May 2009
Molds Manufacturing – Process scheme
Si
Si
2) Photo Resist
deposition
3) Resist
exposure
1) cleaning
4) Resist
development
5) Deposition of
metal
6) Lift-off
Si
Si
Si
Si
SiSi
Si
2) Photo Resist
deposition
3) Resist
exposure
1) cleaning
4) Resist
development
5) Deposition of
metal
6) Lift-off
SiSi
SiSi
SiSi
SiSi
7) Resist
deposition
e-
8) Resist
exposure by
e-beam
9) Resist
development
10) Deposition
of metal
11) Lift-off
11) Dry etching
Si
Si
Si
Si
Si
Si
7) Resist
deposition
e-
8) Resist
exposure by
e-beam
9) Resist
development
10) Deposition
of metal
11) Lift-off
11) Dry etching
SiSi
SiSi
SiSi
SiSi
SiSi
SiSi
12) Removing of
Metallic Mask
13) Antisticking
Mold
Si
Optical Litho E-beam Litho

26. 26
May 2009
Molds Manufacturing
200n
m
200n
m
300nm
µm
-scale
Sub
µm
-scale 300nm300nm
Mold
NIL replica
CAD
4 x 6
Pitch < 10um
3 x 9
Pitch < 5um
3 x 8
Pitch < 2um
4 x 6
Pitch < 10um
3 x 9
Pitch < 5um
3 x 8
Pitch < 2um

27. 27
May 2009
80nm
Printed array of functionalized sensors
110nm
Mold Design Mold Production
NIL
Printed device
100 nm
100 nm
Mold
Re(Z)
- Img(Z)
Pristine (1)
Denaturation (3)
Hybridization
(2)
Electrical detection of complementary ss DNA
~µg/ml @ µm printed sensors (<ng/ml @ 50nm)
Next challenges:
- Sub-100nm printed sensors
- Printed nano-scale sensors in polymer
ssDNA-functionalized Printed Sensors
Printed nano-scale devices
Printed sensors

28. 28
May 2009
E-Beam Litho – work in progress
….Increasing the sensitivity of sensors

29. 29
May 2009
Printing active polymer – Test case
1.3 µm
Feature size
100 nm
Feature size
80 nm
1.60 um
L=100
nm
L= 80
nm
1.32 um
0.8 um
L= 50
nm

30. 30
May 2009
Printed Electrowetting Tech.
Electro-wetting as ultra low cost paradigm for printable
micro fluidic system based on manipulation of discrete
droplets electrically: moved, mixed, pumped….
Main advantages
No pumps or valves, Reconfigurable via SW.
Works with a large variety of liquids.
Extremely energy efficient
Demonstrated:
Surface finishing
Proprietary mold done to print test EW devices
Printed EW devices
Target voltages: 1. 5 V
Next Challenges:
Functionalization of printed EW devices
Sub-picoliter droplet movement
Printed EW Device
C.A ~ 119 C.A ~ 72
V=0 V=25 V
C.A ~ 119 C.A ~ 72
V=0 V=25 V

31. 31
May 2009
System Integration
To be implemented on Silicon or on plastic as well
Cartage
Mix of Bio-Hunter
Cartage
Mix for selective
sequestration
SensingSensing
Rinsing
I/Oapplicationdependent
Sequestration
Detection
Trash
sample
Applicationdependent
• A new proprietary algorithm enhancing the performances in detection has been developed.
Tests demonstrate its ability in very fast operations improving all the known tested
strategies
Pharmaceutical
BioMedIndustry