Printed Organic Diodes and their

Integration for Rectification and Energy

Harvesting
Donald Lupo, Petri Heljo, Miao Li, Kaisa Lilja,
Himadri Majumdar*
Department of Electronics
Tampere University of Technology
Tampere, Finland
Depeartment of Physics and Centre for Functional Mateirals
Åbo Akademi University
Åbo/Turku, Finland

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
Outline

• TUT Introduction
• Town and university
• Organic and printed electronics
• Gravure printed thin film diodes
• Materials and architecture
• Interfaces and effect on device performance
• Rectifier Circuits
• Half-wave vs. full wave
• Printed organic charge pump circuits
• Printed RF energy harvesters
• AUTOVOLT project
• Printed RF harvester and integration to capacitor

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 3

Tampere: “Manchester of the North”

• Founded as a market town in 1775, now third largest city

in Finland (213,000 inhabitants)
• Major growth during industrial revolution (thanks partly
to Tammerkoski rapids)
• Situated between 2 large lakes, Näsijärvi and Pyhäjärvi
• Industry includes paper, mining machinery, glass
manufacturing equipment – and mobile phones!

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
19.12.2012
 4

Tampere University of Technology (TUT)

• Established in 1965
• Started operating in the form of a foundation in 2010
• 11,600 students (2009)
• Strong tradition of university/industry cooperation

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
19.12.2012
 5

Printed Electronics at TUT

Professor Donald Lupo

Organic Electronics Group Printable Electronics Group
Head of group: Prof. Donald Lupo Head of group: Dr. Matti Mäntysalo
Senior scientist: Dr. Sampo Tuukkanen
• electronic devices utilizing solution • electronic system integration and
processable materials and printing manufacturing concepts utilizing
processes printing processes
• diodes, transistors, sensors, • interconnections, systems, reliability
supercapacitors and performance analysis

Over 250 m2 dedicated lab space, incl. dust-free processing laboratory of 60 m2

(non certified but close to ISO 14644-1 class 5)

Printing equipments: Ink-jet (2x iTi MDS 2.0, Dimatix DMP-2831), Gravure
PRINT LAB

(NSM Labratester), Flexo (RK Flexiproof 100), Screen (DEK)

Variety of other deposition and processing tools and equipments for

characterisation of material properties and electrical performance (spin coater,
fibrelaser, drop watcher, semiconductor parameter analyser, profilometer, etc.)

Environmental test equipments (thermal chambers for shock and cycling,

vibration, salt tests, drop tests, etc.)
D. Lupo, TU Darmstadt 20121219
D. Lupo, TPE12 22.05.2012
Variety of analysis tools in University (profilometers, SEMS, AFM, etc.)
 6

Organic Electronics Group

– Focus: understanding Activity areas – Concept development

how printing affects – Printed diodes, transistors – innovative and novel
materials, interfaces and and sensors combinations of materials,
device/system structure and
– Printed energy harvesters manufacturing
performance
– Printed supercapacitors – Scalable unit processes
– Printability of various
– Printed circuits – lab-scale unit processes
formulations of electronic
materials – Printed photovoltaic that are scalable and
modules feasible to cost-effective
– Materials compatibility and industrial production
interfacial properties
– Components and sub-
– Fabrication of devices
systems
– Characterisation of printed – single components (diode,
materials, structures and transistor, sensor, etc.) or
devices simple sub-systems (2-3
– Processes: gravure, screen, integrated components +
inkjet recurring multiples)

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 7

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
Outline

• TUT Introduction
• Town and university
• Organic and printed electronics
• Gravure printed thin film diodes
• Materials and architecture
• Interfaces and effect on device performance
• Rectifier Circuits
• Half-wave vs. full wave
• Printed organic charge pump circuits
• Printed RF energy harvesters
• AUTOVOLT project
• Printed RF harvester and integration to capacitor

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
Challenges for printing organic circuits

• Formulation
• Mass printing needs higher viscosity
• Traditional printing industry additives won‘t work
• Feature size
• Printing makes larger structures and these mean lower
speed, larger footprint etc
• Registration
• Limited by both machine and substrate unless digital
distortion correction possible
• Trade-off between feature size and throughput

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 Organic thin film transistors
Channel

Sourc Drain
e
Semiconductor
The conduction in a thin channel of semiconductor
between two electrodes (source and drain) Insulator
can be turned on and off by adjusting the
voltage at a gate electrode separated from Gate
the semiconductor by a thin insulator (gate
dielectric) Substrate
Current flow is horizontal
Applications in logic, display backplanes, RFID...
Critical parameters include
• Charge carrier mobility
• Issue with organic semiconductors
• Channel length
• Limited by printing resolution
• Gate overlap
• Limited by registration
• Field strength and uniformity
• Limited by thickness and uniformity of
insulator
Several challenges for printing and organics

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 Organic thin film diodes

Most organic thin film diodes (TFDs) are Cathode

Schottky diodes
• Metal/semiconductor contacts are
Semiconductor
Ohmic in one bias and blocking in the
other
• In forward bias, charges are injected
and current can flow Anode
• In reverse bias, the charge injection
barrier is high
• High rectification ratio
Current flow is vertical
Lower requirements for charge carrier
mobility and resolution/registration
than TFTs
Fewer issues for printing

Cebrite, patent application WO04/66410 (2004).

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 12

Diode architecture - expectation

Organic Schottky diodes

cathode
p-type • P-type semiconductor
semic
Semiconductor mobility
• Pentacene 0.15 cm2 / Vs
• PTAA 0.002 cm2 / Vs
- + Electrodes
• PTAA HOMO at 5.1 eV
cathode p-
I type • Cathode: calcium,
semic aluminium…
• Anode: platinum, gold…

+ -

p-type Low w.f.

cathode semic Energy in Cathode PTAA
X eV
I HOMO High w.f.
5.1 eV Anode

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 13

Diode fabrication

Simple three-layer vertical diode structure

High-throughput printing process manufacturing

Silver Ohmic
Contact
PTAA
Al/Cu Wet etched aluminium/copper (screen printed
Rectifying
PET contact etch resist)
PTAA and silver gravure printed
Diodes fabricated and characterised in ambient
conditions
No fine patterning or in-line vacuum processes

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 14

Diode Characteristics – Al cathode

Aluminium, a current density of 0.1-0.5 mA

1E-2
Rectification ratio over 10 000
1E-3
Threshold voltage, probably due
Current Density [A/cm2]

1E-4
to oxide layer on Al
1E-5
0.7 V Slow response (see later slides)
1E-6
1E-7
1E-8
1E-9 1200 nm, Al
1E-10
1E-11
1E-12
-6 -4 -2 0 2 4 6
Voltage [V]

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 15

Diode Characteristics – Cu cathode

Copper, a current density of 0.3 mA/cm 2

1E-2
1E-3
Same rectification ratio and forward
Current Density [A/cm2]

1E-4
1E-5
current as Al but no threshold
1E-6
1E-7
1E-8
1200 nm, Cu
1E-9
1E-10 1200 nm, Al

1E-11
1E-12
-6 -4 -2 0 2 4 6
Voltage [V]

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
19.12.2012
 16

Diode Characteristics

At 5 V, a current density from 0.3 to 2 mA/cm2 for

semiconductor thicknesses of 500 to1200 nm

1E-2
No significant degradation in four
1E-3 weeks after fabrication
Current Density [A/cm2]

1E-4
1E-5
1E-6
1E-7
1E-8 500 nm, Cu
1E-9 700 nm, Cu
1200 nm, Cu
1E-10 1200 nm, Al
1E-11
1E-12
-6 -4 -2 0 2 4 6
Voltage [V]
D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 Interfaces in printed organic diodes

• Good results for Cu/PTAA/Ag diodes

• The i-V curve shows clearly that Cu is the cathode
and Ag is the anode
• But according to the literature, the work function of
Ag is 4.3 – 4.7 and Cu‘s is ca 4.7
• >>> in principle, this shouldn‘t work!
• Plus, the rectification ratio is 100,000 with sputtered
Cu and 1000 with evaporated Cu
• So, something else was happening

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
Interfaces in printed organic diodes –
Kelvin probe

• A Kelvin probe (Au reference

in air) was used to estimate the
work functions of the Cu and
printed Ag electrodes
• Measured work function of Ag
is consistent with oxidation to
Ag2O
• Even accounting for the
uncertainty of Kelvin probe
measurements, the Cu values
K. Lilja et al., ACS Applied Materials and Interfaces 3, 7
do not explain cathode (2011)

behaviour

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
Interfaces in printed organic diodes – i-V
Curves

• Plot log J vs log V for

sputtered and evaporated Cu
diodes
•When current is space charge
limited, J = 9 r 0 V2/8L3 (Child‘s
law)
•SCLC starts ca 0.2 V for
evaporated Cu and ca 2 V for
sputtered Cu on PET
•Clearly a difference in the two
interfaces! K. Lilja et al, J. Phys. D. 44, 295301 (2011)

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 Interfaces in printed organic diodes –
impedance spectra

• Impedance spectra measured at

different voltages for diodes with
sputtered and evaporated copper
from 1 MHz – 10 Hz.
• @ high frequency: only geometric
capacitance
• @ high bias no difference
• @ low bias difference at low
frequency, indicative of interfaces
• >> indicates changes in the metal-
semiconductor interface Cole–Cole plots of the diode impedance at forward bias voltages of 5.0 ,
0.4, 0.2 and 0.1V. The frequency increases from right to left from 10 Hz to
1 MHz. Source: K. Lilja et al, J. Phys. D. 44, 295301 (2011)

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 Interfaces in printed organic diodes –
XPS data

• XPS data indicate presence of

Cu(I) and organic in both layers but
clearly more of each in the sputtered
copper
• Cu(I) believed to be Cu2O
• organic layer could be partially
PET but other impurities as well
• Experiments on ALD of PET for
controlled reference in progress

K. Lilja et al, J. Phys. D. 44, 295301 (2011)

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 Interfaces in printed organic diodes –
interfacial layer

• Based on impedance and XPS data, a model

can be proposed
• Effective Schottky barrier is increased beyond
measured value when semiconductor and
metal (+ Cu2O and organic) are brought into
contact.
• pinning of Fermi level in organic semiconductor
due to tailing of wave function from metal
• change in pinning due to intermediate dielectric
• orientation of dipole potential between two
interlayers has further effect
• Dual dielectric layer present in both
evaporated and sputtered Cu >> can explain
the fact that rectification is seen in both cases.
Thicker layers in sputtered Cu enhance the
effect
• In forward bias, field is high enough to assist
Simplified model for the diode Schottky contact. Source: K.
tunnelling >> identical forward currents at Lilja et al, J. Phys. D. 44, 295301 (2011)
sufficiently high bias
• Modelling at Åbo Akademi supports the
proposed mechanism

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
Outline

• TUT Introduction
• Town and university
• Organic and printed electronics
• Gravure printed thin film diodes
• Materials and architecture
• Interfaces and effect on device performance
• Rectifier Circuits
• Half-wave vs. full wave
• Printed organic charge pump circuits
• Printed RF energy harvesters
• AUTOVOLT project
• Printed RF harvester and integration to capacitor

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 24

Organic rectifier diodes for RF

Rectifiers in RFID
A rectifier circuit converts the AC signal picked up by the
RFID antenna to a DC signal for the chip to use
50 MHz rectifiers by Steudel et al. (Nat. Mater. 4 (2005)
279)
433 - 869 MHz integrated rectifiers by IMEC (Holst Centre) INPUT OUTPUT
– Based on vacuum processing/shadow masking AC DC
Spin coated P3HTdiodes with the -3dB point at 2 MHz by
Kang et al. (Thin Solid Films 518 (2009) 889)
Goal: make an RF rectifier using only mass printing
processes
Key issues
Mobility (response of OSC to AC field)
Capacitance (size and thickness of diode)

S. Steudel, K. Myny, V. Arkhipov, C. Deibel, S. De Vusser, J. Genoe, P.

Heremans, Nat. Mater. 4 (2005) 279.

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 25

Half-wave rectifier

• Half-wave rectifier circuit

• Discrete capacitor and resistor
• CL ~ nF
• RL usually 1 M
• Also printed capacitors have been
used
• CL 0.5 – 2 nF/cm2

• Half-wave rectifier output with 10 V

AC input SC 400 nm
• 6.1 V at low frequencies
• 3.8 V at 13.56 MHz

• Better output with thinner SC layers

• Lower yield

P. Heljo et al., IEEE Trans. Electron. Devices, in

press

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 26

Full-wave bridge rectifier

• Full-wave rectification for better output

characteristics?
• Lower ripple at low frequency application
• Lower output voltage
• Voltage drops over two diodes
• Slower device 5 mm
• Lower operation frequencies
• Also lower output power

P. Heljo et al., IEE Trans. Electron. Devices, in

press

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 27

Printed charge pumps

Fabrication

Monolithically integrated Integrated printed charge pump

printed charge pump
• Printed on a same substrate • Diodes and capacitors printed separately
• Evaporated Cu electrodes • Completely inkjet printed capacitors
• Inkjet printed capacitors • Gravure printed diodes
• Evaporated Cu bottom electrode
• Dielectric + top electrode • Integrated on printed substrate
• Gravure printed diodes • All processing steps in ambient air
• All processing steps in ambient air

P. Heljo et al., Proc. LOPE-C 2011

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
19.12.201
2
 28

Monolithically integrated printed charge pump

Results

• 10 V AC Input amplitude
• Decreases at high frequencies
• Capacitive shunting of the diodes
• 1 M load
• Stage 2 output
• 12.4 V at 100 kHz
• Deterioration of the diode Cu contacts
• Oxidation during treatments above 70 ºC
• Variations between diode properties
• Small capacitors
• Output ripple voltage

P. Heljo et al., Proc. LOPE-C 2011

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 29

Integrated printed charge pump

Results

• 10 V AC Input amplitude
• Decreases at high frequencies
• 1M load

P. Heljo et al., Proc. LOPE-C 2011

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 30

Integrated printed charge pump

Results

• 10 V AC Input amplitude
• Decreases at high frequencies
• 1M load

• Stage 1 output
• 10.6 V at 1 MHz
• 5.9 V at 13.56 MHz

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 31

Integrated printed charge pump

Results

• 10 V AC Input amplitude
• Decreases at high frequencies
• 1M load

• Stage 1 output
• 10.6 V at 1 MHz
• 5.9 V at 13.56 MHz

• Stage 2 output
• 18.1 V at 1 MHz
• 10.4 V at 13.56 MHz
• 2.7 times the output of a
half wave rectifier
• Low ripple voltage

P. Heljo et al., Proc. LOPE-C 2011

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 32

Conclusions – rectifier circuits

• Half-wave rectifier
• Output voltage is not high enough for many applications
• Structure, printing and contacts can still be enhanced
• Better materials
• Benefits of the full-wave rectifier exist at low frequencies
• Smaller capacitors are sufficient for low ripple voltages
• Charge pump approach for higher output voltages
• Possibility to add stages with high impedance loads
• Interesting for many RFID applications
• Gravure printable charge pumps under development
• Avoiding the problems with monolithically printed charge
pumps
• Goal is to provide supply voltage for printed transistor circuit

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
Outline

• TUT Introduction
• Town and university
• Organic and printed electronics
• Gravure printed thin film diodes
• Materials and architecture
• Interfaces and effect on device performance
• Rectifier Circuits
• Half-wave vs. full wave
• Printed organic charge pump circuits
• Printed RF energy harvesters
• AUTOVOLT project
• Printed RF harvester and integration to capacitor

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 34

AUTOVOLT Outline

• AUTOVOLT (Universal autonomous power source combining printed energy

harvesters and integrated voltage control) - funded by Academy of Finland
• Collaborate with Aalto University
• TUT: RF harvester, solar cell, supercapacitor, integration

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 35

Printed RF energy harvesters

• Replace batteries, commonly used in passive RFID tags

• Collect or receive RF energy in a wireless mode (Antenna)
• Provide DC power to a wide range of circuitry (Rectifier: diodes + capacitors)

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 36

Printed RF energy harvesters

Integrated printed RF harvesters

• Inkjet printed antennas and capacitors

• Gravure printed diodes

• All fabrications were performed in ambient

Environment
• The harvester is of the size of a credit card

M. Li et al., Proc. LOPE-C 2012

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 37

Inkjet printed antennas and capacitors

• Maskless, fast prototyping in circuit development

• Also feasible for manufacturing

iTi MDS 2.0 inkjet printer

• Higher speed, large area deposition

• Dielectric ink: SunTonic insulator U5388

• Conductive ink: Harima NPS-JL Silver

• Antenna: 8 turns, total length of 1445 mm

• Capacitor: 1.3 cm 2 , 0.4 nF
Dimatix DMP-2831 inkjet printer M. Li et al., Proc. LOPE-C 2012

• Fast, accurate small pattern

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 38

Printed RF harvester
Results

• 10 V coupling AC input amplitude • Varying DC output 3-5 V

• 1 M Load • Changing the transmitting power
• 13.56 MHz • Adjusting the coupling distance

• Rectifying output: 5 V
• Small ripple

M. Li et al., Proc. LOPE-C 2012

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 Initial Tests on Charging 39

Supercapacitors (benchmarking)
through Organic Diodes
250
20120814 S4 NORIT 50
200

Voltage (mV)
150

100

50
20120814 S4 NORIT
50
0
0 5 10 15 20 25 30
•Signal generator: Vpp 5V, at 13.56MHz Time (Minute)

• Charging rate: 6.056 mV/min

• Discharging: “slowly” discharge itself due to the internal
leakage currents, approximately 0.1-0.3mV/min

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 40

Conclusions – Energy harvesting

• An RF harvester using organic diodes and optimised antennae can be

printed using air stable materials and ambient processing
• Reduction in the SC thickness improves DC output efficiency
• DC output of 5 V for 10 V AC coupling input at 13.56 MHz
• DC outputs of 3-5 V can be provided with the half-wave rectifier configuration
• Output of an organic diode can be used to charge a supercapacitor for interim
power in a printed energy harvesting system, e.g. for operation of a sensor
circuit
• Further development is needed
• Improve organic diode efficiency
• Optimal load (diode modelling)
• Integrate different rectifiers/voltage multipliers

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 Summary and outlook

• Gravure printed Schottky diodes can work quite well – even when they
shouldn‘t
• HF rectifier diodes can be printed using a fully air stable amorphous hole
conductor polymer and no fine patterning steps
• The right circuit (half wave, full wave, charge pump) depends on the
operating frequency and input requirements – and the limits of
performance of the organic diodes
• Printed RF rectifier circuits can be used for energy harvesting

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
 42

Acknowledgements

Dr. Sampo Tuukkanen

Dr. T. Joutsenoja, presently at VTT
Dr. T. G. Bäcklund, presently at Merck Chemicals Ltd.
Prof. R. Österbacka from Åbo Akademi University
Dr. T. Kololuoma and T. Hassinen from VTT
Organic Electronics and Printable Electronics Groups at TUT

Funding
UPM-Kymmene Corporation, Tekes (the Finnish Funding Agency for Technology
and Innovation), Academy of Finland

D.
D. Lupo,
Lupo, TU Darmstadt
TPE12 20121219
22.05.2012
19.12.2012