Renaissance of the Plastic Age

Polymers for Electronics & Photonics

T.P.Radhakrishnan School of Chemistry, University of Hyderabad Hyderabad 500 046, India tprsc@uohyd.ernet.in
http://chemistry.uohyd.ernet.in/~tpr/

This file is available at http://chemistry.uohyd.ernet.in/~ch521/

Materials and civilisation

Stone age (Before 5000 BC) Copper age (5000 - 3000 BC) Bronze age (3000 - 800 BC)

Iron age (800 BC - 40 AD)

Plastic age ?

Types of materials
Metals / Alloys
*

Ceramics

Polymers

Semiconductors

Composites

Biomaterials

Molecular materials
*Courtsey: W. D. Callister, Fundamentals of Materials Science and Engineering

Design of Molecular Materials

Elements / Compounds
Chemical / Physical routes

Materials

Elements / Compounds
Chemical routes

Molecules
Chemical / Physical routes

Crystals

Nanostructures

Thin films / LB films

Polymers

Natural polymers

Synthetic polymers

Polyethylene

Polytetrafluoroethylene (Teflon)

Phenol-formaldehyde (Bakelite)

Polyhexamethylene adipamide (Nylon 6,6)

Polyethyleneterephthalate (PET)

Polycarbonate

Discovery of conducting polymers

1862 1970s
Acetylene gas

Lethby (College of London Hospital) Oxidation of aniline in sulfuric acid Shirakawa (Japan)

HC

CH
Ti(OBu)4 & Et3Al Hexadecane 150oC

Ti(OBu)4 & Et3Al Toluene 78oC

copper-coloured film cis-polyacetylene

silvery film trans-polyacetylene

Polyacetylene (PA)
n

Electrical conductivity (s) cis PA trans PA 10-10 10-9 S cm-1 10-5 10-4 S cm-1
: s (copper) ~ 106 S cm-1 : s (teflon) ~ 10-15 S cm-1

For comparison

Doping leads to enhanced conductivity

Semiconductor s ~ 10-5 S cm-1

+ e-

- e+
n n

Metal s ~ 104 S cm-1

Discoverers - Nobel Prize 2000

A. Heeger, A. McDiarmid, H. Shirakawa

(this photograph taken at the International Conference on Synthetic Metals, 2000, was kindly provided by Prof. Heeger)

Polyacetylene - electronic structure

-electronic energy levels and electron occupation

(a)

(b)

(c)

(d)

(e)

(a) ethylene (b) allyl radical (c) butadiene

(d) regular trans-PA

(e) dimerised trans-PA

How does a conducting polymer work ?

Oxidative doping of polyacetylene by iodine
[CH]n + (3x/2) I2 [CH]nx+ + xI3-

+ I3-

Polaron and its delocalisation

+ I3-

+ I 3-

Excitations
Bipolaron
+ . oxidation + +

Neutral Soliton
isomerisation .

Positive Soliton
oxidation +

Examples of conducting polymers

H Polyaniline (PANI) N N N H N
n

Polypyrrole (PPy)

Polythiophene (PT)

Polyethylene dioxythiophene (PEDOT)

Polyparaphenylene (PPP)
n

Polyparaphenylene vinylene (PPV)

Alkoxy-substituted polyparaphenylene vinylene (MEH-PPV)

n

Electrical conductivities
Copper Platinum Bismuth Graphite Germanium
10+6 10+4 10+2 100 10-2 10-4 10-6 10-8 10-10 10-12

Silicon Polyethylene

Conducting Polymers

Diamond Quartz

10-14 10-16 10-18 S cm-1

Synthesis of PANI

Cathode Anode (ITO plate)

Aniline + dil. HCl

Instead of electrochemical oxidation, chemical oxidation may be carried out : Aniline + acid + oxidising agent ((NH4)2S2O8)

Voltage (~ 0.3 - 0.5 V) applied

Result of electropolymerisation

The green coating on the ITO electrode is due to the formation of emeraldine salt form of PANI

Polyaniline (PANI)
Leucoemeraldine
H N H N H N H N

Colorless
(Insulator)

Emeraldine base

H N

H N

Blue
(Insulator)

Emeraldine salt

H N

H N

H+ N X-

Green
(Conductor)

Pernigraniline Oxidation

Purple
(Insulator)

Applications of conducting polymers

Polyaniline (PANI) Transparent conducting electrodes Electromagnetic shield Corrosion inhibitor Smart windows (electrochromism) Polypyrrole (Ppy) Radar-invisible screen coating (microwave absorption) Sensor (active layer) Polythiophene (PT) Field-effect transistor Anti-static coating Hole injecting electrode in OLED Polyphenylenevinylene (PPV) Active layer in OLED

Polypyrrole - conductivity switching

Enzyme Biosensor Using PPy

Glucose oxidase -D-glucose + O2 + H2O D-gluconic acid + H2O2 H2O2 + 2HCl + Ppy 2H2O + Ppy2+.2Cl-

PANI-PSS

PSSn-(100 kDa) RT = 8.3x10-2 Scm-1

*
n

PSSn-(70 kDa) RT = 3.6x10-2 Scm-1

*

PSSnSO3

Sensors
Typical example : Ammonia sensing by PANI-PSSM film
1.35 1.30 1.25

Resistance change with time Ammonia in Ammonia out

R/Ro

1.20 1.15 1.10 1.05 1.00 0 1000 2000 3000 4000

Time(sec)

Resistance change at 150 sec. for different concentrations of ammonia

2.0

1.8

(R/Ro)150

1.6

1.4

1.2

50

100

150

200

250

Concentration of ammonia (ppm)

Electroluminescence

Electric field +

Metal electrode Organic thin film Transparent electrode (ITO)

Light

Principle of EL

eLUMO LUMO

h+
HOMO HOMO Light

Cathode

Anode

Polymers for Organic Light Emitting Diodes (OLED)

PPV

MEH-PPV

Commercial materials like Mn2+ in ZnS require 100V DC PPV : requires 5 - 10V DC runs even with AC brightness ~40,000 cd/m2 ie. ~100 times brighter than a TV screen

Organic LED driven by organic transistor

D S

Ca/Ag
MEH/PPV Silica Gold P3HT Silica n+-Silicon Aluminium G

Electrochromic devices
Polymer Polythiophene Polypyrrole Polyaniline Undoped Red Yellow-green Yellow Doped Blue Blue-black Green/Blue

Li anode Polymer electrolyte Conducting polymer

ITO electrode

Viewing side

On application of voltage

Li anode Polymer electrolyte Conducting polymer ITO electrode

Viewing side

Conjugated polymers for nonlinear optics

NLO materials interact with light

(C
C C C C C C

Light changes the material properties Changes the properties of the light
C

Polydiacetylene

)n

Photonic Application of Conducting Polymers - Kerr gate

Laser 1 Polariser Crossed Polariser

No light

NLO (c(3)) polymer

Laser 2

Laser 1

Polariser

Crossed Polariser

Future Outlook

All organic transistor

Plastic solar cell based on MDMO-PPV/PCBM (conducting polymer - fullerene composite) on flexible ITO coated PET

Thank you