Conductive polymers

Conductive polymers

(Parte 1 de 3)

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(Advanced Information) The Nobel Prize in Chemistry, 2000:

Conductive polymers

Prize motivation1
What is electrical conductivity?2
Conductive polymers – the story4
Synthesis and processing6
References and further reading15

Contents Conductive polymers – a surprising discovery 1 What makes a material conductive? 3 Applications of conductive polymers 5 Mechanism of polymer conductivity – role of doping 6 Molecular electron-transfer theory 1 Electroluminescent polymers – second-generation conductive polymers 13 From silicon physics to molecular electronics 14

Prize motivation

The Royal Swedish Academy of Sciences has decided to award the Nobel Prize in Chemistry for 2000 to three scientists who have revolutionised the development of electrically conductive polymers.

Professor Alan J. Heeger at the University of California at Santa Barbara, USA Professor Alan G. MacDiarmid at the University of Pennsylvania, USA and Professor Hideki Shirakawa at the University of Tsukuba, Japan are rewarded “for the discovery and development of electrically conductive polymers”.

The choice is motivated by the important scientific position that the field has achieved and the consequences in terms of practical applications and of interdisciplinary development between chemistry and physics.

Conductive polymers – a surprising discovery

We are used to polymers – that is, plastics – being somehow the opposite of metals. They insulate, they do not conduct electricity. Electric wires are coated with polymers to protect them – and us – from short-circuits. Yet Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa have changed this view with their discovery that a polymer, polyacetylene, can be made conductive almost like a metal.

Polyacetylene was already known as a black powder when in 1974 it was prepared as a silvery film by Shirakawa and co-workers from acetylene, using a Ziegler-Natta catalyst (K. Ziegler and G. Natta, Nobel Prize in Chemistry 1966). But despite its metallic appearance it was not a conductor. In 1977, however, Shirakawa, MacDiarmid and Heeger discovered that oxidation with chlorine, bromine or iodine vapour made polyacetylene films 109 times more conductive than they were originally.1 Treatment with halogen was called “doping” by analogy with the doping of semiconductors. The “doped” form of polyacetylene had a conductivity of 105 Siemens per meter, which was higher than that of any previously known polymer. As a comparison, teflon has a conductivity of 10–16 S m–1and silver and copper 108 S m–1. A key property of a conductive polymer is the presence of conjugated double bonds along the backbone of the polymer. In conjugation, the bonds between the carbon atoms are alternately single and double. Every bond contains a localised “sigma” (σ) bond which forms a strong chemical bond. In addition, every double bond also contains a less strongly localised “pi” (π) bond which is weaker. However, conjugation is not enough to make the polymer material conductive. In addition – and this is what the dopant does – charge carriers in the form of extra electrons or ”holes” have to be injected into the material. A hole is a position where an electron is missing. When such a hole is filled by an electron jumping in from a neighbouring position, a new hole is created and so on, allowing charge to migrate a long distance.

Today conductive plastics are being developed for many uses, such as in corrosion inhibitors, compact capacitors, antistatic coating, electromagnetic shielding of computers, and in “smart” windows that can vary the amount of light they allow to pass, etc. A second generation of electric polymers has also appeared (see below) in, e.g., transistors, light-emitting diodes, lasers with further applications such as in flat television screens, solar cells, etc. Polymers have the potential advantages of low cost and that they can be processed, e.g., as film. We may soon be seeing electroluminescent plastics papered on walls for illumination.

What is electrical conductivity? Conductivity is defined by Ohm’s law:

U = R I, (1) where I is the current (in Amperes) through a resistor and U is the drop in potential (in Volts) across it. The proportionality constant R is called the “resistance”, measured in Ohms (Ω). R is measured by applying a known voltage across the resistor and measuring the current through it. The reciprocal of resistance (R–1) is called conductance. Ohm’s law is an empirical law, related to irreversible thermodynamics (Ilya Prigogine, Nobel Prize in Chemistry 1977), the flow I as a result of a gradient in potential leads to energy being dissipated (RI2 Joule s–1).

Not all materials obey Ohm’s law. Gas discharges, vacuum tubes, semiconductors and what are termed onedimensional conductors (e.g.a linear polyene chain) generally all deviate from Ohm’s law.

In Ohmic material the resistance is proportional to the length l of the sample and inversely proportional to the sample cross-section A:

R = ρ l / A (2) where ρ is the resistivity measured in Ω cm (in SI units Ω m). Its inverse σ = ρ–1 is the conductivity. The unit of conductance is the Siemens (S = Ω –1). The unit of conductivity is S m–1.


FIGURE 1 Conductivity of conductive polymers compared to those of other materials, from quartz (insulator) to copper (conductor). Polymers may also have conductivities corresponding to those of

Conductivity depends on the number density of charge carriers (number of electrons n) and how fast they can move in the material (mobility µ):

σ = n µ e (3) where -e is the electron charge. In semiconductors and electrolyte solutions, one must also add in Eq (3) an extra term due to positive charge carriers (holes or cations). Conductivity depends on temperature: it generally increases with decreasing temperature for “metallic” materials (some of which become superconductive below a certain critical temperature Tc), while it generally decreases with lowered temperature for semiconductors and insulators.

FIGURE 2 The conductivity of conductive polymers decreases with falling temperature in contrast to the conductivities of typical metals, e.g. silver, which increase with falling temperature.

What makes a material conductive?

In many materials, such as crystals, stretched polymers or liquid crystals, macroscopic properties such as strength and optical and electrical properties generally depend on direction. They are said to be anisotropic. Similarly, the material’s electrical conductivity may depend on direction and be anisotropic. Three simple carbon compounds are diamond, graphite and polyacetylene. They may be regarded, respectively, as three- , two- and one-dimensional forms of carbon materials (Fig. 3). Diamond and graphite are modifications of pure carbon, while in polyacetylene one hydrogen atom is bound to each carbon atom.

FIGURE 3 Three-, two- and one-dimensional carbon materials: diamond (a) and graphite (b) crystal lattices, and polyacetylene chain (c). An alternative way of writing polyacetylene is also shown (d).

Diamond, which contains only σ bonds, is an insulator and its high symmetry gives it isotropic properties.

Graphite and acetylene both have mobile π electrons and are, when doped, highly anisotropic metallic conductors. The conductivity is about one million times greater in the plane of the graphite rings than at right angles to this plane: σ (parallel)/ σ(perpendicular) = 106 . Correspondingly, the conductivity of stretchoriented polyacetylene is some 100 times higher in the stretch direction than perpendicular to it. The smaller

anisotropy compared to graphite, i.e. non-vanishing σ(perpendicular), could suggest ”short-circuiting” across the chains. Since the polyacetylene chains are not infinite, contacts between them are important if the material is to be macroscopically conductive. This could thus explain the lower conduction anisotropy compared to graphite

Anisotropy is also interesting in other contexts of stretch aligned polymers: when the absorption of light is anisotropic the material acts as a polariser. Also mechanical strength is anisotropic: aligned polyacetylene fibers are known to be very strong along the orientation direction.

Conductive polymers – the story

Conductive polymers are a sub-group of a larger, older group of organic and inorganic electrical conductors. In fact, as early as 1862 H. Letheby of the College of London Hospital, by anodic oxidation of aniline in sulphuric acid, obtained a partly conductive material which was probably polyaniline. In the early 1970s, it was found that the inorganic explosive polymer, poly(sulphur nitride) (SN)x, was superconductive at extremely low temperatures (Tc=0.26 K). Many conductive organic compounds were also known, such as those discovered by K. Bechgaard (Copenhagen) together with D. Jerome (Paris) and famous for being superconductive at rather “high” temperatures (Tc around 10 K). They are salts of inorganic acceptors and organic donors consisting of large, cyclically conjugated π electron systems that form coin-pile stacks in the solid state.

summarised below (see also Refs 7,8)

However, polyacetylene was the conductive polymer that actually launched this new field of research (Refs 1- 4). For details of its history see the excellent review articles by Feast, et al., 5 and by M.G.Kanatzidis, 6

Natta and co-workers prepared polyacetylene in 1958 by polymerising acetylene in hexane using

Et3Al/Ti(OPr)4 (Et= ethyl, Pr=propyl) as a catalyst. Though the resulting material was highly crystalline and of regular structure, it was a black, air-sensitive, infusible and insoluble powder. Ziegler-Natta polymerisation was developed for polymerising alkenes such as ethylene by inserting an unsaturated molecule into the carbon-titanium bond of the growing macromolecule. It depends greatly on the activity of the choice of catalyst system. In the early 1970s Shirakawa and co-workers adapted the method to make well-defined films of polyacetylene.

A major discovery by Shirakawa was that this polymerisation could be effected at the surface of a concentrated solution of the catalyst system in an inert solvent. The synthetic procedure involved adding

Ti(OBu)4 and then Et3Al to a small volume of toluene under an inert atmosphere. The solution was allowed to age at 20oC for 45 minutes and was then cooled to –78oC. The reaction vessel was evacuated and acetylene gas introduced and allowed to react with a film of the catalyst which had already formed on the walls of the reaction vessel. A film of polyacetylene immediately formed there2. The reaction was controlled by evacuating unreacted acetylene gas. This procedure produced a copper-coloured film of all-cis-polyacetylene with a cis content of some 95 %. Shirakawa’s procedure also allowed silvery all-trans-polyacetylene to be formed by running the reaction in n-hexadecane at 150oC. However, its conductivity was relatively modest:

cis-polyacetylene 10–8 -10–7 S m–1 and trans-polyacetylene 10–3

FIGURE 4 All-cis- and all-trans-polyacetylene

In 1975 Professors Alan Heeger and Alan MacDiarmid collaborated to study the metallic properties of a covalent inorganic polymer, (SN)x . They shifted their attention to polyacetylene after MacDiarmid had met

Shirakawa in Tokyo. During a visit at the University of Pennsylvania, Shirakawa refined the polymerisation of polyacetylene. With his experience from the (SN)x materials, MacDiarmid wanted to modify the polyacetylene by iodine treatment. Shirakawa and Ikeda had previously noted that treating silvery polyacetylene films with bromine or chlorine decreased the infrared transmission without altering the colour. MacDiarmid now turned to Heeger in whose laboratory a conductivity of 3000 S m–1 was measured for iodine-modified trans-polyacetylene, an increase of seven orders of magnitude over the undoped material.

The seminal paper received for publication on May 16, 1977, had the title: Synthesis of electrically conducting organic polymers: Halogen derivatives of polyacetylene (CH)x. 1 Two other papers received later in the same year elaborated further on the topic. 3,4

Exciting experiments followed. Shirakawa could now control the ratio of cis/trans double bonds. Cispolyacetylene doping resulted in even higher conductivities. The iodine may first have isomerized the polymer to all-trans material, which then underwent efficient (defect-free) doping so that the degree of orientation in the doped polyacetylene was greater overall. Doping cis-polyacetylene with AsF5 resulted in an increase of conductivity by a factor of 1011. The high conductivity found by Heeger, MacDiarmid and

Shirakawa clearly opened up the field of “plastic electronics”.

Other polymers studied extensively since the early 1980s include polypyrrole, polythiophene (and various polythiophene derivatives), polyphenylenevinylene and polyaniline. Polyacetylene remains the most crystalline conductive polymer but is not the first conductive polymer to be commercialised. This is because it is easily oxidised by the oxygen in air and is also sensitive to humidity. Polypyrrole and polythiophene differ from polyacetylene most notably in that they may be synthesised directly in the doped form and are very stable in air. Their conductivities are low, however: only around 104 S m–1, but this is enough for many practical purposes.

Applications of conductive polymers

The commercialisation exemplified by the following list of materials illustrates the effects of Heeger’s, McDiarmid’s and Shirakawa’s work on the later development of conductive polymers. The principal interest in the use of polymers is in low-cost manufacturing using solution-processing of film-forming polymers. Light displays and integrated circuits, for example, could theoretically be manufactured using simple inkjet printer techniques. 6-10

Doped polyaniline is used as a conductor and for electromagnetic shielding of electronic circuits. Polyaniline is also manufactured as a corrosion inhibitor.

Poly(ethylenedioxythiophene) (PEDOT) doped with polystyrenesulfonic acid is manufactured as an antistatic coating material to prevent electrical discharge exposure on photographic emulsions and also serves as a hole injecting electrode material in polymer light-emitting devices.

Poly(phenylene vinylidene) derivatives have been major candidates for the active layer in pilot production of electroluminescent displays (mobile telephone displays).

Poly(dialkylfluorene) derivatives are used as the emissive layer in full-colour video matrix displays.

Poly(thiophene) derivatives are promising for field-effect transistors: They may possibly find a use in supermarket checkouts.

(Parte 1 de 3)