INTERVIEW with Dr.

Alan Heeger
Could you give us a short overview of the evolution of organic polymer science? In the early days, the 1970s, we were laying out the initial discoveries and then building up the framework of the field. The big thing in the early 1980s was the theoretical work on

n this interview with ESI correspondent Gary Taubes, Dr. Alan Heeger of the University of California, Santa Barbara discusses his work with semiconducting and metallic polymers, and how this work has evolved over the years. In our analysis of high-impact papers in the special topic of conducting polymers, 146 of Dr. Heegers papers were cited a total of 5,881 times, making him the most-cited author in this field. In addition to his work at UCSB, Dr. Heeger is the chief scientist at the UNIAX Corporation and also won the 2000 Nobel Prize in Chemistry.
solitons etc., and then the synthesis of a range of new materials that really began to lead to the promise that we would have soluble, processable polymers that would still have the optical properties of metals and semiconductors. At the beginning of the 1990s, a couple of things happened. First, the field matured to the point that we knew enough about polymers to synthesize stable polymers with specific energy gaps. Around 1990 this led to the discovery of LEDs, the application that was discovered in Cambridge by Richard Friend and his collaborators and that created one focus of much of the work in the 1990s. A second focus was the work on soluble polyaniline. There had been a lot of discussion suggesting that organic polymer metals would never be stable and never be processable. In the early 1990s, Cao, Smith, and I published a series of papers showing that it could be done.

Your most cited publication of the decade was the 1991 paper in Applied Physics Letters, "Visible-Light Emission From Semi conducting Polymer Diodes" (D. Braun, A.J. Heeger, 58[18]: 1982-4, 6 May 1991). What was that about and why did it have such an impact? That was a follow-up on the original LED work done at Cambridge by Friend and his collaborators. That work opened the field of LEDs, but the efficiencies of those LEDS were very low. In effect, you had to almost dark-adapt your eye to see them. The efficiencies were in the neighborhood of 1/1000ths of a percent. Still, that was the beginning of the LED field. But very quickly after that Braun and I were able to get the efficiency up to one percent, which is what this paper was about. It demonstrated that these LEDs might be something that could be commercially interesting. So Friend deserves the credit for the initial discovery without any doubt, but our paper demonstrated that the efficiency could be high enough to be of technological relevance. What is the efficiency of polymer LEDs now, and what is needed to be commercially viable? Well, we reported approximately one percent in that early paper. I think efficiencies have improved up to 8 to 10 percent in polymers. And that is in serious displays that we are making at UNIAX, the company we started here in Santa Barbara, where were actually processing a whole display. There are some reports in the literature with polymers and particularly with small molecules of even higher efficiency. So its gone up by at least a factor of ten in the past decade. Is that enough? Yes and no. Its probably enough to get initial products out. For example, the efficiency we have now with green emitting polymerswhere the eye is most sensitiveare good enough such that if used in the display of a cellular telephone, they would save energy and give more talk time between charges. But theyre not yet good enough in all colors and thats an ongoing problem. Weand thats the global weare pushing toward full-color displays. So far, efficiencies and lifetimes are not good enough in the blue and red for that application. Whats polyaniline and what makes it so important? Its a critical step. Its a conducting polymer that has electrical conductivities approaching those of conventional

metals. We use it for making electrodes. Take LEDs, for example. Polyaniline is a transparent electrode. So it points out one of interesting features of these polymer metals in that they have properties that are different from regular metals in many ways. One is they are not shiny and silvery in the visible part of the spectrum. The plasma frequency is in the infrared. So they look shiny and reflective in the infrared but in the visible spectrum theyre basically transparent. So we use polyaniline to make a bi-layer electrode, with indium-tin-oxide, or ITO, which is a wellknown transparent conductor and which can be put down on glass, for example, or plastic. Then we put a layer of polyaniline from solution on top of that to make the bi-layer. That is pretty much the way all these LEDs are made now. The wonderful thing is you can put this metallic polymer easily onto the surface of ITO, and make this bi-layer electrode because youre just casting the film from solution. The effect is you stabilize the ITO, which otherwise has a tendency to change its work function. This makes the device much more efficient. How would you describe the current state of affairs in your field and its prospects for the future? If you plotted it, it would look like a hockey stick. Were just taking off now. A lot of hard work has been done on the synthesis of new materials and somehow proving the industrial viability. Let me use the LED as an example again. The first device lasted only minutes. While it immediately attracted some attention in the scientific community, there was a lot of skepticism about commercial applications, and rightly so. People felt these materials would never be pure enough to lead to commercially interesting products. Why is that? Think about semiconductor technology. The breakthrough in the 1950s was to make ultra, ultra pure silicon. Were not talking about one percent, but parts-perbillion purity in conventional semiconductors. Now if you think about polymerization reactions and polymers, its a wonderfully creative area to design and synthesize new polymers, but its a lot like cooking. Youre making these things in a soup, with catalysts and this and that, and the idea that you would end up with something sufficiently pure to be used in semiconductor devices was hard for people to accept. So I think only when we began at UNIAX to show lifetimes of many thousands of hours did that become believable. That kind of lifetime is now being produced in many labs around the world. And you know how science is: once you know that something can be done you get there a little bit faster. Im hopeful that progress will be even more rapid from now on in.

What about devices other than LEDs? In a parallel effort, starting around 1987, I published a little paper with two of my students that showed how to make a diode by casting the polymer from solution. That was Tomozawa, Braun, and Heeger and it was a first, in the sense it anticipated a whole development of plastic electronics. We made a diode by casting the active semiconductor polymer from solution. Now whats happening is Philips, for example, has recently has been using semiconductor and metallic polymers, casting from solution and using simple processing methods, to make integrated circuits. Theyve demonstrated integrated circuits with real functionality and thin-film transistor arrays that can be used to drive liquid crystal displays. So the use of these materials in plastic electronic devices is just taking off now. Philipss integrated circuit is a beautiful example. By relatively simple methods, theyre able to make an integrated circuit containing a semiconductor polymer processed from solution that has a whole range of simple applications. They can basically print them onto a label. So the vision is that every item in the supermarket, for instance, would have this kind of circuit on it, and you can do all the pricing and check-out simultaneously by just walking through the check-out stand. This kind of technology is not trying to compete with the elegance and high speed of silicon, which is deeply entrenched and very successful. Polymer mobilities are not nearly as good as those of silicon. But we can go in another direction. We can make functioning, very low-cost circuits by printing techniques and do it in incredible volume. At UNIAX, we put a lot of effort into developing photodetectors and photovoltaic cells from these polymers that stemmed from a Science paper published in 1992. The first author was Sariciftci (N.S. Sariciftci, L. Smilowitz, A.J. Heeger, F. Wudl, "Photoinduced electron-transfer from a conducting polymer to Buckminsterfullerene," 258[5087]: 1474-6, 27 November 1992). That paper also opened a new direction toward photo-detector and photovoltaic cells, which has developed very well in the intervening eight years. Were now making photo-detector arrays that are capable of doing digital photography in color. We are excited about that. Sariciftci, who was the lead author, is now a professor of physical chemistry in Lindz, Austria, and has put together an institute focused on this application. They recently reported solar cells with three-percent efficiency, which is within a factor of two of what amorphous silicon can do. But again, the cost is potentially much lower simply because of the processing advantages of these polymers.

The other advance that comes to mind is lasers. Thats a fun story. In the summer of 1996 we had, as we do every other year, a major international conference in the field. Its called the International Conference on Synthetic Metals. We came to that conference with great excitement and enthusiasm because we had discovered you could make lasers out of these polymers. It turned out three independent groups had come to that meeting, each thinking they had done it first. That was our group, the Friend group from Cambridge, and the Vardeny group from the University of Utah. We all appeared at this meeting with basically the same kind of data. That really gave the field a new kick because suddenly you could imagine lasers of all colors from this technology. We have plenty of lasers from other technologies, but inexpensive thin-film lasers with all colors would open a number of interesting opportunities. Now thats been developing. The community also now has very low-threshold optically pumped lasers. The Holy Grail is still an electrically pumped injection laser, and while we have not yet succeeded in doing that, Im optimistic that we will. People at Bell Labs this summer demonstrated for the first time an electrically-driven laser based upon a single crystal of an organic molecule, which is a good step along the way, and I think that the methods they have developed are applicable to the polymers. So as I review the 1990s in my mind, I see the LED discovery at Cambridge and the work we did quickly pushing up the efficiency. The next step was the demonstration and beginning commercialization of soluble metal polymers that enable all these devices to go. The next step was the discovery of this photo-induced electron transfer, which leads to solar cells, and the next big one was the 1996 discoveries of amplified stimulated emission and lasing done by several groups. Are you surprised at how this has played out over the years? Sometimes things are obvious after the fact. But each one of these things was in a way a surprise. The LED itself was a surprise. With hindsight maybe it shouldnt have been, because light emission from semiconductors was known, but it came out of nowhere in this field. The early polymers had not been luminescent. The idea of very high-efficiency solar cells is incredible. The discovery of lasers and laser action was a real surprise. There had been research and publications that suggested this was never going to happen because of concentration quenching, which is a well-known phenomenon in small molecules. All of those things were a surprise. The last one, in a technology sense, was a surprise

even to me; that we were able as a community to get the purity of these materials up to a level which is sufficient to make electrical devices from polymers that will work and last for years. That was far from obvious. Where would you like to be five years from now, and what are your long-term research goals? There are many. One opportunity I see goes back to the beginning of the research in polymers in metallic forms. We have not even begun to approach the limits to the intrinsic properties of these materials. We are making metals from these polymers but they are relatively poor metals. Theyre very disordered. If you cast a film from solution of a highmolecular-weight polymer what you get is a tangled spaghetti. What you really want, if you want very high performance, is more like spaghetti in the box before you cook it. You want aligned chains that are chain extended. The theoretical work tells us that when you do that, you will have metals which have electrical conductivities significantly higher than copper or anything else and have a strength greater than steel. This is really high performance and something worth going for. The first steps have been taken. In case of polyacetyline, even in the 1980s we were able to demonstrate conductivity approaching that of copper with a strength comparable to steel, and we were nowhere near the intrinsic limit. This is a very interesting goal of polymer science: manipulating polymer chains into forms that are most useful. We need some help in that from the polymer community but I think it can be done. As far as other things, well see the development of these electronic devices in a variety of directions. One thing Im also very interested in right now and were beginning to work toward is biology. Were using these polymers as elements for biosensors. Several groups in the country and around the world are working on that. The work falls on the boundary between physics, chemistry, and biology. And thats where you often find new things. There have also been some reports in the literature around the idea that you might be able to use metallic polymers for the repair of nerve damage. If that were the case, it would obviously have a major impact. Thats something else Id like to look into. Theres a lot of vitality in this field, and lots of new ideas still emerging from the simple fact that what you have here are materials with the electronic and optical properties of metals and semiconductors, while retaining the processing advantages and mechanical advantages of polymers.

Dr. Alan J. Heeger Institute of Polymers and Organic Solids University of California, Santa Barbara Santa Barbara, CA, USA