Hideki Shirakawa - Research Engineer - Nobel Prize Winner

Topic - " for the discovery and development of conductive polymers "

For the ten years from the third grade of elementary school to the end of high school, I lived in the small city of Takayama, a town of less than sixty thousand, located in the middle of Honshu, Japan. Even though it was far away from Japan's principal cities, Takayama has been called a "little Kyoto" because of the similarity of its landform to Kyoto, the city sits in a basin surrounded by mountains with a river flowing through it, and because of its long-established cultural heritage and tradition. In this small town, rich in natural beauty, I spent my days enthusiastically collecting insects and plants, and making radios. My affinity for science was awakened and grew during in these ten years.

Long after I became a polymer scientist, I occasionally remembered a short composition I had written during my last year in junior high school. At that time students compiled a commemorative collection of compositions describing our future dreams. As I recalled, I wrote something about my wish to be a scientist in the future and to conduct research on plastics useful for ordinary people. I cannot be sure what I wrote exactly because I lost the book of essays during repeated moves afterwards. I had long regretted this loss because I wanted to know more about why and how a junior high school boy decided on a future research career in plastics.

Much to my surprise, I found that the full composition I had lost was printed in every japanese newspaper the day after the Royal Swedish Academy of Sciences announced its award of the Nobel Prize in Chemistry for 2000 to two friends and myself. After 45 years, I could finally read the complete composition again. I was deeply impressed with the great power of the Nobel Prize.

I was born in Tokyo in August 1936, the third child of Hatsutarou, a medical doctor, and Fuyuno, a daughter of a chief priest of a Buddhist temple. After me, a sister and a brother were born, joining my elder brother, my elder sister and me. After I was born, my family moved many times, following my father's work, but we finally settled in Takayama, my mother's hometown, in 1944 during the confusion toward the end of the war.

My higher education began when I entered Tokyo Institute of Technology in April 1957. In March 1966, I completed my doctoral course and received the degree of Doctor of Engineering. In the same year, I married Chiyoko Shibuya, and we were later blessed with two sons, Chihiro and Yasuki.

There were three specific fields I wished to study at university. One was polymer chemistry, just as I had written in my junior high school composition. The other possibilities were horticulture and electronics. I had decided to major in polymer chemistry only if I successfully passed the entrance examination for Tokyo Institute of Technology. In April 1957, after entering Tokyo Institute of Technology, I mainly studied applied chemistry during my undergraduate career. In Japanese universities, an undergraduate major in an science course has to belong to one of the laboratories in his department during his final year in order to work on a graduation thesis. I was interested in synthesizing new polymers, so I applied to a laboratory conducting synthesis research. But since there were too many applicants who wanted to enter into the laboratory I had chosen, I had to switch to a laboratory working on poly mer physics. Initially I was reluctant to work in this field, but actually, I realize that my experiences in this laboratory were of great importance to me when I worked with polyacetylene later on.

I finally began working on polymer synthesis, my original interest, in my graduate program, but I started the work on polyacetylene, the work for which I now share the Nobel Prize, just after I received my doctorate and I became a research associate in April 1966. The initial purpose of this study was to determine the polymierization mechanism of polyacetylene using the Ziegler-Natta catalysts. In the fall of 1967, only a short time after we started polyacetylene film through an unforeseeable experimental failure.

With the conventional method of polymerization, chemists had obtained polyacetylene in the form of black powder; however, one day, when one a visiting scientist tried to make polyacetylene in the usual way, he only produced some ragged pieces of a film. In order to clarify the reason for the failure, I inspected various polymerization conditions again and again. I finally found that the concentration of the catalyst was the decisive factor for making the film. In any chemical reaction, a very small quantity of the catalyst, about mmol would be sufficient, but the result I got was for a quantity of mol, a thousand times higher than I had intended. It was an extraordinary unit for a catalyst. I might have missed the "m" for "mmol" in my experimental instructions, or the visitor might have misread it. For whatever reason, he had added the catalyst of some molar quantities in the reaction vessel. The catalyst concentration of a thousand-fold higher than I had planned apparently accelerated the rate of the polymerization reaction about a thousand times. Roughly speaking, as soon as acetylene gas was put into the catalyst, the reaction occurred so quickly that the gas was just polymerized on the surface of the catalyst as a thin film.

But we noticed another important factor besides the concentration of the catalyst. Polyacetylene has a property of being insoluble in any solvent, a property which contributed to the formation of the film. Even more surprising, when we observed the film throug a transmission electron microscope, we saw that the film was composed of long entangled micro-fibers of polyacetylene. These two properties are essential for the formation of any film, and they were inherent in polyacetylene.

One more important factor contributed to the formation of the film was the Ziegler-Natta catalyst we had used. Most of the Ziegler-Natta catalysts tend to form precipitates which give an inhomogeneous solution. From such an inhomogeneous catalyst, it is very difficult to form polyacetylene film. But the Ziegler-Natta catalyst we had used in our experiment was a unique one. It had good solubility in organic solvents to give a homogeneous solution and it also had high activity to give a high molecular weight and crystalline form of polyacetylene. I could say that nature had prepared us for the way to make polyacetylene film. Later, through the measurements of various absorption spectra of this thin film, we determined the molecular structure of polyacetylene, and thus, we fulfilled the initial purpose of our work.

By chance, this glittering, silvery film, caught the eyes of Professor Alan G. MacDiarmid, one of the co-recipients of the prize, and he invited me to work with him in the U.S.A. In September 1976, I went to the University of Pennsylvania, where Professor Alan J. Heeger, another co-recipient, was also working, and I spent one year there.

I still vividly remember the day of November 23, 1976. With Dr. C.K. Chiang, a postdoctoral fellow who was working under Professor Heeger, I was measuring the electric conductivity of polyacetylene by the four-probe method, adding bromine. At exactly the moment we added bromine, the conductivity jumped so rapidly that he couldn't switch the range of the electrometers. Actually, the conductivity was ten million times higher than before adding bromine. This day marked the first time we observed the doping effect, although it was a pity that the expensive equipment was broken. The discovery of chemical doping is one of the representative results of our collaboration in this period.

After returning to Japan, I continued to work on polyacetylene. What I did first was to shed light on the chemical reaction associated with the doping phenomena. In cooperation with many coworkers, I investigated various spectra of the doped polyacetylene films: infrared absorption, Raman scattering, ultraviolet-visible absorption, the Mössbauer effect, and EXAFS. As a result, we found that the emergence of electrical conductivity on the doped polyacetylene was due to the creation of carbocations or positively charged solitons associated with withdrawing of p electrons from polyacetylene by the dopant when iodine was used as an acceptor dopant.

In November 1979, I moved from Tokyo Institute of Technology to the Institute of Materials Science, University of Tsukuba, where I was appointed Associate Professor. In October 1982, I was promoted to full professor and worked on polyacetylene and other conducting polymers. Since my retirement from University of Tsukuba at the end of March 2000, I have withdrawn from scientific research and other educational activities.

Let me mention two of my major contributions to polyacetylene research during my time at Tsukuba. One is the preparation of oriented films. The significance of polyacetylene being a typical quasi-one dimensional material was recognized very early. In this sense, an oriented film was indispensable to study the intrinsic one-dimensional properties. The polyacetylene films synthesized until then were an isotropic material in which the fibrils were entangled in threc-dimensional disorder. I came up with the idea to directly synthesize the uniaxially oriented films by using liquid crystal as a solvent. The same idea was proposed by a scientist from a company. We found that an equimolar mixture of nematic liquid crystals bearing a phenylcyclohexyl moiety was useful for that purpose. We succeeded in simultaneously polymerizing acetylene and synthesizing uniaxially oriented polyacetylene films by orienting the catalyst solution of liquid crystal solvent under flow condition or magnetic field. Further development of this technique enabled us to synthesize helical polyacetylene that consists of clockwise or counterclockwise helical structure of fibrils, by use of chiral nematic liquid crystals. The chiral helicity of the films may be useful for electromagnetic and optical applications.

The other contribution is the synthesis of liquid crystalline conjugated polymers by replacing the hydrogen atom bonded to polyacetylene with a substituent having liquid crystalline nature as the side chain. As these polymers have large substituents, the doping effect is poor. However, these polymers can be modified by introducing various substituents with interesting optical and thermal properties. In addition, they can orient spontaneously in a given range of temperature.



Hideki Shirakawa

Research Engineer

Nobel Peace Prize Winner