INTERVIEW with Professor Françis Garnier
ESI Special Topics,
December 2001
Citing URL - http://www.esi-topics.com/conducting-polymers/Prof-Francis-Garnier.html
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this Special Topics interview, Professor Françis Garnier
discusses his long career in researching conducting polymers.
Prof. Garnier is the lead author of the paper,
"All-polymer field-effect transistor realized by printing
techniques," (Science 265[5179]: 1684-6, 16
September 1994). When Special Topics performed a survey of
research in conducting polymers, this paper was cited a total
of 220 times, placing it among the top 20 papers in its field.
Currently, ISI
Web of Science product shows that
this particular paper has now garnered 281 citations.
Professor Garnier’s work is also well represented in ISI
Essential Science Indicators
Web product, with papers registered in the fields of both
Materials Science and Chemistry. Prof. Garnier is in charge of
the Laboratory of Molecular Materials Research at the Centre
National de la Recherche Scientifique in France.
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What
factors or circumstances led you to your work?
As student at the University of Paris, I was
attracted by both the rigor of physics and the creativity of
chemistry, so I got two Master of Science degrees, one in Physics
and one in Chemistry. I then got my Ph.D. in Physical Chemistry. I
was fortunate enough to attain the rank of Professor when I was 31,
and kept on working in a lab there. Then, around 1980, I was offered
the possibility to create my own lab. I was very enthusiastic, as I
wanted to make use of my multidisciplinary training in physics and
chemistry and I decided to explore a newly emerged area: organic
conjugated polymers. At that time, two main conjugated polymers had
appeared in labs, polyacetylene and polypyrrole. These polymers were
shown to switch between two states, one neutral insulating, and the
other oxidized and electrically conducting.
Polyacetylene showed, however, to be highly
unstable toward air and humidity, and polypyrrole was only stable in
its oxidized conducting state. At that time, I thought that any
interesting development of such classes of polymers required them to
be environmentally stable in their both neutral and conducting
state. Furthermore, as a chemist, I thought it would be interesting
to be able to modulate the properties of the monomers, and
consequently those of the polymers, by subtle chemical substitutions
on the
monomers. Finally, one important drawback of unstable polymers was
the fact that the equipment of my lab was miserable, and I didn’t
have a glove box for working in a controlled atmosphere.
So in 1981 and 1982, I proposed, for the
first time in the literature, "polythiophenes" which were
electrochemically synthesized. These polymers were very stable in
both states, and I spent a lot of time in conferences and in
meetings from 1982-1984 convincing other research labs that, besides
the still highly worked polyacetylene, polythiophenes were very
attractive, owing to their stability and their versatility
associated with the various chemical substitutions which could be
performed on the monomers. The field of polythiophenes finally
started around 1984, and has consistently increased since then.
At that same time, I was already interested
in the neutral state of polythiophenes, which showed a very
long-term stability (it was the only stable neutral polymer at that
time), and which showed to be in fact an organic semiconductor. So,
our first publications on the photovoltaic properties of
polythiophenes stem from 1984. Many labs joined this field of
organic semiconductors based on conjugated polymers, but results
were deceiving: almost all labs found that these polymers were very
bad semiconductors, by a factor of about 105, in terms of carrier
mobility, when compared with the poorest inorganic semiconductor in
practical use, amorphous silicon.
So in the late ‘80s, after tremendous work
on these materials, most labs came to the conclusion that these
conjugated materials could never reach the level for use as active
semiconducting layers in real devices (no foreseen application).
Physics considerations led me to think, however, that purity and
material structure should be the keys for improving these materials,
and against the beliefs and ways of research at that time, I decided
to work not on longer and longer conjugated polymers, as was done in
most labs, but on very short but well-defined conjugated oligomers
(defined short segments of the parent polymers).
I was thus able to show for the first time,
in 1990, that short conjugated oligothiophenes, e.g., sexithiophene,
showed a mobility that was increased by a factor of 104 when
compared with the parent polythiophenes. At that time we published
the first polymer-based device, which was shown to be flexible,
i.e., "flexible polymer electronics." I am very proud of
this 1990 publication, as some other labs tried afterwards (1993) to
claim the first flexible device, but I was the first one to realize
and to analyze such a device, and to point out the potential
interest of their flexibility. It must be said that at the same
time, R. Friend also demonstrated that another polymer, PPV, showed
electroluminescent properties (OLEDs). These two innovations, which
came out about the same time, launched a very important research
effort in many labs, both in universities and in companies. The
decisive step we performed in the improvement of mobility was then
analyzed and interpreted in our lab. In that period (1990-3), I had
many contacts with companies to which I explained my research,
principally Lucent-Bell Labs and IBM. I also had a common research
contract with the Philips Company in the Netherlands, to which we
explained in great detail the complete sequence for making these
polymer-based transistors. Afterwards, these companies went on their
own, Lucent being very fair and citing our work, whereas Philips,
although having learned everything from us during two years of
contract, decided to ignore us in their work and in their citations.
But c’est la vie. In a further step, I decided to make full
use of the organic character of the materials involved in the
fabrication of these devices, and I performed the first
demonstration, in 1994, showing that a device could be realized with
the sole use of printing techniques. This work, published in Science
(1994), was quoted in the front page of the New York Times
and this information was then reproduced all over the world. In the
past months, other printed devices have been proposed in the
literature, which confirm the new route I pioneered some seven years
ago.
A further area in which I have been involved
concerns the previous research theme of conjugated polythiophenes,
which I progressed towards the functionalization of polythiophenes.
In this sense, I considered these conjugated polymers as a
tridimensional network of macromolecular electrically conducting
wires, able to transport information from recognition centers, which
can be covalently bonded along the polymer chains, through the
chemical modification of the monomers. I developed, in 1989, the
concept of "intelligent materials" (the first time this
word was introduced in the literature, and I had to argue with the
editor of Angewandte Chemie to convince him to accept this
terminology). So we first developed ion sensors by grafting crown
ethers, i.e. selective ion complexants, along the polythiophene
chains.
Around 1991-92, I also decided to make an
important move toward biology, and to develop electrochemical
sensors for peptides, enzymes, DNA, and antibodies. The potential
interest of this new class of sensors is to afford an electrical
response, which flows from the recognition center (analogous to a
receptor) through the conjugated conducting macromolecular chains
(analogous to nerves) toward the electrode/computer (analogous to
the brain). So these systems afford a direct real-time reading of
the information, which can be stored and processed in a computer
associated with the electrode, in the image of a living species.
To sum up, I think that the moves I made in
my scientific activity have been mainly governed by:
i) My multidisciplinary training at the
University. This is a necessary condition for developing the theme
of Materials Science, which requires a deep knowledge in a very
broad range of disciplines, starting from synthetic chemistry,
through physical chemistry and up to physics and electronics.
ii) The aim to understand molecular
material characteristics in terms of molecular properties,
allowing thus the control of and the tuning of these material
characteristics
iii) The goal to bring the versatility of
chemistry and the power of chemical synthesis to the field of
electronics
iv) To keep being inspired by the beauty
and power of the organization existing in living species (sensing,
intelligence), and to try to mimic it in controlled
three-dimensional man-made architectures.
What
are your immediate and long-term research goals?
My actual research goals are concentrated
toward the biological recognition of DNA and antibodies, and also
toward the use of organic semiconductors for building new types of
solar cells, as I think, as scientists, that we have the
responsibility to work for the future, 10 or 20 years ahead.
Photovoltaic conversion involves a much more complicated process
than other devices, e.g., transistors and electroluminescent diodes,
but fundamental knowledge and new materials are needed to progress
in this field, which, to my sense, will become one of the major
objectives in the next 20 years.
What
are the social implications of your work, if any?
Social implication is evident, and has been
a constant leitmotiv of the moves I made during my scientific
career. I thought at the very beginning of my work at the interface
between chemistry and physics that we should be able to adapt the
versatility offered by chemistry to the vast and high added value
market of physics. As a matter of fact, I often use the following
picture: the field of polymers (plastics, paints, etc.) came on the
market in the ‘40s, and its success was mainly due to the fact
that chemistry allows the fine-tuning of the mechanical, optical,
thermal, chemical, etc., properties of the polymers. So the
potential interest of organic-based or polymer-based devices will
also rely on the fact that we should be able to tune the mechanical
(flexible), optical (transparent) properties of this new class of
devices. Flexible large-area, lightweight, low-cost displays will be
soon on the market, as well as smart cards with increased space for
memory and logic.
In the field of DNA chips, real-time reading
of information is actually considered by biomedical companies as an
important step.
As a social implication of my work, I would
also like to add that I trained many graduate students (and post
docs) in my lab to this field of materials science, which requires
the understanding of both chemistry and physics. These newly formed
people went out in other labs, and developed the field. For instance
one of them, Jean Roncali, was initially a technician in my lab, and
I convinced him to progress in research. He finally agreed, got his
Ph.D., and is now well established in science in the field of
conjugated polymers.
What
tools or technological advances have been important in your research,
if any?
Of course, the latest techniques such as
near-field microscopes are of importance, but I have to say that
they have not been critical in the decision to move the research in
a new specified area
Did
you expect your work to become highly cited, or is this surprising to
you?
When starting a new research field, I didn’t
really care for the possible citations of my future work, which had
to be accomplished first. But once some steps have been achieved in
your research, publication of results becomes of highest importance
in order to obtain the response of the scientific community to your
work. Then, once your work has been screened by the scientific
community, the citation index becomes one of the most important
observables of the real significance of your work, of its long-term
potential on all levels, i.e., on a fundamental point of view as
well as for the possible applications. So in my own case, during my
experiments I have been mainly motivated by the pleasure and
plenitude brought by research, by the passion to discover and
pioneer new areas, by the infinite happiness of obtaining an
experimental result which meets the prediction made before the
experiment, by the excitement of a new finding. But a good citation
record makes me very glad, of course, due to the fact that it
expresses the agreement of the scientific community with the
accomplished work, and recognition of the validity of my scientific
moves.
In this regard, I would also like to mention
that the way some results are accepted (and sometimes taken over) by
companies is also a significant response to one’s work.
How
rapidly has the state of our knowledge about your field evolved in the
past decade, and what were the key discoveries that furthered the
advancement of the field?
This new area of organic-based devices
raised a large interest, both for the understanding of materials
properties in terms of molecular characteristics, and also for their
large potential of applications. So, we were fortunate in that many
other labs—belonging to companies such as Lucent-Bell Labs, IBM,
and Philips, as well as to universities—invested very strong
research efforts in this field, in all directions (theory,
materials, experimentals, technology). This stream allowed decisive
steps to be made in all of these directions, for the benefit of the
whole area. The scientific community in universities and in
companies is now at the level of prototypes of devices and of real
applications (smart cards, flat panel displays, tags, and low-end
electronics).
What
is your prediction for the state of our knowledge about your field 10
years from now?
There are still strong needs i) in
theoretical models adapted to describe charge transport in organic
materials, ii) in new materials with improved properties, iii) in
technology, which explain the steady effort devoted to this field.
So I am confident that improvements in all these fields will be
realized in the future, and that large sectors of applications based
on the actual use of amorphous-silicon (or even polycrystalline
silicon) as active semiconducting layer will be replaced by
organic-based semiconductors. I envision smart cards, flat and
flexible (transparent?) displays, tags, low weight and flexible
electronics for military applications, etc. Besides, we are just
entering a new area where new mechanical, optical, and thermal
properties can be designed in devices, by subtle chemical variations
on the molecules involved. The a priori control of the electronic
band level energies will also allow building devices possessing a
large set of predetermined characteristics.
So we are in a same position as we were in
the ‘40s, when polymers were launched. Who would have anticipated
at that time the extraordinary development of plastics? I think we
will go in the future to a "Polymer-Based Electronics à la
Carte."
Would
you like to leave any other comments about your work or share a
personal side of yourself?
I would just like to give one comment, which
deals with my move, in 1991, towards the frontier of chemistry and
biology. At that time, in 1991, we in France experienced a very sad
problem linked to AIDS-infected blood, which had been given to young
hemophilic people. There was a lot of concern in France about this
problem, and I remember these young AIDS-infected people who were
interviewed on the TV. Although knowing they were condemned to die,
and although their faces were already very marked by this disease,
they seemed very calm and talked about the need for better
knowledge. I felt myself extremely moved by this situation, and I
decided that it was my responsibility, as a scientist, to try to
bring some new knowledge at the interface with biology. So over one
year I went back to University and attended biology lectures, one
afternoon every week. After that, I analyzed the points where I
could contribute to some level, and I decided to go for the
real-time recognition of DNA and antibodies, based on functionalized
conjugated polymers (functionalized with oligonucleotides or
antigens respectively).
And now, after having invested part-time
over eight years in this completely new field for me, I think
promises have become reality. I have a strong contractual
relationship with the largest biomedical company in France for
developing new DNA chips based on my work. A first series of
prototypes is under development, papers have been published, patents
have been applied, and I am often asked to give lectures on this
topic. I have also written a chapter of a book published by the
National Institute of Health in Bethesda, at their request. I feel
very happy now to have accomplished this trip toward biology, and to
have answered the vow I made to myself some nine years ago.
To sum up in a few words I would like to
leave this message:
For decades, and contrary to the humanists
of some centuries ago, most scientists have specialized in a very
specialized area, defining themselves as experts in the tools used
by chemists or physicists. Universities thus show a collection of
spectroscopists (even subdivided into mass spectroscopy, IR
spectroscopy, surface spectroscopy, etc.), electrochemistry,
photochemistry, kinetics, modeling, low-temperature physics, etc.
In my case, I have always been attracted just by new knowledge,
knowledge by itself, and I have tried to learn enough physics,
chemistry, and biology to allow me to explore some new fields,
mostly at the frontiers between physics, chemistry, and biology.
So I never defined myself as a specialist of any technique in use
in these disciplines—I never wanted to—but rather as trying to
answer to some challenges, whatever the experimental expertise
needed.
Professor Françis Garnier
Laboratory of Molecular Materials Research
Centre National de la Recherche Scientifique
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ESI Special Topics,
December 2001
Citing URL - http://www.esi-topics.com/conducting-polymers/Prof-Francis-Garnier.html
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