Molecular Functional Materials for Ubiquitous

Electronics
Robin Msiska
February 22, 2020

Technology is playing an increasingly important role in modern life around the world. The advent of
new technologies such as the Internet of Things (IoT) further aids our march towards a more connected
world. IoT allows ordinary physical devices such as household appliances fitted with electronic chips to
interconnect through Internet infrastructure. IoT enabled products along with wearable technology and
more traditional electronic devices such as computers, smartphones and tablets have played a central role
in making the world more connected than it has ever been. In a very real sense, electronic devices have
become ubiquitous and mankind only seems to be moving in a direction that will demand more and more
integration with technology. To build the next wave of these ubiquitous devices, certain considerations
have to be made regarding their weight, display size, body size and price. Generally, it will be desirable
to make devices lighter, smaller and reduce their production cost in the process. Modern electronic
devices are still comparatively expensive because they are made from some materials that are difficult to
mine and refine. In addition to cost, these devices are made from rigid materials making them inflexible
and this may be a problem for certain use cases in which more flexible materials are desirable.
The field effect transistor (FET) has found widespread use in electronics and is a key active component
of integrated circuits. Typical FETs have a metal(electrodes)-insulator-semiconductor structure. A
conventional inorganic FET has electrodes that are usually made of gold or indium, an insulating layer
made of SiO2 or some other oxide, and Silicon or Gallium as the semiconductor. The production of
such a FET requires significant industrial investment due to very strict fabrication conditions such as
the need for a cleanroom, high temperature melt furnaces and pure water for washing.
Over the past few years, research into the applications of organic electronics has intensified rapidly.
Organic electronics are receiving more attention because they offer solutions to some of the problems
plaguing conventional electronics. Organics are poised to reduce production costs, offer an enormous
selection of usable materials, as well as remedy the problem of rigid form factor, instead allowing for
the fabrication of light flexible devices. Many organic electronic devices are already in production such
as organic photovoltaics and organic LED displays. Fundamental components such as organic FETs
are required to realize organic electronics. In Organic FETs metallic electrodes are replaced by organic
conductors, insulators by organic condensers, and semiconductors by organic semiconductors.
Traditionally, molecular materials are used to create insulating sheaths for conducting metal parts of
cables and connectors. What makes metals highly conductive is the fact that they possess an opened-
shell electron structure arising from partially filled conduction bands, thus enabling electrons to freely
move within the conduction band. An Insulating molecular material possesses a closed-shell structure.
This means that the valence band is fully occupied by electrons due to covalent bonding. The electrons
cannot move because they are fixed between atoms. A considerable amount of energy is required to
promote electrons into the next free band and therefore closed-structure materials have negligible con-
ductivity. However, molecular materials may be harnessed to produce conducting components. In order
to make conductive molecular materials, it is imperative that we create organic compounds that possess
an opened-shell electronic structure. One such compound is the charge-transfer complex TTF-TCNQ
composed of tetrathiofulvalinium (TTF) and tetracyanoquinodimethan (TCNQ), which exhibits appre-
ciable metallic electric conductivity. To form TTF-TCNQ, two crystals of TTF and TCNQ are brought
into direct contact and metallic conductivity is observed at their interface. At this TTF-TCNQ interface,
electrons transfer from the highest occupied molecular orbital (HOMO) of TTF to the lowest unoccu-
pied molecular orbital (LUMO) of TCNQ. This charge transfer results in the formation of metallic bands
with an opened-shell electron structure, thus fulfilling the requirement for the formation of a conductive

1
molecular material. The resistance of TTF-TCNQ decreases with decreasing temperature, just as it does
in metals[1]. At present, there are more than 1000 known organic conductors including superconductors.
It is also important to find an appropriate material that will act as an organic condenser in the design
of Organic FETs. These condensers can be made from paraelectric or ferroelectric materials. Many
organics exhibit paraelectricity due to the presence of dipoles within them, which means that they do
not maintain polarization when an external electric field is removed. Paraelectric organic materials are
useful for making electronic components such as CPUs, inverters, amplifiers, etc. Some organic materials
exhibit ferroelectricity which means that they have a spontaneous electric polarization that is reversible
by the application of an electric field. They have two possible states of polarization when an electric
field is removed. Such materials are used to make non-volatile memory. J. Harada, et al. proposed
one way of realizing ferroelectric organic compounds by the use of plastic crystals[2]. By exploiting the
malleability property of plastic crystals, powdered samples of soft plastic crystals can be quite easily
made into translucent films by the application of pressure, just as one would flatten clay. This provides
a viable way of fabricating low-cost memory devices from organic compounds.
Certain requirements need to be met in order to fabricate high-performancing FETs. Firstly, it
is vital to remove factors that may disturb the motion of carriers. This is especially important at
the interfaces between the electrodes and the organic semiconductors in organic FETs. Secondly, it is
important to use high mobility materials. These are materials with large intermolecular interactions
and uniform crystallinity. From theoretical considerations[4], the mobility µ can be calculated using
the formula µ = 20(300/T )(m0 /m∗ ), where m0 is the electron rest mass, m∗ is the carrier effective
mass, and T is the temperature. Furthermore, we can express m∗ as m∗ = ~2 /(2tij d2 ), where ~ is the
reduced Planck’s constant, d is the distance of molecular planes and tij is the transfer integral. From
this expression it is evident that a large value of tij results in high mobility. The quantity d cannot be
controlled and this leaves tij as the parameter we can manipulate. Molecules with large values of tij
can be found and synthesized by considering intermolecular interactions. Larger intermolecular overlap
leads to larger mobility. Y. Takahashi, et al.[5] demonstrated that molecular packing arrangement had
a considerable bearing on the value of tij in organic FETs based on hexamethylenetetrathiafulvalene
(HMTTF). According to this study, an intermolecular stacking configuration yielded tij values of 1∼2
meV (which is typical of organics) whereas side-by-side configuration led to tij values of 11 meV, due
to the optimization of carrier injections as well as larger π-π intermolecular interactions. This yielded
values of mobility up to 11.2 cm2 /Vs, demonstrating the feasibility of high mobility Organic FETs.
There are ways of cost effectively producing large sizes of organic semiconductors. One way is the
method of ink-jet printing of organic semiconductors. To understand how this works, one may imagine
the paper of an ordinary printer as the substrate and insulator layer, and imagine the ink as the electrodes
and semiconductor. In this process, the solvent affinity of the soluble materials used has been known to
cause complications in the print-fabrication process. Thankfully there are some known solutions to this
problem. M. Hiraoka, et al.[3] proposed a method to fabricate TTF-TCNQ thin films by utilizing an
ink-jet printing technique in which the soluble donor and acceptor components are printed individually
and then combined on the substrate to form metallic films. The pentacene thin-film transistors with
TTF-TCNQ electrodes produced this way had an electrical conductivity of about 0.6 cm2 /Vs. Another
way to produce organic semiconductors cheaply is to use a copy machine technique. One may think of
this as using a copy machine in which the paper is replaced by the substrate and insulator layer, and
the toner is replaced by the electrodes and semiconductor. The steps in this process are; toner-zing the
semiconducting material, electrotrostatic printing and finally pressing to form an Organic FET. Organic
FETs made this way have been reported to have mobilities of about 0.3 cm2 /Vs[5]. The mobilities in
the devices made by the printing and copy techniques may not be very high but they offer very cheap
ways to make Organic FETs, and there is still active research being done to increase mobility.
Due to the myriad of ways that organics can be synthesized, molecular functional materials offer
the possibility of creating exciting novel electronic devices that would otherwise be impossible to create
with only conventional inorganic materials. For instance, there is a class of electronic devices known as
biodegradable devices which may have medical applications and may help reduce permanent electronic
waste in an increasingly technologically dependent world.

2
References
[1] C. W. Chu, J. M. E. Harper, T. H. Geballe, and R. L. Greene. Pressure dependence of the metal-
insulator transition in tetrathiofulvalinium tetracyanoquinodimethane (ttf-tcnq). Phys. Rev. Lett.,
31:1491–1494, Dec 1973.
[2] Jun Harada, Naho Yoneyama, Seiya Yokokura, Yukihiro Takahashi, Atsushi Miura, Noboru Kita-
mura, and Tamotsu Inabe. Ferroelectricity and piezoelectricity in free-standing polycrystalline films
of plastic crystals. Journal of the American Chemical Society, 140(1):346–354, Jan 2018.
[3] M. Hiraoka, T. Hasegawa, To. Yamada, Y. Takahashi, S. Horiuchi, and Y. Tokura. On substrate
synthesis of molecular conductor films and circuits. Advanced Materials, 19(20):3248–3251.
[4] Shin-ichi Machida, Yasuo Nakayama, Steffen Duhm, Qian Xin, Akihiro Funakoshi, Naoki Ogawa,
Satoshi Kera, Nobuo Ueno, and Hisao Ishii. Highest-occupied-molecular-orbital band dispersion of
rubrene single crystals as observed by angle-resolved ultraviolet photoelectron spectroscopy. Phys.
Rev. Lett., 104:156401, Apr 2010.

[5] Yukihiro Takahashi, Tatsuo Hasegawa, Sachio Horiuchi, Reiji Kumai, Yoshinori Tokura, and Gunji
Saito. High mobility organic field-effect transistor based on hexamethylenetetrathiafulvalene with
organic metal electrodes. Chemistry of Materials, 19(26):6382–6384, Dec 2007.