ORGANIC (POLYMER) FIELD EFFECT TRANSISTORS

Introduction to OFET:
OFETs which are made of conjugated polymers present several potential advantages. First, the deposition techniques for semiconductor films allow large areas to be coated. Many conjugated polymers can be synthesized in a way that they are soluble in organic solvents, so that they can be processed by spin-coating, casting or by various printing methods. Therefore a high-temperature processing is not necessary for producing films. Second advantage is that polymers are mechanically tough and flexible, therefore compatible with plastic substrates. This offers the possibility to realise foldable, flexible products with extremely light-weight.

Device Architecture:
The two OFET architectures that have been considered are the top-gate-bottom-contact (TGBC) structure and used for the verification of the technology design models, and bottom-gatebottom-contact (BGBC) structure, whose measured characteristics have been used to extract the OFET compact model parameters.

The TGBC architecture has in principle a larger injection area and thus a lower contact resistance which enables higher currents for the same applied voltages in comparison to the BGBC structure. It is an easier to manufacture structure since source/drain contacts are patterned on a substrate rather than on a dielectric or OSC layer. However, this structure has limitations because of lack of suitable dielectric materials. On the other hand, the BGBC architecture has been more often used in OFET research . A wider range of potential solution processable dielectrics can be used with BGBC architecture to provide a smooth dielectric/OSC interface. However, the down side of this device structure is a high contact resistance due to the low area for charge injection and extraction.

I-V Characteristics:
Based on the idea of percolation model for variable range hopping, effective mobility is given as where the model parameters and control the influence of the accumulated electron charge on the mobility.

Performance:

a) On-Off: Improvement of the on-off ratio can be obtained by reducing the pinchoff voltage, which can be done by lowering both the thickness of the semiconducting film and its doping level.Defining two limiting cases depending on the doping level of the SC at high doping level the on-off ratio can be

given by the equation:

And in case of low doping level it is given by the equation:

The on-off ratio is not solely dependent on the ratio of mobility to conductivity. It can also be enhanced by using an insulator with high capacitance per unit area, and also by lowering the thickness and doping level of the semiconductor layer.

b) Mobility: i) Hopping: In these materials, transport occurs by hopping of charges between localized states. A main difference between the delocalized and localized transport is that, in the former, the transport is limited by phonon scattering, whereas in the latter, it is phonon assisted. Accordingly, the charge mobility decreases with temperature in conventional semiconductors, the reverse being true in most organic materials. The temperature dependence of the mobility follows a law of the form where is an integer ranging from 1 to 4.There is still controversy as to whether the conductivity in these materials should be described by localized or delocalized transport.

ii) Small Polaron: A polaron results from the deformation of the conjugated chain under the action of the charge. In other words, in a conjugated molecule, a charge is self-trapped by the deformation it induces in the chain.

where J is the electron transfer energy, a the lattice constant, Eb is the binding energy of the polaron.

iii) Field-dependent mobility: The mobility becomes field dependent at high electric field (namely, at fields in excess of ~105 V/cm).In this phenomenon the coulombic potential near the localized levels is modified by the applied field in such a way as to increase the tunnel transfer rate between sites. The general dependence of the mobility is given by

where is the Poole-Frenkel factor and F is the electric field iv) Multiple trapping and release: First, the carriers arriving at a trap are instantaneously trapped with a probability close to one. Second, the release of trapped carriers is controlled by a thermally activated process. The resulting drift mobility D is related to the mobility 0 in the delocalized band by an expression of the form

where Et corresponds to the distance between the trap level and the delocalized band edge, and is the ratio of the effective density of states at the delocalized band edge to the concentration of traps.

Fabrication Techniques:
Organic semiconductors are obtained as thin films; accordingly, OFETs present an inverted architecture, in which the gate electrode is laid down first, the deposition of the semiconducting film usually being the last step. Deposition of the semiconducting film: i) Electro polymerization: First, electro polymerization only occurs on conducting substrates. For this reason, the semiconductor is first grown on the source and drain electrodes, its extension over the insulator being achieved by a lateral expansion of the deposit. This results in a highly disordered film, and a poor quality insulator-semiconductor interface. Second, the CP is obtained in its oxidized, conducting, form, and has to be reduced (generally electrochemically) in order to become semiconducting. But this constitutes an additional source of disorder. ii) Solution-Processed deposition: It allows the production of very homogeneous films with perfect control of their thickness over relatively large areas. A requirement for this technique is a good solubility of the polymer. Unfortunately, a great number of CPs are not soluble. The problem may be overcome either by grafting solubilising groups to the polymer backbone, or by the use of a soluble precursor polymer. iii) Vacuum evaporation: The organic material is put into a metal boat, which is heated by Joule effects, or sometimes with an electron gun, and the substrate placed a few centimetres above the boat. We note that, in principle, this technique cannot be used for polymers, which tend to decompose by cracking at high temperatures. Its main advantages are the easy control of the thickness and purity of the film, and the fact that highly ordered films can be realized by monitoring the deposition rate and the temperature of the substrate.

Pentacene:
Pentacene consists of five aligned condensed benzene rings. Mobility up to 0.62 cm/Vs has been obtained with different deposition techniques attributing to a highly ordered morphology of single crystal. The on-off ratio of Pentacene OFETs was reported to reach 10^8. (Note here Vgs range is -100 V to +100 V).

Tetrabenzoporphine-based OFET:
Structure:

Schematic cross section of 29H,31H-tetrabenzo[b,g,l,q]porphine OFET

Problems faced: High operating voltage (>20V) , low mobility, and high sub threshold swing are the main disadvantages of organic transistors. Also in certain organic compounds like metalloporphyrins which resemble natural oxidation catalysts environmental instability creates extrinsic defects that hinder carrier movement.

Reasons : 1) Because the field-effect drain current is modulated by a low-k gate dielectric( SiO2) the dependence of mobility on accumulated charges in the channel dominates at high operating voltage (around 100V) and leads to high sub threshold swing. 2) As the performance of OFET improves, the contact resistance becomes critical to limiting mobility. 3) A large potential barrier at metal-organic junction also causes poor charge injection. Strategies adopted to prevent above problems: 1) High K, Low K bi-layer gate dielectric: Tantalum oxide Ta2O5 when used as a gate dielectric, accumulates more carriers in the channel than other polymer or silicon dioxide dielectrics due to the high dielectric constant (r ~29). By further applying a very thin SiO2 layer onto the Ta2O5, we can expect to lower leakage current through the gate and to provide better interfacial conditions for photolithography. 2) Self-assembled monolayer (SAM) interfacial layers between organics and metal electrodes: Treating the gold electrodes with thiol-based SAMs improves the charge injection properties by reducing the surface energy difference between electrode and polymer. 3) Encapsulation of thin films with insulating materials: The tetrabenzoporphine was encapsulated with polystyrene (10 wt% in toluene) to protect the air sensitive characteristics of the organic material.

Device Fabrication: Heavily doped n-type Si substrate (resistivity ranging from 0.1 to 1.0 ) - Gate electrode. Immersion of Si wafer in Buffered Oxide Etch (BOE) solution for one minute for removal of native oxide. Deposition of Ta2O5 (1095) on bare Si surface by electron beam deposition. (Rate: 0.1-0.2 /S under the 5.0 10-6 Torr at room temperature). Deposition of thin SiO2 layer (23 ) by Plasma-Enhanced Chemical Vapour Deposition (PECVD) at a power of 50W and a temperature of 300C. Electrodes of 2.5 nm titanium (adhesive layer) and 35 nm gold were patterned by photolithography. Sequential exposure to oxygen plasma and 4-Nitrobenzothio prior to the deposition of the active layer film (Tetrabenzoporphine). Solution-based film deposition: Tetrabenzoporphine was dissolved in Chloroform at 0.7 weight percent and filtered through a 0.2m PTEF filter. The solution was then spin-coated on to the channel region at 1000 rpm to give a film of 50-100 nm thickness. The sample was then annealed at 180C for 20 minutes in order to covert CP to BP (see Fig. 1(b)), which involves the elimination of ethylene. Finally, the device was coated with polystyrene (10 wt% in toluene) followed by heating at 120C for 10 minutes.

Capacitance of bi-layer gate insulator:

Output Characteristics:
Mobility () was obtained from the expression that describes the drain current (ID) of the field effect transistor as given by Isat=0.5(W/L)Ci (VGS-VT)2 Highest saturation regime mobility1.36 cm2/V*secwas extracted for the 40m channel length (VDS=-5V and VGS= -1V~ -5V).

For channel length=5m

For different channel lengths (5,10,20,40,80m)

Sub-threshold Swing:
The sub-threshold swing, taken from the slope of VGS (S = dVGS/d(log ID)) as a function of log ID, was uniform in the range of 0.24-0.32 for the treated sample. Coating of organic film with polystyrene reduced the swing by a factor of 1/3.

Contact Resistance variation: Contact resistance for the SAM-treated electrodes in the linear
regime was almost half of that for the non-treated sample. Despite that the channel resistance is somewhat different between the samples owing to the different accumulated carrier density caused

by the different gate dielectric capacitance, contact resistance decreased with electrode surface treatment.

Potential barrier at metal-organic junction: When using high-K dielectric, more accumulated charges could be gathered at low operating voltages, which reduced the charge injection barrier, and more charges could be added to the channel region with small applied bias. The SAM thiol surface treatment also reduced the injection barrier between the electrodes and the channel region. Comparison of mobility, sub-threshold swing, threshold voltage, current on/off ratio for OFETs having various treatments: Mobility (cm2/V*sec) for saturation Conditions (W/L (m)= 1000/10) As-prepared Polystyrene encapsulation Polystyrene encapsulation + Nitrobenzenethiol treatment 5.6*10-1 0.32 9.6*103 -0.9 8.2*10 3.2*10
-3 -1

Subthreshold swing (V/decade) 1.0 0.36

Ion/Ioff ratio (VDS=-5V VGS=06V) 1.0*10 1.5*10

2 3

regime

VTH (V) 0.58 0.54

Comparison of mobility, subthreshold swing, threshold voltage, current on/off ratio for OFETs having various channel lengths.
Mobility (cm2/V*sec) W/L (m) (Polystyrene encapsulation + Nitrobenzenethiol treatment) 1000/5 1000/10 1000/20 1000/40 1000/80 7.96*10 5.63*10 0.89 1.36 1.32
-1 -1

for saturation regime

Subthreshold swing (V/decade) 0.24 0.32 0.28 0.32 0.28

Ion/Ioff ratio (VDS=-5V VGS=06V) 8.6*10 9.6*10 4.9*10 2.4*10 1.7*10

4 3 3 3 3

VTH (V) -1.2 -0.9 -0.97 -0.97 -0.96

Total resistance was proportional to the channel length leading defects in the channel such as grain boundaries and traps to be critical factors in determining device performance. The Ion/I off ratio obtained from drain currents at the threshold voltage (off state) and at VG=7V (on state) was up to 8.6104 at channel lengths of 5m. Since the Ion/I off ratio is proportional to the ratio between bulk conductivity and mobility and inversely proportional to the gate leakage, the leakier Ta2O5 gate dielectric did not lead to a high ratio. The leakage and stability of the bilayer can be further improved by additional processing such as annealing.

References:
1) Organic Field effect transistors by Gilles Horowitz. 2) Modelling of Organic Field-Effect Transistors for Technology and Circuit Design. 3) A Static Model for Electrolyte-Gated Organic Field-Effect Transistors, 2011, IEEE Transactions on Electron Devices, (58), 10, 3574-3582. 4) Hadziioannou G., Hutten P.F. (eds.) Semiconducting Polymers (Wiley, 2000) (T)(L)(C)(319s) 5) Tetrabenzoporphine-based, low sub-threshold swing, and high mobility organic field effect transistors with improved bi-layer gate dielectric, and self-assembled Nitrobenzenethiol treatment by Jae Won Shim and Ananth Dodabalapur.