Organic Electronics 9 (2008) 11011106

Contents lists available at ScienceDirect

Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

High-mobility tetrathiafulvalene organic eld-effect transistors from solution processing

M. Leufgen a, O. Rost a, C. Gould a, G. Schmidt a,*, J. Geurts a, L.W. Molenkamp a, N.S. Oxtoby b, M. Mas-Torrent b, N. Crivillers b, J. Veciana b, C. Rovira b
a b

Universitt Wrzburg, Physikalisches Institut (EP3), Am Hubland, D-97074 Wrzburg, Germany Institut de Ciencia de Materials de Barcelona (CSIC), Campus UAB, 08193 Cerdanyola, Spain

a r t i c l e

i n f o

a b s t r a c t
We report on mobilities up to 3.6 cm2/V s in organic eld-effect transistors (OFETs) with solution-processed dithiophene- and dibenzo-tetrathiafulvalene (DT- and DB-TTF) single crystals as active materials. In the devices, the channel length varies from 100 lm down to sub 100 nm, and the SiO2 thickness is either 100 nm, 50 nm, or 20 nm. The devices exhibit excellent operation characteristics with an on/off-ratio exceeding 106. Temperature dependent measurements between 50 and 400 K reveal a thermally activated transport with increased activation above 200 K. The mobility exhibits exponential activation with two distinct exponents. 2008 Elsevier B.V. All rights reserved.

Article history: Received 30 January 2008 Received in revised form 29 July 2008 Accepted 16 August 2008 Available online 18 September 2008

PACS: 81.05.Hd 81.07.Pr 81.15.Lm 85.35.p Keywords: Tetrathiafulvalene Band tail Thin-lm transistor OFET MTR Sub-micrometer

1. Introduction Interest in low cost and solution-processed organic electronics has intensied over recent years [13]. Organic eld-effect transistors (OFETs) are a key component of the emerging technology and tetrathiafulvalene derivatives (TTFs) have shown to be excellent candidates as semiconductors in OFETs [4]. These materials are very appealing since they combine high mobility with solubility, which permits the possibility of using inexpensive deposition techniques, such as spin-coating and inkjet printing, over large areas on exible plastic substrates. However, in order
* Corresponding author. Tel.: +931 888 5899; fax: +931 888 5142. E-mail address: schmidt@physik.uni-wuerzburg.de (G. Schmidt). 1566-1199/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.orgel.2008.08.011

to investigate the intrinsic transport properties of organic materials, it is crucial to prepare devices using single crystals. Measurements on single crystals typically yield the highest mobility values for a given material due to their inherent ordered structure. Over recent years, single crystal OFETs of pentacene [5] and rubrene [6] have reached charge carrier mobilities on the order of 10 cm2/V s, which is considered a theoretical limit for van der Waals bound organic crystals [7]. Such devices, however, are carefully vapor-grown and often must be measured under O2- and H2O-free conditions. In solution-processed devices, the highest mobilities (on the order of 1 cm2/V s) have been reported for crystals of dithiophene-tetrathiafulvalene (DT-TTF) and dibenzo-tetrathiafulvalene (DB-TTF) [8,9]. The chemical structures of these molecules are shown in

1102

M. Leufgen et al. / Organic Electronics 9 (2008) 11011106

Fig. 1. Chemical structure of dibenzo- (top) and dithiophene-tetrathiafulvalene (bottom).

Fig. 1. Here we report on new results, partly in deep submicrometer devices, that are aiming to elucidate the intrinsic transport properties of DT-TTF and DB-TTF. We have fabricated OFETs based on these materials, which exhibit mobility values that are almost three times higher than previously reported for DT-TTF. Devices with channel lengths from 100 lm to below 100 nm have been analyzed in order to study the scaling properties of the devices. The performance of the OFET devices over a large temperature range (50400 K) reveals a thermally activated transport mechanism with no or very low activation energy for temperatures smaller than 200 K and an increased activation at higher temperatures. Our results show that high performance TTF transistors can be easily fabricated from solution and used with no extra precautions to ambient conditions and to applied biases. 2. Experimental The devices have been fabricated on thermally oxidised highly-doped silicon substrates. We use a bottom-contact setup, where the substrate serves as a common gate electrode. Metal source and drain electrodes are deposited on top of the oxide using lithography, metallisation, and liftoff. Using UV-optical lithography, we have fabricated electrode structures with channel lengths L from 100 lm down to 500 nm on 50 nm and 100 nm thick SiO2 dielectric (cf. Fig. 2). Structures with sub 500 nm channel length are fabricated using electron beam lithography on SiO2 with a thickness of only 20 nm. In this way, the transverse electrical eld is increased, which helps to keep the devices in the long-channel regime in spite of the enhanced lateral eld, cf. Ref [10]. The source and drain electrodes consist of electron gun evaporated Ti/Pt or Ti/Au, or sputtered Pt. Before

deposition, the samples are cleaned in a solution of H2O2: H2SO4 (1:4) and treated with solutions of hexamethyldisilazane (HMDS) or octadecyltrichlorosilane (OTS). The resulting hydrophobic self-assembled monolayer on the oxide induces a uniform growth of micrometer size TTF crystals randomly distributed on the surface. The synthesis of DT- and DB-TTF has been reported previously [11,12]. TTF deposition is done by drop casting [8,9]. One drop (%0.03 ml) of a 1 mg/ml solution of the TTF derivative in toluene is drop-cast on the substrate and allowed to evaporate slowly (>3 h) in a covered petri dish. This process results in the formation of a limited number of large single organic crystals that form a conducting channel between the source and drain electrodes (see Fig. 2b). Devices that are not covered by crystals show no eld-effect and leakage currents in the I 6 1010 A range. The same low leakage current is measured after mechanical removal of TTF crystals from previously functioning devices. The effective channel width W is determined by optical microscopy. Electrical characterization of the devices at room temperature is performed in air, in the dark, using a variable temperature probe station (Desert Cryogenics) and a semiconductor parameter analyzer (HP4145B). The temperature dependent measurements (50400 K by He-ow cryostat) are carried out in vacuum (102104 Pa, depending on temperature) using the same equipment. 3. Results and discussion In Fig. 3 the characteristics of a L = 30 lm channel DTTTF transistor are presented for two measurement sequences with increasing and decreasing bias, respectively. Output and transfer characteristics both show hardly any hysteresis and follow perfect textbook behaviour. Field-effect mobilities of 3.65 cm2/V s were extracted from both the saturation regime (VDS = 15 V) and the linear transfer curves (VDS = 1 V), respectively. The fact that the values are identical shows that we can neglect limitations by charge carrier injection or displacement currents which would both result in a reduced mobility in the linear regime. Assuming ohmic contacts (cf. [13]), we can estimate the contact resistance to be approx. 30 kX mm, which is rather low for OFETs. For DB-TTF-based OFETs a similarly high performance is measured except for a reduced mobility of 0.5 cm2/V s. For a detailed investigation of the transport properties we rst apply a model of multiple trapping and release (MTR) by trap states [14]. These states induce band tails

a
TTF-material source SiO2 gate L drain

50 m

Fig. 2. (a) Schematic drawing of a transistor. The single crystal is deposited on the prefabricated electrode structure. (b) Micrograph of a TTF crystal on the source drain ngers (L = 50 lm).

M. Leufgen et al. / Organic Electronics 9 (2008) 11011106

-4 -5 -6 -7 -8 -9

1103

-2.5 Output characteristics DT-TTF, L = 30 m forth -2.0 back

1x10

Vgs = -10 V Vgs = -8 V Vgs = -6 V

1x10 1x10 1x10

DT-TTF, L = 30 m forth back

Vds = -15 V

Id (A)

-Ids (A)

-1.5 -1.0 -0.5 0.0 2 0 -2 -4 -6 -8 -10 -12 -14 -16

Vds = -1 V

1x10 1x10 1x10 10 10 10

-10 -11 -12 -13

10

-5

-10

-15

Vds (V)

Vgs (V)

Fig. 3. Electrical output characteristics (left) and transfer characteristics (right) of a single crystal DT-TTF OFET with L = 30 lm at T = 295 K.

which often dominate the transport properties, leading to a exponential thermal activation of the mobility, characterized by the lowest energy state of the band tail [15]. This situation is generally encountered in both organic and inorganic amorphous materials [1518,20]. Recently, it was shown that a similar exponential activation also exists in single crystalline organic semiconductors [18] where the trap states are located at or near the interface and thus can be modeled using a quasi two-dimensional density distribution whose exact properties are dependent on the gate insulator [23]. In temperature dependent mobility measurements on our devices we observe a similar exponential activation as reported for rubrene or pentacene [20]. The MTR activation energy can be extracted from the temperature dependence of the mobility shown in Fig. 4. For DB-TTF we nd a constant mobility between 50 and 200 K and an exponential activation with an activation energy of 58 meV above 200 K. The mobility of DT-TTF, however, follows an activation which can be tted using an exponential with two distinct activation energies; 15 and 108 meV.

1000/ T (1/K)
10
1

20

15

10

DT-TTF DB-TTF

Fit Fit

(cm /Vs)

10

forth back

10

-1

10

-2

50

100

200 400

T (K)
Fig. 4. Temperature dependence of the eld-effect mobility as determined from transfer characteristics of DT-TTF (black) and DB-TTF (grey) OFETs for increasing (forth) and decreasing current (back) direction. The solid lines are (bi)exponential ts to the data.

We have already shown that at room temperature the mobility is not inuenced by charge injection at the contacts. Given the low contact resistance one would also not expect a stronger inuence at lower temperatures [21,22]. In order to make sure that this assumption is valid we can investigate the slope of the activation curves. Because charge injection does not enter the mobility analysis at room temperature, an increasing inuence at lower temperature is only possible if the contact resistance has a higher activation energy than the mobility itself. However, we see only lower activation energies at lower temperatures, indicating that indeed contact effects can be neglected. For both materials the slope of the activation curves indicate that even at low temperature the contact resistance does not inuence the measurements. This simplied analysis only suggests the presence and the approximate depth of band tails, a deeper insight, however, can be gained by using a method as in Ref. [18]. In this method the temperature dependence of the I/V characteristics is used to obtain a detailed picture of the energy distribution of the impurity levels. For this analysis, we rst measure the current in saturation (VDS = 15 V) for different values of VGS and at various temperatures between 50 and 400 K. Changing the gate voltage towards more negative values sweeps the Fermi energy through the gap towards the HOMO level. During the sweep, more and more states contribute to the transport and by analyzing the activation energy at each gate voltage we can identify the energy position of these trap states. Plotted against temperature (Fig. 5), the data reveals similar results for the two materials. For both materials we observe exponential activation with two distinct ranges of activation energies below and above 200 K, respectively. From the thermal activation of the saturation currents we now determine the activation energy of the states in the gap which we then plot over the respective gate voltages (Fig. 6), yielding two datasets for each material corresponding to the low temperature T < 200 K and high temperature regime T > 200 K. For the DB-TTF traps can be observed over the whole energy range between 10 and 180 meV. Below 10 meV the trap energies are too close

1104

M. Leufgen et al. / Organic Electronics 9 (2008) 11011106

1000/ T (1/K)
1E-4 1E-5 1E-6 1E-7 1E-8 1E-9 1E-10 1E-11 1E-12 1E-13 1E-14 48 100 0.020 0.015 0.010 0.005 1E-5 1E-6 1E-7 1E-8 0.020

1000/ T (1/K)
0.015 0.010 0.005
VGS= -15V VGS= -12V VGS= -8V VGS= -4V VGS= 0V

DT-TTF

-I d (A)

-I d (A)

1E-9 1E-10 1E-11 1E-12 1E-13 1E-14 48 100 250 500

DB-TTF
250 500

T (K)

T (K)

Fig. 5. Drain current ID in saturation V DS 15 V at different VGS plotted against temperature (logarithmic scale) for DB-TTF (left) and DT-TTF (right) OFETs. The straight lines correspond to exponential ts.

250

200

DB-TTF
200 150

DT-TTF

Ea (meV)

150 100 50 0 0 -5 -10 -15

Ea (meV)

100

50

0 0 -5 -10 -15

Vgs (V)

Vgs (V)

Fig. 6. Activation energy Ea (extracted from the data in Fig. 5) plotted against gate voltage for DB-TTF (left) and DT-TTF (right). For both materials we distinguish two separate regimes with different ranges of activation energies, extracted from the measurements below (grey) and above 200 K (black). Ea is the energy above the HOMO level. The solid lines are the polynomial t.

to the HOMO to yield a useful signal. Trap energies above 180 meV are too high to be observable in the temperature regime investigated in our experiments. For the DT-TTF the situation is more complex. Here the two datasets leave an energy range between 75 and 95 meV where the density of states is too low to yield any signicant inuence on the I/V curves and is thus undetectable by this method. For further evaluation we t the data points of Fig. 6 by a continuous (polynomial) function [19] which allows us to determine its derivative at any voltage. We then use

NE

 1 C dEa e dV GS

in order to determine the density of states (DOS) in the gap (e is the electron charge and C the capacitance per area of our gate dielectric which we calculate to be 33 nF/cm2 for 100 nm thick SiO2). In order to convert this two-dimensional DOS into a volume DOS, the trap states are assumed to be concentrated within 7.5 nm of the material at the dielectric interface [18]. The results are plotted in Fig. 7.

We have been careful not to evaluate parts of the t which extend beyond or even contain the highest or lowest data points of the curve in Fig. 6. In these parts of the curve the t typically starts to develop small ripples, usually leading to large artifacts in the extracted density of states, which is extremely sensitive to small changes in the derivative of the t function. In the density of states of the DBTTF (Fig. 7 left) we see a band tail extending from the HOMO which has two pronounced local maxima, one at approx. 50 meV corresponding to the activation energy determined using MTR and another maximum at approx. 85 meV. The second peak, however, indicates a much lower density of states explaining why it could not be observed using MTR. For the DT-TTF we observe two separate regimes. The lowest observable energy region of the band tail starts at 20 meV, however, with a density of states three times higher than for the same energy in DB-TTF. We can assume that a maximum exists here, supported by the MTR evaluation (yielding 21 meV activation energy). With increasing energy the density of states decreases, becoming undetect-

M. Leufgen et al. / Organic Electronics 9 (2008) 11011106

1105

1E21

1E21

DB-TTF
DOS N (cm eV )
DOS N (cm eV )
-1

DT-TTF
-1

not detectable

not detectable

not detectable

1E20

1E20

1E19

1E19

20

40

60

80

100

120

140

not detectable

20 40

60

80 100 120 140 160 180

Energy above HOMO (meV)

Energy above HOMO (meV)

Fig. 7. Density of impurity states (DOS) plotted against their activation energy Ea above HOMO for DB-TTF (left) and DT-TTF (right). For DB-TTF a band tail emerges from the HOMO and exhibits two maxima at 50 and 85 meV. For DT-TTF there is a maximum at approx. 20 meV. The DOS decreases until it becomes undetectable at 75 meV. A second maximum can be found at 100 meV with the DOS decreasing again with increasing energy. The datapoints were calculated from the two datasets in Fig. 6 (grey: below 200 K, black: above 200 K).

able at approx. 75 meV. At 95 meV we see the density of states increasing again (now extracted from the data for T > 200 K) towards a maximum at 100 meV corresponding to the 104 meV activation energy determined by MTR. We see that the results obtained from MTR and the more detailed determination of the density of states are in good agreement. However, the latter yield a more detailed picture of the band structure. On the other hand the MTR model is more straight-forward and yields results which are not sensitive to polynomial tting parameters. For example a large trap density in DT-TTF at 21 meV is clearly visible in MTR. In the density of states plot (Fig. 7), the density of states at 20 meV might just as well increase further towards lower energies without yielding a local maximum. The most reliable approach thus seems to be a combination of both methods as performed on our materials. Besides the existence of these impurity states, we still see an untrapped carrier concentration which yields a nite current even at lower temperature. Especially in the case of the DB-TTF, mobility and carrier concentration remain more or less constant below 200 K. This nite carrier concentration also causes the weak dependence of thresh-

old voltage on temperature. A plausible explanation would be that we observe transport either in states which are as close as a few meV to the HOMO or by pure hopping (i.e., not thermally assisted), two effects which cannot be distinguished in the investigated range of temperatures. All transistors have proven to be relatively stable for several weeks in air. The mobility drops only by less then 50% over a timespan of several weeks. During the same period no signicant changes in VTH or off-current Ioff are observed, which we found for other materials to be a main indication of an aging effect in OFET devices. Finally, transistors with reduced channel length L were investigated in order to determine the scaling behaviour of the device properties, especially for L < 1 lm. Fig. 8 presents the mobility and on/off-ratio values for DT-TTF OFETs with channel lengths down to 100 nm on 20 nm thick SiO2. The thin oxide was used in order to make sure that the gradual channel approximation [10] is still valid for these samples. We observe long-channel behaviour down to L = 200 nm, although the mobility starts to decrease below L = 500 nm, probably also due to an increasing inuence of the contact resistance [21,22]. Devices with L below

10 10

9 8 7 6 5 4 3 2

mobility (cm /Vs)

on/off-ratio Ion/off

forth back

10 10 10 10 10 10

0.1

0.01

forth back

0.0

0.5

1.0

1.5

2.0

2.5

3.0

0.0

0.5

1.0

1.5

2.0

2.5

channel length L (m)

channel length L (m)

Fig. 8. Dependence of eld-effect mobility (left) and on/off-current-ratio (right) of DT-TTF OFETs on 20 nm thick SiO2 with channel lengths down to 150 nm. Full symbols correspond to values determined from transfer curves measured with increasing gate source voltage, empty ones from curves measured with decreasing voltage.

not detectable
3.0

-3

-3

1106

M. Leufgen et al. / Organic Electronics 9 (2008) 11011106 [6] V. Podzorov, S.E. Sysoev, E. Loginova, V.M. Pudalov, M.E. Gershenson, Single-crystal organic eld effect transistors with the hole mobility %8 cm2/V s, Appl. Phys. Lett. 83 (2003) 35043506. [7] M. Pope, C.E. Swenberg, Electronic Processes in Organic Crystals and Polymers, second ed., University Press, New York, 1999. [8] M. Mas-Torrent, M. Durkut, P. Hadley, X. Ribas, C. Rovira, High mobility of dithiophene-tetrathiafulvalene single-crystal organic eld effect transistors, J. Am. Chem. Soc. 126 (2004) 984985. [9] M. Mas-Torrent, P. Hadley, S.T. Bromley, N. Crivillers, J. Veciana, C. Rovira, Single-crystal organic eld-effect transistors based on dibenzo-tetrathiafulvalene, Appl. Phys. Lett. 86 (2005) 012110. [10] S.M. Sze, K.K. Ng, Physics of Semiconductor Devices, third ed., John Wiley and Sons, New York, 2007. [11] M. Mizumo, M.P. Cava, Organic metals. A study of the Hurtley Smiles tetrathiafulvalene synthesis, J. Org. Chem. 43 (1978) 416 418. [12] C. Rovira, J. Veciana, N. Santalo, J. Tarres, J. Cirujeda, E. Molins, J. Llorca, E. Espinosa, Synthesis of several isomeric tetrathiafulvalene p-electron donors with peripheral sulfur atoms. A study of their radical cations, J. Org. Chem. 59 (1994) 33073313. [13] G. Horowitz, R. Hajlaoui, D. Fichou, A.E. Kassmi, Gate voltage dependent mobility of oligothiophene eld-effect transistors, J. Appl. Phys. 85 (1999) 32023206. [14] V.Y. Butko, X. Chi, D.V. Lang, A.P. Ramirez, Field-effect transistor on pentacene single crystal, Appl. Phys. Lett. 83 (2003) 47734775. [15] P.G. Le Comber, W.E. Spears, Electronic transport in amorphous silicon lms, Phys. Rev. Lett. 25 (1970) 509511. [16] J.I. Pankove, Optical Processes in Semiconductors, Dover Publications Inc., New York, 1975. [17] G.A.N. Connell, in: M.H. Brodsky (Ed.), Amorphous Semiconductors, vol. 36, Springer, New York, 1979. [18] D.V. Lang, X. Chi, T. Siegrist, A.M. Sergent, A.P. Ramirez, Amorphouslike density of gap states in single-crystal pentacene, Phys. Rev. Lett. 93 (2004) 086802. [19] M.E. Gershenson, V. Podzorov, A.F. Morpurgo, Colloquium: electronic transport in single-crystal organic transistors, Rev. Mod. Phys. 78 (2006) 973989. [20] I.N. Hulea, S. Fratini, H. Xie, C.L. Mulder, N.N. Iossad, G. Rastelli, S. Ciuchi, A.F. Morpurgo, Tunable Frhlich polarons in organic singlecrystal transistors, Nature Mater. 5 (2006) 982. [21] D.J. Gundlach, L. Zhou, J.A. Nichols, T.N. Jackson, P.V. Necliudov, M.S. Shur, An experimental study of contact effects in organic thin lm transistors, J. Appl. Phys. 100 (2006) 024509. [22] L. Burgi, T.J. Richards, R.H. Friend, H. Sirringhaus, Close look at charge carrier injection in polymer eld-effect transistors, J. Appl. Phys. 94 (2003) 61296137. [23] The polynome was chosen with the lowest possible order (6th order). Higher order polynomes can provide a slightly better t, however, they can create oscillations at the rst and last datapoints which cause massive artifacts when the derivative is taken. [24] J.N. Haddock, X. Zhang, S. Zheng, Q. Zhang, S.R. Marder, B. Kippelen, A comprehensive study of short channel effects in organic eld-effect transistors, Org. Electron. 7 (2006) 4554. [25] M. Leufgen, U. Bass, T. Muck, T. Borzenko, G. Schmidt, J. Geurts, V. Wagner, L.W. Molenkamp, Optimized sub-micron organic thin-lm transistors: the inuence of contacts and oxide thickness, Synth. Met. 146 (2004) 341345.

200 nm show an additional strong decrease of Ion/off. This behaviour can be attributed to short-channel effects [24,25]. 4. Conclusion We have investigated OFETs based on both DT- and DBTTF, fabricated by drop casting from solution. These devices reveal an excellent performance and high stability. The eld-effect mobility is as high as 3.6 cm2/V s for DTTTF, which is the highest value reported for solution-processed DT-TTF. The characteristics are textbook-like, with hardly any hysteresis in IV-curves and on/off-ratios of more than 106. Using two different approaches we were able two identify band tails and impurity bands dominating the transport at elevated temperature and a low temperature regime with non or low activation of transport. Even at T = 50 K the performance is outstanding, both materials exhibiting a mobility of 0.01 cm2/V s and higher. Further analysis including the correlation between impurity levels and deposition methods or the effect of purication are ongoing. Acknowledgements We thank A. Morpurgo for fruitful discussions. This work was supported by the EU Integrated Project NAIMO (No. NMP4-CT-2004-500355), DGI Spain (CTQ200606333/BQU) and CIRIT (2005SGR-005951). References
[1] S.R. Forrest, The path to ubiquitous and low-cost organic electronic appliances on plastic, Nature 428 (2004) 911918. [2] G.H. Gelinck, H.E.A. Huitema, E.V. Veenendaal, E. Cantatore, L. Schrijnemakers, J.B.P.H. van der Putten, T.C.T. Geuns, M. Beenhakkers, J.B. Giesbers, B.-H. Huisman, E.J. Meijer, E.M. Benito, F.J. Touwslager, A.W. Marsman, B.J.E. van Rens, D.M. de Leeuw, Flexible active-matrix displays and shift registers based on solutionprocessed organic transistors, Nature Mater. 3 (2004) 106110. [3] I. McCulloch, Thin lms: rolling out organic electronics, Nature Mater. 4 (2005) 583584. [4] M. Mas-Torrent, C. Rovira, Tetrathiafulvalene derivatives for organic eld effect transistors, J. Mater. Chem. 16 (2006) 433436. [5] O.D. Jurchescu, J. Baas, T.T.M. Palstra, Effect of impurities on the mobility of single crystal pentacene, Appl. Phys. Lett. 84 (2004) 30613063.