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The Effect of Magnetic Field on Thick Ir(ppy)3: Ir(mpp)3 Nonmagnetic Organic Transistor With Improved Performance by Film Deposition on Heated Substrate
Abd. Rashid bin Mohd Yusoff, Ying Song, Eikner Holz, Dietmar Schulz, and Saiful Anuar Shuib
AbstractIn this paper, we examined the inuence of magnetic eld with different substrate temperatures during the deposition of the Ir(ppy)3 :Ir(mpp)3 blend layer heterojunction organic nonmagnetic organic transistor. It is shown that substrate heating treatment during evaporation leads to a signicant improvement in the nonmagnetic metal-base transistor performance mainly due to an increase in current gain and ON-to-OFF current ratio. This is attributed to the improvement of thermal energy. Upon heating the substrate to 110 C in the presence of magnetic eld, current gain and ON-to-OFF current ratio of 281 and 3.30 106 were obtained compared to 219 and 2.06 106 for an identical device prepared at 26 C, respectively. Magnetocurrent effect of 28% was obtained with applied 2 T and 110 C. Index TermsBipolar transistor, metal-base transistor, polymer blends.

I. INTRODUCTION

HE discovery of polymeric organic conducting polymer by Shirakawa [1], [2] increased the number of publications and patents. Polyaniline (PANI) is one of the simplest examples of conducting polymer that can be tailored for specic application via doping process [3]. PANI may be prepared by either chemical or electrochemical oxidation of aniline monomer. However, one of the drawbacks of the PANI prepared by chemical oxidation technique over those PANI lms prepared via electrochemical method is regarding the electrical conductivity. The conductivity of chemically prepared PANI is little lower than those of PANI lms prepared electrochemically. Various properties such as electrical conductivity, stability, and surface topography of prepared PANI sturdily depend on diverse reaction conditions namely 1) the kinds and concentrations of oxidant

and dopant; 2) reaction temperature; 3) time; 4) stoichiometry; and 5) solvent. It has been reported that PANI prepared at low temperature produced a good organic transistor performance in terms of leakage current and surface morphology [4]. Recently, the discovery of organic magnetocurrent (OME) from small molecular materials to polymer has attracted a great attention from broad scientic and industrial committees. OME is a change in the current of a device caused by the presence of an external magnetic eld. Since its discovery, many research groups have reported OME values exceeding 50% at weak magnetic elds of < 1 T. While the origin of OME still remains unclear and not well understood, there emerged a few reported works claimed of larger values [5][7]. OME can either be negative or positive in sign and usually observed in the current [5][14]; even similar effects can be observed in the electroluminescence [12], [14][22] and photocurrent [19][25]. The changes in sign depend not only on materials [12] and device architecture [23] but also depend on operating condition [12], [14]. In addition, OME can be observed at room and low temperatures [23], [25] but there are limited works reported on a high temperature. There is a very limited study of OME at high temperature [26]. The observation of OME at room and high temperatures makes it attractive for future electronic applications. In this work, we introduce the controlled substrate heating treatment TFZ Si / PANI during lm deposition as a parameter inuence the layer morphology within a nonmagnetic organic transistors (NOTs) leading to operational NOTs with thick blend layers of up to 150 nm. At certain TFZ Si / PANI , a signicant enhancement of current gain and ON-to-OFF current ratio from 219 to 281 and 2.06 106 to 3.30 106 have been achieved, respectively. We also investigated the OME at a higher temperature ranging from 50 to 250 K. II. EXPERIMENTAL DETAILS The NOTs are fabricated in a custom-made multichamber ultrahigh vacuum evaporation system at a base pressure of 107 mbar. Float-zone silicon (FZ-Si) (Silicon Valley, CA) is used and acts as collector. Prior to the used, substrates are cleaned with HF buffer [27]. The NOTs stack consist of 80 nm of PANI, followed by a blend layer of 150 nm coevaporated Ir(ppy)3 :Ir(mpp)3 (ratio 3:3). For the improvement of charge carrier injection, a layer

Manuscript received May 5, 2011; revised June 20, 2011 and July 19, 2011; accepted September 8, 2011. Date of publication September 29, 2011; date of current version January 11, 2012. The review of this paper was arranged by Associate Editor G. Ramanath. A. R. B. M. Yusoff is with the Departamento de F sica, Group of Organic Optoelectronic Devices, Universidade Federal do Paran a, Paran a 81531-990, Brazil (e-mail: abd@sica.ufpr.br). Y. Song and S. A. Shuib are with Komax Systems Malaysia, 11900 Penang, Malaysia (e-mail: y.song@hotmail.my; s.saiful-anuar@live.com). E. Holz and D. Schulz are with Komax Systems LCF SA, 2301 La Chauxde-Fonds, Switzerland (e-mail: d.schulz@live.com.my; e.holz@live.com.my). Color versions of one or more of the gures in this paper are available online at http://ieeexplore.ieee.org. Digital Object Identier 10.1109/TNANO.2011.2169082

1536-125X/$26.00 2011 IEEE

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Fig. 1. Magnetic common-emitter IV characteristics measured at different base current from 0 to 1 A.

Fig. 2. Magnetic common-emitter current gain as a function of collector emitter voltage.

system of 0.5 nm lithium uoride (LiF) is used [28]. Finally, a 60 nm Al top contact is deposited at the same base pressure. All organic materials have been puried at least ve times by vacuum gradient sublimation to really remove any possible contaminations. The thickness measurements were made by means of Dektak Surface Prolometry. The typical NOT active area is 1 mm2 . The fabricated NOTs were immediately transferred into a glovebox and placed on a homebuilt sample holder. This sample holder was then placed between the poles of an electromagnet with the magnetic eld perpendicular to the direction of current ow in the device. For the magnetic measurements, the magnetic eld was decreased from 2 to 0 T, and increased from 0 to 2 T. The currentvoltage (IV) measurements were performed using an HP 4155A Semiconductor Parameter Analyzer. All measurements were performed in the total darkness and sequentially performed for two times: 1) without magnetic eld applied to the device and 2) with magnetic eld applied to the device. III. RESULTS AND DISCUSSION Fig. 1 shows the dependence of magnetic collector current on the collectoremitter voltage at various base currents. Magnetic collector current is dened as the collector current as a function of collectoremitter voltage with an external magnetic eld applied to the device. The base current controlled in 0.14 nA per step and the characteristics are measured in the dark at room temperature in the presence of magnetic eld. The family curves of NOT show an excellent saturation behavior for each base current over a wide range of collectoremitter voltage (05 V). It is also seen that the leakage current is signicantly low in this device prepared at 110 C. An average value of a leakage current is in the range of 1010 to 1011 A. This remarkable low leakage leads us to remarkable improvement of current gain and ON-to-OFF current ratio. A low leakage current in our NOTs is due to the high-quality base layer where the average surface roughness for all 43 grown PANIs is in the range of 0.23 .5 nm. Fig. 2 depicts the magnetic current gain versus collector emitter voltage extracted from Fig. 1. As stated earlier, the magnetic current gain is an extracted parameter from commonemitter characteristics and is dened as IC /IB under the inuence of a magnetic eld.

Fig. 3. (a) Current gain versus substrate temperature for two different conditions, namely with and without magnetic eld. (b) ON-to-OFF current ratio versus substrate temperature for two different conditions, namely with and without magnetic eld.

As shown in Fig. 2, the magnetic current gain of our device is 281. The current gain for the case in the absence of magnetic eld is 219 (data not shown). The enhancement of 28% obtained from this characteristic leads to the conclusion that the magnetic eld has an inuence on the electron injection efciency. Further investigation is being prepared to study the inuence of magnetic eld on electron injection efciency and will not be treated here. To nd a correlation between TFZ Si / PANI and NOT performance, TFZ Si / PANI is varied during evaporation of the Ir(ppy)3 :Ir(mpp)3 blend layers for different devices from ambient temperature to 130 C. Detailed features of NOT characteristics namely current gain and ON-to-OFF current ratio on the substrate temperature are shown in Fig. 3.

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The most decisive improvement that ultimately leads to the increase in ON-to-OFF current ratio is current gain. From Fig. 3(a) starting with 238 at room temperature, the current gain reached a maximum value of 281 at TFZ Si / PANI 110 C before it dropped to a lower value of about 263 for higher substrate temperature. For the case in the absence of magnetic eld, the current gain is relatively low even at higher temperature. For instance, the current gain at room temperature is 186 however; a notable enhancement is seen as we increased TFZ Si / PANI to 110 C, where the current gain reached up to 219. As we improved TFZ Si / PANI to 130 C, a signicant decrement in current gain occurred. A similar trend can be observed from Fig. 3(b) at room temperature in the absence of magnetic eld, where the ON-to-OFF current ratio is 1.61 106 . The enhancement of about 28% is observed when the device is subjected to external magnetic eld. This enhancement is attributed increment in the ONSTATE current. As we can see in both cases, a sudden change in ON-toOFF current ratio occurred at the TFZ Si / PANI transition from 80 to 90 C. The changes are 39.8% and 40.3% for the measurements with and without magnetic eld, respectively. At an optimal TFZ Si / PANI (110 C), the achieved ON-to-OFF current ratio is 2.58 106 and this ON-to-OFF current ratio is further increased to 3.30 106 as we introduced magnetic eld to the device. Further increment in TFZ Si / PANI leads to a decrement in ON-to-OFF current ratio. From these observations, we conclude that TFZ Si / PANI and magnetic eld have a strong dependence on both current gain and ON-to-OFF current ratio. Throughout these studies, in order to maintain an exceptional value of the ON-to-OFF current ratio, the Ir(ppy)3 :Ir(mpp)3 blending ratio is always kept to 3:3 by weight. If the Ir(ppy)3 :Ir(mpp)3 ratios were 1:3 or 2:1, the device would easily suffer a large leakage current, which would undeniably demolish the switching performance of our NOT. We can conclude that as we increased the temperature, a signicant amount of thermal energy directly inuenced the collector current, which leads to a high current gain and high ON-to-OFF current ratio regardless in the case with or without magnetic eld. There is still room of an improvement for better understanding a direct relation between current gain, ON-to-OFF current ratio, TFZ Si / PANI , and magnetic eld. Fig. 4 shows the OME versus magnetic eld at the total darkness at various different temperatures and xed driving voltage (1 V). In this measurement, the magnetic eld is varied from 2 to 0 to 2 T. As can be seen from these typical curves, weak temperature dependence is observed at 50 and 100 K. As the temperature is increased from 100 to 150 K, strong temperature dependence is obtained. The response continues to grow with moderate temperature dependence as the temperature continues to increase to 250 K. A total increment up to 300% is observed when we changed the temperature from 50 to 250 K. The highest obtained OME is about 28% at 250 K at 1 V. We tried to increase the temperature to a higher value but damage can be seen in the device. Nowadays, the origin of the OME in pure nonmagnetic semiconducting materials and devices still remains unclear. In our fabricated device, we observed only a positive OME, and it can be attributed to the inuence of magnetic eld on a collec-

Fig. 4. (1 V).

Temperature dependence of OME for studied device at xed voltage

tor current. Under a normal operation of a bipolar transistor, a collector current consists of electrons which get into the base and arrive the collector terminal. As seen in Fig. 1, the inuence of magnetic eld contributed to signicant increment in the collector current. We also did not observe any angle orientation dependence of magnetic eld with respect to the direction of current ows in NOT. IV. CONCLUSION In summary, we show that controlled in situ substrate heating during evaporation of Ir(ppy)3 :Ir(mpp)3 can increase NOT performance. It is illustrated that an optimum TFZ Si / PANI equals 110 C for blend NOT consisting of Ir(ppy)3 :Ir(mpp)3 with a ratio of 3:3. The observed effects are explained in terms of extremely low OFFSTATE current. The decreasing performance for TFZ Si / PANI > 110 C is attributed to the changed in the PANI polymer chain. Above all, NOT containing blend layers with a simple in situ substrate heating is a promising method to inuence the device performance. Moderate temperature dependence is observed in this device when we applied different temperature values at a constant voltage. The largest recorded OME of 28% at 250 K can be considered as an important feature for future development of magnetically tunable organic transistor. A possible explanation for this observation is the inuence of magnetic eld on the collector current. ACKNOWLEDGMENT The authors would like to thank Komax Research and Development Division for helpful discussion. REFERENCES
[1] C. K. Chiang, C. R. Fincher, Y. W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis, S. C. Gau, and A. G. MacDiarmid, Electrical conductivity in doped polyacetylene, Phys. Rev. Lett., vol. 39, no. 17, pp. 10981101, Oct. 1977. [2] H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, and A. J. Heeger, Synthesis of electrically conductive organic polymers: Halogen derivatives of polyacetylene (CH)x, J. Chem. Soc. Chem. Commun., vol. 474, no. 16, pp. 578580, May 1977. [3] P. Chandrasekhar, Conducting Polymers, Fundamentals and Applications: A Practical Approach. Boston, MA: Kluwer, 1999. [4] A. R. B. M. Yusoff and S. A. Shuib, Electrochimica Acta, to be published, doi: 10.1016/j.electacta.2011.09.057.

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[5] A. R. B. M. Yusoff, W. J. da Silva, J. P. M. Serbena, M. S. Meruvia, and I. A. Hummelgen, Very high magnetocurrent in tris-(8-hydroxyquinoline) aluminum-based bipolar charge injection devices, Appl. Phys. Lett., vol. 94, no. 25, pp. 253305-1253305-3, Jun. 2009. [6] D. Sun, L. Yin, C. Sun, H. Guo, Z. Gai, X. -G. Zhang, T. Z. Ward, Z. Cheng, and J. Shen, Giant magnetoresistance in organic spin valves, Phys. Rev. Lett., vol. 104, no. 23, pp. 236602-1236602-4, Jun. 2010. [7] P. Desai, P. Shakya, T. Kreouzis, and W. P. Gillin, Magnetoresistance in organic light-emitting diode structures under illumination, Phys. Rev. B, vol. 76, no. 23, p. 235202, Dec. 2007. [8] J. D. Bergeson, V. N. Prigodin, D. M. Lincoln, and A. J. Epstein, Inversion of magnetoresistance in organic semiconductors, Phys. Rev. Lett., vol. 100, no. 6, pp. 067201067204, Feb. 2008. [9] F. L. Bloom, W. Wagemans, M. Kemerink, and B. Koopmans, Separating positive and negative magnetoresistance in organic semiconductor devices, Phys. Rev. Lett., vol. 99, no. 25, pp. 257201257204, Dec. 2007. [10] P. Desai, P. Shakya, T. Kreouzis, W. P. Gillin, N. A. Morley, and M. R. J Gibbs, Magnetoresistance and efciency measurements of Alq3 -based OLEDs, Phys. Rev. B, vol. 75, no. 9, pp. 094423094428, Mar. 2007. [11] S. Majumdar, H.S. Majumdar, H. Aarnio, D. Vanderzande, R. Laiho, and R. Osterbacka, Role of electron-hole pair formation in organic magnetoresistance, Phys. Rev. B, vol. 79, no. 20, p. 201202, May 2009. Mermer, G. Veeraraghavan, T. Francis, Y. Sheng, D. Nguyen, [12] O. M. Wohlgenannt, A. Kohler, M. Al-Suti, and M. Khan, Large magnetoresistance in nonmagnetic -conjugated semiconductor thin lm devices,, Phys. Rev. B, vol. 72, no. 10, pp. 205202205211, Nov. 2005. [13] U. Niedermeier, M. Vieth, R. Patzold, W. Sarfert, and H. von Seggern, Enhancement of organic magnetoresistance by electrical conditioning, Appl. Phys. Lett., vol. 92, no. 19, pp. 193309-1193309-3, May 2008. [14] F. J. Wang, H. B asler, and Z. V. Vardeny, Magnetic eld effects in conjugated polymer-fullerene blends: Evidence for multiple components, Phys. Rev. Lett., vol. 101, no. 23, pp. 236805-1236805-4, Jan. 2009. [15] C. G aditz, A. G. M akl, and M. C ole, Inuence of an external magnetic eld on the singlet and triplet emissions of tris-(8hydroxyquinoline)aluminum(III) (Alq3 ),, J. Appl. Phys., vol. 98, no. 10, pp. 104507-1104507-4, Nov. 2005. [16] Y. Iwasaki, T. Osasa, M. Asahi, M. Matsumura, Y. Sakaguchi, and T. Suzuki, Fractions of singlet and triplet excitons generated in organic light-emitting devices based on a polyphenylenevinylene derivative, Phys. Rev. B, vol. 74, no. 19, pp. 195209-1195209-8, Nov. 2006. [17] J. Kalinowski, M. Cocchi, D. Virgili, P. Di Marco, and V. Fattori, Magnetic eld effects on emission and current in Alq3 -based electroluminescent diodes, Chem. Phys. Lett., vol. 380, no. 56, pp. 710715, Oct. 2003.

[18] T. D. Nguyen, Y. Sheng, J. E. Rybicki, and M. Wohlgenannt, Magnetic eld-effects in bipolar, almost hole-only and almost electron-only tris(8-hydroxyquinoline) aluminum devices, Phys. Rev. B, vol. 77, no. 23, pp. 235209-1235209-5, 2008. [19] T. D. Nguyen, Y. Sheng, J. E Rybicki, and M. Wohlgenannt, Magnetoconductivity and magnetoluminescence studies in bipolar and almost hole-only sandwich devices made from lms of a -conjugated molecule, Sci. Technol. Adv. Mater., vol. 9, no. 2, pp. 024206024209, Jun. 2008. [20] H. Odaka, Y. Okimoto, T. Yamada, H. Okamoto, M. Kawasaki, and Y. Tokura, Control of magnetic-eld effect on electroluminescence in Alq3 -based organic light emitting diodes, Appl. Phys. Lett., vol. 88, no. 12, p. 123501, Mar. 2006. [21] Y. Wu, Z. Xu, B. Hu, and J. Howe, Tuning magnetoresistance and magnetic-eld-dependent electroluminescence through mixing a strongspin-orbital-coupling molecule and a weak-spin-orbital-coupling polymer, Phys. Rev. B, vol. 75, no. 3, pp. 035214-1035214-6, Jan. 2007. [22] P. Desai, P. Shakya, T. Kreouzis, and W. P. Gillin, Magnetoresistance in organic light-emitting diode structures under illumination, Phys. Rev. B, vol. 76, no. 23, pp. 235202-1235202-5, Dec. 2007. [23] E. L. Frankevich, A. A. Lymarev, I. Sokolik, F. E. Karasz, S. Blumstengel, R. H. Baughman, and H. H. H ohold, Polaron-pair generation in poly(phenylene vinylenes), Phys. Rev. B, vol. 46, no. 15, p. 9320, Oct. 1992. [24] P. Desai, P. Shakya, T. Kreouzis, and W. P. Gillin, The role of magnetic elds on the transport and efciency of aluminum tris(8hydroxyquinoline) based organic light emitting diodes, J. Appl. Phys., vol. 102, no. 7, pp. 073710-1073710-5, Oct. 2007. Mermer, G. Veeraraghavan, T. Francis, and M. Wohlgenannt, Large [25] O. magnetoresistance at room-temperature in small-molecular-weight organic semiconductor sandwich devices, Solid State Commun., vol. 134, no. 9, pp. 631636, Jan. 2005. [26] A. R. B. M. Yusoff, D. Schulz, E. Holz, Y. Song, and S. A. Shuib IEEE Trans. Electron Devices, vol. 58, no. 10, pp. 35833586, Oct. 2011. [27] O. Pluchery, Y. J. Chabal, and R. L. Opila, Wet chemical cleaning of InP surfaces investigated by in situ and ex situ infrared spectroscopy, J. Appl. Phys., vol. 94, no. 4, pp. 27072715, Jun. 2003. [28] S. Shi and D. Ma, Effect of Ca and buffer layers on the performance of organic light-emitting diodes based on tris-(8-hydroxyquinoline) aluminum, Thin Solid Films., vol. 518, no. 17, pp. 48744878, Jun. 2010.

Authors photographs and biographies not available at the time of publication.