ARTICLE Nano Approach Investigation of the Conduction Mechanism in Polyaniline Nanofibers ^ Yen-Fu Lin,† Chien-Hsiang Chen,† Wen-Jia Xie,† Sheng-Hsiung Yang,‡, ) Chain-Shu Hsu,‡ Minn-Tsong Lin,§, and Wen-Bin Jian†,* †Department of Electrophysics, and ‡Department of Applied Chemistry, National Chiao Tung University, Hsinchu 30010, Taiwan, §Department of Physics, National Taiwan University, Taipei 10617, Taiwan, and ^Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. ) Present address: Institute of Lighting and Energy Photonics, National Chiao Tung University, Gueiren Township, Tainan, 711, Taiwan. olyaniline has been known for more than 150 years.1 This material and its ABSTRACT A nanotechnological approach is applied to measurements of the electric field P fi counterparts of conducting polymers dependence of resistance under a high electric eld while in low voltage. With this technique, the have aroused considerable interests since conduction mechanism on a mesoscopic scale is explored in a single, nonagglomerated nanofiber. 2 the 1980s, and during that time, most Polyaniline nanofibers are prepared by vigorous mixing of aniline and oxidation agent ammonium reports focused on chemical synthesis, oxi- persulfate in acid solution. They exhibit a uniform nanoscale morphology rather than agglomeration dation-reduction reaction, chemical struc- as that produced via conventional chemical oxidation. The as-synthesized polyaniline nanofibers are tures, lattice phases,3 and the conduction mechanism in polymers.4 Most recently, doped (dedoped) with a HCl acid (NH3 base), and their temperature behaviors of resistances follow -1/2 polyaniline has caught the eyes of scientists an exponential function with an exponent of T . To measure the conduction mechanism in a again because new synthesis processes, single nanofiber, the dielectrophoresis technique is implemented to position nanofibers on top of such as interfacial polymerization, have two electrodes with a nanogap of 100-600 nm, patterned by electron-beam lithography. After the been developed to produce this material devices are irradiated by electron beam to reduce contact resistances, their temperature behaviors with more nanofibrillar morphology in con- and electric field dependences are unveiled. The experimental results agree well with the theoretical trast to granular and agglomerated polyani- model of charging energy limited tunneling. Other theoretical models such as Efros-Shklovskii and line bulk, synthesized with conventional chemical oxidation or electrochemical po- Mott's one-dimensional hopping conduction are excluded after comparisons and arguments. lymerization in aqueous acids.2,5 The grow- Through fitting, the size of the conductive grain, separation distance between two grains, and ing attention on polyaniline is due not only charging energy per grain in a single polyaniline nanofiber are estimated to be about 4.9 nm, 2.8 to manifold applications, such as gas nm, and 78 meV, respectively. The nanotechnological approach, where the nanogap and the 6 7 fi ff 8 sensors, actuators, eld-e ect transistors, dielectrophoresis technique are used for single nanofiber device fabrication, is applied for memory devices,9 and electrochemical determination of mesoscopic charge transport in a polyaniline conducting polymer. capacitors,10 but also to exploration of the mechanism of nanofiber formation5,11 in KEYWORDS: conducting polymer . one-dimensional nanostructures . polyaniline . application to other conducting polymers. hopping conduction . nanofiber Polyaniline consists of three oxidation states including leucoemeraldine, emeraldine, and pernigraniline base form.2 The emeral- polyaniline film conductivity, and proton- dine base form of polyaniline can be doped ation level. They argued that the theory of (protonated) to form emeraldine salt by an charging energy limited tunneling (CELT) acid such as HCl, and conversely, the emer- proposed by Sheng et al.14 gives an ade- aldine salt form can be dedoped back by quate description of the conduction mecha- 2 a base. The protonation process causes nism. They believed that the protonated * Address correspondence to - a conductivity variation from ∼10 10 to polyaniline forms metallic regions, modeled [email protected]. 10 Ω-1 cm-1.12 as a sphere of metal grain, and the unpro- Received for review December 19, 2010 Research into the conduction mechanism tonated polyaniline forms an insulating re- and accepted January 21, 2011. of polyaniline began right after its rediscov- gion which results in a separation between Published online January 31, 2011 ery in the 1980s. Zuo et al.12 studied the conductive grains. According to Sheng's 10.1021/nn103525b temperature-dependent thermopower, the theory, they estimated the most probable temperature and electric field (with an ap- distance of a conductive grain with a grain 15 plied voltage up to 100 V) dependence of separation to be 20-27 nm. Wang et al. C 2011 American Chemical Society LIN ET AL. VOL. 5 ’ NO. 2 ’ 1541–1548 ’ 2011 1541 www.acsnano.org ARTICLE carried out similar experiments and an additional measurement of the temperature-dependent dielec- tric constant. In contrast, they concluded that polyani- line is a one-dimensional (1D) disordered conductor, complying with Mott's variable range hopping (VRH) theory, while an interchain coupling makes these 1D intrachain localized states constitute three-dimen- sional (3D) delocalized states. Li et al.16 proposed a granular-rod model to explain the temperature depen- dence of the conductivity, the doping dependence, the thermoelectric power, and the Pauli susceptibility of polyaniline. Their model was comparable with the 3D VRH theory with an additional assumption of linear temperature-dependent density of states near the Fermi level. Pelstar et al.17 gave a similar model and suggested that the conducting, crystalline regions are surrounded by an insulating, amorphous region. They used their model to estimate the diameter of metallic regions and the barrier width (separation) to be about 8 and 1.6 nm, respectively. Moreover, they implied that the model can also be compatible with Sheng's CELT model. Zuppiroli et al.18 reexamined the implementa- tion of the CELT model to hopping in disordered conducting polymers and used it to evaluate the Figure 1. (a) Sketch of a chemical structure of unprotonated diameter of conducting grains and the separation. and HCl-protonated polyaniline units. (b) Partially proto- They additionally provided a detailed description of nated polyaniline nanofiber. The solid zig-zagged lines and protonation-induced interchain coupling, thus they the green dots represent polyaniline chains and Cl atoms, respectively. The grain feature of protonated regimes is took polaronic clusters as conducting grains. In the implicated, as well. (c) Scheme of entangled polyaniline following years, several other experiments each sup- nanofibers. The internanotubular contacts are marked in ported different models including 3D VRH,19 1D VRH blue on the graph. The inset indicates a close view of the red 20 rectangle area. The 3D green regimes in the inset illustrate with interchain coupling, crystalline regions con- the protonated grain structures in a single polyaniline nected through amorphous regions,20 Efros-Schklovs- nanofiber. kii (ES) hopping conduction,21 CELT (granular metallic) model,22,23 and the localization interaction model.24 In scale, we implement a dielectrophoresis technique, those reports, it is argued that the charge transport which has not been applied to a study of the conduc- should be clarified on a mesoscopic scale and the true tion mechanism in polyaniline yet, to examine tem- mechanism of electron transport in polyaniline is still perature and electrical field dependences of a single under debate. polyaniline nanofiber with a diameter of about 50 nm Recently, a new electrospinning technique has been and a length of 100-600 nm. According to our experi- developed to produce polymeric nanofibers with a mental results, we argue that Sheng's CELT model - submicrometer diameter.25 27 Moreover, electrical gives the best description of electron transport in property measurements on polymer nanofibers and polyaniline on a mesoscopic scale. nanotubes were carried out,28,29 and it was commen- ted that the internanotubular contacts should play a RESULTS AND DISCUSSION vital role on the temperature-dependent conductivity We start to describe and discuss the issue of electron of polyaniline films.28 Until now, there are still a lot of transport in polyaniline before stepping into experi- debates and controversies on the conduction mechan- mental results. Figure 1a shows a chemical structure of ism in polyaniline. The summary of a survey of litera- protonated (emeraldine salt on the left) and unproto- ture indicates that the conductivity problem resides in nated (emeraldine base to the right) polyaniline units. mesoscopic physics and its nanofibrillar nature. Parti- In a first step and starting from a microscopic view- cularly, the field dependence of conductivity shall be point, it is disclosed30 that an unprotonated polyaniline measured and studied in a more careful manner to chain reveals a semiconductor-like band structure with prevent a high applied voltage, leading to high energy a band gap energy of ∼4 eV. This seems to be in damaging effects. In this article, we will briefly describe connection with the Coulomb energy between two conduction mechanisms in polyaniline from micro- non-overlapping electrons sitting