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A comparative study of the polyaniline thin ﬁlms produced by the cluster beam deposition and laser ablation methods
Hyuna Lim and Jong-Ho Choia
Department of Chemistry and Center for Electro- and Photo-Responsive Molecules, Korea University, Anam-Dong, Seoul 136-701, Korea
Received 8 September 2005; accepted 2 November 2005; published online 5 January 2006 Polyaniline PANI thin ﬁlms have been prepared by applying the novel neutral and ionized cluster beam deposition NCBD and ICBD methods and the pulsed laser deposition PLD technique to the PANI samples of half-oxidized emeraldine base EB-PANI and protoemeraldine base forms in a high-vacuum condition. Characterization of the oxidation states and structural changes of pristine and doped thin ﬁlms has been performed by Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and x-ray photoelectron spectroscopy. Spectroscopic measurements demonstrate that the dominant structure of NCBD and ICBD thin ﬁlms corresponds to the reduced leucoemeraldine base state, whereas the chemical composition of PLD thin ﬁlms depends critically on the laser ﬂuence and the molecular weight of PANI target. The congruent deposition is only obtained for the PLD ﬁlms deposited by the laser-induced decomposition of the low-molecular-weight targets in the low to intermediate ﬂuence regime below 100 mJ/ cm2 with a pulse duration of 7 ns . The surface morphology examined by atomic force microscopy measurements shows that the cluster and laser beams are effective in producing smooth, uniform polymeric thin ﬁlms. After I2 and HCl doping, the electrical conductivities of the NCBD, ICBD, and particularly PLD thin ﬁlms are increased signiﬁcantly. The higher conductivity of PLD ﬁlms is ascribed to higher amounts of quinoid di-imine doping sites in the EB-PANI state, and the overall structure-conductivity characteristics are consistent with the spectroscopic observations. © 2006 American Institute of Physics. DOI: 10.1063/1.2141508
Conducting conjugated polymers have attracted much attention in future commercial optoelectronic devices as ﬂexible and economical alternatives to traditional silicon-based inorganic devices. In all of the conducting polymers being investigated, the environmentally stable polyaniline PANI family has been recognized as one of the promising organic polymers due to the excellent electrical, optical, and magnetic characteristics in the potential applications to displays, microelectronic devices, secondary batteries, and molecular sensors.1–4 PANI has ﬁve distinct base forms represented by the following molecular formula:5 – C6H4 – NH – C6H4 – NH – – C 6H 4 – N v C 6H 4 v N –
1−y n ,
where y = 0 corresponds to the fully oxidized pernigraniline base, y = 0.25 to the nigraniline base, y = 0.5 to the halfoxidized emeraldine base EB , y = 0.75 to the protoemeraldine base PEB , and y = 1 to the fully reduced leucoemeraldine base LEB . In particular, the EB form has been known to show the highest electric conductivity after the doping processes with a protonic acid such as HCl and H2SO4.6–9 In the development of polymeric thin-ﬁlm devices, the ﬁlms are, in general, prepared by spin casting, chemical syna
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thesis, or electrochemical methods.10–17 However, in employing such wet procedures most conventional methods undergo unavoidable incompatibility with the existing integratedcircuit fabrication processing. The lack of suitability is ascribed mainly to poor solubility in water and most organic solvents, unwanted incorporation and/or contamination of solvent molecules, the difﬁculties in controlling the growth parameters for producing high-quality thin ﬁlms, etc. Many of such obstacles have been overcome by adopting the simple physical vapor deposition PVD method, in which the sample molecules evaporated through resistive heating are condensed onto the substrate in a high-vacuum condition.18–23 Even though the PVD method is effective in producing thin ﬁlms of low-molecular-weight materials, however, only the limited number of adjustable parameters such as the evaporation and substrate temperatures remains as drawbacks. Other less popular but promising methods in depositing polymeric thin ﬁlms are applying neutral and ionized cluster beam deposition NCBD and ICBD and pulsed laser deposition PLD methods.24–31 In the case of the cluster beam deposition, the neutral cluster beam produced by the adiabatic expansion of sample vapor molecules into a high vacuum is utilized. Whereas in NCBD the neutral cluster beam is directly deposited onto the target substrate, in ICBD partial ionization is made by electron impact and then the resulting ionized cluster beam is accelerated and deposited. The cluster beam consisting of weakly bound molecules
© 2006 American Institute of Physics
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195. or KBr pellet substrates.aip. where the ionized beam was accelerated to travel the drift region and then deposited onto the substrate. In this paper. 124. and here only a brief relative account is presented. and the substrate. the neutral PANI clusters were directly deposited onto the glass.0-mm-long nozzle and was resistively heated up to 350 ° C. and electrical properties of the novel PANI thin ﬁlms prepared by the NCBD. the ionization and extraction electrodes. 1.31–37 It has been known in polymer ablation that whereas the chemical composition and velocity distribution in the ejected plume are quite complicated and depend upon the absorption cross section of target polymer and irradiation conditions. and PLD methods. In the NCBD scheme. Lim and J. and the average base pressure was kept below 1 10−6 Torr. The starting PANI powder Aldrich Co. Schematic diagrams of a cluster beam deposition CBD and b pulsed laser deposition PLD apparatus.41. the partially ionized clusters were generated by the electron impact source composed of a cylinder-shaped grid anode surrounded by a ﬁlament cathode. The schematic diagrams of the two systems employed in this work are shown in Fig.25 The CBD apparatus consists of the evaporation crucible cell. reactive deposition. PEB form of molecular weight M w = 5000 and EB form of M w = 65 000 was deposited in a high-vacuum condition by the homemade CBD and PLD systems.152. 3000 l / s bafﬂed diffusion pump. The acceleration voltage Va determined by the potential difference between the grid anode and the extraction electrode was adjusted between 0 and 1 kV. From a practical point of view. II. Especially. The CBD chamber was pumped by a 10-in. The possibility of utilizing those methods is attractive from both fundamental and practical interests.0 mm diameter and 1. in the ICBD scheme. ICBD. which cannot be easily processed through conventional solution or thermal techniques. thermal energies to highly directional translational motion and the subsequent condensation resulted in the formation of weakly bound neutral clusters at the working pressure of ca. 1. We have also investigated the structural changes and enhancement of the electrical conductivity after doping the as-deposited nonconducting PANI thin ﬁlms with iodine I2 and a protonic acid such as HCl. in ICBD the electric charge of the ionized cluster provides more adjustable deposition parameters such as ionization and acceleration voltage. quartz.-H. The extent of ionization was determined by the cathode emission current. ion current density. and stoichiometric transfer. the preparation of thin ﬁlms of hardly processable materials using laser ablation is deﬁnitely a promising new scheme and a variety of polymer materials have been studied. The ion current Downloaded 11 Aug 2009 to 163. In the case of the PLD method. the clusters undergo facile fragmentation into individual molecules followed by active surface migration resulting in well-deﬁned smooth and uniform thin ﬁlms. EXPERIMENT FIG. deposited ﬁlms maintaining the desirable physical and chemical properties of original PANI samples might be available. see http://jcp. Chem. Phys. The CBD system was described in detail elsewhere. The resulting ionized cluster beam was extracted by the extraction electrode. 014710 2006 shows the unique advantages such as the high directionality and high translational kinetic energy. surface morphology. the PLD method might be applied to the formation of PANI thin ﬁlms. we present the characterization studies of the structures. Therefore.30 In consideration of the possible control of deposition parameters through the selection of the wavelength and power of the laser beams used for ablation. Choi J. after the collisions with the target substrate. where the distance between the crucible cell and the substrate was 190 mm. the drift region. On the other hand. 10−5 Torr. it remains unclear whether high-molecular-weight PANI can be evaporated or ablated without signiﬁcant structural degradation. The starting material PANI powder was placed inside the enclosed cylindrical graphite crucible with a 1.014710-2 H. the advantages of PLD include inherent simplicity.jsp . The conversion of random. Redistribution subject to AIP license or copyright. The evaporated PANI sample underwent an adiabatic supersonic expansion through the nozzle. From a fundamental viewpoint. etc. congruent evaporation.org/jcp/copyright.
152. The growth rate of the PANI ﬁlm was generally dominated by the temperature of the crucible cell and was monitored by a thickness monitor Maxtek Inc. The angle of incidence was maintained at 45° and the laser ﬂuence ranging from 40 to 200 mJ/ cm2 was used for 30 min. ICBD. for the XPS analysis. The Fourier transform infrared FTIR spectroscopy Bomen MB-104 .41. measured by a picoammeter Keithley Co. 1400 l / s bafﬂed diffusion pump. the monochromatic x-ray generated from an Al anode at the K line 1486. 124. The I2.aip. The substrate was kept at 40 ° C and the thickness was measured by an alpha step surface proﬁle monitor Tencor Corp. The HCl vapor was generated from the reaction of ammonium chloride NH4Cl with sulfuric acid H2SO4 .5 mm diameter spot with a 600 mm focal length fused silica lens at the surface of the PANI pellet target.and HCl-doped PANI ﬁlms were prepared by exposing the ﬁlms in a glass vial ﬁlled with I2 for 48 h and with HCl for 2 min. FTIR spectra of a iodine. the target pellet was attached to the holder coupled to the motor MDC BRM133-01 in a constant rotary motion and was simultaneously raster scanned by the laser beam through the focusing lens mounted in a precision translator. ultraviolet-visible UV-VIS Hewlett Packard 8452A spectroscopy. the substrate was kept at room temperature throughout the deposition processes and normally seven substrates were deposited simultaneously. For good shot-to-shot ablation stability.org/jcp/copyright. The conventional doping methods with iodine I2 and hydrochloric acid HCl were utilized to improve the electrical conductivity of as-deposited nonconducting NCBD. Laser ﬂuence dependence of FTIR spectra for PLD thin ﬁlms of b PANI M w = 5000 and c PANI M w = 65 000 . The surface morphology of the thin ﬁlms was examined by atomic force microscopy AFM PSIA XE-100 and surface proﬁler Veeco DEKTAK3 . The PANI thin ﬁlms were deposited on the substrate placed at a distance of 4 cm away from the center of the target at the working pressure of ca. ICBD. and PLD methods. The third harmonic output 355 nm of a Q-switched Nd:YAG laser beam Continuum Surelite II10.and b HCl-doped PANI = 65 000 thin ﬁlms produced by NCBD. 3. respectively. 30 nA. . The PLD system consists of the pulsed Nd:YAG yttrium aluminum garnet laser and the deposition vacuum chamber containing the rotating target holder and the substrate. was typically ca. a FTIR spectra of PANI M w = 5000 pellet and NCBD and ICBD thin ﬁlms. Phys. . and x-ray photoelectron spectroscopy XPS Physical Electronics PHI 5700 were applied to examine the as-deposited and doped PANI thin ﬁlms. The exposure to air and water vapor was minimized during the doping processes. 10 Hz repetition rate was loosely focused to an approximately 2. 10 mm in diameter and 1 mm thick. The electrical conductivity for the undoped and doped PANI thin- FIG. Especially.195. and PLD thin ﬁlms. The PLD chamber was pumped by a 6-in. The typical rate was measured to be ca. 2.014710-3 Polyaniline thin ﬁlms J.6 eV at 12 kV and 350 W was employed in an ultrahigh-vacuum condition at 2 10−10 Torr.7 Å / s. see http://jcp. and the average base pressure was maintained below 1 10−6 Torr. Redistribution subject to AIP license or copyright. 7 ns pulse duration. In both NCBD and ICBD schemes. Chem. 014710 2006 FIG. 10−5 Torr.jsp . 0. Mw Downloaded 11 Aug 2009 to 163.
Those peaks are assigned to the out-of-plane bending vibration of phenyl C–H. On the other hand. 014710 2006 FIG. 1304. RESULTS AND DISCUSSION A. The observed chemical reduction might be ascribed to the higher reactivity of the quinoid di-imine moieties of the thermally evaporated chain segments formed during the heating pro- cess.39 Two weak bands near 740 and 690 cm−1 are attributed to the out-ofplane wagging modes of ﬁve adjacent C–H on the end phenyls and appear clearly resolved in the PANI samples with molecular weight below 50 000. Downloaded 11 Aug 2009 to 163. the relative intensities of characteristic quinoid di-imine bands at 1168 and 1597 cm−1 decrease signiﬁcantly in the NCBD and particularly ICBD ﬁlms.195. III. 2 b . Fourier transform infrared spectroscopy FTIR spectroscopy is an extremely useful tool to examine the oxidation states and structural changes in the asdeposited thin ﬁlms produced through several deposition methods in this study. and stretching vibrational modes of C–N. Choi J. The initial sample pellet shows ﬁve strong absorption bands at 832.13. In the cases of the slightly violet PANI ﬁlms produced using the NCBD and ICBD at acceleration voltage Va of 250 V methods shown in Fig. In addition.41. and quinoid di-imine. Redistribution subject to AIP license or copyright. benzenoid diamine. 1168. characteristic vibration of quinoid di-imine. little ﬂuence dependence can be observed in the IR spectra and the bands are in almost the same position as those in the initial target sample. the structural change can be obviously discerned in Fig. 2. b Laser ﬂuence dependence of UV-VIS spectra of PLD thin ﬁlms of PANI M w = 5000 . Geometric structures of LEB-PANI and EB-PANI before and after doping. Chem. ﬁlm samples was measured at room temperature through applying the four-point probe technique called the van der Pauw method.22.15.5 The vibrational spectra of the EB-PANI samples with M w = 65 000 not shown have been found to be very similar except the broadened out-ofplane wagging bands over the 650– 800 cm−1 range. indicating that the dominant structure of the ﬁlms corresponds to the reduced LEB-PANI form.aip. the FTIR spectra of the PLD ﬁlms produced by ablation at 355 nm show strong dependence on both the molecular weight of the initial PANI sample and the laser ﬂuence. For the PEB-PANI target with M w = 5000. Lim and J. which results in the formation of the thermodynamically more stable LEB-PANI state. Phys.jsp . 4. 1506. respectively. and 100 mJ/ cm2 .-H. 2 a .014710-4 H. In the low to intermediate ﬂuence regime 40. see http://jcp. the persistent observation of two out-of-plane wagging bands over the 650– 800 cm−1 range for all NCBD and ICBD ﬁlms reveals that the degree of polymerization occurring on the substrate is not believed to be extensive during the evaporation and deposition processes.38. Typical FTIR spectra of several undoped PEB-PANI M w = 5000 samples are displayed in Fig. leading to the shortening of the average conjugation length in the LEB-PANI ﬁlms.org/jcp/copyright. However. 60.12. there are almost no changes in the absorption bands due to the benzenoid diamine units compared to those observed in the initial powder pellets M w = 5000 and 65 000 . a UV-VIS spectra of PANI M w = 65 000 samples dissolved in N-methyl pyrrolidinone NMP solution and NCBD and ICBD thin ﬁlms. 5. and 1597 cm−1. In the high ﬂuence re- FIG.152. 124.
UV-VIS spectra of a iodine. the intensities of the 748. For laser ablation of polymers. the laser-induced decomposition of principal chains in the low to intermediate ﬂuence regime is believed to generate the plume of fragment radicals. the ablation process is more difﬁcult to proceed due to the higher mass of the sample target. photochemical and photothermal mechanisms are generally proposed depending on the absorption cross section of the target material at the ablation wavelength.and b HCldoped PANI M w = 65 000 thin ﬁlms produced by NCBD.152. the ablation process is mainly governed by the photochemical mechanism.014710-5 Polyaniline thin ﬁlms J. ICBD. the deposition of the thin ﬁlm begins to be observed at 60 mJ/ cm2 due to the higher molecular weight. C w N. Carbonyl groups must be formed through the reaction of radical fragments with oxygen when the PLD chamber is exposed to air. For the high-M w PANI target.aip. and the larger amount of quinoid di-imine units as observed in Fig. which undergoes repolymerization on the substrate to form the PEB-PANI thin ﬁlms with the same chemical composition with the target. N1s core-level XPS spectra of a an initial EB-PANI sample and b NCBD. 2 b . the strong absorption of laser photons induces the direct photodecomposition of target molecules. leading to the melting of the charred target surface. however. and PLD methods. c ICBD. and d PLD thin ﬁlms. however. 2 c . 124. For the EBPANI target with M w = 65 000 in Fig. Redistribution subject to AIP license or copyright. By increasing laser ﬂuence. As the laser ﬂuence increases. Such non-PANI-like PLD ﬁlms formed from the ab- FIG.* transition to be discussed in the next section. 6. Chem. Phys. In the photochemical model. Downloaded 11 Aug 2009 to 163. it is presumed that the structure for the resulting PANI ﬁlm is highly likely to be the PEB-PANI state with C v O. However. 014710 2006 FIG. the laser energy is converted into heat of evaporation via the rovibrational motions of the target molecules. the observation of both the band broadening and the increase of the 2218 cm−1 C w N stretching band suggest clearly that both signiﬁcant structural change and the complicated incongruent deposition are induced. additional portions of the chains are broken in the quinoid di-imine and particularly benzenoid diamine units due to the weaker chemical binding. the portion of quinoid di-imine units is similarly enhanced. see http://jcp. In the case of the photothermal ablation. gime 200 mJ/ cm2 .jsp . and 2218 cm−1 bands are gradually increased and the band broadening occurs over the 1000– 1500 cm−1 range. and also the surplus laser energy induces some chemical changes such as the formation of nitrile groups.41.195. Therefore. Also a new band attributed to C w N stretching appears at 2218 cm−1. 1597. Since the PANI target in this study absorbs strongly the 355 nm photons through the . For the low-M w PANI target. 7. As the laser ﬂuence increases. and the ejected fragments leaving behind the cleanly etched surface result in the smooth deposition of congruent ﬁlms and the decrease in the molecular weight.org/jcp/copyright. the band intensity due to the characteristic vibration of quinoid di-imine at 1597 cm−1 increases with a little shoulder at 1713 cm−1 which is assigned to C v O stretching.
ICBD M w = 65 000 . 5. lation of high-M w PANI target are not within the scope of this study and are ruled out in the following sections. most of the major bands in the doped ﬁlms are redshifted with more uniform intensities. UV-VIS spectroscopy The optical UV-VIS spectrum of commercial PANI M w = 65 000 sample dissolved in N-methyl pyrrolidinone NMP solution is displayed in Fig. Compared with the spectra of the as-deposited pristine ﬁlms.12. see http://jcp. the shift of the bands assigned to the quinoid di-imine units appears to be particularly considerable. Phys. The above photochemical model is also consistent with the UVVIS and XPS results below. The geometric structures of various doped PANI states containing the semiquinone cationic radicals are demonstrated as the polaron lattice in Fig. In particular.014710-6 H.aip.13 B.31 Figure 3 demonstrates the FTIR spectra of three different NCBD. 124. and PLD obtained from the low-M w PANI ablation at 40 mJ/ cm2 thin ﬁlms after doping the as-deposited LEB. Such a spectral shift is in good agreement with the previous work conducted by Zeng and Ko.152.and d – f HCldoped NCBD.jsp . where the extensive development of various functional groups and aromatic ring condensation might take place.-H. Choi J.and EB-PANI ﬁlms with iodine and HCl.195. 014710 2006 FIG.41. The strong absorption band observed at 329 nm which is common to all forms of PANI is associated with the .* transition giving rise to the band gap.13 The structures are described in more detail in the following section. Redistribution subject to AIP license or copyright. ICBD. The characteristic 638 nm absorption band is assigned to a “molecular exciton” band due to a chargetransfer excitonlike electronic transition from the highest occupied molecular orbitals HOMOs centered on the ben- Downloaded 11 Aug 2009 to 163.12. Chem.org/jcp/copyright. and PLD thin ﬁlms. indicating that the doping reactions mostly occur at the quinoid di-imine units in the PANI molecular chains. A similar broadening in the high ﬂuence region has also been reported in the ablation process of several high-M w polymers. 4. Lim and J. N1s core-level XPS spectra of a – c iodine. 8.
the broad feature continuing to the far-infrared region is.* absorption band demonstrate the signiﬁcant structural change such as formation of C w N and the incongruent deposition due to the large surplus laser energy. a – c I3d 5/2 and d – f Cl2p 3/2 core-level XPS spectra of the doped NCBD. Besides.org/jcp/copyright. 014710 2006 FIG. whereas for HCl-doped PANI thin ﬁlms a band at 415 nm and a strong. and PLD thin ﬁlms. For all doped thin ﬁlms. New absorption bands can be understood in terms of the electronic structure associated with the polaron lattice of the oxidized PANI salts formed after doping shown in Fig. Instead.152. broad band at 1050 nm and below are observed. for I2-doped PANI thin ﬁlms a strong absorption band at 380 nm and a broad band at 850 nm and below are observed. in fact. the gradual decrease in the exciton band as well as the blueshift in the . resulting in the stable leucoemeraldine base form. see http://jcp.014710-7 Polyaniline thin ﬁlms J.* absorption bands at 310 nm appear as before. The congruent deposition is also consistent with the infrared spectra. attributed to another low-frequency intraband through the optical absorption excited within the ﬁnite width of the polaron Downloaded 11 Aug 2009 to 163. which is also in good agreement with the persistent observation of two out-ofplane wagging bands over the 650– 800 cm−1 range. Such a change in the oxidation state is consistent with the signiﬁcant decrease in the intensity of characteristic quinoid di-imine bands at 1168 and 1597 cm−1 displayed in the FTIR spectra.41. 9. On the other hand. Chem. zenoid rings to the lowest unoccupied molecular orbitals LUMOs centered on the quinoid rings.15 The absorption spectra of the as-deposited ﬁlms shown in Fig. where the bands due to both the quinoid di-imine and benzenoid diamine moieties clearly appear. the strong . but the molecular exciton band at 630 nm associated with the quinoid di-imine units is eliminated. 5 further support the chemical reduction observed in the infrared spectra. as suggested in the infrared spectra. the two absorption bands are redshifted to longer wavelengths due to the extension of the -conjugation system. Redistribution subject to AIP license or copyright.195. 124. Figure 6 shows the optical UV-VIS spectra of I2-and HCl-doped PANI thin ﬁlms. The very weak molecular exciton band in the as-deposited NCBD and ICBD M w = 65 000 ﬁlms can be deﬁnitely understood by the chemical reduction of the quinoid di-imine units to the stable benzenoid diamine units. As the molecular weight increases. ICBD. as pointed out in the previous section. in the case of the PLD ﬁlms M w = 5000 the clear observation of the molecular exciton band in the low ﬂuence regime implies the polymer deposition with the same chemical composition with the pristine PEB-PANI materials. In addition. 4 and are interpreted as optical excitations to the only half-occupied polaron band located within the band gap.aip. the blueshift of the absorption bands due to the . By increasing the laser ﬂuence.* band-gap transition suggests the shortening of the average conjugation length in the NCBD and ICBD ﬁlms. Phys.jsp .
Choi J. the N1s peaks of the initial EB-PANI M w = 65 000 sample consist of mainly quinoid di-imine and benzenoid diamine with the ratio of 1:1. Chem.9 eV signiﬁes the Downloaded 11 Aug 2009 to 163. In the cases of the NCBD and especially ICBD ﬁlms.aip. XPS is another powerful method to probe the structures and properties of the various PANI samples with different oxidation levels.5 Å . 014710 2006 FIG. and the higher reactivity of ionized species participating in the ICBD scheme appears to enhance the reduction to a greater extent. Phys. oxidized amine. respectively. Figure 7 shows the N1s core-level XPS spectra of the initial EB-PANI sample and NCBD.8 Å . Such drastic changes are attributed to the chemical reduction of the initial EB-PANI form to the LEB-PANI state. The peak intensities for the PEB-PANI sample which correspond to the quinoid di-imine and benzenoid diamine units with the ratio of 2:1 are still maintained. 399. the relative intensities of the quinoid di-imine peaks decrease. a large number of oxidized amines of semiquinone cationic radicals are formed.4.-H. whereas the intensities of the benzenoid diamine peaks remain almost unchanged and the intensities of the oxidized amine peaks increase considerably. and c PLD thin ﬁlms thickness= 227 Å. On the other hand.6 and 198. The N1s core-level XPS results reveal that the quinoid di-imine nitrogens of the PANI molecular chain are preferentially doped by iodine and HCl.2 eV. The overall band characteristics in the observed UVVIS spectra are also consistent with the combined theoretical and optical investigations performed by Stafstrom et al. corresponding to the I− 3 and I− anions. and PLD ﬁlms above are in very good agreement with the results examined through the IR and UV-VIS spectroscopies described in the previous sections. and protonated imine.014710-8 H. suggesting that the congruent stoichiometric transfer is apparently involved in the formation of the PLD ﬁlms.4.12. corresponding to the four nonequivalent nitrogen sites of quinoid di-imine. X-ray photoelectron spectroscopy In combination with the FTIR and UV-VIS spectroscopies. ICBD. the smaller contents of I− 5 anions relative to that of I− anions indicate that the doping 3 level for the three ﬁlms is not a signiﬁcant proportion due to the insufﬁcient exposure doping to the iodine vapor present in gas phase.40 C. Each spectrum can be best deconvoluted into four peaks.7 and 620. 4. conﬁrming the optical transitions in the UV-VIS spectroscopic results due to the formation of the polaron lattice in the previous section. and 402. Rrms = 88.41. In comparison to the work per5 formed by Zeng and Ko on the iodine-doped PANI ﬁlms prepared in the solution phase. ICBD.jsp . 10.5 Å . whereas the intensities of the benzenoid diamine peaks increase signiﬁcantly. b ICBD thickness= 637 Å. Rrms = 11. It should be noted that the higher binding-energy peak at about 198. The overall N1s-XPS results for the structural changes of the asdeposited NCBD. 2D AFM images of a NCBD thickness= 817 Å. The I3d 5/2 spectra can be resolved into two peaks at about 618. the relative intensities of the quinoid di-imine peaks decrease drastically. Figure 9 shows the I3d 5/2 and Cl2p 3/2 XPS spectra of the doped thin ﬁlms. two major components lying at about 197. Rrms = 56.13 In the Cl2p 3/2 spectra.org/jcp/copyright.195. 124. Redistribution subject to AIP license or copyright. respectively.41–44 As clearly manifested.9 eV. such an obvious chemical reduction is not demonstrated in the spectra of the PLD ﬁlms produced through the ablation of the initial PEB-PANI M w = 5000 pellet at 40 mJ/ cm2. As a result. benzenoid diamine. band. Lim and J.152.9 eV are attributed to the two different types of chloride anion Cl− species and the minor peak at about 200. 400.0 eV is related to the covalently bonded chlorine −Cl species. see http://jcp. 398. and PLD thin ﬁlms. Figure 8 shows that after doping the as-deposited thin ﬁlms with iodine and HCl.5. as in the scheme demonstrated in Fig.
Before doping. The doping process of the thin ﬁlms in gas phase requires some improvement to enhance the electrical conductivity and more extensive investigations are currently under investigation. Figure 11 displays the current-voltage characteristics measured at room temperature for the I2.jsp .CD + RBC. 9 c consist of a relatively ﬂat surface with some localized globularlike conglomerates. The quantitative values of the root-mean-square roughness Rrms have been obtained through conducting section analysis using the built-in software of the AFM apparatus. Electrical conductivity The characterization of surface morphology for the asdeposited NCBD.45 Figure 11 shows the electrical probe arrangement consisting of a current source and a voltmeter. the as-deposited pristine ﬁlms are found to be insulators with the electrical conductivities below 10−10 S / m. ICBD. the electrical conductivities are increased signiﬁcantly. Typical roughness estimates for the NCBD and ICBD ﬁlms are 55 and 90 Å. In the case of the PLD method.41.CD + RBC.195. ICBD.CD f . The observed large lateral dimensions of the grains suggest that they are not individual polymer chains or oligomers.and HCl-doped PANI thin ﬁlms produced by NCBD. Chem. For the thin-ﬁlm samples with a uniform thickness d.and HCl-doped NCBD. presence of the Cl− species in a more positive local environment associated with the polaron lattice in Fig. the weakly bound cluster beam is effective in transforming the translational kinetic energy into the surface migration energy. Both NCBD and ICBD ﬁlms consist of densely packed grains.DA where f is deﬁned as a solution of exp ln 2/f RAB.152. Figure 10 shows typical two-dimensional micrographs for the three thin ﬁlms taken over 3 3 m2. 11. where the congruent repolymerization reaction to form the islands of PEB-PANI polymer takes place. which is ascribed to the EB-PANI states with higher amounts of quinoid di-imine doping sites compared to the NCBD and ICBD ﬁlms with the LEB-PANI structures.DA RAB.33–37 Such a lower roughness for the PLD ﬁlms implies that after irradiating the PEB-PANI target M w = 5000 at a ﬂuence of 40 mJ/ cm2. The typical Rrms value is 12 Å. see http://jcp.CD = VDC / IAB and RBC. 4.DA = VAD / IBC can be measured separately. the resistivity as the reciprocal of the conductivity is given by the following equation: = d RAB. However.014710-9 Polyaniline thin ﬁlms J. the gradual growth of the islands leads to the extremely smooth and ﬂat thin PLD ﬁlms observed in the micrograph. and PLD thin ﬁlms on the quartz substrates has been performed by recording AFM images. the ﬁlms in Fig. Furthermore. D. ICBD. the doped PLD ﬁlms show the highest conductivities.aip. Espe- The four-point probe technique called the van der Pauw method has been employed to measure the resistivity for undoped and doped PANI thin ﬁlms. Atomic force microscopy E. as manifested in the aforementioned spectroscopic investigations. which is considerably lower than those reported in other PLD works. 124. Such structure-conductivity characteristics are in very good agreement with the spectroscopic results discussed in the previous sections.DA f arccosh = 2 RAB.org/jcp/copyright. and PLD methods. all doped ﬁlms demonstrate that although the absolute values are rather low. Redistribution subject to AIP license or copyright.DA ln 2 . and PLD thin ﬁlms. Since the thermally evaporated chain segments produced during the heating process of the initial EB-PANI samples M w = 65 000 would be less than two or three repeating units. respectively. the small energetic segments undergo the cross-linking reactions and the reduction of molecular weight upon contact with the substrate. Downloaded 11 Aug 2009 to 163. Phys. cially after a long irradiation about 30 min . the hyperthermal plasma plume ejected might be efﬁcient in migrating to the favorable pinning sites.CD − RBC. I-V characteristics for iodine. In particular. 014710 2006 FIG. ln 2 2 RBC. which induces the formation of smooth thin ﬁlms composed of LEB-PANI dominant grains. in which two resistances RAB.
Choi. Tan. Heeger. Lefrant. 26 J. Phys. Rev.aip. 3 E. 21 R. 751 1988 . Polym. and H. and J. V. Redistribution subject to AIP license or copyright. Kim. Kim.-M. 135. T. 343. 8070 1989 . Stevens. Kaplan. J. Kuzmany. Am. several polymeric thin-ﬁlm devices using PANI composites blended with nanocrystal such as carbon nanotubes and GaN nanowires are currently under investigation. Kim. S. T. G. G. J. 44 T. Sci. 263. Baughman. Woo. Photobiol. D 24. Part B: Polym. Puretzky. J. N. Shacklette. Caple.-J. 13 2000 . W. 31 S. Surf. Synth. A. Kim. Synth. Sadighi. and K. W. 12 IV. 9 K. M. E. Am. Ohki. B.195. and XPS. Wolf. 88. and H. and C. You. Y. Chem. J. G.152. 23. Phys. and J. 59. Birkin. B 50. MacDiarmid. Wei. E. 23 R. Chem. E. Ko. G. Lee. and M. G. Chandra. Kang. Vac. which have been little explored so far. G. Synth. Lee. P. J. Epstein. Caple. J. J. G. Neugebauer. M. Chem.41. C. 2711 1992 . MacDiarmid. Atomic force microscopy measurements show that three methods are effective in producing smooth. G. 1 1997 . and A. Goto. Gould. W. Appl. Nishio. 37 Y. Neoh. and M. Chem. 277 1998 . Choi. Synth. 234 1999 . 10 Y. W. Phys. Cao. Bloor. 124. S. Cao. Phys. Synth. A. S. C. MacDiarmid. 743 2003 . D. 35 M. Bloor. B. T. Rouleau. K. 153. and G. G. Yoshimura. P. B. W. G. M. M. Met. 121. 2436 1994 .-X. Ginder. Phys. Conwell. Lee.-H. Chiba. 38 E.-R. S. Denton. S. J. J. A. and K. P. K. B 49. E. 22 R. T. R. Choi. Soc. 33 1996 . J. Muller-Schwanneke. J. 11 S. M. J. 1 Downloaded 11 Aug 2009 to 163. Heeger. Rev. Nishio. Electroanal. 110. Y. S. Hany. Throughout our experiments. 1993 1997 . Huang. Stevens. The electrical conductivity demonstrates that the electrical conductivities for all doped ﬁlms are increased signiﬁcantly and the overall structureconductivity characteristics are very consistent with the spectroscopic observations. S. MacDiarmid. J. Tasaka. J. J. Santier. 1219 1992 . Jin. Chem. 122. 7647 1988 . E. M. and S. G. T. L. Chem.L. N. J. Yoneyama. A. Sci. Tanaka. B 45. and R. Kamo. Kang. Kim. J. 1677 2001 . Ha. and S. M. A. Bullock. Y. Benally. Opt. Amsterdam. Technol. DiNardo. Photochem. Sato and S. D 20. You. 25 1995 . Park. Ram. Tan. 2977 1994 . G. M. Phys. 20 T. J. Tamura. 6 Y. T. L. 60. H.-H.jsp . 61.-T. P. 43 A. Shin. M. and J. Phys. Wiesinger.-S. Phys. 19 D. Min. and J. 3237 1994 . D. Sci. see http://jcp. 3955 1988 . Choi. E. ICBD. Met. and Y. Lim. J. Phys. and PLD methods in a high-vacuum condition have been characterized by applying spectroscopic methods such as FTIR. Polym. J. Ueda. Met. H. Wei. This work was ﬁnancially supported by NRL-KOSEF. Ricco. S. 40 S. J. 70. T.-I. B. A. A. J. Neth. and A. Phys. Met. and J. 5 L. and K. Lett. Furukawa. J. Cornelison. Porter. J. Zhang. 17 A. Tan. 4768 1992 . 24 E. Louarn. Polymer 39. H. J. D. 205 2005 . Tan. Wagenhals. Z. Oblakowski. Lett. 1464 1987 .-H. In addition. 28 Y. 419 1984 . 4530 1990 . Stevens. and A. J. Kawagoe. Met. 81 1988 . G. Vohs. and J. X. 52. G. L. Phys. G. F. Y. C. P. P. Friend. K. 13 X. C. Malhotra. J. and S. H. 8 J. 61. Phys. 27 H. Synth. A.org/jcp/copyright. Epstein. Phys. Appl. Vohs. 4190 1992 . Monkman. Masters. 45 G. B. N. K. and J. D. 41 K.-Y. Mater. CONCLUSIONS The structural changes and oxidation states of pristine and doped PANI thin ﬁlms prepared by NCBD. 1187 1998 . 33 M. Rev. D. and D. and J. H. Joo. 42 K. G. R. Chem. Phys. Met. 455 2002 . Rev. Choi. Stafstrom. Science 273. Y. Phys. G. G. 1297 1988 . Stevens. Phys. Itaya. Appl. Phys. Plank. 1441 1985 . UV-VIS. 92. Rev. Lett. J. and A. Lett. M. 85. Sci. Chem. Soc. Choi. J. and S. M. and A. 4189 1999 . MacDiarmid. 18 S. Choi. Phys. C. B.-H. 16 N. W. Kang. Tanner. DiNardo. Lett. Epstein. A. Roth. Kim. Y. 18. The original chemical composition is only retained for the PLD thin ﬁlms deposited by the laser ablation of the low-M w PANI targets in the low to intermediate ﬂuence regime. Technol. Y. Dillingham. K. Pouget. M. 153. G. Oh. Y. and E. Synth. Kim. Smith. V. Tan. A. Synth. Buchwald. Ko. 209 2005 . M. Park. 64. Thin Solid Films 360. Mackewitz.014710-10 H. 738 1991 . B. 30 D. S. 94. Ha. J. J. Scherr. and R. and J. J. Chem. 7606 2000 . 7198 1996 . 79. Lett. Misra. Genies. 2441 1994 . R. the chemical composition of PLD thin ﬁlms depends critically on the laser ﬂuence and the molecular weight of PANI target. Sato. 2 E. 32 H. 15 J. B. 29 E. Lowndes.-W. 25 J. 14 S. E. Wrighton. and J. A. Shin. 39 X. M.-M. V. Geohegan. Usami. 15 1993 . J. 4 P. 5382 1991 . While the dominant structure of NCBD and ICBD thin ﬁlms corresponds to the reduced LEB-PANI state. Prog. Monkman. Townsend.. Richter. and A. Quillard. Phys. 72. Joo. L. A 12. M. 21. Sariciftci. Appl. Instrum. and S. J. Y. Paul. Cornelison. J. L. J. Met. 101. Appl.-H. 91. G. T. J. uniform PANI thin ﬁlms. 7 Z. gratefully acknowledges the support of BK21 fellowships. Vac. J. 538 1997 . K. Plank. T. K. H. Sci. Zeng and T. Neckel. Zeng and T. Appl. Cha. Choi J. 1 2001 . Lee. Epstein. Neoh. F. A. 014710 2006 Chem. A. and A. ACKNOWLEDGMENTS One of the authors H. 36 S. J. 161. Wang. G. Du. Treacy. G. Pandey. 89. B 39. Yudasaka. Technol. Robitaille. S. Phys. Met. Shin. Kobayashi. Rev. Kim. T. Vohs. H. Koo. E. and T. 1944 2002 .-R. DiNardo. Sci. 12496 1994 . Bredas. Plank. Phys. and A. MOST. and A. C 18.-Y. 35. D. T. A. H. Wei. J. N. Phys. Bartlett and P. J. Weir. E. F. Lim and J.-H. Sci. Appl. J. L. 898 1996 . Neoh. Norton. 87 1995 . 34 Y. J. N. A 12. Tsuboi. Vac. 2177 1999 . Matsuzaki. A 15. Macromolecules 21. Electrochem. P. Interfacial Electrochem. T. and C. Dillingham. Hansen and T. we hope to gain some insights into the preparation of polymeric thin ﬁlms which cannot be easily processed through conventional solution or thermal techniques. S. 1337 1987 . H. 96. Y. M. Appl. J. S.-H. 89. M. MacDiarmid. Bullock.
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