Interactions of evaporated aluminum atoms with polyaniline lms: An x-ray photoelectron spectroscopic study

S. L. Lim and K. L. Tana)

Department of Physics, National University of Singapore, Kent Ridge, Singapore 119260, Singapore

E. T. Kang
Department of Chemical Engineering, National University of Singapore, Kent Ridge, Singapore 119260, Singapore

Received 6 June 1997; accepted 24 September 1997 X-ray photoelectron spectroscopy was employed for the in situ study of the interactions between thermally deposited Al atoms and polyaniline lms of different intrinsic oxidation states. Quantitative changes in the N 1s core-level line shape, the evolution of the Al 2p core-level spectra, and the changes in surface stoichiometry of these lms throughout the Al deposition process were carefully tracked. Although the nitrogen sites appear to be more attractive to the incoming Al atoms and the emeraldine and nigraniline lms undergo an apparent decrease in intrinsic oxidation state N / NH ratio as a result of Al deposition, there is no direct interaction between the two species, and the adsorbed oxygen from the bulk of the polymer lm plays a dominant role in the interfacial interactions between the polymer and the metal. 1998 American Vacuum Society. S0734-21019803301-6 I. INTRODUCTION Over the last decade, many studies have been performed on metal/polymer systems, due to the technological potential in their applications in microelectronics and packaging industries. Conjugated polymers have emerged as promising materials for the design of new electronic devices, due to their unique electronic, structural and physicochemical properties. The fabrications of all-organic light-emitting diodes13 and transistors4 have illustrated how these novel organic materials can be exploited to produce devices with similar characteristics as those made of conventional inorganic semiconductors, but with added new properties such as exibility and processability. A fundamental understanding of the materials interactions at the metal/polymer interfaces is hence vital, in relation to the electronic properties as well as the mechanical/thermal stability of the new devices. Polyaniline PANI has been known for nearly a century,57 but has become the subject of recent renewed interest due to its tunable electrical conductivity.8,9 The structure of the aniline polymers has the general formula BNHBNH y BNQN 1 y ] x , in which B and Q denote the C6H4 rings in the benzenoid and quinonoid forms, respectively. Hence, the aniline polymers are basically polyp-phenyleneamineimines, in which the intrinsic oxidation state can range from that of the fully oxidized pernigraniline PNA, y 0 to that of the fully reduced leucoemeraldine LM, y 1. The 50% oxidized form has been termed emeraldine EM, y 0.5.10,11 Recent x-ray photoelectron spectroscopy XPS studies on chemically12,13 and electrochemically14,15 synthesized PANIs have demonstrated that the quinonoid imine N structure and benzenoid amine NH structure corresponding to any particular intrinsic oxidation state can be quantitatively differentiated in the properly curve-tted N 1s core-level spectrum. They cora

respond to peak components with binding energies BEs at about 398.4 and 399.6 eV, respectively. XPS has thus provided a unique tool for the quantitative tracking of changes in the intrinsic structure of PANIs. The present work deals with the electronic and chemical properties of metal/polymer interfaces. In this article, we report on the changes in the intrinsic oxidation state and surface elemental stoichiometry of PANI lms during Al deposition, as studied by the XPS technique. The present work supplments the earlier ne work of Lazzaroni et al.16 by providing a quantitative assessment of the effect of metal deposition on the intrinsic oxidation state of the PANI, as well as taking into account of the role of adsorbed oxygen on the metalpolymer interaction. II. EXPERIMENT In this study, PANI was synthesized chemically via the oxidative polymerization of aniline monomer by NH4) 2S2O8 in aqueous 1 M H2SO4 solution, according to the method reported earlier.11 The EM base in powder form was obtained by treating the corresponding salt with excess 0.5 M NaOH solution. Free standing and lightly crosslinked EM lm was prepared by heating the concentrated Nmethylpyrrolidinone NMP gel solution containing 8% EM base by weight at 150 C for 6 h, followed by exhaustive pumping under reduced pressure. The intrinsic oxidation state of the EM base lm can be substantially enhanced to almost that of 75% intrinsically oxidized nigraniline NA by one cycle of acid-base treatment.17 The fully reduced LM lm, on the other hand, was obtained by treating EM base lm with phenylhydrazine, according to the method of Green and Woodhead.6,7 The chemical structures for the various intrinsic oxidation states of PANI are shown in Fig. 1. The thermal deposition of Al was performed using an evaporator installed inside the XPS preparation chamber which is connected to the XPS analysis chamber via a gate
1998 American Vacuum Society 13

Author to whom all correspondence should be addressed. J. Vac. Sci. Technol. A 161, Jan/Feb 1998

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0734-2101/98/161/13/9/$10.00

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FIG. 1. Chemical structures of the various intrinsic oxidation states of PANI.

valve. The evaporator laments were made of either tungsten or tantalum 99.9% purity or better from Goodfellow Inc., Cambridge, UK. High purity Al wire segments 99.999% purity from Goodfellow Inc. were attached to these laments for evaporation. Each evaporation was carefully controlled to last only a few seconds to minimize overexposure. The pressure in the preparation chamber during the deposition remained below 1 107 mbar. In this work, the amount of Al deposited onto the PANI lms is expressed in terms of the ratio of the concentration of Al to that of nitrogen, i.e., Al/N. This is believed to be a more direct and quantitative parameter for monitoring the interaction of Al atoms with the conjugated polymers. However, in order to facilitate comparison with results in more conventional units, e.g., nm or ML, some deposited lms of known Al/N ratios have been analyzed by the Rutherford backscattering RBS technique. For a ratio of 2.5, the deduced thickness by RBS analysis is about 9 nm, whereas for a ratio of 0.15, the thickness is much lower and not quantiable since the polymer lms are not topologically at. Hence, the thickness of the deposited Al is not well dened in such a study, especially at the initial stages of Al deposition. The problem is further aggravated by the fact that Al atoms are known to agglomerate into islands before forming continuous lm see Sec. III. The XPS measurements were made on a VG ESCALAB MKII spectrometer with a Mg K x-ray source photon energy of 1253.6 eV, at a constant retard ratio of 40. The x-ray source was run at a reduced power of 120 W 12 kV with emission current of 10 mA to minimize possible damage in the polymer lms. All reported spectra were for take-off angle with respect to the lm surface of 75. The pressure in the analysis chamber was maintained at 1 108 mbar or lower during each measurement. In peak synthesis, the linewidth full width at half maximum, FWHM of the Gaussian-shaped peaks was kept constant for all components in a particular spectrum. To compensate for surface charging effect, all BEs were referenced to the neutral C 1s peak at 284.6 eV. Surface elemental stoichiometry was determined from the peak-area ratios after correcting with the experimentally determined sensitivity factors, and is reliable to 10%. The sensitivity factors were determined using stable binary compounds of well-dened stoichiometries.
J. Vac. Sci. Technol. A, Vol. 16, No. 1, Jan/Feb 1998

FIG. 2. N 1s core-level spectra of the as-cast EM lm a before Al evaporation, and b e at different stages of the Al deposition process.

III. RESULTS AND DISCUSSION

A. Changes in intrinsic oxidation state of PANI with Al deposition

Figures 2a and 3a show the N 1s core-level spectra for the as-cast and the once acid-base cycled PANI lms, respectively, before Al evaporation. Each N 1s spectrum can be well-resolved into four components. The two major components with BEs at about 398.4 and 399.6 eV are attributable to the nitrogen atoms of the quinonoid imine N and benzenoid amine NH , respectively.1215 The relative proportion of the N and NH components provides a direct measure of the intrinsic oxidation state of each polymer.10,11,17,18 Thus, the intrinsic oxidation state of the EM lm has been substantially enhanced through a simple acid-base treatment, as reported earlier.17 The peak assign-

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FIG. 3. N 1s core-level spectra of the acid-base cycled EM lm a before Al evaporation, and b e at different stages of the Al deposition process.

FIG. 4. N 1s core-level spectra of the fully reduced LM lm a before Al evaporation, and b e at different stages of the Al deposition process.

ment is also entirely consistent with the fact that, in the case of the fully reduced LM, only one major N 1s component with a BE at about 399.6 eV, attributable to the benzenoid amine, was observed Fig. 4a. The residual high BE components in the N 1s core-level spectra above 400 eV may have resulted, at least in part, from surface oxidation products or weakly charge transfer complexed oxygen species.13 This assignment is consistent with the presence of a fairly strong O 1s core-level signal for most PANI base samples. The contribution of the imine nitrogen shake-up satellite to the high BE tail of the N 1s spectrum has also been suggested.14,16 Finally, contribution from interchain hydrogen bonding in thermally induced PANI aggregates may also have to be taken into account.19 After Al deposition, the N 1s line shapes in the as-cast and the once acid-base cycled lms were considerably modied. Figures 2b 2e and Figs. 3b 3e show the
JVST A - Vacuum, Surfaces, and Films

changes in the N 1s core-level line shapes for the two types of lms, respectively, at different stages of the metal deposition process. The intrinsic oxidation states N / NH ratios of the lms are observed to decrease rapidly with increasing Al coverage. Such changes are found to be more drastic in lms which have been subjected to an acidbase treatment cycle and thus have a higher initial intrinsic oxidation state, as compared to that of the as-cast EM lm. The calculated ratios of the N and NH components of these lms are tabulated in Table I. It can be noted that this ratio decreases by about 2.5 and 3.5 times, respectively, for the as-cast and the acid-base cycled lms. The observation of decreasing intrinsic oxidation state in the as-cast and the acid-base cycled lms seems to suggest that Al atoms deposited onto the lms affect predominantly the imine sites along the conjugated backbone of the polymer. Related the-

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TABLE I. Intrinsic oxidation states and surface elemental stoichiometries of three different types of PANI lms before and at different stages of Al deposition. Al/N N / NH As-cast EM lm 0.00 0.10 0.52 1.0 1.4 Acid-base cycled EM lm NA state 0.00 0.56 0.41 0.31 0.29 0.21 1.5 Surface elemental stoichiometry C: N: O: Al 6.8 : 1.0 : 0.29 : 0.00 6.6 6.9 7.7 8.3 : : : : 1.0 1.0 1.0 1.0 : : : : 0.51 : 0.10 1.3 : 0.52 2.3 : 1.0 3.0 : 1.4

calization of the extra charge density brought in by the Al atoms over the entire NQN segment. Based on the present experimental observations, it seems reasonable to suggest that, while the N sites appear to be more attractive to the evaporated Al atoms during the initial stages of deposition, the interaction between Al atoms and N sites should be an indirect one, and most probably would involve other atoms. The disruption of -electron conjugation has been proposed to be a type of indirect interaction between Al atoms and conjugated polymers.16,22,23
B. Changes in surface elemental stoichiometry with Al deposition

6.7 : 1.0 : 0.52 : 0.00

0.18 0.32 0.67 1.3 3.5 7.7 0.00

0.79 0.59 0.49 0.42 0.39 0.40 0.00

6.9 : 1.0 : 0.84 : 0.18 7.1 : 1.0 : 1.2 : 0.32 7.5 : 1.0 : 1.8 : 0.67 7.7 : 1.0 : 3.0 : 1.3 9.4 : 1.0 : 6.1 : 3.5 11 : 1.0 : 12 : 7.7 6.5 : 1.0 : 0.19 : 0.00

Fully reduced LM lm

0.084 0.26 1.5 3.4 12

0.00 0.00 0.00 0.00 0.00

6.7 : 1.0 : 0.36 : 0.084 6.8 : 1.0 : 0.73: 0.26 7.5 : 1.0 : 2.4 : 1.5 9.1 : 1.0 : 5.1 : 3.4 11 : 1.0 : 9.1 : 12

oretical calculations have also indicated that the imine quinonoidimine groups are relatively more reactive.20,21 Similar decrease in the intrinsic oxidation state of EM base lm upon increasing Al coverage was also suggested by earlier investigators,16 but based on the reduction in the iminerelated N 1s shake-up intensity, rather than on the quantitative changes in the N 1s line shape. The deposition of Al does not seem to result in any discernible changes in the N 1s line shape of the fully reduced LM lm, as can be seen in Figs. 4b 4e and Table I. The present results, thus, indicate that the deposited Al atoms do not interact directly with the NH sites along the backbone of LM, EM and once acid-base cycled polymer lms. Although drastic changes in the intrinsic oxidation state have been observed in the EM and the acid-base cycled lms, it is interesting to note that the deposition of Al does not give rise to any signicant shift in the BEs of the N and NH components in these lms. Furthermore, no new component has been observed in the N 1s signals as a result of Al deposition. Given the tendency of Al atoms to donate electrons, one would initially expect a direct interaction of Al atoms with the nitrogen sites to result in a shift of the N 1s peak towards lower BE, or the evolution of a new component in the lower BE region. The absence of such features seems to suggest that there is no direct charge transfer between the deposited Al atoms and the nitrogen sites. Similar observation has also been made by Lazzaroni et al.16 and they attributed the absence of new feature to the deloJ. Vac. Sci. Technol. A, Vol. 16, No. 1, Jan/Feb 1998

Based on carefully calibrated instrumental sensitivity factors of the elements involved, the surface stoichiometries of the three types of lms, both before and after different stages of Al deposition, were deduced from the corresponding XPS core-level spectral intensities Table I. The stoichiometry of carbon in the as-prepared lms deviated from the ideal value, probably due to experimental error in sensitivity factors as well as surface hydrocarbon contaminants. Such discrepancy is commonly encountered when concentration of carbon is determined. In each case, the carbon to nitrogen ratio was observed to increase rapidly with increasing Al coverage. This is consistent with the earlier observation that the N sites are the preferred sites of interaction for the deposited Al. Excess deposited Al atoms are known to agglomerate into islands before forming continuous lm.24,25 Such nucleation of Al atoms around nitrogen sites would naturally result in the attenuation of N 1s signal intensity and hence translate into a decrease in the observed surface stoichiometric concentration of nitrogen, or an increase in the C/ N ratio. As similar changes in the C/N ratios were observed for all three types of lms, it seems to suggest that the nitrogen sites in the polymer are more attractive to the deposited Al atoms. Finally, the persistence of a xed N concentration even at high Al coverage Table I and Figs. 2 and 3 must have resulted from the contribution of polymer chains in the sub-surface layer which is still within the probing depth of the XPS technique, but is inaccessible to the incoming Al atoms. Although a slight increase in oxygen content has been observed for the acid-base cycled lm, the observed initial oxygen contents for the as-cast EM and the LM lms are relatively low Table I and are comparable to the values reported in literature, such as that of the electrochemically prepared EM base lm.16 In order to account for the rapid and substantial increase in oxygen concentration upon increasing Al coverage, similar Al deposition was performed onto a chemically etched26 at Si100 substrate. Figure 5 shows the rate of increase in oxygen concentration as a function of Al concentration both normalized with respect to the substrate Si concentration. It was observed that the evaporation process, including the transferring of samples between the evaporation chamber and the analysis chamber, introduced only a negligible amount of oxygen throughout all stages of the Al deposition process. In Fig. 5 the correspond-

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be described by two distinct curves, with a somewhat lower oxygen migration rate for the LM lm. The latter phenomenon is consistent with an initially lower oxygen content of the LM lm TableI. Based on the above observations, i.e., a b c d the deposited Al atoms interact preferentially and strongly with N sites Figs. 2 and 3, the absence of features associated with direct charge transfer interaction Figs. 24, the changes in the elemental stoichiometries of nitrogen and carbon Table I, and the observed relationship between the oxygen and Al concentrations Fig. 5,

it can be proposed that the interaction between Al atoms and nitrogen sites at the initial stages of deposition is an indirect one, and must have involved oxygen atoms, i.e., through the formation of N -AlOz complexes.

C. Al spectra and the N -AlOz complex

FIG. 5. Increase in surface oxygen stoichiometry as a function of Al deposition for a PANI lms and b Si100 substrate.

ing data for the deposition of Al onto the three polymer lms is also shown, for direct comparison purpose. In this case, both oxygen and Al concentrations are normalized with respect to the nitrogen concentration of the polymer substrates. Thus, the large increase in oxygen concentration must have been contributed from the migration of trapped oxygen atoms to the surface from the bulk of the polymer lms in response to the Al deposition. Given the reactive nature of the conjugated polymer chain, the bulk of a PANI lm probably can be perceived as an oxygen reservoir. Since oxygen in the bulk can readily migrate to surface to react with incoming Al atoms, the oxygen must have existed predominantly as a physically adsorbed species. An analysis of the O 1s spectra indicates that the O 1s signal changed shape immediately upon Al deposition, and subsequently remained practically unchanged throughout the various stages of Al deposition. The O 1s signal, upon Al deposition, could be tted with a major component ( 60% with a BE of about 531.9 eV, which is characteristic of the oxidized Al species, such as -Al2O3 . 27 The observed surge in oxygen content after Al deposition has also been noted by other researchers on similar work of Al deposition onto non-oxygen containing, conjugated polymers.28,29 An Alx Oy complex has also been proposed for the Al/polyp-phenylene interface,28 while the complex formation between adsorbed oxygen and deposited Al or Ca have been found to have a strong inuence on the band bending at the polyp-phenylene vinylene/ metal interfaces, as it prevents direct interaction between the polymer and the metal.29 It should also be noted in Fig. 5 that the data points associated with the three polymer lms can
JVST A - Vacuum, Surfaces, and Films

The Al 2p core-level spectra acquired at different stages of the Al deposition, for the as-cast, the once acid-base cycled and the fully reduced lms are shown, respectively, in Figs. 68. The spectra corresponding to the initial stages of Al deposition can be resolved into two components. The component with BE at about 75.6 eV is assigned to Al oxides, i.e., Alx Oy , 28,30 whereas that with a lower BE of about 74.6 eV is attributed to the N -AlOz complex, considering the lower electronegativities of the nitrogen atom and the aniline unit compared to that of oxygen. It is noted that the intensity of the N -AlOz component is highest at initial stages of deposition, i.e., at lowest Al coverage. This component subsequently decreases in intensity relative to the Alx Oy component, with increasing Al coverage. At high Al coverage, a minor third component starts to appear at the higher BE of about 76.9 eV and may be attributed to another form of Al oxide. At very high coverage of Al, a fourth minor component was observed to emerge at a BE of about 72.9 eV, attributable to the formation of metallic Al.28,3032 The formation of N -AlOz complex disrupts the electron conjugation in the quinonoid imine units and reduces the N sites to a state similar or equivalent to that of the NH, thus accounting for the observed decrease in the N / NH ratio upon Al deposition. This conclusion is also consistent with the appearance of a weak C 1s satellite structure, indicating the presence of a more localized polymer structure after the Al deposition. In Fig. 9, we present a plot of the concentration of N -AlOz complex versus that of total Al, both normalized with respect to the total nitrogen concentration. It is observed that, initially, the concentration of N -AlOz complex increases sublinearly with that of total Al. This observation is consistent with the earlier proposal that formation of N -AlOz complex is the preferred interaction mechanism at low Al coverage. At higher Al coverage, the linear dependency gradually levels off. The latter phenomenon, together with the fact that the initial slopes are

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FIG. 6. Evolution of the Al 2p core-level spectra of the as-cast EM lm at various stages of the Al deposition process.

all less than unity, are consistent with the presence of a competitive mechanism that results in Al oxides. To understand the relationship between the formation of N -AlOz complex with changes in the intrinsic oxidation state of the polymer lms, we plot the decrease in relative concentration of N at different stages of Al deposition, i.e., N Al0-N Al)/total N, against the relative concentration of the N -AlOz complex both normalized with respect to the total nitrogen concentration in Fig. 10. At the initial stages of deposition, an approximately linear one-to-one correspondence between the decrease in N concentration and the increase in N -AlOz concentration was observed for both the as-cast and the once acid-base cycled lms. In other words, at very low Al coverage N -AlOz /N 0.3, reduction of each N site or the reduction of each quinonoid unit along the conjugated polymer chain is associated with the formation of approximately one N -AlOz complex. However, this linearity was observed to level off at high coverage of Al. Upon increasing Al coverage, all the N sites at the top surface must have been depleted. As the N units in the sub-surface layer are inaccessible to the incoming Al atoms, the N Al0J. Vac. Sci. Technol. A, Vol. 16, No. 1, Jan/Feb 1998

FIG. 7. Evolution of the Al 2p core-level spectra of the acid-base cycled EM lm at various stages of the Al deposition process.

N Al)/total N ratios cease to increase. The continuing increase in the Al 2p component intensity at 74.6 eV, originally attributed to the N -AlOz species, must have now resulted from the contribution of other species, such as the AlOC complex. The formation of AlOC complex has been widely reported repeatedly in other works involving Al/polymer24,25,28,30,31,33 and metal/polymer3436 interfaces. The AlOC complex has been reported to have a BE similar to that of the present N -AlOz complex and intermediate between that of metallic Al and that of Al2O3 . 24,30 It is conceivable that the formation of the AlOC species at very high Al coverage could result in an overestimation of the deduced concentration of N AlOz complex from the Al 2p core-level spectra. Alternatively, after the depletion of the quinonoid N units at the surface, the deposited Al atoms will now switch to interact with the benzenoid NH to give

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FIG. 9. Deduced concentration of N -AlOz complex as a function of total Al stoichiometry for the three types of PANI lms during the initial stage of Al deposition.

FIG. 8. Evolution of the Al 2p core-level spectra of the fully reduced LM lm at various stages of the Al deposition process.

rise to the same N -AlOz species. This interaction will not result in further changes in the N 1s line shape. Furthermore, this interaction may also account for the presence of similar Al species with component BE at about 74.6 eV and the lack of any signicant changes in the N 1s line shape when Al atoms are deposited onto the fully reduced LM lm Fig. 8. IV. CONCLUSION The interactions of thermally deposited Al atoms with three different oxidation states of PANI lms, namely the as-cast EM lms, the acid-base cycled EM NA state lms, and the fully reduced LM lms have been investigated. Changes in elemental stoichiometry of these lms with Al deposition seem to suggest that the nitrogen sites are relatively more attractive than carbon sites. Drastic increase in the concentration of oxygen with Al deposition further sugJVST A - Vacuum, Surfaces, and Films

FIG. 10. Reduction in percentage concentration of the imine units vs the deduced concentration of N -AlOz complex for the three types of PANI lms during the initial stage of Al deposition.

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gests the migration of trapped oxygen atoms from the bulk of the polymer lms towards the deposited Al atoms at the surface, testifying to the important bridging role played by oxygen in the interactions of Al atoms with such polymers. From the observed decrease in the N component of the as-cast and the acid-base cycled lms, it is obvious that the surface of the polymer lms were reduced to lower intrinsic oxidation states by the evaporated Al atoms. The corresponding Al 2p spectra seem to indicate the existence of two Al species at low Al coverage. The component at BE of about 74.6 eV was attributed to the N -AlOz complex. It is believed that the formation of N -AlOz complex disrupts the -electron conjugation in such polymers, hence reduces the N sites to a state similar to that of NH. On the other hand, for the fully reduced LM lm, no signicant changes are observed in the corresponding N 1s spectra, leading again to the argument that the Al atoms and the NH sites interact indirectly.
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