Pergamon

NanoStructured Materials, Vol. 11, No. 8, pp. 11811193, 1999 Elsevier Science Ltd Copyright 2000 Acta Metallurgica Inc. Printed in the USA. All rights reserved. 0965-9773/99/$see front matter

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CLUSTER SIZE EFFECT OBSERVED FOR GOLD NANOPARTICLES SYNTHESIZED BY SOL-GEL TECHNIQUE AS STUDIED BY X-RAY PHOTOELECTRON SPECTROSCOPY
S. Shukla and S. Seal*
Advanced Materials Processing Analysis Center, Department of Mechanical, Materials and Aerospace Engineering, University of Central Florida, Orlando, Florida (Received August 23, 1999) (Accepted November 21, 1999)
AbstractGold nanoparticles have been synthesized by sol-gel technique. AFM analysis shows the presence of 1214 nm and 40 60 nm sized particles for H2S/not heated and H2S/heated samples respectively. XPS analysis of H2S/not heated sample reveals that the core-level Au 4f7/2 B.E. is shifted by 0.3 eV with increase in the FWHM by 0.2 eV relative to the respective bulk values of 84.0 eV and 1.1 eV. The results are interpreted in terms of the changes in the electronic structure due to finite cluster size and creation of ve charge over the surface of cluster during the photoemission process itself. The electronic structure of Au nanoparticles (or clusters) produced by present sol-gel technique is compared with that of Au clusters deposited by evaporation method described in the literature. 2000 Acta Metallurgica Inc.

Introduction The physicochemical properties as well as magnetic and optical properties of nanometer sized materials are very unique and are different from their bulk counterparts (1). Besides, the requirement for higher functionality, increased memory density, and higher speed are driving the need for smaller dimensions in various microelectronic industries. Nanomaterials, thus, hold promising future as precursors for building components of chips (2), for the development of sensors (3), for generating very small active elements in magnetic recording (4), and also as functional biological materials (5). Work is under progress in our laboratory to synthesize (by sol-gel method) and characterize sulfide nanoparticles of group IB elements of the periodic table (6,7). Synthesis and the characterization of CuS nanoparticles of size 25 nm have already been reported (6). The present article discusses the synthesis of gold nanoparticles by sol-gel method and their subsequent morphological and chemical characterization by Atomic Force Microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). XPS is a powerful technique to probe the electronic structure of very small clusters of atoms (8 22). XPS analysis of these Au nanoparticles showed that the core-level 4f electrons in gold atoms, within the nanoparticles synthesized by present sol-gel technique, are either tightly or loosely bound to the nucleus than those in the bulk metal depending upon the processing conditions. Detail analysis revealed some interesting factors causing these changes in the electronic structure of nano-sized gold particles. Similar experimental observations have been reported earlier for variety of noble- Au, (8 16) Ag, (13,1719) Cu, (13,23) and transition- Pt, (20,21) Pd, (19,20,22,23) Ni, (23) supported metal clusters.
*To whom correspondence should be addressed.

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Figure 1. Block diagram showing different processing steps involved in the synthesis of gold nanoparticles by sol-gel method.

The remarkable difference between these experiments and the present work is that almost all earlier investigations involved examining the clusters produced by evaporation technique whereas, in the present work, the Au nanoparticles are produced by chemical synthesis method. Hence, the objective of the present article is to report and discuss these findings. Experimental Gold nanoparticles were produced by organometallic synthesis (modified sol-gel) followed by gas diffusion and are deposited on silica based substrates. The procedure for the preparation of nanoparticles is already described elsewhere (6). Figure 1 shows the block diagram of various processing steps involved (here referred as method-I). In short, 0.5 g of HAuCl4 3H2O and 0.29 g of silica sol were dissolved in 100 ml of methanol containing 0.5 g of hydroxypropyl cellulose (HPC). The preparation of silica sol and the importance of HPC are already discussed elsewhere (6). Gold powder was also prepared by the process (here referred as methodII) involving generation of H2S gas, by the reaction between potassium sulfide and hydrochloric acid, diluted with distilled water, K2S 2HCl 3 2KCl H2S1

and passing this gas into the solution of HAuCl4 3H2O dissolved in methanol.

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The precursor film, in method-I, was formed on the glass plate by a dip drying method at room temperature. The SiO2 plates were dipped (once) in the solution for 12 minutes and were dried for 3 4 minutes before H2S exposure, (here referred as no H2S/not heated sample). The nano-sized gold/gold sulfide particles dispersed film was obtained by exposing the precursor film to H2S gas (here referred as H2S/not heated sample) for 2 to 5 seconds which results in following reaction: 2HAuCl4 3H2S 3 Au2S3 8HCl1

However, gold sulfide is found to decompose partially to pure gold via following reaction: Au2S3 3 2Au 3S

Heating the film in a vacuum furnace (1 10 4 Torr) at 150 180 C for 1h (hereafter referred as H2S/heated sample) subsequently followed the gas exposure. The particle size analysis for H2S/not heated and H2S/heated samples was then carried out by DI Atomic Force Microscopy (AFM) while the surface chemistry of nanoparticles deposited on SiO2 substrate was studied by 5400 PHI ESCA (XPS) spectrometer having a base pressure of 10 10 torr using MgK X-radiation (1235.6 eV) at a power of 350 watts. Both survey and high resolution narrow spectra were recorded with an electron pass energy of 44.75 and 35.75 eV to achieve the maximum spectral resolution. The binding energy (B.E.) of the Au 4f7/2 at 84.0 0.1 eV was used to calibrate the B.E. scale of the spectrometer. Any charging shifts produced by the samples were carefully removed by using a B.E. scale referred to C(1s) B.E. of the hydrocarbon part of the adventitious carbon line at 284.6 eV (24). A method described by Sherwood was adopted to remove non-linear backgrounds from the spectra (25). Non-linear least square curve fitting was performed using a Gaussian/Lorentzian peak shape (25,26) after the background removal. Results The morphology of the Au nanoparticles produced by organometallic synthesis are further studied by AFM. Figures 2(a) and 2(b) represent AFM photographs of H2S/not heated and H2S/heated samples respectively. After H2S exposure, the surface of the film appears to be quite smooth; Figure 2(a), even at nanometer level, indicating the presence of 1214 nanometer sized particles. Precise particle size determination is, however, difficult due to very small size of the particles, beyond the resolution limit of the instrument. Heating the film at 150 180 C for 1h has a drastic effect on the film morphology. The surface, as indicated by the Figure 2(b), appears to be quite rough after heating, revealing the growth of the particles from 1214 nm to 40 60 nm. Moreover, the particles are seen to form agglomerates/clusters at some places and are identified in the Figure 2(b) by circles. The boundaries in between these particles appear to be straight, as indicated by the black lines which, we believe, suggest the faceted nature of the particles. Broad scan XPS analysis within the B.E. range of 0 1100 eV for the organometallic film undergoing various processing steps is presented in the Figure 3. Au was found to be present near the surface of the film throughout the process. Prior to H2S exposure, Figure 3(a), the additional presence of Cl was detected on the surface and is expected since HAuCl4 was used as a precursor. Exposing this film to H2S gas results in sulfur pick up at the surface of the film, Figure 3(b), indicating the formation of gold sulfide through the reaction mentioned earlier. In fact, as discussed later, the gold sulfide formed is found partly to decompose to gold. The formation of gold (and not gold

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Figure 2. Atomic force micrographs of (a) H2S/not heated and (b) H2S/heated samples. In (a) particle size is 1214 nm. and in (b) the particle size is 40 60 nm. The circles enclose agglomerated gold nanoparticles while the lines indicate the straight interface boundaries between the particles indicating their faceted nature.

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Figure 3. XPS survey spectra for Au nanoparticles produced by sol-gel synthesis, method-I: (a) no H2S/not heated sample, (b) H2S/not heated sample, (c) H2S/heated sample, and (d) Au powder produced by method-II.

sulfide) nanoparticles through the direct reduction of gold chloride to gold by H2S gas has been reported earlier by Yang et. al. (27). Heating the film at 150 180 C for 1h completely eliminates S from the surface, Figure 3(c), indicating that the decomposition of any residual gold sulfide to pure gold is further aided by the heat treatment. Powder synthesized by method-II shows the prominence presence of gold and sulfur on the surface, Figure 3(d). Narrow and high resolution XPS of Au (4f) within the B.E. range of 80 100 eV revealed interesting spectral features related to the surface of nanoparticles, occurring during different processing steps, and are presented in the Figure 4. First, in Figure 4(a), immediately after H2S gas exposure, two peaks can be identified and are labeled as I and II. The first peak (I) corresponds to lower B.E. side and is that of pure Au (B.E. 84.3 eV, FWHM 1.3 eV) and the peak corresponding to higher B.E. side (II) is of Au2S3 (B.E. 86.0 eV, FWHM 1.35 eV) (7). In fact, the peak-II is chemically shifted at 85.7 eV and further shift of 0.3 eV is caused by the cluster size effect as discussed later. Scaini et. al. reported the B.E. of 85.1 eV for gold in Au2S when they studied the reaction of aqueous Au1 sulfide species with pyrite (28). The relatively higher B.E. of gold, peak-I in the Figure 4(a), hence indicates the higher oxidation state of gold i.e. Au3 , and the formation of Au2S3. This is also in agreement with Yang et. al. who discussed the formation of Au2S3, rather than Au2S, by the present sol-gel technique (27). The Au 4f7/2 peak corresponding to the bulk Au was found to be at 84.0 eV (FWHM 1.1 eV), Figure 4(b), and is also indicated in the Figure 4 by a vertical line. Thus, the core-level B.E. of electrons in gold nanoparticles of size 1214 nm is shifted by 0.3 eV with an increase in the FWHM by 0.2 eV with respect to the B.E. and FWHM of core-electrons in the bulk gold. This strongly suggests the

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Figure 4. XPS Au (4f) spectra for (a) Au nanoparticles (H2S/not heated sample) produced by method-I and (b) solid pure Au. The peak I corresponds to pure Au and peak-II corresponds to Au2S3.

occurrence of Cluster Shift (and not a chemical shift) phenomena in the gold nanoparticles synthesized by sol-gel method. This point will be discussed in detail in the next section and an attempt will be made to correlate the observed particle size, B.E. shift, and FWHM by comparison with the literature data. Secondly, heating the film at high temperature results in the elimination of the peak-II, Figure 5(a). This suggests the complete decomposition of gold sulfide to gold, at least at the surface of the particles, as detailed by XPS. In addition to this, the peak-I in Figure 5(a) is observed to be shifted at a lower B.E. side (B.E. 83.2 eV) with a marginal increase in FWHM (1.5 eV) relative to that of peak-I in the Figures 4(a) and 4(b). Thus, heating the film at 150 180 C for 1h has caused the particles to decompose; but further growth and agglomerates have been observed. This has been reflected in a decrease in the core-electron B.E. From the Figure 5(b), no presence of gold sulfide (peak-II) is detected near the surface of the gold powder particles, although the Figure 3(d) does reveal a very small presence of sulfur. It is suggested that the high power of X-rays might have caused further decomposition of Au2S3, which has a greater tendency to decompose to gold (27). The Au 4f7/2 B.E. corresponding to powder particles is also found to be shifted to a lower B.E. side relative to bulk value and appears at 83.3 eV (FWHM 1.3 eV). Thus, the core electron B.E.s are almost identical for Au powder and coarse and agglomerated Au nanoparticles.

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Figure 5. XPS Au (4f) spectra for (a) Au nanoparticles (H2S/heated sample) produced by method-I and (b) Au powder produced by method-II.

Discussion The most important findings made in the present work is a positive upward shift of X-ray photoemission core-level Au (4f) spectra of Au nanoparticles of size 1214 nm. The shift is towards higher B.E. side by 0.3 0.1 eV accompanied by a line broadening of the Au (4f) spectrum relative to that of bulk Au. This shift is not a chemical shift and hence draws more attention. In general, the measured B.E. of an electron in the jth orbital of an atom (A), EmA(j), in a particular chemical environment (say 1) is expressed as (29): EmA(j) 1 EmF N 1 EmI N (1)

Where, EF (N-1) energy of an atom, A, with (N-1) electrons in a frozen state, after the photoemission process, and EI (N) energy of an atom, A, with N electrons in the initial state. This orbital B.E. is highly sensitive to the chemical surrounding of an atom, and hence, results in a chemical shift for the same atom in two different environments, as given by the following equation (29): EmA(j) EmA(j) 2 EmA(j) 1 (2)

In the present investigation, the peak-II (related to Au2S3), in the Figure (4a), is found to be chemically shifted from the peak-I (related to pure Au nanoparticles), EmAu(4f), by 0.7 eV due to different chemical surroundings of Au atoms in Au2S3 and pure solid gold.

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Interestingly, the peak-I is itself shifted from the bulk value of 84.0 eV by 0.3 eV. This shift is, however, nothing but a cluster size effect (and not a chemical shift) observed in many transition as well as noble metal clusters when examined by XPS (8 22). All of the earlier investigations (8 22) related to the cluster shift effect were devoted to understand the physical phenomena causing this type of shift. The clusters of controlled sizes studied in almost all of these investigations were produced by evaporation technique. Hence, the cluster size effect observed here with Au nanoparticles synthesized by sol-gel technique is really striking, and hence, one can now roughly calculate the particle size variation in the nanomaterials knowing the core-level binding energy shift. The ( ve) B.E. shifts observed in the supported metallic clusters are in fact exactly opposite in nature relative to (ve) shifts observed for the surface atoms of bulk metal (30,31). Citrin et. al. (30) studied the core-level Au (4f) spectrum as a function of take off angle and observed that the corelevels for surface atoms shift by 0.4 eV towards lower B.E. side (i.e. ve shift) relative to the bulk value of 84.0 eV. They also observed ve shifts in the valence band spectrum of surface atoms in gold. According to the authors, reduction in the co-ordination number for surface atoms results in the localization of the valence d-electrons which are further localized by decrease in the degree of s 3 d hybridization (32). This not only results in narrowing of the valence d-band but also reduces the energy gap between the fermi level and the centroid of the d-band. The valence d-band, hence shifts towards the fermi level as fermi level is often fixed by the bulk. This is then reflected in the shift of core-electron B.E. of surface atoms to the lower side. In a cluster, the ratio of total number of surface to bulk atoms is very high. Hence, decrease in the cluster size should reduce the B.E. of the core electrons. However, as observed in the present work and by others for Au (8 16) the core-level (and valence level, too) shifts are generally ve relative to the bulk value and increase with decrease in the cluster size. Similar observations have also been reported for the number of other systems such as Ag, (13,1719) Pt, (20,21) Pd, (19,20,22,23). The mechanisms which overcome the surface effect and produce a net ve B.E. shift in the core as well as valence band spectra are now well recognized as initial and final state effects (14). The former is related to the electronic structure of clusters, while the latter is related to the ve charge left on the surface of the cluster during the photoemission process. According to Mason, (14) the ve B.E. shifts observed in the transition and noble metals can be attributed to the reduction in the repulsive force between d-electrons and core electrons as d-electron count decreases with decrease in the cluster size (33). Moreover, the photoemission from the cluster results in the creation of a core-hole which, if not effectively screened, may result in the additional ve B.E. shift in the photoemission. However, this latter phenomena is highly dependent upon the cluster size (16,36) and the conductive nature of the substrate (14,36). The relative importance of initial and final state effects (14), described above, is still a matter of controversy for ve B.E. shifts observed in the supported Au clusters. For example, Wertheim et. al. (15) studied the core-level shifts in Au clusters supported on vitreous carbon substrate and attributed the ve B.E. shifts to the final state effect. Liang et. al. (9) observed similar shifts in Au film (also clusters) deposited on Al2O3 and ascribed it to the initial state effect. According to DiCenzo et. al. (16), similar shifts in Au clusters supported onto amorphous carbon substrate are the effect of both, initial and final state effects. It is interesting to note that all these investigations involved non-conducting substrates. As the changes in the electronic structure of clusters are inevitable as cluster size changes (14), irrespective of the substrate material means that the initial state effect will always have its own contribution, although varying, to the B.E. shift. Mason strongly argued that for weakly interacting substrates and host metals, the energy shifts in the photoemission are the effect of initial state properties only (14). He compared XPS and XAS shifts for Cu supported on C, as reported by two different investigators (34,35) and found that both shifts are identical. As the final state in XPS and XAS are

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nearly the same, it was suggested that complete screening occurs after photoemission process for clusters supported on weakly interacting substrates (at least in the case of Cu-C system). From this comparison, it was also concluded that the final state effect has no contribution to the observed B.E. shifts for weak interacting substrate like C. However, large difference between XPS and XAS shifts was noticeable for Pd-C system (0.85 eV) which was neglected on the basis of experimental error. We, on the other hand, believe that the above difference suggests incomplete screening of ve charge for Pd clusters supported on weak interacting carbon substrate. The complete screening of the charge for the clusters supported on other poor conductive substrates such as SiO2 and Al2O3 is also seems to be highly unlikely. The ve charge left on the surface of the cluster due to photoemission process can be neutralized by local, external and metallic screening processes (36). Hence, the contribution to the total B.E. shift by the final state effect is dependent upon the total degree of freedom available for neutralizing this charge. Hence, it is necessary to examine at least qualitatively, which of these screening mechanisms are likely to be operative in the present work where Au nanoparticles are formed on silica substrate which produce a total B.E. shift of 0.3 eV relative to the bulk value. First, Mason (14) reported Au 4f7/2 B.E. as a function of metal coverages for Au supported on carbon, SiO2 and Al2O3 (Figure 7). From that figure, we note that the B.E. shift of 0.3 eV, as observed in the present investigation (sol-gel method), corresponds to a narrow coverage range of 12 1015 2 atoms/cm (evaporation technique). In a study, Mason (14) further reported cluster size of approximately 70 90 atoms within this coverage range for Au supported on carbon. DiCenzo et. al. (16) has shown that for Au clusters, supported on the carbon support, minimum of 150 atoms are required to possess metallic properties. This shows that, the clusters corresponding to the coverage range of 12 1015 atoms/cm2 are likely to have non-metallic character. Further, Oberli et. al. (13) reported the cluster size of 2.5 nm for the coverage of 1.1 1015 2 atoms/cm , when they examined the behavior of Au clusters deposited on amorphous carbon. Since, this cluster size is comparable with the predicted size of Au nanoparticles (H2S/not heated sample) produced by sol-gel technique, as discussed later on, and also as observed experimentally by AFM ( 12 nm, present investigation) and TEM (3 nm, by Yang et. al. (27)). This makes us to believe that the Au nanoparticles produced just after H2S treatment are possibly non-metallic in nature, and hence, have minimum metallic screening effect. Second, literature studies reported a drastic reduction in the B.E. of Au 4f7/2 relative to the cluster size within the coverage range of 1014 to 12 1015 atoms/cm2 (14). It is to be noted that within this range, B.E. shifts were independent of semi (C) and nonmetallic substrates (Al2O3 and SiO2). The slope of this variation can be determined from the graph (Figure 7 in ref. (14)) and it is found to be equal to 4 10 16 eV.cm2/atom. Similar variation of B.E. shifts as a function of coverage has been reported by Wertheim et. al. (36) for Sn deposited on carbon substrate within the coverage range of 1014 to 12 1015 atoms/cm2. We estimated the approximate slope of this line and it is found to be equal to -8 10 16 eV.cm2/atom, almost comparable with that obtained for Au. Hence, the variation in the B.E. as a function of coverage within the coverage range of 1014 to 12 1015 atoms/cm2 appears to be a characteristic feature of noble and transition metals. Interestingly, Wertheim et. al. (36) reported the complete elimination of B.E. shift (although with small ve shift) for Sn deposited on Metglass within the coverage range of 1014 to 12 1015 atoms/cm2. This clearly indicates that for the narrow range of 12 1015 atoms/cm2 (considered to be the upper end of above coverage range), the final state effect do have its own contribution to the B.E. shift, which is unaffected for semi and non-metallic substrates and is eliminated completely for metallic substrates. This shows that the external screening by the substrate is ineffective at the coverage of 12 1015 atoms/cm2 when the Au clusters are supported on SiO2 substrate.

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Figure 6. A plot of FWHM (eV) vs B.E. (eV) for core-level Au 4f(7/2). The data is obtained from the literature (8,9,17). The open circle indicates the position of the data point (B.E. 84.3 eV and FWHM 1.3eV) obtained for H2S/not heated sample. f - indicates the position of data point (B.E. 85.8 eV and FWHM 1.5 eV) obtained for H2S/heated sample, in the present investigation.

Thus, it appears in the present investigation, that the ve charge created by the photoemission process is screened only by local screening process and not by external (substrate) or metallic screening processes. Hence, as the degree of freedom for neutralizing the ve charge are reduced, we believe that the total B.E. shift of 0.3 eV observed here for Au nanoparticles (H2S/not heated sample) supported on SiO2 substrate is the effect of both initial and final state phenomenon, in accordance with DiCenzo et. al. (16). A plot of FWHM for Au 4f7/2 is illustrated in the Figure 6 as function of B.E. by collecting the data from the literature (8,9,16) and subsequently comparing with our data. The solid line drawn represents the best-fit curve obtained by regression analysis. The FWHM is found to increase with an increase in the B.E. and follows an empirical relationship of the form: FWHM in eV 0.6768 * B.E. in eV 55.774 (3)

This equation predicts a FWHM of 1.28 eV for the B.E. of 84.3 eV. (This data point is indicated by an open circle in Figure 6). This value is in well agreement with the experimental value of 1.3 eV obtained for H2S/not heated sample. It is to be noted that the above equation is obtained by using the data reported for Au clusters produced by evaporation technique while our data corresponds to the sol-gel derived Au nanoparticles and are in well agreement with each other. Attempt is also made here to estimate the cluster size from the observed B.E. shift of 0.3 eV. In Figure 7, the B.E. shift of Au 4f7/2 is plotted as a function of cluster size for Au by collecting the data from the literature (12,13). It shows that below a cluster size range of 1.5 to 2.5 nm, the B.E. shift increases rapidly with decrease in the cluster size while above this range it changes marginally with increase in the cluster size. It is well known that when cluster shifts are caused by the coulomb interaction between photoelectron and vely charged cluster, the B.E. shift ( B.E.) is related to the cluster size as (15) B.E. e2/r (4)

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Figure 7. A plot of B.E. shift (eV) vs cluster size (nm) for Au clusters produced by evaporation technique. The data is obtained from the literature (13,14). The graph predicts the cluster (particle) size of 23 nm corresponding to the B.E. shift of 0.3 eV observed for the H2S/not heated sample. indicates that 12 nm particle size corresponds to B.E. shift of 1.52.0 eV.

where r is the cluster radius. This equation shows that the product of cluster radius and B.E. is a constant. Hence, the nature of graph in the Figure 7 is understandable. We observe that for the B.E. shift of 0.3 eV, this graph predicts the cluster size of 23 nm. AFM measurements (Figure 2(a)) indicated the particle size of 12 nm, however, precise measurement could not be made and needed TEM observations in future. TEM examination by Yang et. al., however, did show the presence of 3 nm sized Au particles synthesized by present sol-gel technique (27). They also reported very narrow size distribution for these particles. Seal et. al. (6) reported CuS nanoparticles of size 25 nm produced by this technique. As discussed earlier, the heating of the film at 150 180 C for 1h resulted in the growth and agglomeration of the particles followed by ve B.E. shift relative to the bulk value. As reported by many investigators for Au (9,10,12,14,16) and also for other noble and transition metals (13,19,22,36), with increase in the cluster size, B.E. shift decreases. Moreover, non-metallic clusters become metallic and exhibit metallic screening (i.e. screening by conduction electrons) beyond a particular cluster size. After this stage, the B.E. doesnt change drastically and approaches the bulk value with further increase in the cluster size (16,36). Here, for Au powder and heated sample, the shifts are becoming ve relative to bulk value. The sizes of the Au powder and nanoparticles (in H2S/heated sample: 40 60 nm) are, in fact, large enough to exhibit bulk behavior. Hence, it appears that something else is happening apart from the particle size effect, which may be common for both heated sample and powder. The ve B.E. shifts of this kind are reported for Au, and also for W; but only under specific conditions of testing (14,30,31). The ve B.E. shifts (relative to bulk value) are generally ascribed either to the interacting substrate (14) or to the surface effect (30,31). In the present investigation, Au nanoparticles are formed on SiO2 substrate which is non-interacting with respect to Au (4f) band (14). Citrin et. al. reported ve B.E. shift of 0.4 eV from the surface atoms of Au obtained from angle resolved XPS measurements (30). The angle resolved experiments are, however, not conducted in the present investigation and the -ve B.E. shifts, obtained for H2S/heated and powder Au specimens, are also somewhat larger than the reported value.

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It is to be noted that for H2S/heated sample, not only the B.E. is shifted to ve side but also the FWHM is increased from 1.1 (for bulk) and 1.3 eV (H2S/not heated sample) to 1.5 eV. This is in agreement with Duc et. al. (31) who reported a ve shift of 0.3 eV with increase in the FWHM for surface atoms of W relative to that of the bulk atoms. This comparison, on the other hand, supports the hypothesis that the observed ve B.E. shifts, in the present investigation, may be a surface phenomena. From AFM photographs, we observe the straight interface boundaries in H2S/heated sample, which indicate the faceted nature of the particles as mentioned earlier. Through TEM analysis of CuS and Au nanoparticles, both Seal et. al.(6) and Yang et. al. (27) also claimed these particles to be faceted by observing abrupt changes in their boundaries. Hence, it appears here that the random orientation of these facets (which may form the surface of nanoparticles) relative to X-radiation, during photoemission process, may produce an effect similar to the angle resolved experiments, giving rise to ve B.E. shifts and increase in the FWHM of core-level Au (4f) spectrum. This might happen if the structure is either order/disorder or in form agglomerates. No other direct experimental support for this hypothesis, other than above observations, can be presented at this stage. More investigation in this direction is in progress. In summary, the observations made on the changes in the core-level B.E. and FWHM, for Au nanoparticles produced by sol-gel synthesis, relative to those for bulk, appear to follow the same general trend exhibited by Au clusters produced by evaporation technique. Conclusions (1) Au nanoparticles of size 1214 nm (H2S/not heated) and 40 60 nm (H2S/heated) have been successfully synthesized by the present sol-gel method. (2) Average particle size of 23 nm is estimated for the H2S/not heated sample from the observed core-level B.E. shifts and is comparable with our and reported experimental results. (3) The core-level Au 4f7/2 shift of 0.3 eV, relative to the bulk value of 84.0 eV, observed for H2S/not heated sample is attributed to the initial as well as final state effects. (4) ve core-level B.E. shift accompanied by peak broadening, relative to the bulk values, as observed for H2S/heated and Au powder sample may be a result of faceted nature of the particles. (5) The differences in the electronic structure of atoms in Au nanoparticles (or clusters) synthesized by sol-gel technique (present article) and that of Au clusters produced by the evaporation technique (reported in the literature), as studied with the help of XPS, appear to be similar in nature. Acknowledgments The authors thank Prof. V. Desai, University of Central Florida, Orlando, for the encouragement given for publishing the paper. The authors also thank AMPAC graduate student support. The authors also acknowledge the use of UCF-CIRENT Materials Characterization Facility. References
1. 2. 3. 4. 5. S. K. Khanna, in Handbook of Nanophase Materials, ed. A. N. Goldstein, p. 1, Marcel Dekker Inc., New York (1997). R. T. Bate, Solid State Technol. 32, 101 (1989). J. W. Grate and M. H. Abraham, Sensors Actuators B3, 85 (1991). C. L. Cein, J. Q. Ziao, and J. S. Jiang, J. Appl. Phys. 73, 5309 (1993). D. P. E. Dickson, Nanomaterials: Synthesis, Properties and Applications, ed. Edelstein and R. C. Cammarata, p. 459, Institute of Physics Publishing, Bristol (1996).

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6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36.

S. Seal, L. Bracho, S. Shukla, and J. Morgiel, J. Vac. Sci. Technol. 17(5), 1 (1999). S. Seal and S. Shukla, Surf. Interface Anal. J. communicated. K. S. Kim and N. Winogard, Chem. Phys. Lett. 30, 91 (1975). K. S. Liang, W. R. Salaneck, and I. A. Aksay, Solid State Commun. 19, 329 (1976). H. Roulet, J-M. Mariot, and C. F. Hague, J. Phys. F: Metal Phys. 10, 1025 (1980). S.-T. Lee, G. Apai, and M. G. Mason, Phys. Rev. B. 23 (2), 1981. L. Oerli, R. Monot, H. J. Mathieu, D. Ladolt, and J. Bttet, Surf. Sci. 106, 301 (1981). W. F. Egeloff, Jr., J. Vac. Sci. Technol. 23, 668 (1982). M. G. Mason, Phys. Rev. B. 27, 748 (1983). G. K. Wertheim, S. B. Dicenzo, and S. E. Youngquist, Phys. Rev. Lett. 52, 2310 (1983). S. B. DiCenzo, S. D. Berry, and E. H. Hartford, Jr., Phys. Rev. B. 38(12), 8465 (1988). M. G. Mason and R. C. Baetzold, J. Chem. Phys. 64, 271 (1976). G. Apai, S. T. Lee, and M. G. Mason, Solid State Commun. 37, 213 (1981). G. K. Wertheim, S. B. DiCenzo, and D. N. E. Buchanan, Phys. Rev. B. 33, 5384 (1986). T. T. P. Cheung, Surf. Sci. 127, L129 (1983). M. K. Bahl, S. C. Tsai, and Y. W. Chung, Phys. Rev. B. 21, 1344 (1980). Y. Takasu, R. Unwin, B. Tesche, A. M. Bradshaw, and M. Grunze, Surf. Sci. 77, 219 (1978). W. F. Egeloff, Jr. and G. G. Tibbetts, Solid State Commun. 29, 53 (1979). T. L. Barr and S. Seal, J. Vac. Sci. Technol. A13, 1239 (1995). P. M. A. Sherwood, in Practical Surface Analysis by Auger and Photoelectron Spectroscopy, ed. D. Briggs and M. P. Seah, p. 445, Wiley, London (1983). P. M. A. Sherwood, in Data Analysis in XPS and AES in Practical Electron Spectroscopy, ed. D. Briggs and M. P. Seah, Appendix 3, p. 555, Wiley, New York (1990). W. Yang, H. Inoue, Y. Nakazono, H. Samura, and T. Saegusa, in Nanotechnology: Molecularly Designed Materials, ed. G. M. Chow and K. E. Gonsalves, p. 205, ACS Symposium Series, Chicago (1996). M. J. Scaini, G. M. Bancroft, and S. W. Knipe, Am. Minerologist. 83, 316 (1998). T. L. Barr, Modern ESCA: The Principles and Practise of X-Ray Photoelectron Spectroscopy, p. 5, CRC Press, Inc., Boca Raton, FL (1994). P. H. Citrin, G. K. Wertheim, and Y. Baer, Phys. Rev. Lett. 41, 20 (1978). T. M. Duc, C. Guillot, Y. Lassailly, J. Lecante, Y. Jugnet and J. C. Vedrine, Phys. Rev. Lett. 43, 11 (1979). C. Lackmann, Adv. Phys. 16, 393 (1967). M. G. Mason, J. Gerenser, and S. T. Lee, Phys. Rev. Lett. 39, 288 (1977). W. F. Egeloff, Jr. and G. G. Tibbetts, Phy. Rev. B. 19, 5028 (1979). G. Apai, J. F. Mamitton, J. Stohr, and A. Thompson, Phys. Rev. Lett. 43, 165 (1979). G. K. Wertheim, S. B. DiCenzo, D. N. E. Buchanan, and P. A. Bennett, Solid State Commun. 53, 377 (1985).