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Plasmonic phenomena in indium tin oxide and ITOAu hybrid lms

Stefan Franzen,1,* Crissy Rhodes,1 Marta Cerruti,1 Ralph W. Gerber,1 Mark Losego,2 Jon-Paul Maria,2 and D. E. Aspnes3
1

Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, USA 2 Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695, USA 3 Department of Physics, North Carolina State University, Raleigh, North Carolina 27695, USA *Corresponding author: Stefan_Franzen@ncsu.edu

Received May 28, 2009; revised August 8, 2009; accepted August 14, 2009; posted August 27, 2009 (Doc. ID 112025); published September 15, 2009 The observation of surface-plasmon resonances in indium tin oxide (ITO) thin lms is complemented with the effects of hybrid ITO/Au conducting layers where charge densities can be tuned. Where carrier densities are similar (ITO and nanoparticle Au), the plasmonic behavior is that of a monolithic ITO thin lm. Where the carrier density of one layer is much greater than that of the other (ITO and Au metal), boundary conditions lead to cancelation of the surface plasmon. In the latter case a capacitivelike plasmon resonance is observed for sufciently thin lms. 2009 Optical Society of America OCIS codes: 240.0310, 240.5420, 240.6680, 240.6490, 260.5740.

For more than 100 years [1] the plasmonic periodic table has been dominated by two elements, gold and silver. Plasmonic absorption and scattering in Au and Ag particles, also called localized surface plasmon resonance (SPR), has a long history in optics as effective-medium theory and is now being applied to sensor technology [2,3]. Noble-metal nanoparticle and island lms have fascinated researchers, because their associated plasma frequencies p occur in the visible and near ultraviolet, respectively, and their associated surface-eld-enhancement effects are shape tunable [2,4]. In addition, plasmonic waveguides [5] and surface-enhancement phenomena [6,7] have received increasing attention as improved fabrication methods enable more reproducible and even tailored effects. The change in the surface plasmon (SP) polariton signal in Au thin lms is currently one of the most widely used methods for detecting binding interactions in biological systems [811]. It would be advantageous to tune plasmon resonances in other ways, for example by varying the intrinsic properties of materials. A mechanism for doing this is suggested by the free-electron model of Drude [12], which relates the carrier concentration n of a material to p. This provides a fundamental link between the electrical and optical properties of a conducting material. Although n and therefore p are xed for elemental metals such as Au and Ag, the effective values of n for Au and Ag can be modied through nanostructural engineering. Alternatively, one may use any of a number of conducting metal oxides, for example indium tin oxide (ITO), where n can be engineered directly by altering crystal chemistry and/or defect equilibrium. ITO is an n-type degenerate semiconductor where Sn4+ atoms at In3+ sites act as donors when the oxygen stoichiometry is properly controlled. However, research on these materials for plasmonic applications has been sparing [1318]. In this communication we follow up on our earlier demonstration of plasmons in ITO [13,19] by combining
0146-9592/09/182867-3/$15.00

ITO and Au layers to create plasmons that are intrinsically different from those previously reported [2024]. The hybrid plasmonpolariton structures reported here originate in the ITO layer and are modulated by the properties of the Au layer [1316,19,25]. The absence of band-to-band transitions in ITO permits direct observation of the three regimes of interaction with electromagnetic radiation: conducting, resonant, and insulating. In the conducting regime , = bp, where bp is the frequency of the p/ (screened) bulk plasmon and is the IR dielectric constant. Here, electrons follow the incident electric eld, leading to complete reection in the absence of absorption losses. For metals such as Cr and Al, bp lies above 9 eV, in the ultraviolet, hence these metals are good reectors in the visible. The reecting regime of ITO occurs in the near and mid-IR below 1 eV 8000 cm1 [14,15], which leads to its widespread use as a heat-shield coating for windows [26]. The second regime is resonance, where bp. As a longitudinal excitation, the BP cannot be optically excited in bulk material. However, as predicted 50 years ago by Abeles [27], a polariton resonance associated with the BP can be observed in lms that are sufciently thin to allow the separated charges to communicate across the lm. This type of polariton cannot be observed Ag or Au because of interfering band-to-band transitions [28]. In the third regime, bp and the conductor behaves optically as an insulator. Free-electron conductors such as ITO are transparent. However, the noble metals Cu, Ag, and Au do not exhibit transparency due to strong bandto-band transitions, which cause signicant deviations from the Drude free-electron model. Our results are summarized in Fig. 1, which exhibits various plasmonic phenomena involving ITO and ITO/Au hybrid thin lms. These illustrate similarities between ITO and nanoparticle (NP) Au lms and also how Au can be used to affect the behavior of plasmonic phenomena of ITO. Our ITO lms were pre 2009 Optical Society of America

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Fig. 1. (Color online) Rp / Rs data illustrating the effect of ITO thicknesses and Au overlayers on plasmonpolariton structures in reectance spectra of ITO and hybrid ITO/Au lms. Angles of incidence increase from 42 to 53 in steps of 0.35 as the colors advance from orange to violet. For each sample the conguration and layer thickness or thicknesses in nanometers are shown to the right of the corresponding data. The charge separations of the capacitive (CP) and surface (SP) plasmons underlying the capacitive plasmon resonance (CPR) and surface plasmon resonance (SPR) structures of A, D and C, F, respectively, are shown in E. For the reference 80 nm ITO lm (B) neither the SP nor the CP is fully activated. However, either the associated CPR (A, D) or SPR (C, F) can be made to dominate by controlling the properties of the Au overlayer (A, C) or the ITO thickness (D, F). The high energy feature in (C,F) is a nonresonant (NR) contribution. A metallic Au overlayer effectively reduces the ITO thickness, as seen by comparing (A) and (D). Alternatively, (C) and (F) show that the thickness of the ITO layer is effectively increased when the ITO is covered by a NP-Au overlayer fabricated so its effective carrier concentration matches that of the underlying lm. The above data can be completely understood in terms of effective-medium theory and the Fresnel equations for the three- (substrate/overlayer/ambient) and four-phase (substrate/ overlayer/overlayer/ambient) models.

pared by rf magnetron sputtering from an In2O3 target with 10 wt.% SnO2 onto BK-7 glass substrates [19]. Reectance spectra Rp and Rs, the reectances of light polarized parallel and perpendicular to the plane of incidence, respectively, were obtained in the Kretschman conguration and are given as the ratio Rp / Rs for various congurations as shown to the right of the data panels in Fig. 1. The Kretschmann conguration itself, shown schematically in Fig. 1C, uses a prism to couple the incident light into the lm. In the data panels, angles of incidence range from 42 (orange) to 53 (violet) in steps of 0.35. The two geometries shown for coupling of radiation into a thin conducting lm exhibit two distinct types of plasmonic phenomena. The SP is an electronic oscillation with an in-plane charge motion at the interface and can only occur within the skin depth of a conducting lm. When the appropriate condition is met the induced dipole gives rise to extinction and scattering, reducing the reected intensity and leading to a detectable signal that is the basis for SPR sensors. For sufciently thin lms a second type of polariton occurs at the frequency bp, where the charge motion is orthogonal to the surface, as in a capacitor. Although the actual conguration is different (the charge appears on either side of a single conducting lm rather than on two conducting lms separated by an insulator), we refer to this as a capacitive plasmon (CP) with an associated capacitive plasmon polariton. By analogy with the SP, a CP driven by an electromagnetic eld results in a capacitive plasmon resonance (CPR). The CPR provides an analog of localized SPR, where one of the principal axes of the ellipsoid has collapsed essentially to zero. This collapse causes a similar reduction in the reected intensity.

We consider rst the results for ITO alone. Figure 1B shows data obtained on an ITO lm that is poised at a thickness where neither the SP nor the CP is fully developed. By decreasing or increasing the thickness we realize either the CPR (Fig. 1D) or the SPR (Fig. 1F), respectively. The charge separations appropriate to the CP and SP, from which the CPP and SPP derive, are shown in Fig. 1E. We see that the CP and SP are mutually exclusive, since their associated charge motions are orthogonal. Hence the respective polaritons must be driven by different components of the incident eld. This distinction is further enhanced by their different dependences on lm thickness. These thickness dependences follow from basic physics: for thick lms charge communication across the lm is suppressed, eliminating the CP but at the same time establishing the necessary condition for the SP. Thus when the SPR appears the CPR is quenched, and vice versa. Direct experimental evidence is seen in Figs. 1D and 1F. We now consider the hybrid ITO/Au results. Figure 1A shows that the deposition of 50 nm Au completely suppresses the SPR marginally seen in Fig. 1B, leaving the CPR as in Fig. 1D even though the ITO lm of Fig. 1A is substantially thicker. This follows because the metallic Au overlayer inhibits electric eld components parallel to the interface, thereby effectively negating 50 nm of ITO and quenching any tendency to form the SP. However, the CP is allowed because its charge separation is perpendicular to the interface. Thus essentially angle-independent CPR is seen in both Figs. 1A and 1D. What is more interesting is the fact that the ITO CPR dominates the spectrum, effectively imposing its behavior on the metallic Au overlayer.

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For the NP-Au overlayer the opposite effect is observed. This overlayer was fabricated with alternating layers of 12 nm and 2.6 nm Au particles such that its effective carrier density is similar to that of the underlying ITO [29]. The result is a NP-Au overlayer that does not affect the tangential electric eld at the interface and effectively behaves as a continuation of the ITO lm. Hence a SPR that is strongly dependent on the angle of incidence observed in Fig. 1C, similar to that seen in Fig. 1F. However, in this structure the SP actually occurs in the NP-Au layer. Thus, this particular NP-Au lm and the underlying ITO exhibit the same behavior. This is a simple example of changing the effective value of n in metallic lms by nanostructural engineering. We note that all effects seen in Fig. 1 are well described by the Bruggeman effective-medium theory [30] and Fresnel multilayer models [13,19]. Returning to Fig. 1A, in the plasmon picture the quenching of the SP in the ITO/metallic Au hybrid structure arises because the frequency p 52,400 cm1 in Au metal is much larger than p 18,700 cm1 of the ITO lm. Hence the Au functions as a nearly perfect reector for the conditions that drive the SP in ITO. The boundary condition therefore suppresses electric eld components parallel to the surface, required for the SP, while the component perpendicular to the surface is allowed, leaving only the CP. Although bulk Au cannot be tuned, Fig. 1A shows that it can adopt the frequency of underlying resonances. Also, we have shown that the properties of Au-based composites can be matched to the underlying ITO by constructing a mixture of Au and voids, as indicated in Fig. 1C. This NP-Au lm has a theoretical plasma frequency p 18,350 cm1, which is comparable to that of ITO. Hence, to lowest order the NP-Au layer simply acts as a continuation of ITO, as clearly seen in Fig. 1C. Our demonstration of these plasma effects in ITO and ITO/Au composites in the near-infrared expands the repertoire of practical plasmonic materials to include hundreds of conducting metal oxides and structured-NP layers in monolithic and composite thin-lm systems. These materials include sp-type metal oxides (e.g., uorine-doped tin oxide [15]), d-type metal oxides (e.g., ruthenium oxide), and structured layers of Au and Ag fabricated by nanoparticle depositions. The salient feature of these thin lms is that their properties can be varied systematically, hence preparation of materials such as conducting metal oxides, and nanostructures such as composite metal lms, provides a wide range of opportunities for tuning optical responses based on properties that can be predicted. Our observations demonstrate that these materials provide an ideal platform to test the various limits and effects of structural excitations used for example in nanoparticle plasmon spectroscopy, surfaceenhanced Raman scattering, and related phenomena. In particular, the low optical absorption and the capability of tuning various parameters in conducting metal oxides provide a unique advantage over metals

for the fundamental study of plasmonic phenomena [31]. Our ndings also suggest a range of new applications, since the IR plasmonic activity of metal oxides makes them suitable for SPR sensing, plasmonic waveguides, and electromagnetic surface enhancement on silicon-based microelectronics/microphotonics platforms. References
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