Surface plasmon damping effects due to Ti adhesion layer in individual gold nanodisks

The adhesion layer used in nanofabrication process of metallic nanostructures affects the surface plasmon modes. We characterize the localized surface plasmon resonances (SPRs) of gold nanodisks of various diameters and heights while varying the thickness of the Ti adhesion layers. Scattering, absorption, and extinction coefficient calculations show a significant dependence of the SPR on the size of nanostructures and the adhesion layer thickness. Comparisons of peak resonance wavelengths of different Ti adhesion layer thicknesses indicate a significant red shift and a reduction in amplitude as the Ti thickness increases. A comparison of spectral broadening of the plasmon mode indicates a linear increase with Ti thickness and percentage. In addition, the decay time of the plasmon mode decreased significantly as the adhesion layer size increases. These observations aid in understanding size dependent adhesion layer effects and optimized fabrication of single nanoplasmonic structures. ©2016 Optical Society of America OCIS codes: (240.6680) Surface plasmons; (250.5403) Plasmonics; (160.0160) Materials; (160.4760) Optical properties; (290.5850) Scattering, particles; (290.0290) Scattering. References and links 1. K. A. Willets and R. P. Van Duyne, “Localized surface plasmon resonance spectroscopy and sensing,” Annu. Rev. Phys. Chem. 58(1), 267–297 (2007). 2. E. Hutter, J. H. Fendler, and D. Roy, “Surface Plasmon Resonance Studies of Gold and Silver Nanoparticles Linked to Gold and Silver Substrates by 2-Aminoethanethiol and 1,6-Hexanedithiol,” J. Phys. Chem. B 105(45), 11159–11168 (2001). 3. K.-T. Yong, Y. Sahoo, M. T. Swihart, and P. N. Prasad, “Synthesis and plasmonic properties of silver and gold nanoshells on polystyrene cores of different size and of gold–silver core–shell nanostructures,” Colloids Surf. A Physicochem. Eng. 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B 107(26), 6269–6275 (2003). Vol. 7, No. 1 | 1 Jan 2017 | OPTICAL MATERIALS EXPRESS 74

Fabrication of nanostructures made of noble metals using electron beam lithography on a glass substrate requires an adhesion layer such as Cr [25][26][27][28][29], Ti [26][27][28][29], or their oxide forms [30][31][32].Significant effort has been made to understand the effects of adhesion layers on plasmon resonance as a source of chemical interface damping with an emphasis on periodic [32,33] or thin film structures [34].Measurements of reflectance for gold split-ring periodic structures have indicated a red-shift in the resonance frequency due to the thin Ti adhesion layer [32].Comparison of surface Raman resonance of periodic gold nano-cylinders with and without various adhesion layers (Ti, Cr, TiO 2 , ITO, Cr 2 O 3 and MPTMS) at a constant thickness (2 nm) indicates a reduction of the amplitude in the extinction spectra and in Surface Raman enhancement when adding these adhesion layers [35].Analysis of the Au -Ti single nanorod demonstrated a drastic decrease in field enhancement and an increase of decaying time (dephasing time) by 40% in comparison with a pure gold nanorod on silica substrate has been reported [36].The presence of a Ti adhesion layer has been shown change nonlinearly the line broadening, and peak wavelength as a function of Ti% and also reduce the acoustic vibration damping time in Au nanodisks using single-particle transient extinction spectroscopy [37].Many experimental methods have been developed to mitigate the effect of the adhesion layer by the use of metal oxides, functionalized molecules as adhesion layer [30][31][32], or fabricating structures without an adhesion layer such as dry-lift-off process [33] or "sketch and peel" lithography (SPL) [38].Despite such efforts, most nanofabrication relies on the use of adhesive layers.
There are few studies that directly investigate adhesion layer damping and shifting of plasmon resonance wavelengths in single nanoparticles from a simulation perspective [35], [39].Numerical analysis techniques such as finite element method (FEM) [39,40], finite difference time domain [42] and discrete dipole approximation [43] can be used to solve for the scattering properties of nanostructures on a substrate.In this paper, we used FEM, as it provides a powerful means to generate finer meshes in small regions to demonstrate surface plasmon damping changes due to thickness and percentage change of a Ti adhesion layer on single Au nanodisks of various sizes.
The focus of this work is to understand and predict the influence of device geometry limited to thicknesses below the skin-depth in the optical and near-infrared electromagnetic regions.Results from this work expand on previous explanations of layer interfaces altering resonance positions and broadening spectra, by applying thin film effective material models to predict the influence that Ti layers have upon the resonance behavior of the nanodisks in the quasi-static regime.We also use the results to analytically model the dependence of the plasmon linewidth on adhesion layer thickness and percentage in order to quantitatively describe dephasing time.

Method
Finite element method (FEM) [40] simulations were conducted to solve the wave vector form of the time-dependent harmonic electric field [41]: where ˆˆ x is the electric field, 0 2 / k π λ = is the incident electric field propagation wave vector of wavelength λ, and r ε and r μ are relative permittivity and permeability, respectively.In the simulation, near-field and far-field results of a gold nanodisk with a thin titanium adhesion layer of the same diameter surrounded by an effective medium are determined.For the far field, the normalized scattering efficiency, Q scat is obtained by integrating the time averaged power flow on a surface far from the nanoparticles as [42][43][44]. , where E scat and H scat are the scattered electric field and magnetic field, respectively.Q scat is the normalized scattering efficiency, r is the radius of the nanodisk, A is an arbitrary boundary surrounding the gold nanodisk, |I 0 | = 1/2cԑ 0 ԑ r E 0 2 is the intensity of the incident wave E 0 , and c is the speed of light.The normalized absorption efficiency, Q scat , is determined from the fraction of integrated resistive heating over the nanodisk volume V divided by the incident power density where J tot is the total electrical current density.Inside the integral, the first part of the sum represents resistive loss (Joule heating) and the second part represents the magnetic loss.The summation of Q scat and Q abs is defined as the extinction efficiency, To investigate the adhesion layer, we considered gold nanodisks with diameter D ranging from 75 − 200 nm.The thickness of the gold nanodisk, t Au , varied from 10 -15 nm, which is below the skin depth in the optical and infrared region.We also modeled some disks to have a Ti adhesion layer with a thickness, t Ti , ranging from 1 -5 nm.As data for the dielectric constants as a function of wavelength are not available for all wavelengths of light used in this paper, interpolated dielectric constants of gold and titanium obtained from [46,47] were used.The incident light amplitude was set to 1 V/m, polarized in the x-direction, and propagating parallel to the axis of the nanodisk placed in the x-y plane.Nanostructures are usually fabricated on SiO 2 , and surrounded by air; therefore, the surrounding dielectric environment is treated as having an effective relative dielectric constant [48], The far field Q scat is evaluated on an imaginary spherical surface at a distance larger than half of the wavelength of the incident field enclosing the nanostructures.A perfectly matched layer (PML) surface of thickness 250 nm enclosing the imaginary surface was used as an outer boundary to avoid any backscattering.

Results and discussions
First, the effect of the Ti adhesion layer was determined; the results are plotted in Fig. 1.A fixed diameter of 75 nm was used, with t Ti changing from 0 − 5 nm with an increment of 1 nm.The total thickness, t tot , varies from 15 to 20 nm as t Ti increases since t tot = t Au + t Ti .The disks in 1(a) indicate what ideal nanofabricated structures looks like.The peak position of the Q scat spectra in 1(a) does not change, but it does slightly broaden and the amplitude decreases as t Ti increases.Comparing the amplitude of the spectra, the absorption Q abs is the dominant source for the extinction.The result demonstrates that the surface plasmon resonance wavelength, as well as the extent of the plasmon enhancement, is highly dependent on the size and shape of the structure [48][49][50][51][52]. Increasing t Ti blue shifts Q abs and Q ext by about 50 nm, a trend not shared by the Q scat resonance Fig. 2(a).This difference arises because scattering integrates the far field signal that predominantly originates from the surface of the Au while absorption measures the near field contribution that comes from both from Au and Ti [54].This can be explained by the effective medium determined by the real and imaginary part of the dielectric constant of Au and Ti.At resonant wavelength when t Ti = 0 nm and t Au = 15 nm, ԑ Au = −11.26+ 1.33i and ԑ Ti = −5.06+ 12.52i, approximating the Au and Ti nanodisk effective medium by the volume aspect ratio, ԑ Ti + Au = (ԑ Ti t Ti + ԑ Au t Au )/(t Ti + t Au ).The significant increase in effective dielectric constant as shown in Fig. 2(b-c) results in the resonance shift of the absorption and extinction efficiency.In addition, increasing t Ti results in significant broadening of the spectra as well as a decrease in the amplitudes.These results are useful in understanding the role the absorptive adhesion layer has on the surface plasmonic response of noble metals, allowing for optical tunability.The graph in Fig. 3 shows the maximum values of Q abs, Q scat and Q ext for four diameters (75, 100, 140, and 200 nm) as a function of t Ti .These results indicate that the Q scat peak value, which is a measure of the far-field [55], decreases independently of the size as t Ti increases.Such a reduction of amplitude has been reported; the presence of a Ti or Cr adhesion layer results in a reduced fluorescence signal enhancement [30] and dark-field scattering measurements [36].Q abs peak amplitude shows strong decrement for the same t Ti as the diameter changes.Small Au nanodisks have larger amplitude peak values than the bigger Au nanodisks.This trend is the opposite in the maximum amplitude of the Q scat spectra.Results from amplitude of ext Q shows similar trend as Q abs .In particular, the peak value is strongly affected for t Ti up to 2 nm.Results for each diameter in this study are included in the interpolated color plot Fig. 3 (d), 3(e) and 3(f).The values obtained in Fig. 3(d), 3(e) and 3(f) are generally consistent with the four selected diameters in Fig. 3 (a), 3(b) and 3(c), indicating that, in addition to peak broadening, the plasmonic scattering, absorption, and extinction peak amplitude response is also highly influenced by the thickness of the Ti adhesive layer.As t Ti decreases, the amplitude of Q scat for the nanodisk with D = 200 nm drops below smaller diameters.This is because the normalization area is significantly larger for the large diameters so it reduces the amplitude.The peak resonance wavelength (λ max ) from the simulated Q scat spectra for Au nanodisks of D = 75, 100, 140, 160, and 200 nm and t Ti ranging from 0 to 5 nm are illustrated in Fig. 4 (a).For a nanodisk with a t Au = 15 nm and a fixed t Ti , the resonance peak blue-shifts as D decreases as shown in Fig. 5(a).As t Ti increases, for D = 75 nm and D = 100 nm the peak resonance dropped by ~50 nm.But for D = 140 nm, 160 nm, and 200 nm, the peak position was not altered independently of the Ti layer.This is similar to experimental results for nanorod antenna [57] of length 150 nm to 200 nm and Ti thickness ranges from 1 nm to 5 nm, where the resonance "peak wavelengths barely change."The effect the Ti layer has on the Au nanodisk is that of a less negative real component for the dielectric constant, which is expected to cause a strong red-shift of the resonance.As the diameter increases, the peak resonance wavelength shows a significant red shift.This effect is normally the dominant effect; however, when the Ti thickness increases, it causes a shift in the ratio of the real to imaginary part of the dielectric constant.As the particles become smaller, the effect of the Ti layer becomes more pronounced on the peak resonance than the diameter, resulting in a blue shift for smaller particles, indicating that the ratio of the surface area of the Au to Ti is important.

Spectral broadening
In order to characterize the profiles of the spectra, we now consider the plasmon resonance width, an important parameter in fully characterizing the behavior of an oscillatory system at the resonance position.The plasmon resonance width is the full width at half maximum (FWHM) of the spectrum.The shape of the peaks of the spectrum unveils the plasmon mode damping characteristics.Larger damping is manifested as a broad Lorentzian peak that follows the Lorentz-Drude profile of the dielectric constant.The exact information on plasmon broadening is obtained by fitting a Gaussian profile from the Q scat spectra [57][58][59] This width is plotted versus t Ti for various diameters in Fig. 4(b); the width increases linearly as t Ti increases.A simple empirical model fits a linear equation obtained from the graph, Δλ res = Δλ 0 + mt Ti , where Δλ res is the change in the FWHM for a given nanodisk diameter, Δλ 0 is the FWHM without Ti, and m is the proportionality constant.The major result from the fitting is that m is almost constant at m = ~10.2,independent of D. Narrower linewidth is obtained without the adhesion layer and broader width when there is an adhesion layer.The FWHM is as small as 80 nm for nanodisks with diameters of ~85 nm, and 140 nm for a nanodisk with D = 200 nm with no adhesion layer.This shows the FWHM increases with the D, for each t Ti .Overall, these results show that the Ti adhesion layer greatly affects the surface plasmon resonance bandwidths of nanostructures.Thus the Ti adhesion layer can significantly broaden the surface plasmon resonance bandwidth due to the additional absorption in the Ti layer.The quantum efficiency (η), which is defined as the ratio of Q scat to Q ext at their respective resonance wavelengths, increases with increasing diameters for each t Ti as shown in Fig. 5(a).Without a Ti layer, the efficiency is ~0.217 for D = 75 nm and 0.635 when D = 200 nm.This increase of the quantum efficiency is due to increases in the scattering efficiency for the larger size resulting from the increases of the imaginary part of the dielectric constant of Au since the larger D results in a larger resonance wavelength.According to [61][62][63][64], studies of multiple nanoparticles showed that η depends on geometrical parameters such as aspect ratios and sizes of gold nanoparticles.The result of η for t Ti = 0 ranges from 0.2 -0.65.This matches well with other results for Au nanostructures [61][62][63][64].The major impact is that adding 5 nm of Ti decreases η by ~0.1 for all diameters.This is due to the imaginary part of the dielectric of Ti causing additional absorption.
Two important parameters in characterizing surface plasmon resonances are introduced: (a) plasmon spectra quality factor and (b) dephasing time.

Quality factor
Another parameter that is commonly used to quantify the damping of surface plasmon resonance is the quality factor, or Q-factor.The quality factor is defined as the energy E stored in an oscillator, divided by the energy dissipated per solid-angle radian of the integration space.In terms of the peak wavelength's resonance energy, E res , and the energy of full-width of the plasmon peak at half its maximum amplitude, Γ, the quality factor is given as (Q = E res /Γ).Besides determining the number of oscillations until the oscillation is damped, Q further elaborates, indirectly, the effect of an adhesion layer on the field enhancement.Figure 5(b) shows the quality factor as a function of the t Ti for five selected diameters Q decreases by ~3 when the t Ti increases from 0 to 5 nm.

Dephasing time
So far, the qualitative approach implemented to analyze the decay mechanism has relied on characteristics without explanation of specific details of the physics behind the possible decay dynamics and sources.Several factors contribute to plasmon dephasing; it can reasonably be assumed that each term of the line broadening effects is independent and hence the aggregate impact are quantified by writing the plasmon linewidth Γ as a sum of several plasmon damping terms contributions as [24], [65], [66] where γ b , Γ rad , and Γ e-surf , Γ interface correspond to bulk damping, radiation damping, damping due to electron surface scattering, and damping due to interfacial effects, respectively.The bulk damping term γ b originates from electron scattering in the metal and is characteristic of the material.It is well described by the complex dielectric function of the metal and is therefore frequency dependent.The second term in Eq. ( 5) describes the energy loss mechanism due to the coupling of the plasmon oscillation to the radiation field, also known as radiation damping.The Γ e-surf shows significant dependence on the size of the Au nanodisks.
As smaller sized nanodisks become shorter than the electron mean free path, the predominant damping contribution comes from electron surface scattering.The last term in Eq. ( 5), Γ interface is solely dependent on the surrounding environment of the dielectric metal.In our case this is the Ti adhesion layer contributing in the form of chemical interface damping which leads to a dephasing time T 2 , which includes all the possible parameters of surface plasmon resonance damping sources.Based on the strength of damping contribution in Eq. ( 5) we can neglect contributions of bulk broadening effects, and electron−surface scattering [56].The effect of the dielectric substrate, in this study the effective medium (air + quartz), is negligible when the permittivity doesn't have a loss factor.FDTD calculations and experimental values of linewidth for gold nanorods on quartz in [66] showed consistent results; interface damping due to charge interactions between the gold nanorods and quartz is ruled out as an additional contribution to the plasmon linewidth, in agreement with the results from the quasi-static model.
The period in which the plasmon amplitude has decayed to 1/e times its maximum value is T 2 .From the individual Au nanodisk homogeneous linewidth (Γ) obtained from the spectra, the dephasing time is obtained using the relation T 2 = 2ћ/Γ [66,67].According to Fig. 5(c), there are two important outcomes to be noticed.First, for a fixed diameter the dephasing time decreases as t Ti gets larger.The smaller Au nanodisks show significantly larger changes in comparison to the larger Au nanodisks.In addition, as D gets above 140 nm, the dephasing time for t Ti up to 2 nm shows nearly equal values.The second result is that for the same t Ti the value of T 2 for larger nanodisks is greater than that of small nanodisks.This is a good indication of how the Ti adhesion layer affects the oscillations, increasing the absorption of the enhanced plasmon field as well as the field that did not get attenuated in the Au disk.
In order to gain more insight into the effects of the adhesion layer, we followed a second approach wherein we gradually increase the percentage of titanium, Ti%, from 0% to 33%, while the total thickness is fixed, t tot = t Au + t Ti = 15 nm.According to Fig. 6(a), λ max gradually shifts to a longer wavelength when the Ti% increases from 0% to 33% while such consistency has not been observed in case of a fixed Au thickness, Fig. 2(a).This indicates the resonance wavelength varies with the thickness of the Au for nanodisks.Calculations show that plasmon resonance linewidth broadens as the Ti% increases, as illustrated in Fig. 6(b); these results are similar to those in Fig. 2(b).Figure 7 shows the dephasing time of Au nanodisks of diameter 75 nm and 200 nm for the two cases.In the first case, which is indicated in blue for both figures, the thickness of gold was kept constant at t Au = 15 nm.The Ti thickness was increased from 1 -5 nm, thereby varying the percentage from 5% to 25%.In both conditions, the dephasing time decreases up to ~40% with the increase of Ti%; similar results have been shown for nanorods [36].These results illustrate the addition of Ti layer facilitates the decaying of the SPRs mode faster as a chemical interface damping source.

Conclusions
Surface plasmon resonances of individual Au nanodisks were investigated as a function of t Ti from a simulation perspective.Results from our techniques characterize the values η, Q, and T 2 as a function of t Ti allowing one to control these parameters by adjusting t Ti .We observed a strong dependence of the surface plasmon resonance on the size of the particles.Strong spectral broadening and reduced field enhancement when using titanium adhesion layers were observed as well.The broadening reveals that there is a linear relation with the thickness or percentage of the adhesion layer.Field enhancement evaluated from the quality factor deteriorates as Ti% increases.The imaginary component of permittivity for Ti contributes more significantly to the loss factor than that of Au.The spectral decaying mode that is related to the dephasing time decreases significantly with t Ti .These are due to charge interactions between the Ti layer and Au nanodisk electron screening process, which creates chemical interface damping.The analytical model as well as the other methods in this work can be extended for other nanostructures such as nanorod and nanowires, etc.The results in this work provide a useful tool for optimizing a nanofabrication process that includes adhesion layers on a dielectric substrate with controlled size and shape.

Fig. 1 .
Fig. 1.Spectra for various t Ti when t Au = 15 nm D = 75 nm.(a) Calculated scattering spectra.Calculated (b) absorption spectra and (c) extinction spectra for the same parameters as in (a).

Fig. 2 .
Fig. 2. (a) Peak resonance wavelength for scattering, absorption and extinction spectra for D = 75 nm disk with t Au = 15 nm as a function of t Ti .Effective (b) real and (c) imaginary dielectric calculated from the volume fraction of Au and Ti.

Fig. 3 .
Fig. 3. Comparison of the peak amplitude of spectra for various disk diameters with t Au = 15 nm.Maximum (a) absorption coefficient, (b) scattering coefficient and (c) extinction coefficient as a function of t Ti .(d-f) are similar results from above, but include more values for D.

Fig. 4 .
Fig. 4. The comparison of peak resonance mode and linewidth of gold nanodisks as a function of t Ti .(a) The comparison of the peak resonance of five diameters obtained from extinction efficiency spectra.(b) FWHM calculated from the scat Q spectra as a function of t Ti .Linewidths of the gold nanodisks are extracted by fitting Gaussian functions to the scattering spectra.

Fig. 5 .
Fig. 5. Calculated broadening and damping parameters of nanodisks with t Au = 15 nm as a function of t Ti for all considered diameters.(a) quantum efficiency (yield), (b) quality factor, and (c) plasmon modes dephasing (decay) time.

Fig. 6 .
Fig. 6.Calculated peak plasmon resonance wavelength (a) and the full width at half maxima (FWHM) (b) of nanodisks as a function of Ti% for four selected diameters, 75 nm, 100 nm, 150 nm and 200 nm.

Fig. 7 .
Fig. 7. Calculated dephasing time of nanodisks of diameter of 75 nm (a) and 200 nm (b) as a function of Ti%.