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Adsorption-induced fluctuations and noise in plasmonic metamaterial devices

O. Jaki, I. Joki and Z. Jaki


Center of Microelectronic Technologies Institute of Chemistry, Technology and Metallurgy University of Belgrade, Serbia

Introduction
The investigation represented here is focused on fundamental intrinsic fluctuations caused by the adsorption and desorption (a-d) of surrounding particles on the active surface in plasmonic metamaterial devices. Plasmonic metamaterials (MM) assume an especially important position in nanophotonics. They are nanostructures utilizing the propagation of surface plasmon polaritons (SPP) and exhibiting properties not ordinarily met in nature [1]. A plethora of practical applications of plasmonic MM has been proposed [2-6]. Each plasmonic metamaterial has to be surrounded by some kind of ambient characterized by some value of refractive index. Typically the particles of the surrounding fluid impinge on the metamaterial surface where they may adsorb and thus change the effective value of its surface refractive index. The true nature of adsorption-desorption (a-d) process is stochastic, its dynamics determining both the useful signal and its fluctuations that limit device performance. We developed a simple method to apply this model to the new generation of plasmonic metamaterial-based chemical sensors and introduced an effective adsorption factor that takes into account the fine structure of the metamaterial unit cell. We performed a comparative stochastic analysis of the exact second-order kinetic model of adsorption versus the approximate linear first-order model. We determined the limits of the applicability of the latter as determined by the analyte partial pressures, with a caveat that these limits are also set by the ranges of existence of the gas phase as defined by the phase diagrams for a given analyte. Our results show that the level of a-d noise is proportional to the surfaces with negative e, thus furnishing higher noise for nanostructured sensors. In a number of practical situations, especially those for smaller structures (micro and nanosystems) the linear model furnishes high accuracy results comparable to those of the exact model. Thus our approach allows the use of a vast mathematical heritage utilized for linear systems, at the same time vastly simplifying and speeding up the calculations.

Results
According to our results, the first method may be used in all situations where a-d process can be treated as Poissonian and with a pseudo first-order kinetics. Since it addresses equilibrium fluctuations, it is also naturally constrained to situations where a-d processes reach the equilibrium before the device response is formed. For plasmonic devices with nanosecond dynamics [7] one has to use the second method. There are two conditions that justify the use of the pseudo first order kinetic model. The first one is that the number of particles in the system N0 greatly exceeds the number of adsorption sites on the surface M and hence, the number of adsorbed particles Na at any instant: N0 >> M Na. The second condition is that the reciprocal equilibrium constant (the ratio between the rate of the adsorption and the rate of the desorption) is much greater than the sum of the two: kd/ka >> 2(N0+M). The use of the results obtained by the use of a pseudo-first order kinetic model is justified if any of these conditions is met. Fig. 2 gives a comparison of a) the mean refractive index change, b) reciprocal time constants and equilibrium variance c), d) calculated by using the first order kinetic i.e. linear (index "L") model and the second-order kinetic model.

Figure 2
neff,L/neff
80 40 1 100 100 10
5

10 10

270 K, 102 m2 300 K, 102 m2 270 K, 104 m2

/ L

10

a)
103 102

t, s

105

p, Pa

b)

10 300 K, 104 m2 270 K, 106 m2 -1 10 -6 -4 -2 10 10 10

10

10

p, Pa

103

2eL/ 2e

2eL/ 2e

Methods
We consider the influence of fluctuations of the number of adsorbed particles at the plasmonic metamaterial surface to the value of effective refractive index. We consider a metasurface (quasi-2D MM), Fig. 1 surrounded by dielectric superstrate with a permittivity ed, to which an analyte monolayer with a thickness h and ed+de is adsorbed. The unperturbed MM properties are calculated utilizing the standard effective medium theory. We give comparative analysis of two different approaches in noise analysis: the analysis of equilibrium fluctuation dynamics based on Langevin method [7] where first order kinetics is presumed and the more general approach of the stochastic analysis based on solving Kolmogorov differential equations for probability functions [8]. The stochastic analysis based on solving Kolmogorov differential equations for probability functions is developed for general case, without any assumptions and gives more informative results (insight into fluctuations of transient response as also insight in fluctuations of steady-state response).

101 100

104 m2 106 m2

102 m2

102 101 100

280 K 300 K

250 K

290 K Benzene A = 10-2 m2 V=10-4 m3 104 102 100 102

101 102 103 106

Benzene T = 250 K V=10-4 m3 104 102 100 102

101 102

c)

p, Pa

d)

103 6 10

p, Pa

Conclusions
The presented models are applicable as tools for the design and characterization of metamaterial-based affinity sensors [6] whose very function is based on a-d processes, but can be also used to predict behavior of all other metamaterial devices exposed to any liquid or gaseous environment. In a number of practical situations, especially those for smaller structures (micro and nano systems) the first order kinetic model furnishes high accuracy results comparable to the more exact second order kinetic model.

ed z y

h em

Metal area Am ed+de

Figure 1
Unit cell of the MM sensor adsorbent surface. A part of the adsorbate to the left is removed to reveal the underlying metal-dielectric structure. Circular single split ring is chosen as an example only, real geometry may be any negative e-positive e material combination.

esub x

Bibliography

Dielectric area Asub

b a

We give the limits for the validity of these methods in terms of system parameters. The validity of expressions for the mean value and the variance of the refractive index change calculated by the use of the approximate model depends on the proportion between the following three values: the reciprocial equilibrium constant, the number of particles in the system N0, and the number of adsorption sites on the surface M.

[1] W. Cai, V. Shalaev, Optical Metamaterials: Fundamentals and Applications, Springer (2009). [2] A. V. Kabashin, P. Evans, S. Pastkovsky, W. Hendren, G. A. Wurtz, R. Atkinson, R. Pollard, V. [3] A. Podolskiy and A. V. Zayats, Nature Mater. 8, 867 (2009). [4] W. Cai, U. K. Chettiar, A. V. Kildishev, V. M. Shalaev, Nature Photonics 1, 224-227 (2007) [5] H. Chen, C. T. Chan, P. Sheng, Nature Mater. 9, 387 (2010). [6] Z. Jaki, S. M. Vukovi, J. Matovic and D. Tanaskovi, Materials 4, 1 (2011). [7] Z. Jaki, O. Jaki, Z. Djuri, C. Kment, J. Opt. A-Pure Appl. Opt. 9, S377 (2007). [8] Kolar-Ani, L.; upi, .; Vukojevi, V. and Ani, S., 2011 The dynamics of nonlinear processes; (Belgrade: Faculty of Physical Chemistry) [in Serbian]

IV International School and Conference on Photonics, 26-30 August 2013, Belgrade, Serbia
This work has been funded by the Serbian Ministry of Education and Science within the project TR32008.

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