- Nano Express
- Open Access
Enhanced sensitivity of surface plasmon resonance phase-interrogation biosensor by using oblique deposited silver nanorods
Nanoscale Research Lettersvolume 9, Article number: 476 (2014)
Sensitivity of surface plasmon resonance phase-interrogation biosensor is demonstrated to be enhanced by oblique deposited silver nanorods. Silver nanorods are thermally deposited on silver nanothin film by oblique angle deposition (OAD). The length of the nanorods can be tuned by controlling the deposition parameters of thermal deposition. By measuring the phase difference between the p and s waves of surface plasmon resonance heterodyne interferometer with different wavelength of incident light, we have demonstrated that maximum sensitivity of glucose detection down to 7.1 × 10-8 refractive index units could be achieved with optimal deposition parameters of silver nanorods.
Optical sensors, the devices which can transform the information of light-matter interactions into the analytic electronic signal, become more and more important nowadays for the fields such as security for environment and food[1, 2], energy, remote sensing, and medical diagnostics because of their ultrafast responsibility and remote sensing ability. Among the numerous optical sensors, plasmonic nanosensors have great promise due to their spectral tunability and much better adaptability to modern nanobiotechnologies. Surface plasmon resonance (SPR) as a kind of electromagnetic resonance of the conduction electrons on metal surface is very sensitive to the environmental refractive index variation, which can be considered as a useful sensing parameter. For the plasmonic sensing applications, using the so-called Kretschmann geometry[6, 7] to excite the SPR at the metal/target analyte interface is very fascinating because of its low-cost, compact, and flexible experimental setup. Being launched under the Kretschmann geometry, the spectral reflection dip of SPR mode can be monitored to follow any changes that take place in the proximity. Generally speaking, there are several choices of parameters that can be used to accomplish the SPR sensing process based on Kretschmann geometry.
Since the first observation of surface plasmon resonance (SPR), various optical methods have been explored to excite SPR at a metal-dielectric interface. Such an excitation can be utilized to achieve sensing of various interfacial phenomena with extreme sensitivity. These include, for example, chemical and biological sensing[10–18], film-thickness sensing, temperature sensing, and angular measurement. Among various plasmonic sensing techniques, it has been quite well-known that the ‘phase interrogation’ technique is by far the most sensitive one in many applications[11, 13–17, 19, 20]. Recently, we have found that the wavelength of incident light will affect the detection sensitivity in the SPR monitoring of temperature. We also observed that high-resolution angular measurement and biological sensing can be achieved by SPR phase interrogation at optimized incident wavelength[17, 20]. However, the value of the optimal wavelength will change when the film thickness varies. It is thus possible to reach optimal sensitivity by tuning the thickness of metallic film at fixed wavelength of incident light. Furthermore, modification of the surface roughness of the metallic film will also change the sensitivity of SPR sensor[9, 21, 22].
In this paper, we demonstrate that the sensitivity of the Kretschmann-based plasmonic sensor shown in Figure 1 can be further improved through the use of the oblique angle deposition (OAD) technique[23, 24] to fabricate the oblique Ag nanorods on the precoated Ag thin film. The OAD technique as a kind of high-throughput nanofabrication technology is very useful in various applications of nanophotonic components such as achromatic waveplates, metamaterials with negative refractive index, and antireflection coating. The range of tilt angle between the nanorod and the Ag film can be controlled by varying the vapor incident angle. J. Fu et al. also discussed the reflectance of nanorod-based SPR sensor by using effective medium theory. Comparison between theoretical calculations and experimental results are fully discussed. In this article, we have discussed the optimization conditions of the sensitivity of SPR phase-interrogation biosensor enhanced by nanorods fabricated by OAD method operated at different incident wavelengths.
For fabrication of the Ag nanostructures, at first the 50-nm-thick Ag thin film is deposited on the cleaned transparent BK7 glass substrate (Matsunami cover glass, 22 × 22 mm2, 0.15-mm thickness, Matsunami, Kishiwada, Osaka, Japan) by thermal deposition method under Ar pressure of 5 × 10-6 Torr (deposition rate approximately 0.5 Å/s). Subsequently, the vapor incident angle between the substrate and horizontal line is set as 85°, which means the tilting angle between the substrate and Ag source is 5° for generating the tilted Ag nanorods on the Ag thin film. Figure 2a is the scanning electron microscope (SEM) image of the fabricated Ag nanostructures. In the SEM image, irregular Ag nanoparticles are observed. Some Ag nanoparticles are aggregated into the cluster, which may be associated to the self-aggregation behavior of the cooling down Ag materials in deposition. The sizes of the Ag nanostructure range from around 50 to 200 nm. As shown in Figure 2b, which is the cross-sectional SEM image of the fabricated nanostructure, the substrate, Ag thin film with thickness of 50 nm, and the tilted Ag nanorods can be clearly distinguished. The tilt angle between the nanorod and the Ag film is around 35° ± 5°, which is larger than the tilting angle between the substrate and Ag source. This result is similar to the results reported by Y. J. Jen et al.. The average length and diameter of the nanorods are around 300 and 50 nm, respectively. Similar observation result of surface morphology can be obtained under the atomic force microscope measurement (Nanosurf Mobile S, AFM, Nanosurf, Liestal, Switzerland) in contact mode (Figure 2c). In AFM image, the random distribution of the Ag nanorods can be observed, and the variation of the height is around 25.3 nm.
Results and discussion
Figure 3 shows the measured results of the phase difference between the p and s waves of the wavelength 1,150 nm. Four different thicknesses, 6, 8, 10, and 12.5 nm, of the nanorod thin films are considered. As we can see, the resonance angle increases as the concentration of the glucose solution increases. This is a consequence of the SPR taking place, and satisfying the condition
where is the parallel component of the incident wave vector with the dielectric function of prism ε p and the incident angle θ, and k sp is the wave vector of the SP waves. Though k sp is very complicated due to the surface roughness of the nanorod thin film, it can be roughly approximated by the form of the SP wave on a plane,
where ε rod is the effective dielectric function of the nanorod thin film and ε g is the dielectric function of the glucose solution. In our samples, the nanorod thin films are almost filled by silver, so ε rod can be roughly estimated by the dielectric function of silver ε Ag = -61.35 + 4.18i at the working wavelength λ = 1,150 nm. On the other hand, since the concentration of the glucose solution is very low, the refractive index can be expressed by a linear relation
where n w = 4/3 is the refractive index of water, α is the concentration of the glucose solution, and b is some dimensionless fitting constant. Substituting Equations 2 and 3 into Equation 1, one can verify that the resonance angle increases as the concentration increases.
Another feature shown in Figure 3 is that there are two types of the phase change near the resonance angle, see Figure 3a,d. For the thinner nanorod film, the phase changes from higher to lower values while the reverse takes place when the nanorod film becomes thick. These behaviors are caused by the competition between the two damping rates: the internal damping and the radiation damping[10, 31]. For the thinner nanorod films, the energy of the SP waves are mainly dissipated via radiation damping, in which the EM fields are coupling backward to the prism side and then radiate to space. When the film thickness increases, the internal damping dominates and the energy transfers to the thermal loss in silver. Moreover, Figure 2b,c shows that though the dominating damping is mainly determined by the film thickness, it also slightly depends on the concentration of the glucose solution.
In order to seek the optimal thickness of the nanorod layer, we follow the definition of Nelson to consider the quantity: σ n = (Δn/Δϕ)σ ϕ , which indicates the smallest change of the refractive index that can be resolved by the measuring instrument, where Δn/Δϕ is the change of the refractive index per unit phase difference, and σ ϕ is the finest resolution available of the measuring instrument, which is 0.01° from the lock-in amplifier used in our experiment. The refractive index of different glucose concentrations can be calculated by using the Fresnel equations. Because this quantity indicates the smallest change of the refractive index that can be resolved by the measuring instrument, it can be treated as the definition of the sensitivity of the SPR sensor.Figure 4 shows the sensitivity of the nanorod thin film as functions of thickness. Except the original wavelength (1,150 nm) used in Figure 3, we also consider a short wavelength, 632.8 nm. As one can see, the thickness with the best sensitivity is around 10 nm in both wavelengths. The reason is that the enhancement of the sensitivity is due to the strong local field caused by the surface roughness, while the wavelength plays a minor role in this system.
The optimal thickness can be treated as a result of the balance between two factors: the coupling efficiency of the fields between the prism side and the solution side and the local field enhancement due to the surface roughness of the nanorod thin film. Nanorods thicker than the optimized thickness, the field coupled from the prism side of the Ag film is weaker, and thus reduce the strength of the field in the solution side and leads a lower sensitivity. On the other hand, if the thickness of the nanorod film is thinner than the optimized thickness, the surface becomes smooth and thus suppresses the local field enhancement. Therefore, the optimal thickness is a trade-off of the thickness that provides enough surface roughness to support the high concentrated local fields and also keeps the coupling effect strong enough.
Similar results can be observed from our previous study of the nanoparticle system. In that system, the better sensitivity can be obtained when the sizes of the nanoparticles reduce. This is also due to the strong coupling efficiency from the prism side to the solution side. One can note that the performance of the nanoparticle system is overall better than the nanorod system. The reason is that because the size of both nanoparticles and nanorods in our study is much smaller than the wavelength, and the resonances of these nanoobjects are dominated by the dipole mode. It is well-known that the nanoparticle has a spherical symmetry, and hence is a better ‘container’ of the dipole mode.
In this study, we have demonstrated the capability of the oblique deposited Ag nanorods as a SPR sensing chip. The sensitivity is dominated by the thickness of the nanorods, while the dependence of the incident wavelength is relative weak. Experimental results show that with the optimal thickness 10 nm of the nanorods, the sensitivity down to 7.1 × 10-8 can be achieved. Since the enhancement of the sensitivity is due to the strong local fields, the optimal thickness of the nanorod film comes from the balance between the coupling efficiency and the surface roughness.
Rodriguez-Mozaz S, Marco MP, de Alda MJ L, Barcelo D: Biosensors for environmental applications: future development trends. Pure Appl Chem 2004, 76: 723.
Richter ER: Biosensors: applications for dairy food industry. J Dairy Sci 1993, 76: 3114. 10.3168/jds.S0022-0302(93)77650-X
Owicki JC, Parce JW: Biosensors based on the energy metabolism of the living cells: the physical chemistry and cell biology of extracellular acidification. Biosens Bioelectron 1992, 7: 255. 10.1016/0956-5663(92)87004-9
Higson S: Biosensors for Medical Applications. Cambridge: Woodhead Publishing; 2012.
Homola J, Yee SS, Gauglitz G: Surface plasmon resonance sensors : review. Sensor Actuator B 1999, 54: 3. 10.1016/S0925-4005(98)00321-9
Kretschmann E, Raether H: Radiative decay of nonradiative surface plasmons excited by light. Z Naturforsch 1968, 23a: 2135.
Kretschmann E: Die bestimmung optischer konstanten von metallen durch anregung von oberflachenplasmaschwingugnen. Z Phys 1971, 241: 313. 10.1007/BF01395428
Piliarik M, Homola J: Surface plasmon resonance (SPR) sensors: approaching their limits? Opt Express 2009, 17: 16505. 10.1364/OE.17.016505
Raether H: Surface Plasmons on Smooth and Rough Surfaces and on Gratings. Berlin: Springer; 1988.
Chiang HP, Yeh HT, Chen CM, Wu JC, Su SY, Chang R, Wu YJ, Tsai DP, Jen SU, Leung PT: Surface plasmon resonance monitoring of temperature via phase measurement. Opt Commun 2004, 241: 409–418. 10.1016/j.optcom.2004.07.045
Chiang HP, Chen C-W, Wu JJ, Li HL, Lin TY, Sánchez EJ, Leung PT: Effects of temperature on the surface plasmon resonance at a metal-semiconductor interface. Thin Solid Films 2007, 515: 6953–6961. 10.1016/j.tsf.2007.02.034
Nelson SG, Johnston KS, Yee SS: High sensitivity surface plasmon resonace sensor based on phase detection. Sens Actuators B 1996, 35: 187. 10.1016/S0925-4005(97)80052-4
Peng T-C, Lin W-C, Chen C-W, Tsai DP, Chiang H-P: Enhanced sensitivity of surface plasmon resonance phase-interrogation biosensor by using silver nanoparticles. Plasmonics 2011, 6: 29–34. 10.1007/s11468-010-9165-4
Jung LS, Campbell CT, Chinowsky TM, Mar MN, Yee SS: Quantitative interpretation of the response of surface plasmon resonance sensors to adsorbed films. Langmuir 1998, 14: 5636. 10.1021/la971228b
Homola J: Present and future of surface plasmon resonance biosensors. Anal Bioanal Chem 2003, 377: 528. 10.1007/s00216-003-2101-0
Chiang H-P, Lin J-L, Chen Z-W: High sensitivity surface plasmon resonance sensor based on phase interrogation at optimal incident wavelengths. Appl Phys Lett 2006, 88: 141105. 10.1063/1.2192622
Jensen TR, Malinsky MD, Haynes CL, Van Duyne RP: Nanosphere lithography: tunable localized surface plasmon resonance spectra of silver nanoparticles. J Phys Chem B 2000, 104: 10549. 10.1021/jp002435e
Hulteen JC, Van Duyne RP: Nanosphere lithography: a materials general fabrication process for periodic particle array surfaces. J Vac Sci Technol A 1995, 13: 3.
Lin WC, Huang SH, Chen CL, Chen CC, Tsai DP, Chiang HP: Controlling SERS intensity by tuning the size and height of silver nanoparticle array. Appl Phys A 2010, 101: 185–189.
Zhao YP, Chaney SB, Zhang ZY: Absorbance spectra of aligned Ag nanorod arrays prepared by oblique angle deposition. J Appl Phys 2006, 100: 063527. 10.1063/1.2349549
Chaney SB: Aligned silver nanorod arrays produce high sensitivity surface-enhanced Raman spectroscopy substrates. Appl Phys Lett 2005, 87: 031908. 10.1063/1.1988980
Gish DA, Nsiah F, McDermott MT, Brett MJ: Localized surface plasmon resonance biosensor using silver nanostructures fabricated by glancing angle deposition. Anal Chem 2007, 79: 4228–4232. 10.1021/ac0622274
He Y, Fu J, Zhao Y: Oblique angle deposition and its applications in plasmonics. Front Phys 2014, 9: 47. 10.1007/s11467-013-0357-1
Sobahan KMA, Park YJ, Kim JJ, Shin YS, Kim JB, Hwangbo CK: Nanostructured optical thin films fabricated by oblique angle deposition. Adv Nat Sci: Nanosci Nanotechnol 2010, 1: 045005.
Jen YJ, Lakhtakia A, Yu CW, Lin CF, Lin MJ, Wang SH, Lai JR: Biologically inspired achromatic waveplates for visible light. Nat Commun 2011, 2: 363.
Jen YJ, Lakhtakia A, Yu CW, Lin CT: Vapor-deposited thin films with negative real refractive index in the visible regime. Opt Express 2009, 17: 7784. 10.1364/OE.17.007784
Sood AK, Pethuraja G, Sood AW, Welser RE, Puri YR, Cho J, Schubert EF, Dhar NK, Wijewarnasuriya P, Soprano MB: Development of large area nanostructure antireflection coatings for EO/IR sensor applications. Proc SPIE 2012, 8512: 85120R-85121R. 10.1117/12.974239
Fu J, Park B, Zhao Y: Nanorod-mediated surface plasmon resonance sensor based on effective medium theory. App Opt 2009, 48: 4637. 10.1364/AO.48.004637
Palik ED: Handbook of Optical Constants of Solids. Boston: Academic; 1985.
Glover FA, Goulden JDS: Relationship between refractive index and concentration of solutions. Nature 1963, 200: 1165. 10.1038/2001165a0
Chiang HP, Lin JL, Chang R, Su SY, Leung PT: High-resolution angular measurement using surface-plasmon-resonance via phase interrogation at optimal incident wavelengths. Opt Lett 2005, 30: 2727. 10.1364/OL.30.002727
The authors acknowledge financial support from the Ministry of Science and Technology, Taiwan under grant numbers MOST 100-2112-M-019-003-MY3 and MOST 103-2112-M-019-003-MY3. They are also grateful to National Center for High-Performance Computing, Taiwan, and Research Center for Applied Sciences, Academia Sinica, Taiwan, for their support.
The authors declare that they have no competing interests.
HYC drafted the manuscript. CCC carried out the whole experiments. PCW and MLT participated in AFM and SEM measurements. WCL participated in the fabrication of nanorods. CWC participated in SPR phase-interrogation measurements. HPC designed the experiments, revised the manuscript, and approved the final version. All authors read and approved the final manuscript.