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J. Semicond. > 2014, Volume 35 > Issue 9 > 092001

SEMICONDUCTOR PHYSICS

The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals

Jing Ju, Yuqin Zhou and Gangqiang Dong

+ Author Affiliations

 Corresponding author: Zhou Yuqin, Email:yqzhou@ucas.ac.cn

DOI: 10.1088/1674-4926/35/9/092001

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Abstract: We studied the infrared transmission properties of gold films on ordered two-dimensional non-close-packed polystyrene (PS) colloidal crystal. The gold films consist of gold half-shells on the PS spheres and gold film with 2D arrays of holes on the glass substrate. An extraordinary optical transmission phenomenon could be found in such a structure. Simulations with the finite-difference time-domain method were also employed to get the transmission spectra and electric field distribution. The transmission response of the samples can be adjusted by controlling the thickness of the gold films. Angle-resolved measurements were performed using polarized light to obtain more information about the surface plasmon polariton resonances of the gold films. As the angle changes, the transmission spectra change a lot. The transmission spectra of p-polarized light have quite different properties compared to those of s-polarized light.

Key words: SPPextraordinary optical transmissionnon-close-packed colloidal crystalpolarized light

Periodically nanostructured noble metals are widely used to tailor plasmonic responses in current research[1-4]. The phenomenon of extraordinary optical transmission (EOT), which was first reported by Ebbesen et al.[1], has attracted extensive interest in recent years for their potential applications. The EOT was found through an optically opaque metal film perforated with regular arrays of submicrometer holes. The phenomenon was due to tunneling through the surface plasmons formed on each metal-dielectric interface. A lot of work has been done to study their dependence on lattice symmetry, metal film thickness, adjacent dielectric media, shape of the holes, and so on[5, 6]. These metallic films were fabricated on a flat substrate and the holes were made using focused ion-beam milling, or electron-beam lithography combined with reactive ion etching.

Metal film over colloidal crystals exhibits optical transmission properties of striking resemblance with perforated flat films, although the morphology is rather different[7-11]. Attempts have been made in both visible[8-10] and infrared[7] frequencies to exploit the optical response. Ordered arrays of gold half shells were constructed by controlled gold vapor deposition on the colloidal crystal substrate. Nanosphere lithography[12] was used as the sample production technique. Compared to conventional lithography, this method has several advantages, such as the relative ease of large casting, high quality and low cost.

In this report, we study the infrared transmission properties of gold films coated on ordered two-dimensional non-close-packed polystyrene colloidal crystal. Here we use the reactive ion etching method to fabricate the non-close-packed polystyrene colloidal crystal, which is used as a substrate. Then the gold films deposited on the substrate consist of gold half-shells on the PS spheres and gold film with a 2D array of holes on the glass substrate. We study the transmission dependence on the thickness of the gold film and the incident angle of the light. To support the experimental measurements we performed FDTD simulations, and the simulation results help us to uncover more details about the electric field distribution. This study is interesting not only for the understanding of the anomalous optical properties of periodically nanostructured noble metals but also for their potential applications for optical sensors, surface-enhanced Raman scattering, and solar cells[13-15].

We prepared the two-dimensional close-packed colloidal crystal monolayers by a vertical surface method[16]. PS particles were first assembled into a close-packed monolayer on a vortical water surface; the monolayer then was transferred onto the substrate by a withdrawer. A hexagonal two-dimensional close-packed colloidal crystal monolayer was organized on the glass substrate. The diameter of the PS spheres is 2.5 μm. To get a non-close-packed colloidal crystal monolayer, a reactive ion etching (RIE) process with O2 was used. The pressure during the etching was 250 mTorr. The plasma etched the PS spheres and reduced the diameter of the spheres to 1.6μm. Finally, a thin layer of gold was deposited onto the non-close-packed colloidal crystal monolayer by thermal evaporation. We fabricated three samples with different thicknesses of gold films as 20, 25 and 30 nm, respectively. The thicknesses of the gold films were measured by a DektakXT stylus surface profiler on flat glass substrates. In addition, due to the curved surface of the non-close-packed CC template, a lateral variation of the metal thickness was created on the spheres.

Figure  1.  Schematic representation of the sample fabrication and the SEM picture of the sample.

The surface of the structured Au film was investigated by a Hitachi S-4800 scanning electron microscope (SEM). Optical spectra were obtained on a spectrophotometer (Hitachi UV-4100).

The optical transmission properties were simulated using the finite-difference time-domain method (FDTD, Lumerical). A unit cell of the structure was simulated under periodic boundary conditions in the x-and y-directions and perfectly matched layer (PML) boundary conditions in the z-direction. The dispersion of gold was based on the Palik model in the material library of the software. The structures were illuminated with a plane wave directed along the z-direction.

Figure 2(a) shows the SEM image of a hexagonal 2D non-close-packed colloidal crystal monolayer coated with gold film. After the RIE process, the diameter of the PS spheres reduced to 1.6 μm uniformly, and the spheres were able to maintain order. Since the initial diameter of the spheres was 2.5 μm, the distance between the two etched spheres is 2.5 μm. However, the surface of the spheres became rougher compared to that before the RIE process.

A typical transmission spectrum of the microstructured gold film (thickness is 20 nm) compared with that of the bare non-close-packed colloidal crystal monolayer is shown in Fig. 2(b). The overall transmission of the structured Au film is strongly decreased as compared to the transmission of the etched PS spheres. Furthermore, the optical spectrum of the gold film is significantly structured, and three transmission resonances are clearly seen from it. In particular, a strong extraordinary transmission peak at 2010 nm is observed, which is much stronger than the other two peaks appearing at 1430 nm and 1110 nm, respectively. For metallic films with a regular array of submicrometer holes, the transmission peaks appear at λ=am2+n2εmεdεm+εd[17]. Here εm is the dielectric constant of the metal, εd is that of the interface medium, a is the period, and m,n are integers. The positions of peaks are corresponding to the selected values of (m,n). Assuming that when m2+n2=1, the first peak appears at 2010 nm. Calculated according to the formula, the second peak then appears at 1421 nm when m2+n2=2, compared with the experimental value (1430 nm), the deviation is only 0.6%. The third calculated peak appears at 1005 nm when m2+n2=2. Compared to the experimental value (1110 nm), the deviation is about 9%. It may be due to the fact that the position of this peak is hard to determine as the corresponding resonance is very weak. Overall, the spectral features of our samples resembled those of metallic films with a regular array of submicrometer holes reported previously.

Figure  2.  (a)SEM image of a hexagonal 2D non-close-packed colloidalcrystal monolayer coated with gold film.(b)Transmission spectra for:a structured gold film with a thickness of 20 nm(curve 1);bare nonclose-packed colloidal crystal monolayer(curve 2)

To further study the influence of the thickness of gold film on transmission spectra, three samples with thicknesses of 20, 25 and 30 nm gold films were fabricated. In Fig. 3 the transmission spectra of microstructured gold films with different thicknesses are compared. The main features in the three transmission spectra were kept. However, blue-shifts of the resonances were observed when the thicknesses of the gold films increased from 20 to 30 nm. The strongest peak shifted from 2010 to 1875 nm. For ultra-thin metal film, the dielectric constant changes with the thickness of the metal film. With the change of the dielectric constant of the gold films, the resonances display a blue-shift[18]. On the other hand, the transmission decreased slightly as the thickness of the gold film increased. It provided an easy way to adjust the transmission response in a long wavelength range by simply controlling the thickness of the gold film.

Figure  3.  Transmission dependence on the thicknesses of gold films

The simulated periodic structure is illustrated in Fig. 4(a). The dotted line indicates the cross-section in which the electric fields are mapped, as discussed below.

Figure 4(b) presents the simulated and measured transmission spectra of the microstructured gold films (20 nm gold film over 1.6 μm PS spheres). The overall shape of the computed spectrum almost matches that of experimental ones, albeit they are not identical. The measured and simulated spectra are in good agreement in terms of the peak positions. However, the simulated transmittance is much higher than that of the measured ones. It is possibly due to the roughness of the metal surface, which can be seen from the SEM picture (Fig. 2(a)). The other reason might be the defects presented in the array. The intensities of the simulated three peaks are almost the same, which are quite different to the measured ones. The possible reasons may be the absorption of the PS spheres and the weak SPP resonances at the short wavelength.

In order to gain more information on the nature of excitations presented in the metallic microstructures, we computed the configurations of the electric field intensity at two selected wavelengths: 2011 nm, at the transmission maximum, and 1623 nm, at the transmission minimum. Only the result for x-polarized incident light is presented here. Figures 5(a) and 5(b) present the electric field intensity at wavelength 2011 nm and 1623 nm, in the xz cross-section (indicated by the dotted line in Fig. 4(a)). A few fundamental differences are observed between the electric field configurations. At the transmission maximum wavelength, the electric field below the PS sphere and in the lower half was stronger than the electric field at transmission minimum. This indicated that the light penetrates through the gold film at transmission maximum while at transmission minimum it penetrates a little. The electric field above the PS sphere indicates that part of the light is reflected back at both transmission maximum and minimum, but the intensity at transmission minimum was stronger.

Figure  4.  (a)Scheme of the simulated periodic structure, the dotted line marks the cross-section in which the electric fields are analyzed.(b)Simulated transmission spectrum of 20 nm gold film(curve 1) and measured transmission spectrum(curve 2)
Figure  5.  Electric field intensity in the xz cross-section at (a) transmission maximum wavelength and (b) transmission minimum wavelength

To investigate further information about SPP resonances of the metallic microstructures, angle-resolved measurements are performed using polarized light from θ = 0 to 28 with an interval of 4. Figure 6 shows the angle-resolved transmission spectra of 30 nm thick gold film. For s-polarized incident light, as shown in Fig. 6(a), with the increase of the incident angle, the SPP resonances decrease gradually. When the angle is 24 and 28, the SPP resonances almost disappear. For p-polarized incident light, as shown in Fig. 6(b), with the increase of the incident angle, the SPP resonance peaks shift, and new resonance peaks appear. When the incident angle is changed from 0 to 12, the peak displays a red-shift. Further increase in θ leads to the appearance of a small blue-shift, and the transmission around 2200 nm increases, resulting in the valley becoming quite flat. When the angle is 28, the peak at 1875 nm shifts to 1635 nm, and a new peak appears at 2353 nm.

Figure  6.  (Color online)Transmission spectra of the 30 nm thick sample as a function of incident angle.Spectra are taken in steps of 4ı from 0 to28ı for(a)s-polarization and(b)p-polarization

When the periodically metallic microstructures are radiated, SPPs can be excited if their momentum (Ksp) matches the momentum of the incident light. The equation is shown as follows[1, 8, 19]:

Ksp=K0εmεiεm+εi=K0sinθ±Gpq

(1)

where K0 is the in-plane wave vector of light, and θ is the angle of incident light. When the angle of incidence is 0, Ksp=Gpq, the SPP modes will be excited. For p-polarized incident light, with increasing the angle of the incident light, two different SPP modes (K0sinθ+Gpq,K0sinθGpq) will be excited. This means that the transmission peak will move when θ increases, and a new peak will appear. For s-polarized incident light, the coupling between the SPPs and s-polarized light is independent of θ, the transmission peak will not move, and no new peak will appear.

In conclusion, we have fabricated metallic microstructures on ordered two-dimensional non-close-packed polystyrene colloidal crystals. Extraordinary optical transmission can be observed though the gold film. The simulated results match the experimental ones quite well, and the electric field distribution is simulated at both transmission maximum and minimum wavelengths. The observed transmission dependence on the metal film thickness shows that the transmission response can be adjusted by simply controlling the thickness. To obtain more information about SPP resonances of the metallic microstructures, angle-resolved measurements are performed using s-and p-polarized light. The transmission spectra were very sensitive to the polarization of the light, which are determined by the incident angle θ and the in-plane wave vector K0. This fabrication method is cost-effective and provides a promising approach for large scale plasmonic crystals. The findings give us a good understanding of the SPP resonance in the metallic microstructures and will further exploit their potential applications in the near-infrared spectral region.



[1]
Ebbesen T W, Lezec H J, Ghaemi H F, et al. Extraordinary optical transmission through sub-wavelength hole arrays. Nature, 1998, 391:667 doi: 10.1038/35570
[2]
Martín-Moreno L, García-Vidal F J, Lezec H J, et al. Theory of extraordinary optical transmission through subwavelength hole arrays. Phys Rev Lett, 2001, 86:1114 doi: 10.1103/PhysRevLett.86.1114
[3]
Bravo-Abad J, Degiron A, Przybilla F, et al. How light emerges from an illuminated array of subwavelength holes. Nature Phys, 2006, 2:120 doi: 10.1038/nphys213
[4]
Miyamaru F, Kamijyo M, Takano K, et al. Characteristics and generation process of surface waves excited on a perfect conductor surface. Opt Express, 2010, 18(16):17576 doi: 10.1364/OE.18.017576
[5]
Degiron A, Lezec H J, Barnes W L, et al. Effects of hole depth on enhanced light transmission through subwavelength hole arrays. Appl Phys Lett, 2002, 81:4327 doi: 10.1063/1.1526162
[6]
Kim T J, Thio T, Ebbesen T W, et al. Control of optical transmission through metals perforated with subwavelength hole arrays. Opt Lett, 1999, 24:256 doi: 10.1364/OL.24.000256
[7]
Zhan P, Wang Z L, Dong H, et al. The anomalous infrared transmission of gold films on two-dimensional colloidal crystals. Adv Mater, 2006, 18:1612 doi: 10.1002/(ISSN)1521-4095
[8]
Wang Z B, Ye Y H, Zhang Y A, et al. Visible transmission through metal-coated colloidal crystals. Appl Phys A, 2009, 97:225 doi: 10.1007/s00339-009-5184-4
[9]
Cai Z Y, Liu Y J, Leong E S P. Highly ordered and gap controllable two-dimensional non-close-packed colloidal crystals and plasmonic-photonic crystals with enhanced optical transmission. J Mater Chem, 2012, 22:24668 doi: 10.1039/c2jm34896a
[10]
Farcau C, Giloan M, Vinteler E, et al. Understanding plasmon resonances of metal-coated colloidal crystal monolayers. Appl Phys B, 2012, 106:849 doi: 10.1007/s00340-011-4849-9
[11]
Endo T, Takizawa H, Imai Y, et al. Study of electrical field distribution of gold-capped nanoparticle for excitation of localized surface plasmon resonance. Appl Surf Sci, 2011, 257:2560 doi: 10.1016/j.apsusc.2010.10.022
[12]
Haynes C L, Van Duyne R P. Nanosphere lithography:a versatile nanofabrication tool for studies of size-dependent nanoparticle optics. J Phys Chem B, 2001, 105:5599 doi: 10.1021/jp010657m
[13]
Walsh G F, Negro L D. Engineering plasmon-enhanced Au light emission with planar arrays of nanoparticles. Nano Lett, 2013, 13:786 doi: 10.1021/nl304523v
[14]
Bhattacharya J, Chakravarty N, Pattnaik S, et al. Comparison of optical properties of periodic photonic-plasmonic and randomly textured back reflectors for nc-Si solar cells. Journal of Non-Crystalline Solids, 2012, 358:2313 doi: 10.1016/j.jnoncrysol.2011.12.108
[15]
Ferry V E, Verschuuren M A, Li H B T, et al. Light trapping in ultrathin plasmonic solar cells. Opt Express, 2010, 18(S2):A237 doi: 10.1364/OE.18.00A237
[16]
Pan F, Zhang J Y, Cai C, et al. Rapid fabrication of large-area colloidal crystal monolayers by a vertical surface method. Langmuir, 2006, 22(17):7101 doi: 10.1021/la053323n
[17]
Ghaemi H F, Thio T, Grupp D E. Surface plasmons enhance optical transmission through subwavelength holes. Phys Rev B, 1998, 58(11):6779 doi: 10.1103/PhysRevB.58.6779
[18]
Jensen T R, Malinsky M D, Haynes C L, et al. Nanosphere lithography:tunable localized surface plasmon resonance spectra of silver nanoparticles. J Phys Chem B, 2000, 104:10549 doi: 10.1021/jp002435e
[19]
Rather H. Surface plasmons on smooth and rough surfaces and on gratings. Berlin:Springer, 1988
Fig. 1.  Schematic representation of the sample fabrication and the SEM picture of the sample.

Fig. 2.  (a)SEM image of a hexagonal 2D non-close-packed colloidalcrystal monolayer coated with gold film.(b)Transmission spectra for:a structured gold film with a thickness of 20 nm(curve 1);bare nonclose-packed colloidal crystal monolayer(curve 2)

Fig. 3.  Transmission dependence on the thicknesses of gold films

Fig. 4.  (a)Scheme of the simulated periodic structure, the dotted line marks the cross-section in which the electric fields are analyzed.(b)Simulated transmission spectrum of 20 nm gold film(curve 1) and measured transmission spectrum(curve 2)

Fig. 5.  Electric field intensity in the xz cross-section at (a) transmission maximum wavelength and (b) transmission minimum wavelength

Fig. 6.  (Color online)Transmission spectra of the 30 nm thick sample as a function of incident angle.Spectra are taken in steps of 4ı from 0 to28ı for(a)s-polarization and(b)p-polarization

[1]
Ebbesen T W, Lezec H J, Ghaemi H F, et al. Extraordinary optical transmission through sub-wavelength hole arrays. Nature, 1998, 391:667 doi: 10.1038/35570
[2]
Martín-Moreno L, García-Vidal F J, Lezec H J, et al. Theory of extraordinary optical transmission through subwavelength hole arrays. Phys Rev Lett, 2001, 86:1114 doi: 10.1103/PhysRevLett.86.1114
[3]
Bravo-Abad J, Degiron A, Przybilla F, et al. How light emerges from an illuminated array of subwavelength holes. Nature Phys, 2006, 2:120 doi: 10.1038/nphys213
[4]
Miyamaru F, Kamijyo M, Takano K, et al. Characteristics and generation process of surface waves excited on a perfect conductor surface. Opt Express, 2010, 18(16):17576 doi: 10.1364/OE.18.017576
[5]
Degiron A, Lezec H J, Barnes W L, et al. Effects of hole depth on enhanced light transmission through subwavelength hole arrays. Appl Phys Lett, 2002, 81:4327 doi: 10.1063/1.1526162
[6]
Kim T J, Thio T, Ebbesen T W, et al. Control of optical transmission through metals perforated with subwavelength hole arrays. Opt Lett, 1999, 24:256 doi: 10.1364/OL.24.000256
[7]
Zhan P, Wang Z L, Dong H, et al. The anomalous infrared transmission of gold films on two-dimensional colloidal crystals. Adv Mater, 2006, 18:1612 doi: 10.1002/(ISSN)1521-4095
[8]
Wang Z B, Ye Y H, Zhang Y A, et al. Visible transmission through metal-coated colloidal crystals. Appl Phys A, 2009, 97:225 doi: 10.1007/s00339-009-5184-4
[9]
Cai Z Y, Liu Y J, Leong E S P. Highly ordered and gap controllable two-dimensional non-close-packed colloidal crystals and plasmonic-photonic crystals with enhanced optical transmission. J Mater Chem, 2012, 22:24668 doi: 10.1039/c2jm34896a
[10]
Farcau C, Giloan M, Vinteler E, et al. Understanding plasmon resonances of metal-coated colloidal crystal monolayers. Appl Phys B, 2012, 106:849 doi: 10.1007/s00340-011-4849-9
[11]
Endo T, Takizawa H, Imai Y, et al. Study of electrical field distribution of gold-capped nanoparticle for excitation of localized surface plasmon resonance. Appl Surf Sci, 2011, 257:2560 doi: 10.1016/j.apsusc.2010.10.022
[12]
Haynes C L, Van Duyne R P. Nanosphere lithography:a versatile nanofabrication tool for studies of size-dependent nanoparticle optics. J Phys Chem B, 2001, 105:5599 doi: 10.1021/jp010657m
[13]
Walsh G F, Negro L D. Engineering plasmon-enhanced Au light emission with planar arrays of nanoparticles. Nano Lett, 2013, 13:786 doi: 10.1021/nl304523v
[14]
Bhattacharya J, Chakravarty N, Pattnaik S, et al. Comparison of optical properties of periodic photonic-plasmonic and randomly textured back reflectors for nc-Si solar cells. Journal of Non-Crystalline Solids, 2012, 358:2313 doi: 10.1016/j.jnoncrysol.2011.12.108
[15]
Ferry V E, Verschuuren M A, Li H B T, et al. Light trapping in ultrathin plasmonic solar cells. Opt Express, 2010, 18(S2):A237 doi: 10.1364/OE.18.00A237
[16]
Pan F, Zhang J Y, Cai C, et al. Rapid fabrication of large-area colloidal crystal monolayers by a vertical surface method. Langmuir, 2006, 22(17):7101 doi: 10.1021/la053323n
[17]
Ghaemi H F, Thio T, Grupp D E. Surface plasmons enhance optical transmission through subwavelength holes. Phys Rev B, 1998, 58(11):6779 doi: 10.1103/PhysRevB.58.6779
[18]
Jensen T R, Malinsky M D, Haynes C L, et al. Nanosphere lithography:tunable localized surface plasmon resonance spectra of silver nanoparticles. J Phys Chem B, 2000, 104:10549 doi: 10.1021/jp002435e
[19]
Rather H. Surface plasmons on smooth and rough surfaces and on gratings. Berlin:Springer, 1988
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    Jing Ju, Yuqin Zhou, Gangqiang Dong. The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals[J]. Journal of Semiconductors, 2014, 35(9): 092001. doi: 10.1088/1674-4926/35/9/092001
    J Ju, Y Q Zhou, G Q Dong. The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals[J]. J. Semicond., 2014, 35(9): 092001. doi: 10.1088/1674-4926/35/9/092001.
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    Received: 21 February 2014 Revised: 08 April 2014 Online: Published: 01 September 2014

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      Jing Ju, Yuqin Zhou, Gangqiang Dong. The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals[J]. Journal of Semiconductors, 2014, 35(9): 092001. doi: 10.1088/1674-4926/35/9/092001 ****J Ju, Y Q Zhou, G Q Dong. The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals[J]. J. Semicond., 2014, 35(9): 092001. doi: 10.1088/1674-4926/35/9/092001.
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      Jing Ju, Yuqin Zhou, Gangqiang Dong. The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals[J]. Journal of Semiconductors, 2014, 35(9): 092001. doi: 10.1088/1674-4926/35/9/092001 ****
      J Ju, Y Q Zhou, G Q Dong. The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals[J]. J. Semicond., 2014, 35(9): 092001. doi: 10.1088/1674-4926/35/9/092001.

      The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals

      DOI: 10.1088/1674-4926/35/9/092001
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      • Corresponding author: Zhou Yuqin, Email:yqzhou@ucas.ac.cn
      • Received Date: 2014-02-21
      • Revised Date: 2014-04-08
      • Published Date: 2014-09-01

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