Smart Component for Switching of Plasmon Resonance by External

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Smart component for switching of plasmon resonance by external electric field Jan Svanda, Yevgeniya Kalachyova, Petr Slepicka, Vaclav Svorcik, and Oleksiy Lyutakov ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b08334 • Publication Date (Web): 10 Dec 2015 Downloaded from http://pubs.acs.org on December 11, 2015

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ACS Applied Materials & Interfaces

Smart Component for Switching of Plasmon Resonance by External Electric Field

J. Švanda, Y. Kalachyova, P. Slepička, V. Švorčík, O. Lyutakov* Department of Solid State Engineering, University of Chemistry and Technology, 166 28 Prague, Czech Republic ABSTRACT New approach for preparation of active plasmonic component with capability to switch on/off localized

surface

plasmon

resonance

(LSPR)

by

piezoelectric

effect

is

described.

Polyvinylidenfluorid (PVDF) was patterned by polarized KrF excimer laser beam. The polarization was perpendicular to polymer orientation introduced during poling procedure. Consequently the silver nanoclusters were sputtered onto polymer surface. Application of an external electric field leads to polymer stretching and surface smoothening. Simultaneously, silver clusters are elongated and interconnected, this process leads to dramatic decrease of surface resistance and complete quenching of plasmon related absorption.

KEYWORDS: polyvinylidenefluoride, silver nanostructures, excimer laser patterning, plasmonic tunability, piezoelectric switching *Corresponding author (O.L.) Email: [email protected]

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1. INTRODUCTION Demand for active plasmonic devices which would enable light control at subwavelength scale significantly increased during last decade mostly due to their potential applications e.g. in integrated nanophotonics, 3D imaging, optical data storage, SERS, etc.1-4 Real-time control of optical parameters such as position and width of extinction band and transmission characteristics requires accurate design of metallic nanostructures and surrounding medium.5-7 Many possibilities of optical properties control of media sensitive to various input parameters were reported. Localized surface plasmon resonance (LSPR) can be modulated mechanically, thermally or photochemically, if the photochromic molecules are adsorbed onto the surface of metallic nanocrystals, or by chemical means involving changes either in pH or in oxidation/reduction state.8-10 In the one of the more popular case - noble metal nanoparticles embedded in pH sensitive polymer, the change in pH causes alternation in nanoparticle distance and refractive index of surrounding medium. This approach has two major drawbacks, the first one is that LSPR is shifted by about 10 nm (predictable due small differences of a refractive index of polymers), the second drawback is based on fact that achievable modulation is too slow.8,9 Switching speed can be successfully enhanced by utilization of liquid crystals, whose arrangement is controlled by an electric field, but this approach also suffer from a small change in a refractive index.11 To avoid these problems, polymers can be replaced by inorganic electro optical materials, which can be affected by the same stimuli. Besides the significant changes in a refractive index, some of them are also able to undergo various transitions (e.g. semiconductor/metal, crystalline/amorphous) accompanied by dramatic alteration of their optical properties.8,12 Plasmonic modulation by an external electric field is suitable due to several physical phenomena including thermo-plasmonic effect, Pockels effect, electrochemical metallization, plasmonic–molecular resonance coupling, and free carrier dispersion.13-15 In particular, plasmon phenomena can be divided into two main groups: localised surface plasmon and surface plasmon polariton (SPP).16 Both plasmonic phenomena – LSP and SPP can be tuned by the changing of above mentioned parameters. Usually, tuning of the SPP allows highly speed of modulation and greater absorption value changes.17-19 Oppositely, LSP-based tuneable plasmonic structures are slower, but enable to achieve higher wavelength shift. Requirements such as high speed operation, low operation voltage, large optical bandwidth and small dimensions of devices can be satisfied by use an active components based on graphene. 17-19 Optical transmission properties of graphene can be controlled through electrical gating by shifting the Fermi level. However, such modulation is feasible only in IR wavelength spectrum and so its applications cover mainly modulation of optical mode in waveguides, LSPR of metallic structures in this spectral region or graphene plasmons present in 2 ACS Paragon Plus Environment

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micro-engineered hybrid structures enabling coupling of electromagnetic radiation.20-24 Shifting operation capability into the visible regime requires reduction of its dimensions under 10 nm or by large change in Fermi level induced by increasing carrier concentration.25,26 Thus far it is problematic for top-down techniques, but is attainable by exploitation of aromatic molecules in solution as a molecular version of graphene. Slow electrochemical switching makes this method unsuitable in active plasmonics.25 The latter was calculated in graphene/nanowire hybrid structure near the vicinity of Ag nanowire.18 Promising is the idea of electrochemical switching of conductive polymers since their dielectric function allows the great shift (192 nm) or quenching of LSPR in microseconds using few volts potential.27,28 On the other hand, deposition of a polymer film in acidic electrolytes may lead to corrosion of other device elements.29 Even faster switching could be achieved by using light pulse systems in integrated plasmonics where fast modulation and switching of surface plasmon-polaritons are needed. These methods are based on gallium solid/liquid transition, excitation of quantum dots, nonlinearity revelation in employed aluminum or acoustic ultrafast lattice vibration, which differs in operating frequency, energy and modulation depth.2,7 The main disadvantage is necessity of costly femtosecond laser during the operating regime and often its higher pump fluence exceeding 10 mJ cm-2. Piezoelectric driving elements mainly in the form of inorganic crystals or their organic counterpart (polyvinylidenfluorid, PVDF) are used frequently in sensorics30 and optics31 for decades, but as far as we know, never for active plasmonics. Although PVDF possesses piezoelectric activity of more than one order of magnitude lower with respect to the inorganic crystals, apart from them, PVDF based system constitutes flexible and low-cost component capable of further miniaturization and integration. To ensure appropriate piezoelectric properties, PVDF has to be poled before using. It could be attained by several procedures including mechanical stressing and electrical poling, especially in case of PVDF as bulk material.32 In this work we describe the construction of a smart component enabling piezoelectric control over plasmonic response, as illustrated in Figure 1. Conditions for nanopatterning of PVDF followed by silver deposition and determination of proper LSPR position were investigated. The application of voltage on silver deposited PVDF resulted in deformation of silver nanostructures and fine quenching of LSPR. This component can find application in construction of components based on metamaterials, where instant modulation of optical properties is necessary.33

2. EXPERIMENTAL SECTION



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2.1. Materials. PVDF – piezoelectric, uni-axially oriented film of a thickness of 110 µm was supplied by Goodfellow (UK). The deposition of silver was accomplished from silver target (purity 99.99 %, provided by Safina, CZ). 2.2. Samples preparation. PVDF films were irradiated with KrF excimer laser pulses (40 ns, λ = 248 nm) at the repetition rate of 10 Hz (Lambda Physik Compex Pro 50). The laser beam was polarized linearly with a cube of UV grade fused silica with active polarization layer. Irradiated area was 1.0×0.5 cm2. To attain the suitable surface morphology, fluence varied from 5 to 150 mJ cm2 and pulse count varied from 6 000 to 100 000, respectively. Laser treatment was carried out in ambient air and at normal angle of incidence. The sputtering of silver layers onto the PVDF was accomplished on Balzers SCD 050 device from silver target (supplied by Goodfellow). The deposition conditions were: DC Ar plasma, gas purity 99.995 %, discharge power of 7.5 W, sputtering time 10–30 s, and current 20 mA. Contacts were deposited with colloidal silver at a distance of 6.5 mm from each other. Sample's annealing was performed under 150°C in argon atmosphere. For annealing the samples with deposited silver (sputtering time 90 s, current 20 mA) were used. 2.3. Measurement techniques. Surface morphology of samples was examined using AFM (atomic force microscopy, Digital Instruments CP II Veeco), working in tapping mode with silicon P-doped probes RTESPA-CP and with a spring constant of 50 N m-1. The shape and properties of the resulting structures created on the polymer layer were also studied using upright laser confocal microscope Olympus Lext working with a 405 nm laser light. For the sample observation an objective lens with 50× magniﬁcation was used. UV/Vis spectra were measured using UV/Vis Spectrometer Lambda 25 (Perkin-Elmer) in spectral range 250 – 1000 nm. Electrical sheet resistance of samples was determined by a standard two-point technique using KEITHLEY 487 picoampermeter. Additional silver contacts were constructed by sputtering using contact mask. Measurements were conducted under electric intensities up to 0.85 V µm-1.

3. RESULTS AND DISCUSSION The scheme of structure which enables the LSPR switching is introduced in Figure 1. Depending on the sputtering conditions, metal clusters or layer on the patterned polymer surface can be formed. This phenomenon was reported in our previous works.34,35 Initial structure is shown in the Figure 1(ii), where the metal clusters are not connected (will be discussed later). Surface resistivity is close to that of pristine polymer and LSPR, typical for silver clusters, can be expected. Applied electric field affects the underlying PVDF through piezo-electric mechanism which leads to polymer longitudinal extension, surface smoothing and interconnection of metal clusters. Pristine 4 ACS Paragon Plus Environment

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PVDF has positive piezo-response in the direction 3-1 and 3-3, and introduced external electric field induces polymer stretching. As a result, silver clusters become interconnected, surface conductivity reaches finite value and LSPR disappears because of electrically continuous metal coating formation, i.e. without the boundaries, where LSPR could be excited. Various methods for preparation of structures based on polymer nanopatterning followed by metal deposition were proposed. Among the common methods of PVDF nanopatterning, the template-assisted approach and nanoembossing have been reported.27 We have chosen the excimer laser modification, which allows not only the patterning of the polymer surface but also improves the surface adhesion for further metal deposition. It should be noted that surface patterning of PVDF has been previously investigated but with no positive results. It appears that application of low laser fluencies leads more likely to surface smoothening and no patterns are created. Increase of laser fluence leads to undesired surface graphitization, on contrary. However, careful choice of laser irradiation conditions can lead to required surface patterning. In our case, applied laser fluence (31 mJ and 36 000 pulses) was significantly below the ablation threshold of PVDF. It was also found that previous PVDF orientation, introduced during polymer poling (which is necessary step for proper PVDF piezo-electric response) strongly affects the resulting pattern. AFM images of pristine PVDF and PVDF after laser beam treatment with polarization perpendicular or parallel to the PVDF surface orientation are shown in Figure 2. It is evident that pristine polymer surface (Figure 2A) exhibits some deviations from smooth surface, which were created apparently during polymer poling. Laser treatment with polarization parallel to the direction of pristine polymer features leads to their deepening and formation of non-regular quasi grating (Figure 2C). However, if the laser light was polarized perpendicularly to pristine polymer, a system of dots was formed (Figure 2B). The latter structure was found to be suitable for further experiments. In the next step, surface changes caused by the application of an electric field were studied by AFM technique. Surface profiles measured at the same position at the sample surface without and with electric field are shown in the Figure 3. Without an electric field the sample exhibits rough profile as can be seen from Figure 3A. After application of an increasing electric field, surface remained unchanged up to the intensity of 0.15 V µm-1 (Figure 3B,C). Application of higher electric field intensity leads to surface flattening (Figure 3D) and this process continues until a substantially smooth surface is achieved. (Figure 3E,F and G). Therefore it can be concluded, that an electric field really affects the surface of poled PVDF and flattens laser induced surface patterns. The whole process is reversible, and after the electric field is switched off, the PVDF surface returns to its initial patterned state. It should be also noted that the maximum applied intensity of an electric field (0.75 V µm-1) was well below the intensity 160 V µm-1 necessary for the electric breakdown of 5 ACS Paragon Plus Environment


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PVDF. Additionally, parts B and C of Figure 3 show the confocal images of surface with and without electrical triggering. These images are introduced with the aim to provide more detailed information of surface smoothening under the application of 0.6 V µm-1 electric field intensity. Silver clusters were deposited on the top of PVDF surface pattern by vacuum sputtering. According to scheme shown in Figure 1, surface electric resistivity of pristine foil was expected in the case of patterned polymer and a significant decrease of resistivity was expected after application of an electric field (EF) which leads to silver clusters interconnection. Moreover, the change should be reversible. This was verified by the following experiment, the results of which are shown in Figure 4, where five consecutive cycles of on- and off- switching of electric field can be seen. It is evident that the application of electric field leads to dramatic changes of surface resistivity. Without application of electric field the surface resistivity was well above measuring limit of our equipment, i.e. 1014 Ohm cm-2. After application of the electric field exceeding the threshold the surface resistivity decreases and achieves the value by 107 orders of magnitude lower. Switching off of the electric field leads to slower increase of the surface resistivity, which achieves the initial immeasurable value in tens of seconds. To rule out any possible doubts, we examined the effect under different conditions. If position of the measuring electrodes with regards to electrodes used for electric field application was changed or the polarity of the triggered electric field was reversed the effect was unchanged. No effect was observed on pristine, nanopatterned PVDF and non-poled, patterned PVDF without piezo-response. It can be concluded with certainty that the observed dramatic changes can be attributed to the triggering of the surface morphology by piezo-effect in case of poled and patterned PVDF. Additionally, cycling of surface resistivity changes indicates that metal structures cracking did not occur. The dynamics of Ag clusters interconnection and material relaxation after electric field switch off was also studied and the results are presented in the Figure 4C and D for time dependent surface resistivity after rapid electric field switch on- and off-. Surface resistivity was checked immediately after material preparation (Figure 4C) and after five consecutive cycles of material triggering by the electric field (Figure 4D). From the graph it is evident, that surface resistivity is immediately decreased after electric field switch on. It was not detected any delay on the available equipment. Probably, the material behavior is determined by the piezo-electric response of PVDF. According to the literature, PVDF can support periodical EF triggering with frequency 3.104 Hz and higher.36,37 So, the time response of prepared structures is expected to be below 0.1 millisecond after electric field application. The situation is rather different after electric field switch off. In this case, the material relaxation proceeds slowly and takes several seconds (Figure 4C). Probably, in this case Ag clusters interaction acts against material relaxation and decelerates the process. 6 ACS Paragon Plus Environment

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Application of several consecutive cycles of material triggering slightly decreases the relaxation time (Figure 4D). UV-Vis spectra of the prepared structures taken from the samples without and with applied electric field are presented in the Figure 5. Figure 5A shows the typical absorption spectra measured on the patterned PVDF sample with silver clusters with and without of an electric field (silver was sputtered 20 s and an applied electric field intensity was 0.75 V µm-1). The regions where the optical absorption changes by applied electric field are well visible. Wavelength position of this region corresponds with typical position of localized surface plasmon resonance for the randomly arranged silver clusters.38 For better clarity we used the absorbance difference (i.e. absorbance of non-triggered sample minus absorbance measured under an applied electric field). Figure 5B shows how this difference is changed with increasing voltage. It is evident that at 0.15 V µm-1 the change in optical properties of silver clusters is negligible – i.e. the absorbance difference is near to zero. Voltage increase leads to dramatic changes in the spectra and appearance of pronounced absorbance peak located at 530 nm. So, it can be concluded that the localized surface plasmon resonance, typical for silver clusters deposited on patterned polymer surface, disappears after application of external voltage. In other words, we can switch off plasmon properties of the structure by external triggering. It was confirmed that the application of the electric field leads to PVDF surface smoothening due to piezo-response, interconnection of the silver clusters and disappearance of the plasmon response. We also examined how the amount of sputtered silver can affect the position and the switching of the plasmon resonance (see Figure 5C). It is evident that the increase of silver sputtering time leads to a shift of plasmon resonance to longer wavelength and to increase of its intensity. Application of an external electric field also inhibits the plasmon resonance. So, we can predetermine position of plasmon absorption peak by the amount of sputtered silver and reversibly switch on/off this absorption by the application of the electric field through piezo-effect, which induces morphological changes on the polymer surface. The LSPR strength was further increased by the deposition of continuous silver layer followed by the sample's annealing. It is well known, that the silver layer under higher temperature tends to form cluster structure with a strong peak of plasmon absorption.35,39 Structures prepared by this procedure are very often used in the field of plasmonics, as example, for SERS analysis.40 Prepared samples were also examined using UV-Vis absorption spectroscopy with and without external electric field triggering. Results are presented in the Figure 6A. It is evident that pristine sample exhibits well visible LSPR absorption peak. The strength of absorption is apparently increased, compared with the previous results (Figure 5). Like as in previous case, application of 7 ACS Paragon Plus Environment


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external electric field leads to damping of LSPR and plasmon absorption peaks significantly decreases at the intensity of 0.85 V.µm-1. The mechanism of plasmon quenching is the same – polymer flattening and clusters interconnection. It must be also noted, that described phenomenon needs application of the highest voltage, compared with previous case. Probably, partial loss of PVDF orientation and decrease of piezo-electric strength occurs during the annealing procedure. Since the better LSPR structure was obtained after annealing, the surface morphologies of pristine and annealed samples are also given in the Figure 6. From their comparison it is evident, that the samples surface morphologies undergo only minor changing during the annealing procedure. The main changes can be attributed to slight increase of pattern depth and surface roughening due to the tendency of silver to form the island like structure under the applied temperature. One of possible conformation of LSPR excitation is to measure the SERS excitation of analyte deposited onto plasmon-active surface. As analyte R6G was used due to its optimal SERS response. Raman measurements were performed onto patterned PVDF samples with deposited silver clusters under and without external electric field. Obtained results are presented in the Figure 7. From the Figure 7 it is evident, that non-triggered samples show significant SERS spectra. With the application of the electric field triggering the SERS intensity remains approximately constant (0.15 and 0.3 V.µm-1), then decrease for the highest voltage (0.45 V.µm-1) and it is significantly damped by the use of even more voltage (0.6 V.µm-1). It is well known, that the strongest SERS response is achieved when the LSPR is excited. The intensity of SERS response depends on the quality and quantity of so-called hot spots, that are determined by the Ag clusters size and the distance between them in our case. From SERS measurement it can be concluded, that the number and response of hot spots remains constant up to application of 0.3 V.µm-1. Further increase of voltage leads to cluster interconnection, suppression of the LSPR, which are reflected by decrease of SERS intensity. It must be also noted, that SERS intensity is not damped completely, but it is well known, that continuous, but rough silver layer can support SERS excitation.

4. CONCLUSION Reversible switching of electrical and optical properties of silver clusters deposited onto patterned surface of piezoelectric polymer PVDF was reported. Surface of PVDF was patterned by excimer laser beam with polarization perpendicular to polymer orientation introduced during poling procedure. Consequentlyy the silver nanoclusters were sputtered onto polymer surface. In the pristine state the silver clusters are separated and prepared structure exhibits resistance of pristine foil and pronounced plasmon resonance. Application of external electric field leads to polymer 8 ACS Paragon Plus Environment

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stretching and surface smoothening. Simultaneously silver clusters are elongated and interconnected, the process which leads to dramatic decrease of surface resistance and almost complete quenching of plasmon related absorption. Prepared structure can find application in the intensively developing field of smart plasmonics and realization of devices based on metamaterials, where instant modulation of optical properties is necessary.

ACKNOWLEDGEMENTS This work was supported by the GACR under the projects 15-19485S, 15-19209S and by the TACR under the project TH01010997

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Figure caption Figure 1. Schematic representation of preparation steps and expected properties of structure based on uniaxially oriented PVDF: (i) – laser treatment of polymer; (ii) silver deposition and formation of metal clusters; (iii) – application of electric field on prepared structures (leads to reversible changes of silver clusters morphology). Figure 2. AFM images of polymer surface morphology: A – pristine uni-axially oriented PVDF; B – after patterning by laser with polarization perpendicular to PVDF surface; C - after patterning by laser with polarization parallel to the PVDF surface. Figure 3. A - Surface profile acquired on pristine and patterned PVDF sample (laser polarization perpendicular to PVDF surface, number of pulses 36 000) without applied voltage and with 12 ACS Paragon Plus Environment

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different electric field intensity; B – Confocal image of patterned PVDF surface without electric triggering; C - Confocal image of patterned polymer surface with applied electric field of 0.75 V µm-1 intensity. Figure 4. Time dependence of applied voltage intensity (A) and surface resistivity (B) of silver clusters deposited onto patterned PVDF surface (silver sputtering time 20 s, voltage intensity 0.6 V µm-1); C, D – time behavior of surface resistivity after rapid electric field switch on and switch off, measured on the „fresh“ sample (C) and on five time pretreated sample (D). Figure 5. A - UV-Vis spectra of pristine PVDF and PVDF deposited by Ag clusters with and without triggering by electric field (0.6 V µm-1), differential UV-Vis spectra for samples exposed with different voltage intensity (B) (silver sputtering time s) and deposited with different silver sputtering times (voltage intensity 0.6 V µm-1) (C). Figure 6. A - UV-Vis spectra of annealed Ag/PVDF films with and without triggering by electric field; B 2D AFM image of PVDF deposited by Ag clusters before annealing C - 2D AFM image of PVDF deposited by Ag clusters after annealing. Figure 7. SERS spectra of R6G deposited onto Ag clusters with and without triggering by electric field.



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Graphical abstract


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Figure 1



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A

B

C

Figure 2


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Figure 3



C

14 13

0,6

12

OFF

0,4

ON

11

OFF

10 9

0,2

8 7

0,0 -2

B

D

14

1x10

15 14

13

8x10

13 12

13

6x10

OFF

ON

OFF

11

13

4x10

10 9

13

2x10

8 0

7 0

200

400

600

800

1000

1200

0

Time (sec.)

5

10

Time (sec.)

Figure 4


15

20

Logaritmus of Surface Resistivity

-1

Applied Intensity (V µm )

A

Surface Resistivity (Ω cm )

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Absorbance

Absorption (-)

A

PVDF / Ag

1,5

Pristine Voltage OFF Voltage ON

1,0

0,5

0,0 400

600

800

Wavelength (nm) -1

B

0,14

C

10 sec 15 sec 20 sec 30 sec

0,06

0,12 0,10 0,08

0,04

0,06 0,04

0,02

0,02 0,00

0,00 400

600

800

400

Wavelength (nm)

600

Wavelength (nm)

Figure 5


800

∆ Absorbance

0.15 V*µm -1 0.3 V*µm -1 0.45 V*µm -1 0.6 V*µm

Absorption Difference (-)

0,08

∆ Absorbance Absorption Difference

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A

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B

C

Figure 6


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8000

Raman Intensity (a. u.)

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0 V*µm

-1

6000 0.15 V*µm

-1

4000 0.3 V*µm

0.6 V*µm

2000

-1

-1

0.85 V*µm 500

-1

1000

1500 -1

Raman shift (cm ) Figure 7


Smart Component for Switching of Plasmon Resonance by External

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