Fabrication and study of optical properties of multilayer metal insulator metal nanocups

VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY VU MINH THONG FABRICATION AND STUDY OF OPTICAL PROPERTIES OF MULTILAYER METAL – INSULATOR – METAL NANOCUPS MASTER’S THESIS Hanoi, 2019 VIETNAM NATIONAL UNIVERSITY, HANOI VIETNAM JAPAN UNIVERSITY VU MINH THONG FABRICATION AND STUDY OF OPTICAL PROPERTIES OF MULTILAYER METAL – INSULATOR – METAL NANOCUPS MAJOR: NANOTECHNOLOGY CODE: PILOT RESEARCH SUPERVISORS: DR PHAM TIEN THANH PROF DR NGUYEN HOANG LUONG Hanoi, 2019 Acknowledgements First of all, I would like to express my sincere thank to my supervisors: Dr Pham Tien Thanh, and Prof Nguyen Hoang Luong, for their guidance, encouragement to completed this thesis Second of all, I would also like to thank Mr Nguyen Van Tien, and Mrs Nghiem Ha Lien, for their support in fabricating Polystyrene nanoparticles Third of all, I would like to express my sincere thank to my classmate Mr Pham Dinh Dat Thank to you, I got basic knowledge of FDTD method Thank you for your willing to help Forth of all, I would like to thank Vietnam Japan University and staff working here for their necessary supports Last but not least, I also would like to express my sincere thank to my family, for their fully support i TABLE OF CONTENTS Chapter 1: Introduction Research background 1.1 Surface plasmon resonance (SPR) 1.1.1 Theory 1.1.2 SPR in metal – insulator – metal (MIM) structure 1.2 Localized Surface Plasmon Resonance (LSPR) 1.2.1 Mie theory 1.2.2 LSPR in nanocups structure 1.3 Application of SPR and LSPR phenomena 1.3.1 Application of SPR phenomenon 1.3.2 Application of LSPR phenomenon 1.4 Finite Difference Time Domain (FDTD) approach 1.4.1 Theory 1.4.2 Calculation transmittance model of MIM nanocups str Chapter 2: Experimental procedures 2.1 Fabrication 2.1.1 Polystyrene nanoparticles fabrication 2.1.2 Silane coupling preparation 2.1.3 Glass substrate treatment 2.1.4 Fabrication of monolayer Polystyrene nanosphere on g substrate 2.1.5 Sputtering three layers Gold – Magnesium Fluoride – monolayer Polystyrene nanoparticles on a glass substrate 2.1.6 Dispersing MIM nanocups into water 2.1.7 Deposit sample onto Silicon wafer 2.2 Measurement Chapter Results and Discussion 3.1 SEM images 3.1.1 SEM images of monolayer polystyrene 3.1.2 SEM images of substrates after separate particles 3.1.3 SEM images of nanocups on Silicon wafer 3.2 Optical Properties 3.2.1 Optical properties of MIM nanocups structure on Glas Substrate 3.2.1.1 Confirmation of thickness of each layer ii 3.2.1.2 Transmittance properties of samples on substrate 3.2.1.3 Transmittance properties of substrate after separate particle 3.2.2 Optical properties of MIM nanocups in water Conclusion References iii List of Fig.s Fig 1.1 Fig 1.2 Fig 1.3 Fig 1.4 Fig 1.5 Fig 1.6 Fig 1.7 Fig 1.8 Fig 1.9 Fig 1.10 Fig 2.1 Fig 2.2 Fig 2.3 Fig 2.4 Fig 2.5 iv Fig 2.6 Proced nanocu Sputter monola Disper substra water Deposi Transm (b), Me nanocu SEM i 200nm SEM im nm dia SEM im SEM im SEM im particle SEM im particle SEM im SEM im Transm Transm Transm Transm PS200 straigh Transm PS500 straigh Schem nanopa Transm separat straigh Fig 2.7 Fig 2.8 Fig 2.9 Fig 2.10 Fig 3.1 Fig 3.2 Fig 3.3 Fig 3.4 Fig 3.5 Fig 3.6 Fig 3.7 Fig 3.8 Fig 3.9 Fig 3.10 Fig 3.11 Fig 3.12 Fig 3.13 Fig 3.14 Fig 3.15 v Fig 3.16 Transm separat (black curve) Transm particle separat straigh Transm water a, Imag propert Simula particle Fig 3.17 Fig 3.18 Fig 3.19 Fig 3.20 vi List of abbreviations ATR: CTAB KPS: LSPR: MIM: PMMA: PS: PVD SDS: SEM: SPP SPR: Attenuated Total Reflection Cetyl trimethyl ammonium bromide Potassium Persulfate Localized Surface Plasmon Resonance Metal – Insulator – Metal Poly(methyl methacrylate) Polystyrene Physical Vapor Deposition Sodium Dodecyl Sulfate Scanning Electron Microscope Surface Plasmon Polariton Surface Plasmon Resonance vii ABSTRACT The Metal – Insulator – Metal (MIM) nanocups structure on glass substrate and in water were fabricated by chemical method and sputtering, studied by transmittance properties The morphology of the sample was studied by Scanning Electron Microscope, and transmittance properties were studies by UV-Vis-NIR, and simulated by Finite Difference Time Domain (FDTD) method The result showed that MIM nanocups have surface plasmon resonance (SPR) and localize surface plasmon resonance (LSPR) phenomena, that depend on size of Polystyrene (PS) and thickness of metal and insulator layers The purpose of this thesis is: - Deposit monolayer PS nanoparticles on glass substrate - Fabrication MIM nanocups structure with core of Polystyrene PS nanoparticles - Study SPR and LSPR phenomenon of Metal – Insulator – Metal nanocups structure on substrate and in water viii Au(21nm) – MgF2(38nm) – Transmittance (%) 60 50 40 30 20 10 300 400 500 600 700 800 Wavelength (nm) Figure 3.11 Transmittance properties of Au – MgF2 – Au thin film (MI) and Gold – Magnesium Fluoride – Gold (MIM) and result of transmittance properties from simulator by using transfer matrix (Fig 3.9; Fig 3.10; Fig 3.11) As we can see in three Fig.s: Fig 3.7; Fig 3.8; Fig 3.9, the results from measurement transmittance properties of M, MI, MIM nearly fit their result from simulator Therefore, the thickness of each layer is: first layer is 21 nm Au, second layer is 38 nm MgF2 and final layer is 19 nm Au 3.2.1.2 Transmittance properties of samples on substrate Au(19nm we Now, have peaked at around 530nm and transmittance percentage is analysis about 48% Therefore, the existence of PS nanoparticle in sample transmittance cause this red shift This phenomenon is continued when properties of sputtering 38 nm MgF2 on sample sample PS200MIM 36 and PS500MIM which are shown in Fig 3.12 and Fig 3.13 respectively As we see, can for sample using PS nanoparticle with diameter is 200 nm, peak of PS200M is 560 nm, percentage of transmittance is 33% compare to peak of Gold thin film with the same thickness (21 nm) which PS200M, the peak is red shift to around 580nm and the transmittance properties increase by 3% However, when final layer (19 nm gold layer) sputtering on sample 40 Transmittance (%) PS200MI 30 20 PS200MIM 10 300 400 500 600 Wavelength (nm) 700 800 Figure 3.12 Transmittance properties of PS200M (red straight curve), PS200MI (green straight curve), and PS200MIM (black straight curve) on glass substrate PS200MI, blue shift occurs, from peak at 580nm to peak at approximate 520nm with transmittance properties sharply decrease from 36% to about 15% (more than half) We can predict that there is another peak in wavelength longer than 800nm Fig 3.13 showed transmittance properties of sample using PS nanoparticle with diameter is 500 nm as core For sample PS500M, with existence of PS nanoparticle, there are peaks The first one is at 540nm, and second one at 740nm with transmittance property is 16% and 15%, respectively Sample PS500MI also has two peaks as sample PS500M The peak at 540nm red shifts to 560nm and transmittance property goes down by 2% The second peak at 740nm shifted to 760nm, and transmittance property dramatically increases to 16% When the final layer (19 nm gold) was sputtered on the sample, the transmittance property of sample 37 20 Transmittance (%) PS500MI 15 10 PS500M PS500MIM Figure 3.13 Transmittance properties of PS500M (red straight curve), PS500MI (green straight curve), and PS500MIM (black straight curve) on glass substrate significantly decreases by 5.5% for a peak at 510nm and 10% for a peak at around 710nm The second peak of the sample can be explained as LSPR is occurred in here, also the interaction between neighbor particle [9] Those phenomena can be explained as follow The second peak of sample PS500MIM maybe peak of LSPR of the sample Using the simple approximation of an array of interacting point dipoles, the direction of the resonance shifts for in-phase illumination can be determined by considering the Coulomb forces associated with the polarization of particle [11] As Fig 3.14, the restoring force acting on the oscillating electrons of each particle in the chain is either increased or decreased by the charge distribution of neighboring particles Depending on the polarization direction of the exciting light, this leads to a blue- shift of the plasmon resonance for the excitation of transverse modes, and a red-shift for longitudina l modes 38 Figure 3.14 Schematic of near-field coupling between metallic nanoparticles for the two different polarizations In conclusion, multilayer Metal – Insulator – Metal nanocups structure on glass substrate enhance SPR and LSPR signal dramatically 3.2.1.3 Transmittance properties of substrate after separate particles After separate particles from sample PS500MIM and PS200MIM, transmittance properties of samples were also studied Fig 3.15 showed transmittance property of sample PS500MIM before and after separate particle, also compare with MIM structure with the same thickness As Fig presented, transmittance property sharply increased to around 42% at peak around 510nm, and second peak at around 720nm disappeared It can be explained as after separate particle from sample, create MIM structure with holes Therefore, LSPR phenomenon did not occur lead to the disappearance of the second peak at 720 nm, and only display characteristic of normal MIM thin film structure Also because of holes, the transmittance property is higher than the transmittance property of MIM structure by 20% Transmittance properties of sample PS200MIM after separate particle rocketed by more than 40%, higher than Transmittance (%) 40 30 20 10 300 400 500 600 700 Wavelength (nm) 800 Figure 3.15 Transmittance properties of sample PS500MIM: before separate particle (red dashed curve), after separate particle (red straight curve); and MIM structure (green straight curve) 60 Transmittance (%) 50 40 30 20 10 300 400 500 600 700 Wavelength (nm) 800 Figure 3.16 Transmittance properties of sample PS200MIM: before separate particle (black dashed curve), after separate particle (black straight curve); and MIM structure (green straight curve) MIM structure by 30% (Fig 3.6) This phenomenon can be also explained as same 40 as explanation for this phenomenon of sample PS500MIM Comparison of transmittance properties samples PS200MIM and PS500MIM and MIM structure illustrated in Fig 3.17 According to Fig 3.17, after separate particle, both samples PS200MIM and sample PS500MIM have the peak at the same position as the peak of MIM structure (approximately 520nm), with transmittance 60 Transmittance (%) 50 40 30 20 10 Figure 3.17 Transmittance properties of sample PS200MIM after separate particle (black straight curve), sample PS500MIM after separate particle (red straight curve) and MIM structure (green straight curve) property is about 55%, 42%, and 22%, respectively In conclusion, MIM nanocups on glass substrate have both SPR and LSPR phenomenon from MIM structure and sphere structure 3.2.2 Optical properties of MIM nanocups in water Transmittance properties of sample PS500MIM particle in water was showed in Fig 3.18 Difference with this sample on the substrate, transmittance curve of PS500MIM particle in water have not a single peak from range of wavelength from 41 Transmittance (%) 80 75 70 65 60 300 400 500 600 700 Wavelength (nm) 800 Figure 3.18 Transmittance property of sample PS500MIM particles in water 300nm to 800nm We can predict that peak of transmittance of sample shift to near – a75 b 70 65 60 55 50 45 300 400 500 600 700 800 Wavelength (nm) Figure 3.19 a, image of PS200MIM particles in water; b, Transmittance property of sample PS200MIM particles in water Infrared area The transmittance property of sample is very high (around 78%) Sample PS200MIM particle in water has two peaks from incident light wavelength 42 from 300nm to 800nm (Fig 3.19) As transmittance property curve is shown in Fig 3.19b, there are two peaks at about 540nm and around 730nm Maybe because the density of PS200MIM particle in water is low, therefore, the signal is not clear (Fig 3.19a) The simulator of PS200MIM particle in air, using FDTD method was done with the set up as same as calculation model in the introduction (Fig 3.20) In result of simulation, the first peak is around 480nm and the second peak is around 700nm, difference with experience result (540nm and 740 nm) The difference is because of Transmittance (%) reasons The first reason is the simulator was done in air with refractive index 1, Figure 3.20 Simulation result of transmittance properties of PS200MIM particle in air while the experience was in water with refractive index 1.33 The second is the structure use in simulation is a bit difference with the real, therefore, the result of simulator was different from result of experience, also the difference between the refractive index of gold used in calcuation and refractive index of gold in experience The final reason is in simulation, only structure was calculated, in the specific direction, while in experience, there are many particles, with difference structure, and in difference direction 43 CONCLUSION In this thesis, we successfully made nearly monolayer Polystyrene nanosphere on glass substrate We successfully fabricated Gold – Magnesium Fluoride – Gold nanocups structure with core of 200 nm and 500 nm diameter of Polystyrene nanoparticle In case of sample PS – Gold – Magnesium Fluoride – Gold on the substrate, the plasmonic properties of sample increase when sample has Metal – Insulator – Metal nanocups structure For more detail, for sample PS200MIM, the transmittance properties of sample sharply decrease, when compared with transmittance properties of sample PS200M (by 18%) and the peak is blue shift from 530nm to 520nm For sample PS500MIM, the transmittance curve appeared peaks at 510 and 710 nm (which cause by LSPR phenomenon), the transmittance properties dramatically went down In case of sample PS – Gold – Magnesium Fluoride – Gold in water, the signal is not clear For sample PS200MIM, the transmittance 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MINH THONG FABRICATION AND STUDY OF OPTICAL PROPERTIES OF MULTILAYER METAL – INSULATOR – METAL NANOCUPS MAJOR: NANOTECHNOLOGY CODE: PILOT RESEARCH SUPERVISORS: DR PHAM TIEN THANH PROF DR NGUYEN... substrate - Fabrication MIM nanocups structure with core of Polystyrene PS nanoparticles - Study SPR and LSPR phenomenon of Metal – Insulator – Metal nanocups structure on substrate and in water... 1/kz into insulator and into metal is equal Continuity of φ and ε ensure continuity of the tangential field components and the normal field components of the dielectric displacement and require