Towards the Plasmonc Nanopore Platform with Nanoslits
For single Molecule Sensor
Seong Soo Choi*
Distinguished professor, Research Center for Nano-Bio Science
SunMoon University, Ahsan 31460, Korea
Collaborators :
Yong Min Lee, Sae-Joong Oh
Research Center for Nano-Bio Science, SunMoon University 31460, Korea
Hyun Tae Kim, Soo Bong Choi
Department of Physics, Incheon National University, Incheon, Korea
Byung Seong Bae
School of Electronics and Display, Hoseo University, Ahsan, Chungnam 31499, South Korea
*sscphy2010@gmail.com
2019 SNAIA, Dec 10- 13, Paris, France
1
Contents
I. History : From Cell counter to Nanopore Sensor
II. Our Fabrication History of Nano-aperture:
Fabricating Plasmonic Nano-Aperture
III. Fabricating Au nano-pore ; Diffusion and Drilling
- Physics and Chemistry point: Ostwald ripening, and Spinodal Decomposition
- melting temperature dependent upon the size and Atomic magic number
< Platos’s 5 solid body structures ~
` Tetrahedron, Cube, Octahedron, Dodecahedron, Icosahedron>
IV. Nano Pore array with nanoscale double slits
- Optical intensity variation dependent upon the separation
V.
Results and Discussion:
-focusing difficulty, stability, optimization
Coulter Cell Counter; 1940’
3
To measure the numbers of blood cell, 1940’s
10 mm
By Reimar Spohr - Own work, CC BY-SA 3.0,
https://commons.wikimedia.org/w/index.php?curid=16938198
Nanopore sensor for Single Molecule Detection
Single-molecule sensing with nanopores
with electronic sensing
Cited from
Murugappan Muthukumar, Calin Plesa, and Cees Dekker,
Physics Today 68, 8, 40 (2015)
Prof. Hagan Bayley, Oxford University
5
Portable Single Molecule Detection device:
The Potential and Challenges of Nanopore Sequencing,
“D. Branton et al,” Nature Biotechnology, 26, 1146 (2008)
Electronically driven/ Electronic recognition
~ 100 pN at 100 mV
History : From of Nano-Aperture to Nanopore,
since 1995
Our History of Nano-Aperture Fabrication ,
since 1995
Year 1995
Year 2000
Year 2010
Year 2015
~100 nm
~ 50 nm
~ 5 nm
Etching and deposition
technique
FIB drilling
Electron beam
induced Diffusion
technique
Fabrication of NSOM cantilever array
with ~ 95 nm diameter aperture
Fabrication of electron beam induced Carbon AFM tip
on cantilever
History of Nano-pore Fabrication since 1995
Year 2015
Drilling a Au thin film
by using focused electron beam
Drilled Nanohole on the diffused Au-C mebrane
On the pyramidal apex
Graphical Abstract
“Fabrication of Nanopore on Pyramid,”
Applied Surface Science, V 310, 196-203(2013).
Fabrication Process
1.
Si microfabrication Process followed by vacuum deposition
of Au film
2.
Diffusion or Drilling:
FIB drilling followed by Electron beam irradiation
a) Pore formation by FESEM electron beam irradiation
b) Pore formation by TEM electron beam irradiation
I. Fabrication Process of Au Nano-Aperture
(a) Oxidation 1120 nm
(b) PR Patterning &
Dry Etching
(e-1)
(c) PR strip &
V-groove Formation
After metal deposition
(d) Re-Oxidation
SiO2 = 1626 nm
(e) Back-side Si Bulk
Etching
(f) Metal deposition and
FIB drilling
Si
SiO2
PR
(f-1)
~ 200 nm
After FI B drilling
Metal
Dept. of Physics and Nanoscience, College of Natural Science, Sun Moon University, Ahsan, 336-708 Korea
FESEM images of
Nano-Aperture Array on pyramidal apex
TEM images for Pyramidal Array
Pyramidal Nanopore Platform
Melting temperatures
dependent upon the size and the shape
Where TM and TMB are the melting temperature of nanoparticle and Bulk material, respectively.
“Size effect on the melting temperature of gold particles”,
P. Buffat and J. Borel, Phys. Rev. A 13, 2287(1076).
“Irregular variations in the melting point of size-selected atomic clusters,”
M. Schmidt, etc, Nature V 393, 238(1998).
Magic Numbers: 5 Platonic Soli Stucture
Vacuum –deposited Au Film consists of Au clusters ,
following the Platonic Solid Structure: Atomic Magic Number
Melting temperature versus Al cluster size
Blue: cluster cations
Red: cluster anions
Various Au Cluster formation in the deposited film
Platos’ Five Body structures,
And Atomic Shell Model for Melting Temperature
Tetragonal, Cube, Octagonal, decahedral, Icosahedral
Multiply twinned particle (MTP)
with Icosahedral structure,
and decahedral structure
“Surface structure and energetics of multiply twinned particles,”
L. Marks, Philosophical Magazine, Vol 49, NO 1, 81-93(1984)
High Electron beam Irradiations by
using TEM : diffusion
Dynamical Formation Process ;
reduction of Au circular nanopore (51 pA, 300 KeV TEM)
11 days later in air
Sept 29
45 min exposure
21 nm
43 min exposure
Oct 10
18 nm
34 nm
( 3.8 x 20.8 ) nm
300 keV TEM(Jeol, JEM-3011HR)
Controlled nanopore formation by using TEM
1 pA electron beam at 300 keV with 10 min interval
TEM images of the FIB drilled Au aperture on the 200 nm thick Au film. Successive irradiations by electron
beam with 5 min intervals using 1 pA, 300 keV were carried out. After 48 min of irradiation with 1 pA electron
beam at 300 keV, the nanopore became almost closed. The ring of the Au islands is shown. The separation of the
big Au island from the surrounding thick Au area is presented (inside the dotted circle) in (d). The diameter of the
nanopore was gradually closed from ∼70 nm to ∼0 nm.
22
Controlled nanopore formation on the diffused membrane
under electron beam irradiation (300 keV, 0.5 pA)
S11-4-10-2-B (0.5pa) 10 min interval
(a)
Before
(b)
d = 96.11 nm
(e)
40 min
d = 43.31 nm
10 min
(c)
50 min
d = 26.08 nm
(d)
d = 62.85 nm
d = 81.03 nm
(f)
20 min
(g)
50 nm
d = 52.41 nm
60 min
d = 6.38 nm
30 min
(h)
20 nm
65 min
d=0
Optical Characteristics of Metallic Hole
Nonlinear Behavior of Light Transmission:
Schwinger’s Variational Principle
Schwinger’s
Variational principle
O:
Boukamps Calculation
Kirchoff’s
Approximation
Pore region
On the theory of Diffraction by an Aperture in an Infinite Plane Screen. II,
Harold Levine, Julian Schwinger, PR 7, 1423-1432(1949).
1965
Nano-Aperture with Grooved Patterns
(a)
(e)
(b)
(f)
(c)
(g)
(d)
(h)
SiO2
Si
Metal
Apertures with Groove
Fabrication procedure of Aperture on the flat plane
Output Intensity dependent upon Pitch of 100 nm wide Groove :
Maximum Intensity: 5 grooves with 300 nm pitch
1000
Output Intensity (a.u.)
Al (300nm) coated on Oxide (264 nm) Plate
100
10
1
Pitch 300nm,Groove width100 nm, 4-groove
Pitch 500nm,Groove width100 nm, 5-groove
Pitch 300nm,Groove width100 nm,, 5-groove
Single
Single hole
Aperture
100
200
300
400
Aperture Diameter (nm)
500
600 700 800
Eperpendicular (Ez) just above the metal surface
30
: without Groove
: with Groove
At the Metal Surface
20
10
Grooves
Without
Groove
0.4
0.2
0.0
-2
0
Horizontal Axis (mm)
2
Sharp peaks : Radiation due to the scattering of SP with periodic grooves
Comparison between
Plate Probe and Pyramidal Probe (D = 300 nm)
Plate
Pyramid
Intensity
(XZ)
Without Groove
With Groove
With Groove
Without Groove
Ex
No Groove
Ex
With Groove
Ex (XZ)
Al 400 nm-Plate
Al 400 nm-Cone
Backward -Diffraction of Light dependent upon polarization
Physical Review E 65 p046611
‘‘Orbital’’ representation of the angular radiated power of the tip.
The figure shows the important backward emission in the P plane
passing through the tip axis and containing the effective electric dipole P.
Tuning localized plasmonic cavity in nanostructured substrate for surface
enhanced Raman Spectroscopy, N.M. B. Perney, J.J. Baumberg, etc,
Optics Express, Vol 14, 848(2006).
Optical Enchancement from Pyramid
with groove patterns
FIG. 4. (Color online) (a) Rectangular, (b) circular, and (d) elliptic periodic groove patterns
fabricated using 30 keV FIB are shown in top view (upper) and tilted view (lower). (d)
Schematic of the pyramidal probe (side view).
S.S. Choi et al., J. Vac. Sci. Technol. B, Vol. 33, No. 6, Nov/Dec 2015, p06F203
103 fold increase from Elliptically patterned pyramidal aperture
Highlight
S.S. Choi et al, J. Vac. Sci. Technol. B, Vol. 33, No. 6, Nov/Dec 2015, p 06F203
Transmitted Optical Intensities via Various Au apertures
J. Vac. Sci. Technol. B, Vol. 33, No. 6, Nov/Dec 2015, p 06F203
SERS peaks from 3D pyramid with / without groove patterns
This optical measurements was carried out at Professor Luke Lee’s Lab,
Dept of Bioengineering, UC-Berkeley.
Utilizing Nanoscale Double Slits
Classical Young’s Double Slit Experiment
Plasmon-assisted Nanoscale Double Slits
II. Experimental Design for Nanoscale Slits with different Gaps
L = 5 mm
15 mm
W= 5 mm
w= 15 mm
w= 10 mm
10 mm
4 mm
3 mm
20 mm
w= 20 mm
3 mm
10 mm
20 mm
Fig.1
Thickness: 200 nm Au
Slit width : 20 nm - 200 nm
40
Transmitted Intensity (Normalized)
21-20-2
6-10-1-A
6-10-1-C
6-10-1-G
Single slit
5 mm pitch
10 mm pitch
6-10-1-E
6-10-1-I
15 mm pitch
20 mm pitch
Name
Designed Pitch
Total Area
Integrated Intensity
Ratio
21-20-2
Calibration Hole
1𝟖𝟓. 𝟕𝟖 𝝁m𝟐
886,847.2
1.0000
6-10-1-A
Single Slit
0.87 𝝁m𝟐
227,171.8
0.2562
6-10-1-C
5.07 𝜇m
1.75 𝝁m𝟐
279,288.9
0.3149
6-10-1-G
10.14 𝜇m
1.75 𝝁m𝟐
88,999.0
0.1004
6-10-1-E
15.19 𝜇m
1.75 𝝁m𝟐
150,213.9
0.1694
6-10-1-I
20.30 𝜇m
1.75 𝝁m𝟐
62,952.3
0.0710
41
Transmitted Intensity versus Wavelength
5000
(666,4263)
4000
Nor. Intensity
(a.u. / unit area)
Calibration Hole
A : Single Slit
C : Slit Pitch 5
E : Slit Pitch 15
G : Slit Pitch 10
I : Slit Pitch 20
3000
2000
5 mm pitch
10 mm pitch
Single slit
15 mm pitch
1000
0
400
500
600
700
800
900
1000
Wavelength (nm)
Effects of Surface Plasmons on spectral switching of polychromatic light with Au double slit,
M.Verma et al, J. Opt. Soc. Am. A v29, 196(2012)
42
Transmitted Intensity Comparison
With and without Nanoscale Double Slits
8 fold increase at red shifted peak position
for the (7x7) nanohole array with nanoscale double slits.
780 nm
Enhancement factor
5
530nm pitch
780nm pitch
1060nm pitch
4
3
2
(713 , 1.72)
1
(588, 0.52)
0
600
650
700
Wavelength (nm)
750
800
1060nm
530nm pitch
780nm pitch
1060nm pitch
10
8
(719, 8.36)
6
4
2
0
550
780nm
530nm
1060 nm
Enhancement factor
530 nm
550
600
650
700
750
800
Wavelength (nm)
Effects of surface Plasmons on spectral switching of polychromatic light with Au double slit,
M.Verma et al, J. Opt. Soc. Am. A v29, 196(2012)
Conclusions
Transmitted optical intensity from the Au nano-aperture array
with double nanoscale slits has been observed.
The fabricated Au optical platform < nano-aperture array with
nanoscale slits > can be utilized as single molecule sensing device.