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2d Nanomaterials Processing And Integration In Miniaturized Devices Matteo Cocuzza
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9. Contents
About the Editors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Candido Fabrizio Pirri and Matteo Cocuzza
Editorial for the Special Issue on 2D Nanomaterials Processing and Integration in Miniaturized
Devices
Reprinted from: Micromachines 2021, 12, 254, doi:10.3390/mi12030254 . . . . . . . . . . . . . . . . 1
Yang Yang, Ruhao Pan, Shibing Tian, Changzhi Gu and Junjie Li
Plasmonic Hybrids of MoS2 and 10-nm Nanogap Arrays for Photoluminescence Enhancement
Reprinted from: Micromachines 2020, 11, 1109, doi:10.3390/mi11121109 . . . . . . . . . . . . . . . 3
Lixiu Zhang, Xiaoyi Wei, Junhai Wang, Yuhou Wu, Dong An and Dongyang Xi
Experimental Study on the Lubrication and Cooling Effect of Graphene in Base Oil for
Si3N4/Si3N4 Sliding Pairs
Reprinted from: Micromachines 2020, 11, 160, doi:10.3390/mi11020160 . . . . . . . . . . . . . . . . 15
Alessio Verna, Simone Luigi Marasso, Paola Rivolo, Matteo Parmeggiani, Marco Laurenti
and Matteo Cocuzza
Lift-Off Assisted Patterning of Few Layers Graphene
Reprinted from: Micromachines 2019, 10, 426, doi:10.3390/mi10060426 . . . . . . . . . . . . . . . . 23
Jianfa Zhang, Qilin Hong, Jinglan Zou, Yuwen He, Xiaodong Yuan, Zhihong Zhu and
Shiqiao Qin
Fano-Resonance in Hybrid Metal-Graphene Metamaterial and Its Application as Mid-Infrared
Plasmonic Sensor
Reprinted from: Micromachines 2020, 11, 268, doi:10.3390/mi11030268 . . . . . . . . . . . . . . . . 35
Francesco Ruffino, Maria Censabella, Giovanni Piccitto and Maria Grazia Grimaldi
Morphology Evolution of Nanoscale-Thick Au/Pd Bimetallic Films on Silicon Carbide
Substrate
Reprinted from: Micromachines 2020, 11, 410, doi:10.3390/mi11040410 . . . . . . . . . . . . . . . . 43
Peng Xiao, Yicong Zhou, Liao Gan, Zhipeng Pan, Jianwen Chen, Dongxiang Luo, Rihui Yao,
Jianqiu Chen, Hongfu Liang and Honglong Ning
Study of Inkjet-Printed Silver Films Based on Nanoparticles and Metal-Organic Decomposition
Inks with Different Curing Methods
Reprinted from: Micromachines 2020, 11, 677, doi:10.3390/mi11070677 . . . . . . . . . . . . . . . . 55
Olga Volovlikova, Sergey Gavrilov and Petr Lazarenko
Influence of Illumination on Porous Silicon Formed by Photo-Assisted Etching of p-Type Si with
a Different Doping Level
Reprinted from: Micromachines 2020, 11, 199, doi:10.3390/mi11020199 . . . . . . . . . . . . . . . . 67
Axiu Cao, Li Xue, Yingfei Pang, Liwei Liu, Hui Pang, Lifang Shi and Qiling Deng
Design and Fabrication of Flexible Naked-Eye 3D Display Film Element Based on
Microstructure
Reprinted from: Micromachines 2019, 10, 864, doi:10.3390/mi10120864 . . . . . . . . . . . . . . . . 83
Maria Laura Coluccio, Salvatore A. Pullano, Marco Flavio Michele Vismara, Nicola Coppedè,
Gerardo Perozziello, Patrizio Candeloro, Francesco Gentile and Natalia Malara
Emerging Designs of Electronic Devices in Biomedicine
Reprinted from: Micromachines 2020, 11, 123, doi:10.3390/mi11020123 . . . . . . . . . . . . . . . . 93
v
11. About the Editors
Matteo Cocuzza
Matteo Cocuzza got his M.D. in Electronic Engineering from Politecnico di Torino, Turin, Italy,
in 1997, and his Ph.D. degree in Electronic Devices in 2003. He is currently a Professor at the Dept.
of Applied Science and Technology of Politecnico di Torino and associated researcher of IMEM-CNR.
In 1998, he was one of the founders of the Chilab-Materials and Microsystems Laboratory. He is
currently a lecturer of master’s degree courses related to MEMS, micro- and nano-technologies, also
in the framework of the International Master Degree in Nanotechnologies for ICT (joined master
between Politecnico di Torino, INPG Grenoble and EPFL Lausanne). His research activity is focused
on MEMS and microsensors for industrial applications, on the development of microfluidics and
lab-on-a-chip for biomedical applications and, more recently, on the development and application of
polymeric 3-D printing technologies.
Fabrizio Pirri
Candido Fabrizio Pirri is Full Professor at the Dept. of Applied Science and Technology of
Politecnico di Torino and Responsible for the Chilab-Materials and Microsystems Laboratory since
1998. He joined the Center for Sustainable Future Technologies, Istituto Italiano di Tecnologia,
Genova, Italy, as Director in 2011. Since 2005, he has been Director of the National MIUR Excellence
Laboratory “Latemar”, whose mission is the development of advanced technologies for genomics
and proteomics. He is a lecturer of courses on physics of matter and introduction to nanotechnologies
with Politecnico di Torino.
vii
14. Micromachines 2021, 12, 254
graphene on the patterned seed layer guaranteed high quality of the resulting 2D material
and a 10 µm patterning resolution was demonstrated.
Volovlikova et al. [5] analyzed the effect of illumination intensity and p-dopant con-
centration on the dissolution properties of silicon for its photo-assisted etching with no
external bias or metals to produce porous silicon. A thorough characterization was per-
formed, providing valuable data for the control of porous silicon thickness and porosity.
Ruffino et al. [6] provided a valuable basic study on the growth and coalescence characteris-
tics of a nanoscale-thick bimetallic film of Au/Pd on a silicon carbide substrate. The kinetic
of the growth process was studied from the initial 3D clustering to the final continuous
rough thin film formation. Xiao et al. [7] performed a full comparison, with special atten-
tion to electrical resistivity and adhesion, between ink-jet-printed silver thin films based on
nanoparticle ink and metal–organic decomposition ink cured by two different approaches,
that is to say, UV exposure and heat-assisted approaches. Cao et al. [8] fabricated (through
a combination of lithography and nanoimprint technology) and characterized a flexible
3D display film element consisting of two integrated structures of a microimage array and
microlens array.
Finally, in their review article, Coluccio et al. [9] revised and critically described
nanoscale transport phenomena and biomedical applications of different emerging elec-
trochemical devices whose working principle relies on the interaction between ions and
conductive polymers.
Last, but not least, we would like to thank all the contributing authors and all the
involved reviewers for their precious contribution to the assembly and quality of this
Special Issue.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. Yang, Y.; Pan, R.; Tian, S.; Gu, C.; Li, J. Plasmonic Hybrids of MoS2 and 10-nm Nanogap Arrays for Photoluminescence
Enhancement. Micromachines 2020, 11, 1109. [CrossRef] [PubMed]
2. Zhang, J.; Hong, Q.; Zou, J.; He, Y.; Yuan, X.; Zhu, Z.; Qin, S. Fano-Resonance in Hybrid Metal-Graphene Metamaterial and Its
Application as Mid-Infrared Plasmonic Sensor. Micromachines 2020, 11, 268. [CrossRef] [PubMed]
3. Zhang, L.; Wei, X.; Wang, J.; Wu, Y.; An, D.; Xi, D. Experimental Study on the Lubrication and Cooling Effect of Graphene in Base
Oil for Si3N4/Si3N4 Sliding Pairs. Micromachines 2020, 11, 160. [CrossRef] [PubMed]
4. Verna, A.; Marasso, S.; Rivolo, P.; Parmeggiani, M.; Laurenti, M.; Cocuzza, M. Lift-Off Assisted Patterning of Few Layers
Graphene. Micromachines 2019, 10, 426. [CrossRef] [PubMed]
5. Volovlikova, O.; Gavrilov, S.; Lazarenko, P. Influence of Illumination on Porous Silicon Formed by Photo-Assisted Etching of
p-Type Si with a Different Doping Level. Micromachines 2020, 11, 199. [CrossRef] [PubMed]
6. Ruffino, F.; Censabella, M.; Piccitto, G.; Grimaldi, M. Morphology Evolution of Nanoscale-Thick Au/Pd Bimetallic Films on
Silicon Carbide Substrate. Micromachines 2020, 11, 410. [CrossRef] [PubMed]
7. Xiao, P.; Zhou, Y.; Gan, L.; Pan, Z.; Chen, J.; Luo, D.; Yao, R.; Chen, J.; Liang, H.; Ning, H. Study of Inkjet-Printed Silver Films
Based on Nanoparticles and Metal-Organic Decomposition Inks with Different Curing Methods. Micromachines 2020, 11, 677.
[CrossRef] [PubMed]
8. Cao, A.; Xue, L.; Pang, Y.; Liu, L.; Pang, H.; Shi, L.; Deng, Q. Design and Fabrication of Flexible Naked-Eye 3D Display Film
Element Based on Microstructure. Micromachines 2019, 10, 864. [CrossRef] [PubMed]
9. Coluccio, M.; Pullano, S.; Vismara, M.; Coppedè, N.; Perozziello, G.; Candeloro, P.; Gentile, F.; Malara, N. Emerging Designs of
Electronic Devices in Biomedicine. Micromachines 2020, 11, 123. [CrossRef] [PubMed]
2
15. micromachines
Article
Plasmonic Hybrids of MoS2 and 10-nm Nanogap
Arrays for Photoluminescence Enhancement
Yang Yang 1,† , Ruhao Pan 1,†, Shibing Tian 1, Changzhi Gu 1,2 and Junjie Li 1,2,3,*
1 Beijing National Laboratory for Condensed Matter Physics, Institute of Physics,
Chinese Academy of Sciences, P.O. Box 603, Beijing 100190, China; yang.yang@iphy.ac.cn (Y.Y.);
panruhao@iphy.ac.cn (R.P.); tianshibing@iphy.ac.cn (S.T.); czgu@iphy.ac.cn (C.G.)
2 School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
3 Songshan Lake Materials Laboratory, Dongguan 523808, China
* Correspondence: jjli@iphy.ac.cn
† These authors contributed equally to this work.
Received: 17 October 2020; Accepted: 10 December 2020; Published: 15 December 2020
Abstract: Monolayer MoS2 has attracted tremendous interest, in recent years, due to its novel physical
properties and applications in optoelectronic and photonic devices. However, the nature of the
atomic-thin thickness of monolayer MoS2 limits its optical absorption and emission, thereby hindering
its optoelectronic applications. Hybridizing MoS2 by plasmonic nanostructures is a critical route
to enhance its photoluminescence. In this work, the hybrid nanostructure has been proposed by
transferring the monolayer MoS2 onto the surface of 10-nm-wide gold nanogap arrays fabricated using
the shadow deposition method. By taking advantage of the localized surface plasmon resonance
arising in the nanogaps, a photoluminescence enhancement of ~20-fold was achieved through
adjusting the length of nanogaps. Our results demonstrate the feasibility of a giant photoluminescence
enhancement for this hybrid of MoS2/10-nm nanogap arrays, promising its further applications in
photodetectors, sensors, and emitters.
Keywords: monolayer MoS2; 10-nm nanogap; localized surface plasmon resonance; photoluminescence
1. Introduction
In the past ten years, two-dimensional (2D) transition metal dichalcogenides (TMDs) have
received plenty of research interest, due to their striking physical properties and applications in
optoelectronic devices [1,2]. Molybdenum disulphide (MoS2) is a representative member of the
TMDs family [3,4], in which the bandgap can transit from indirect to direct [5,6], when the thickness
is reduced to a monolayer. The bandgap shifts from 1.29 eV for the bulk MoS2 to 1.9 eV for the
monolayer MoS2, accompanied with an enhancement of the photoluminescence (PL) up to 104 [5].
Therefore, the direct-bandgap characteristic of the monolayer MoS2 leads to attractive applications
in phototransistors [7], photodetectors [8], light emitters [9], and photocatalysis [10]. However,
the thickness of 2D MoS2 is too thin to absorb sufficient light, which limits the light-harvest efficiency
and consequently restricts its practical applications. Therefore, efficiently enhancing the light absorption
and photoluminescence (PL) emission of MoS2 has become an important issue for exploring the practical
applications in optoelectronic devices. In recent years, integrating MoS2 with plasmonic nanoscale
metals has been demonstrated to be an effective route to promote the optical properties of MoS2 [11–13].
Plasmonic nanoscale metals, including noble metal nanoparticles and nanostructures, can strongly
enhance the electromagnetic (EM) fields of the excitation light, due to the localized surface plasmon
resonance (LSPR) on the surface of nanoscale metals [14–16]. Gao et al. have prepared the hybrids
of MoS2 and Ag nanoparticles, including shape-controlled cubes, octahedra, and spherical particles,
3
16. Micromachines 2020, 11, 1109
and systematically studied the influences of the morphology of nanoparticles on the PL emission of
MoS2 [17]. Compared with nanoparticles, nanostructures fabricated using advanced nanofabrication
techniques exhibit higher controllability, reproducibility, and large-scale periodicity [18]. By modulating
the diameter of nanodiscs, the 12-times PL enhancement was achieved in the hybrids of nanodisc arrays
and monolayer MoS2 [19]. Among the various species of nanostructures, nanogaps have exhibited
a prominent PL enhancement due to the EM field and the strong LSPR effect in the nanogap zone.
The EM field intensity is strengthened as the nanogap size decreases, especially when the width of
nanogaps is smaller than 10 nm [20,21]. Wang et al. reported a giant PL enhancement up to 20,000-fold
for the hybrid of WSe2 on 12-nm nanotrenches [22]. In 2018, Cai et al. proposed a hybrid of MoSe2 on
large area ultranarrow annular nanogap arrays (ANAs), which were fabricated using atomic layer
deposition and polystyrene spheres lithography techniques [23]. Nanofabrication techniques, such as
E-beam lithography (EBL) and focused ion beam (FIB) milling have been explored to directly fabricate
10-nm nanogap arrays [24–26]. However, the fabrication processes based on these techniques are
relatively complex, due to fact that the small size of the nanogap is close to the limitation of resolution.
In 2018, Hao et al. proposed a hybrid of MoS2 and patterned plasmonic dimers fabricated by a facile
approach utilizing porous anodic aluminium oxide (AAO) templates during the angle-resolved shadow
deposition [27]. The shadow deposition method, which is based on the inclined deposition of materials
on the prefabricated pattern, has been demonstrated as a feasible way to fabricate 10-nm nanogap
arrays over a large area [28,29]. However, the MoS2 hybrids based on 10-nm nanogap arrays fabricated
by the shadow deposition method is still rarely reported.
In this work, a type of plasmonic hybrid composed of 10-nm Au nanogap arrays and monolayer
MoS2 was proposed for PL enhancement. The 10-nm Au nanogap arrays were fabricated using
the shadow deposition method, which was composed by depositing nanostrips with a 20 degree
inclining angle on the nanostrips previously fabricated. By adjusting the length of nanogaps, the PL
enhancement can be significantly boosted up to ~20-fold for the MoS2/nanogaps hybrid formed with
240-nm-length nanogaps under the excitation of a 532-nm laser. Combined with the finite-different
time-domain (FDTD) simulation, the mechanism behind the PL enhancement was analyzed. Our results
provide a feasible method to prepare large area MoS2-nanostructure plasmonic hybrids with a giant
photoluminescence enhancement, promising their further applications in photodetectors, sensors,
and emitters.
2. Materials and Methods
The monolayer MoS2 used in this work was fabricated on a single-crystalline sapphire substrate
using the chemical vapor deposition (CVD) method [30]. The 10-nm nanogap arrays were fabricated
using the shadow deposition method, a combination of EBL and electron beam deposition (EBD)
techniques. Figure 1 illustrates the fabrication processes for the hybrid of MoS2 and nanogap arrays,
which mainly include six steps. First, as presented in Figure 1a, a polymethyl methacrylate (PMMA)
495 A5 layer with a 200-nm thickness was spin coated onto the Si substrate, and the film was pre-baked
on a hot plate at 180 ◦C for 60 s. Then, the EBL was used to write the patterns of nanostrips along the
y-axis. Third, metallic nanostrips can be transferred by EBD on a 60-nm Au film and followed lift-off
processes. After that, the nanostrips with a 60-nm-height were observed, as presented in Figure 1d.
Fourth, the nanostrips along the x-axis were written by the alignment lithography, as illustrated in
Figure 1e. Then, the shadow deposition of Au with a 20 degree inclining angle was applied to the Au
strips formed in step 3, the thickness of Au was also 60-nm in the shadow deposition process, as shown
in Figure 1f. Since the shadow origins from the deposition angle and steps, 10-nm nanogaps can be
obtained, as illustrated in Figure 1g. Finally, the MoS2 was transferred on top of the nanogap arrays,
forming a plasmonic MoS2/nanogaps hybrid, as shown in Figure 1h. The MoS2 flake was removed
from the substrate to Au nanogap arrays using a PMMA-assisted wet transfer procedure, which has
been applied to transfer 2D materials [22,31]. In order to investigate the plasmonic enhancement effect
of the Au nanogaps on the PL emission of MoS2, another type of MoS2-nanogaps hybrid, in which
4
17. Micromachines 2020, 11, 1109
the nanogap arrays were fabricated directly on the CVD-grown MoS2 on the sapphire substrate
(nanogaps/MoS2) was fabricated for comparison.
Figure 1. Schematic fabrication procedures of the MoS2/Au nanogap hybrid. (a) Substrate coated
with polymethyl methacrylate (PMMA). (b) Nanotranches formed after the first E-beam lithography
(EBL) process. (c) First Au deposition process. (d) Au nanostrips obtained after lift-off process.
(e) Nanotrenches formed after the second EBL process. (f) The second Au shadow deposition process.
(g) Nanogaps obtained by crossover of nanostrips. (h) Hybrid structure formed after MoS2 transferred.
An enlarged view of the nanogap obtained was illustrated in the middle.
The morphology and dimensions of the fabricated Au nanogaps are detected using a scanning
electron microscope (SEM). Figure 2a presents the SEM images of the fabricated 10-nm Au nanogap
arrays with a periodicity of 1 µm. It can clearly be seen that the nanogaps formed on the right
side on each cubic island. Since the nanogaps were formed as a result of the shadow of first-layer
nanostrips, the width of the nanogap obviously depended on the inclining angle for the deposition
of the second-layer nanostrips. As exhibited in Figure 2b, the gap width widens with increasing
the inclined deposition angle. The 10-nm nanogaps have been successfully fabricated by fixing the
inclining angle at 20 degrees, as shown in Figure 2c. The length of this nanogap was determined
as ~240 nm, since the line-width of the nanostrips was set at 240 nm. Therefore, the length of the
nanogaps can be feasibly modulated by adjusting their line-width. Figure 2d shows the SEM image of
the monolayer MoS2 transferred onto the nanogap arrays. It can be seen that the nanogap arrays are
fully covered with the MoS2 monolayer.
Photoluminescence (PL) and Raman measurements were carried on a micro-confocal Raman
spectrometer (Horiba HR Evolution) equipped with a microscope (BX41, Olympus, Tokyo, Japan).
A 100 × (NA = 0.9) objective lens was used for focusing the laser on the sample surface and collecting
the PL signal. The 532-nm laser was used as the excitation sources for PL measurements and the
laser power on the sample was about 0.5 mW in order to prevent the overheating effect. The spectra
acquisition time was 30 and 10 s for Raman and PL acquisition, respectively. Figure 3a exhibits the
schematic setup of the PL measurements on the MoS2/nanogap hybrids. As illustrated in Figure 3a,
the laser beam was a normal incident on the sample surface, and the polarization direction of the
5
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