Materials & Design 227 (2023) 111743

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Materials & Design

journal homepage: www.elsevier.com/locate/matdes

Joint process of laser shock polishing and imprinting for metallic

nanostructure fabrication
Baocai Zhang a, Haifeng Yang b,⇑, Chengfeng Pan a, Peng Zhao a,⇑
a
The State Key Laboratory of Fluid Power and Mechatronic Systems, Zhejiang University, Zhejiang 310027, China
b
School of Mechatronic Engineering, China University of Mining and Technology, Xuzhou 221116, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Joint process of laser shock polishing

& imprinting (LSPI) can efficiently
fabricate nanostructures without any
pre-process.

LSPI liberates the limitation of raw
material without the lubricant layer,
greatly improving efficiency and
reducing cost.

LSP and LSI techniques are similar in
principle, thus can be performed with
the same set of equipment.

The nanostructures fabricated by LSPI
have higher forming accuracy,
integrity and uniformity compared to
LSI technique.

a r t i c l e i n f o a b s t r a c t

Article history: Most fabrication methods of metallic nanostructures are time-consuming with multi-steps, which are
Received 26 November 2022 difficult to achieve low-cost batch processing. In this study, joint laser process of laser shock polishing
Revised 8 February 2023 & imprinting (LSPI) is proposed to efficiently fabricate large-area nanostructures on the surface of cheap
Accepted 11 February 2023
industrial aluminum foil without any pre-processing step. LSPI tailors the laser parameters of single laser
Available online 18 February 2023
manufacturing equipment to apply laser shock polishing (LSP) to polish the aluminum foil, and then laser
shock imprinting (LSI) to obtain nanostructures with high accuracy, integrity and uniformity. This unique
Keywords:
characteristic of proposed LSPI is enabled by pre-taking LSP process to improve the yield of following LSI
Nanostructures
Laser shock polishing
process through significantly decreasing the surface roughness of aluminum foil. LSPI also reduces the
Laser shock imprinting aluminum residue inside the silicon mold, which improves the integrity of resultant nanostructure and
Metal foil facilitates the reuse of the mold. The working mechanism of LSPI are also investigated to reveal its fun-
Demolding damental fabrication principle, which may inspire other low-cost and efficient batch fabrication method
for metallic nanostructures manufacturing in the future.
Ó 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

With the continuous expansion of the consumer electronics

Abbreviations: LSPI, laser shock polishing & imprinting; LSP, laser shock market, miniaturization of electronic products has become an
polishing; LSI, laser shock imprinting. important trend [1–3]. Along with the size decreasing and demand
⇑ Corresponding authors. increasing of electronic devices, fabricating techniques with high
E-mail addresses: 4841@cumt.edu.cn (H. Yang), pengzhao@zju.edu.cn (P. Zhao).

https://doi.org/10.1016/j.matdes.2023.111743
0264-1275/Ó 2023 The Author(s). Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
B. Zhang, H. Yang, C. Pan et al.
accuracy and efficiency are required to make components with
micro/nano structures. The common fabrication method of micro/-
nano structures (e.g. chip structures) is photolithography [4]. How-
ever, current photolithography techniques suffer from high
manufacturing cost, low efficiency, and long processing cycles,
which make them not suitable for batch processing [5–7]. Alterna-
tive to photolithography, researchers are putting efforts to develop
micro/nano structure manufacturing technologies to overcome
these limitations. The common alternative techniques are micro-
injection molding, micro-extrusion, 3D printing, laser etching,
nanoimprinting, etc [2,8–16]. Micro-injection molding and micro-
extrusion utilize the thermosetting property of polymer to fabri-
cate micro/nano structures. However, the heating and cooling pro-
cess of polymer may introduce defects such as residual stress
which may cause warping in the molding structure. The micro-
injection molding is not able to fabricate metal micro/nano struc-
tures. Although, micro-extrusion technique is capable of fabricat-
ing both polymers and metals, the minimum feature of
fabricated structures is generally large and therefore not suitable
for the preparation of nanostructures [8–10]. 3D printing tech-
niques use powdered metals, thermal plastics and even biological
cells to construct designed structures by layer-by-layer printing.
However, 3D printing techniques also share similar limitation of
low printing accuracy. The widely use of 3D printing technique
for the batch fabrication of micro/nanoscale structures is also limit
by its relatively low fabrication speed and expensive equipment
[11]. The principle of laser etching is to focus the laser beam on
the material surface and use the aggressive interaction between
the high-power light and the target material to ablate and vaporize
the material at radiating spots to obtain micro/nano structures.
Although laser etching has high yield and good stability the fabri-
cation efficiency is relatively low due to the gradual etching pro-
cess of laser [3,12,13].
Nanoimprinting is an economical and reliable method for batch
production of micro/nano structures, which has been widely used
in microelectronics, sensors, precision optics and aerospace [14–
16]. However, the mainstream nanoimprinting techniques are
mainly indirect nanoimprinting (i.e. nanoimprint lithography),
which firstly imprint on resist to create specific nanostructures,
and then integrate through a series of etching as well as epitaxial
growth processes. The fabrication process requires multiple steps,
which also greatly reduces the production efficiency and prolongs
the production cycle. Although nanoimprint lithography can fabri-
cate nanometer-scale patterns using polymers [15,16], and metal-
lic glasses [17], the direct nanoimprinting of crystalline metals is
still infeasible [18]. At present, the fabrication of metallic nanos-
tructures mostly depends on time-consuming, multi-step methods
[19–22].
In this regard, Gary et al. [18] presented a new method of laser
shock imprinting (LSI), which can direct nano-shape metallic
sheets and produce smooth 3D nanostructures with high through-
put under ambient condition. However, this method requires that
the used imprinted metal sheet has excellent surface condition,
i.e., the surface roughness (Sa, see Appendix A – Text. A1 for the
reason of using Sa to indicate roughness) of metal foil should be
low enough to avoid non-uniformity of the imprinted nanostruc-
tures and potential damage to the silicon mold due to its irregular
surface bugles. The metal foil used for LSI also requires metal
sheets deposited with an additional ultra-thin dry lubricant, such
as thin gold film, to reduce friction during LSI processing to
improve the resolution of fabrication. Otherwise, the high friction
between the mold and the metal sheet would significantly affect
the formability of the nanostructure and also damage the silicon
mold. This pre-process of metal sheets greatly increases the cost
and thus limits the boarder use of LSI technique as an emerging
high-efficiency nanostructure fabrication technique.
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Materials & Design 227 (2023) 111743
To address the current limitations of LSI technique and achieve
low-cost batch production of metallic nanostructures, a batch pro-
cessable fabrication method of joint laser process of laser shock
polishing & imprinting (LSPI) is proposed to reduce the cost and
increase the efficiency of LSI technique without sacrificing the fab-
ricating accuracy. The key point of LSPI is to replace the costly
metal foil with a low-cost industrial metal foil by applying laser
shocking polishing (LSP) to polish the surface before laser shock
imprinting (LSI) to obtain the nanostructure. Therefore, LSPI can
also liberate the limitation of the raw material of metal foil without
the requirement of dry lubricant layer, which greatly reduces the
fabrication costs. Moreover, LSP and LSI techniques are similar in
principle, thus can be performed with the same set of laser manu-
facturing equipment.
Systematic study has been conducted to reveal the effect of LSP
treatment on LSI, including the improvement of accuracy, integrity
and uniformity of the imprinted nanostructures, and the reduction
of silicon mold damage. This study provides a new method for low-
cost and high-efficiency batch manufacturing of metallic nanos-
tructures, which may inspire other laser-based batch fabrication
methods for metal nanostructures manufacturing in the future.
2. Experimental section
2.1. Fabrication principle
As shown in Fig. 1, similar fabrication principles of LSP and LSI
leads to that these two processes can be conducted with same laser
manufacturing equipment. LSP and LSI are cost-effective metal
forming techniques enabled by plastic deformation of thin metallic
sheet with ultra-high strain rate, which is induced by the high-
pressure and high-density plasma generated by laser-induced
shock wave peak pressure. The difference between LSP and LSI is
that LSI requires a silicon mold with female nanostructures,
whereas for LSP the mold is replaced by an ultra-smooth glass sub-
strate. A glass substrate with ultra-smooth surface (K9 glass with a
Sa of 3.1 nm, see Appendix A – Fig. A1) is used for LSP process in
this work. The silicon mold in LSI is reusable and thus cost-
effective, though it is fabricated by photolithography. As the sche-
matic of fabrication mechanism of LSP and LSI shown in Fig. 1, the
pulsed laser beam passes through the confinement layer and
focuses on the surface of ablation layer, which is gasifies into a
high-density plasma (1017 –1019 cm3) due to the rapid absorption
of the laser energy and the formation of plasma plume during the
ionization process [23]. The confinement layer constrains the high-
speed diffusion of the plasma plume, which produces an ultrashort
continuous shock wave [24]. According to the Fabbro’s model [25],
the peak pressure induced by the laser shock can reach several
gigapascals (see Appendix A – Text. A2 for a detailed calculation),
this extremely high shock pressure far exceeds the dynamic yield
strength of the metal foil, and can induce plastic deformation (plas-
tic flow) with the strain rate on the order of 106 –107 s1 [18]. For
LSP process shown in Fig. 1a, since the aluminum foil is placed on
the upper surface of an ultra-smooth glass substrate, the down-
ward plastic deformation is constrained by the rigid substrate,
which induces the extrusion collision between the metal foil and
the glass substrate. Due to the ultra-smooth constrain layer, colli-
sion directly deforms the micro-bugles on the foil surface (the root
cause of Sa) plastically, thus achieving the polishing effect. As
shown in Fig. 1c. the polished foil surface exhibit ultra-smooth
and mirror-like finish which reflects the ballpoint pen tip super
clearly, and even clearly reflecting the carbon ink of the tip. The
LSP process is not the traditional ‘‘polishing” using abrasives, but
‘‘polishing” using deformation. The ‘‘polishing” is named according
to the result of roughness reduction. For the following process of
B. Zhang, H. Yang, C. Pan et al.
Fig. 1. Fabrication principle of laser shock polishing & imprinting (LSPI) method: (a) fabrication principle of LSP; (a1) schematic diagram of the lower surface of the ultra-
smooth metal foil after LSP. (b) fabrication principle of LSI; (b1) schematic diagram of the smooth nanostructure after LSI. (c1) lower surface of the aluminum foil after LSP, in
which the polished area is in the square frame, and the original area is outside the square frame [26]; (c2) lower surface of the aluminum foil after LSP.
process shown in Fig. 1b, the extrusion collision is constrained by
the silicon mold, in which the nanostructure walls of the mold
act as ‘‘energy guides”, which directs the concentrated laser shock
wave energy to the base of the mold (bottom of the nanostructure).
Since the strength of silicon mold is much higher than the metal
foil, part of foil is punched into nano-holes of the mold as plastic
flow, which results in a nanostructure on the surface of the metal
foil corresponding to the mold, as shown in Fig. 1(b1). In Fabbro’s
model, the peak pressure generated by laser shock on different
metals far exceeds its dynamic yield strength, resulting in ultra-
high strain rate plastic deformation [18,23–26]. Therefore, LSPI is
also suitable for other types of metal foil. LSPI technique makes
it possible to directly fabricate ultra-smooth metal foil surfaces
with surface roughness as small as 10 nm in batch first, which
can reduce friction for the following LSI process.
2.2. Materials and equipment
The metal layer used in this work is industrial aluminum foil
with thickness of 20 lm (see Appendix A – Table. A1 for detailed
element composition). Prior to the LSPI process, foils need to be
annealed at 473 K for 1 h to eliminate the original defects in the
foils. The silicon mold with nano-holes pattern is fabricated by
conventional photolithography. The mold has a thickness of
2 mm and a length and width of 15 mm, and the scanning electron
microscope (SEM) photograph of the surface of this mold is shown
in Fig. 2.
As shown in Fig. 2, the surface of silicon mold is smooth without
detectable crack and defect. The mold contains periodical circular
nano-holes pattern with hole diameter of 700 nm and hole-hole
distance of 1400 nm. Fig. 3 shows the morphology of silicon mold
characterized by atomic force microscopy (AFM). The consistent
morphological profiles of different nanostructure sections further
demonstrate the perfect periodical nano-circular holes and show
great uniformity in the depth of nano-holes (Fig. 3b).
Laser shock damage tests were conducted to determine the
suitable laser parameters by measuring the damage threshold for
LSI process. The overlap rate was set as 50 % (see Appendix A –
Fig. A2 for the reason) and laser pulse energies were selected based
on ‘‘bisection method”. The comparison experiments of LSPI and
LSI were then performed with these parameters to investigate
the effect of LSP pre-process on the quality of resultant nanostruc-
tures of LSPI including forming accuracy, forming height and distri-
bution uniformity of the imprinted nanostructure, the surface state
3
Materials & Design 227 (2023) 111743
and structural integrity of the silicon mold, and the surface ele-
ment distribution of the silicon mold (to determine the fracture
and residue of the nanostructures).
LSPI contains two fabrication processes of LSP and LSI, which
can be conducted by same set of laser manufacturing equipment
due to the similar fabrication principle. A laser manufacturing plat-
form was developed, which can perform controllable adjustment of
laser parameters in a wide range, and can adjust the relative posi-
tion between the sample and laser focus. Fig. 4 shows the compo-
sition of this platform, including a pulse laser generator, a
computer control center, a laser attenuation module, a motion con-
troller, a focusing lenses, a reflector, and a heating table. The high-
energy laser pulse is output by the laser generator (Hercules 1000-
TH) with the parameters of 1 Hz pulse frequency and 7 ns pulse
width. The spot size of focused laser beam is set as 0.6 mm and
1.2 mm for LSP and LSI, respectively, which are controlled by the
defocus, i.e., the distance between the laser focus plane and the
upper surface of the metal foil. The detailed fabrication parameters
can be found in Appendix A – Table. A2.
K9 glass with a thickness of 2 mm was selected for the confine-
ment layer due to its high resistance to laser damage and high
transmittance to laser light (transmittance > 99 %). The ablation
layer is the sacrifice material that is used to generate the laser
shock wave under laser ablation and protect the surface of target
metal layer from high-power laser ablation. The thickness of abla-
tion layer needs to be selected carefully to avoid the poor protec-
tion when the ablation layer is too thin, or poor transmission
efficiency of laser shock wave when the ablation layer is too thick.
In this work, aluminum foil with a thickness of 100 lm was
selected as the ablation layer. In addition, a clamping device was
used to ensure the tight fit of the confinement layer, the ablation
layer, the metal layer and the substrate (or mold). The clamping
force in these experiments was set as constant to generate the
clamping pressure of less than 1 MPa, which is negligible com-
pared to the peak laser shock wave pressure and the yield strength
of the aluminum foil during LSP and LSI process.
3. Results and discussion
3.1. Laser shock damage test
Due to the high manufacturing cost of silicon mold, laser shock
damage tests were conducted by using ‘‘bisection method”, and the
damage threshold under laser shock can be determined with the
B. Zhang, H. Yang, C. Pan et al. Materials & Design 227 (2023) 111743

Fig. 2. Silicon mold and their surface nanostructures (a) silicon mold. (b), (c) and (d) micro morphologies of silicon mold obtained by FSEM under the magnification of 10000,
40,000 and 60000, respectively.

Fig. 3. Silicon mold: (a) surface nanostructures of the silicon mold. (b) section profiles of their nanostructures.

minimum number of experiments. The range of laser pulse energy energy range were ordered, and the laser shock damage tests were
was set as 10–1000 mJ with the energy interval of 10 mJ for each started from the minimum and the maximum pulse energy. The
p
group. As shown in Fig. 5, the laser pulse energies within the status of silicon mold is recorded and marked as and  to indi-

4
B. Zhang, H. Yang, C. Pan et al.
Fig. 4. Experimental platform of laser shock processing (LSP and LSI).
Fig. 5. Bisection method for laser shock damage test.
cate whether the mold is damaged after the laser shock damage
tests. If the silicon mold was damaged, the median value of laser
energy was taken to continue the damage tests until no damage
was found on the silicon mold.
Fig. 6 shows the SEM images of surface morphology of the sili-
con mold after laser shock damage tests. As shown in Fig. 6a, the
laser shock leaves no trace and damage on the mold when the
pulse energy is 10 mJ. However, the silicon mold is not only dam-
aged but also broken into several pieces when pulse energy is
1000 mJ, (Fig. 6f). Referring to Fig. 5 and Fig. 6, it can be found that
the silicon mold is damaged and has clusters of aluminum residues
when the laser energy is higher than 100 mJ, which can be consid-
ered as the damage threshold for the input laser energy. The corre-
sponding damage threshold of laser shock pressure is 1.82 GPa and
the laser power density is 0.45 GW cm2 (see Appendix A – Text.
A3 for the detailed calculation).
3.2. Influence of LSP-treatment on LSPI
A laser energy of 100 mJ and the overlap rate of 50 % were used
to conduct LSI and LSPI experiments to investigate the effect of LSP
treatment on the LSPI results. As the SEM image shown in Fig. 7a,
the aluminum foil without LSP pre-process exhibits rough surface
with multiple micro bulges. This poor surface smoothness results
in the resultant nanostructures by LSI with poor forming accuracy
5
Materials & Design 227 (2023) 111743
including shallow forming height, uneven size, fuzzy edges, irreg-
ular shapes, and even failure of formation at some spots (Fig. 7b
and c). In contrast, LSP treatment of LSPI significantly reduces the
surface roughness of aluminum foil (Fig. 7d), resulting in the resul-
tant nanostructures obtained by LSPI having better forming accu-
racy including accurate forming height, clear edges, good
straightness, and good integrity (Fig. 7e and f). This comparison
reveals the important role of LSP and demonstrate the capability
of proposed LSPI method to accomplish large-area metallic nanos-
tructures imprinting with high fabrication accuracy and uniformity
by using cheap industrial aluminum foil. Small irregular protrusion
with the size ranging from 20 to 300 nm on the surface of the
nanostructures can be found on the resultant workpiece fabricated
by either LSI or LSPI due to post-imprinting demolding process
(separation of the foil from the silicon mold).
3.3. Influence of LSP-treatment on demolding process
In conventional nanoimprinting processes, the demolding pro-
cess of the imprinted nanostructures from the silicon mold deter-
mines the final quality of imprinted workpiece and the lifetime of
the mold [27,28]. Thus, any deformation or damage of the nanos-
tructures during demolding should be avoided for quality control
especially for the large-area nanoimprinting. The LSI process will
induce the adhesion between the imprinted structure and the
B. Zhang, H. Yang, C. Pan et al. Materials & Design 227 (2023) 111743

Fig. 6. Results of laser shock damage test with the pulse laser energy of (a) 10 mJ (b) 100 mJ (c) 130 mJ (d) 250 mJ (e) 500 mJ (f) 1000 mJ.

Fig. 7. Surface of aluminum foil (a) original aluminum foil. (b,c) nanostructures of original aluminum foil surface after imprinting. (d) LSP-treated aluminum foil. (e, f)
nanostructures of LSP-treated aluminum foil surface after imprinting.

female mold pattern, which may cause the damage of imprinted
structure and leave fractured residues inside the nano-holes after
demolding process. A flawless demolding process is one of the
main challenges that restricts the large-scale (wafer size) imple-
mentation of nanoimprinting technique and the manufacturing
of high aspect ratio structures [29,30].
In this study, the proposed LSPI applies LSP-treatment to polish
the original material of industrial aluminum foil before manufac-
turing nanostructures. This joint laser fabrication method reduces
the damage of nanostructure during demolding to some extent.
In the current research on conventional nanoimprinting process,
some scholars have gained experiences by using different demold-
ing methods or adding lubricants to reduce the impact of demold-
ing [14,16,31–33]. However, studys on the treatment of original
materials to reduce the impact of demolding on nanostructures
are scarce. The peel-off demolding method was used in this work

6
B. Zhang, H. Yang, C. Pan et al.
to investigate the effect of LSP treatment on the demolding process
for LSPI method [14,31,34].
Fig. 8 shows the SEM images of the silicon molds after LSI pro-
cessing the industrial aluminum foil and the LSP-treated aluminum
foil, respectively. The results show that almost all nano-holes have
residues of irregular nanoparticles (with length and width in the
range of 250–500 nm) after LSI processing the untreated aluminum
foil. The composition of residue inside nano-holes are aluminum
was measured by the EDS surface scanning as shown in Fig. 9a.
The EDS results in Fig. 9a also show concentrated aluminum ele-
ment distributing inside the nano-holes of the mold with an ele-
ment content of 7.33 %, indicating the fracture of nanostructures
and poor demolding process for LSI processing the untreated alu-
minum foil. It is due to that the surface of the original aluminum
foil is rough (as shown in Fig. 7a and Appendix A – Fig. A3a, b
and c), which results in a larger friction between the side walls
of the aluminum nanostructure and the inner walls of the nano-
holes of the mold. This appreciable frictional force induces the frac-
ture of imprinted nanostructures and leave aluminum residues
inside the nano-holes of the silicon mold, which reduces the fabri-
cation quality of the nanostructure and also affects the reuse of the
silicon mold.
The SEM images of the silicon mold after LSPI process are shown
in Fig. 8c and d. The edges of the nano-hole structure are well
defined with limited aluminum residues at the edges. As the EDS
Fig. 8. Surface morphology of silicon molds after demolding (a, b) original aluminum foil demolded after LSI. (c, d) LSP-treated aluminum foil demolded after LSI. (x, y) test
locations for EDS surface scanning.
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Materials & Design 227 (2023) 111743
scanning results shown in Fig. 9b, the nano-holes of the silicon
mold have sparse distribution of aluminum element inside with
content of 2.76 %, which is significantly less than the residue con-
tent after the unpolished aluminum foil directly fabricated by LSI.
This is because the LSP-treatment reduces the surface roughness of
the aluminum foil (Fig. 7d), which significantly reduce the friction
between the side walls of the imprinted aluminum nanostructures
and the inner walls of nano-holes of the silicon mold. LSP-
treatment also improves the fracture strength of aluminum foil
as the results presented in our previous work [26]. As a result,
the imprinted nanostructures are less likely to be fractured during
the demolding process. Compared to LSI processing the industrial
aluminum foil, LSPI method can fabricate high-quality metallic
nanostructure, and facilitate the reuse of the silicon mold and its
service life.
4. Conclusion
In this study, the joint laser fabrication method of laser shock
polishing & imprinting (LSPI) is proposed to combine LSP with
LSI techniques to manufacture metallic nanostructures from low-
cost industrial aluminum foil. The key point of LSPI is applying
LSP-treatment to polish the aluminum foil before LSI process by
using the same set of laser manufacturing equipment. The
improvement effect of LSP treatment on LSI and demolding process
B. Zhang, H. Yang, C. Pan et al.
Fig. 9. EDS surface scanning results of silicon nanomold after demolding (a) original aluminium foil demolded after LSI. (b) LSP-treated aluminium foil demolded after LSI.
are systematically investigated by revealing the working mecha-
nism of LSP treatment to improve the forming accuracy, integrity,
and uniformity of imprinted nanostructures and reduce the
demolding damage after imprinting. The main conclusions are as
follows:
a. LSPI technique allows cost-effective batch fabrication of
large-area nanostructures on cheap industrial aluminum foil
surface. LSI technique has strict requirements on the metal
foil used for imprinting, and its surface should be extremely
smooth, which greatly increases the cost and limits the
development of LSI for high-efficiency nanostructure fabri-
cation. LSP used in this work reduces the surface roughness
of industrial aluminum foil from 148 nm to 3.7 nm with a
polishing rate of 97.5 %, which completely enables industrial
aluminum foil to meet the LSI process requirements for the
target material, freeing up the limitations of the original
material and eliminating the need to add additional lubri-
cants. In addition, LSP and LSI are similar in fabrication prin-
ciple and share the same manufacturing equipment, which
greatly improves efficiency at the same time of cost
reduction.
b. The ‘‘bisection method” determines the damage threshold of
the mold under laser shock with a minimum number of
experiments. The damage threshold of silicon mold is the
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Materials & Design 227 (2023) 111743
shock wave energy generated by the laser energy of
100 mJ (1.82 GPa). When the laser energy exceeds 100 mJ,
the LSI will cause damage to silicon mold.
c. The nanostructures fabricated by LSPI technique have higher
forming accuracy, integrity, and uniformity compared to LSI
technique. The LSI effect of the original aluminum foil is poor
and almost unsuccessful. In contrast, LSPI can accomplish an
exact replication of the nanostructures, and the large-area
imprinting results of its nanostructures also have high accu-
racy and uniformity. The uniform size of the nanostructure
features indicates that LSI of LSP-treated aluminum foils is
a controllable process.
d. By reducing the roughness of aluminum foil and increasing
its mechanical properties, the LSP treatment reduces the
damage to the nanostructure during the demolding process
after LSI and significantly reduces the residual aluminum
inside the nanostructure of the mold, which not only pre-
serves the integrity of the nanostructure but also facilitates
the reuse of the silicon mold. A relatively concentrated Al
element is distributed inside the nano-hole of the demolded
mold after LSI, with an element content of 7.33 %. This is
mainly the nanoparticles that fractured from the imprinted
nanostructures during the demolding process. The nano-
holes of the silicon mold after the LSI of the LSP-treated alu-
minum foil and then demolded have a sparse distribution of
B. Zhang, H. Yang, C. Pan et al.
Al elements inside, with an elemental content of 2.76 %,
which is significantly less than that remaining inside the
nano-holes of the silicon mold demolded after the original
foil LSI. This is mainly because only minimal damage is gen-
erated in the nanostructures obtained by LSI of LSP-treated
aluminum foil during the demolding process.
This study provides a new idea for low-cost and high-efficiency
batch manufacturing of metal nanostructures, and to a certain
extent, contributes a certain basis for proposing other ideas or
new technologies and understanding its manufacturing mecha-
nism in the future.
Data availability statement
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
CRediT authorship contribution statement
Baocai Zhang: Conceptualization, Methodology, Software, Vali-
dation, Investigation, Writing – original draft, Writing – review &
editing. Haifeng Yang: Methodology, Investigation, Funding acqui-
sition, Writing – review & editing. Chengfeng Pan: Methodology,
Writing – review & editing. Peng Zhao: Funding acquisition, Pro-
ject administration, Supervision, Writing – review & editing.
Data availability
Data will be made available on request.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors would like to acknowledge the financial support
received from the National Natural Science Foundation Council of
China (Nos. 51875519 and 52275224), the ‘‘Pioneer” and ‘‘Leading
Goose” R&D Program of Zhejiang Province (No. 2022C01069), and
the Key Project of Science and Technology Innovation 2025 of
Ningbo City (No. 2021Z044).
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.matdes.2023.111743.
References
[1] G. Wu, X. Wu, X. Zhu, et al., Two-dimensional hybrid nanosheet-based
supercapacitors: From building block architecture, fiber assembly, and fabric
construction to wearable applications, ACS Nano 16 (7) (2022) 10130–10155,
https://doi.org/10.1021/acsnano.2c02841.
[2] R.N. Widmer, D. Bischof, J. Jurczyk, et al., Smooth or not: Robust fused silica
micro-components by femtosecond-laser-assisted etching, Mater. Des. 204
(2021), https://doi.org/10.1016/j.matdes.2021.109670 109670.
[3] J. Ko, R. Berger, H. Lee, et al., Electronic effects of nano-confinement in
functional organic and inorganic materials for optoelectronics, Chem. Soc. Rev.
50 (5) (2021) 3585–3628, https://doi.org/10.1039/D0CS01501F.
[4] L.F. Thompson, An Introduction to Lithography, Introduction to
Microlithography, ACS Publications, Washington, 1983, pp. 1-13.
[5] H.J. Levinson, Principles of lithography, Second ed., SPIE press, Washington,
2005.
[6] T. Ito, S. Okazaki, Pushing the limits of lithography, Nature 406 (6799) (2000)
1027–1031, https://doi.org/10.1038/nphoton.2009.251.
Materials & Design 227 (2023) 111743
[7] H. Quentin, P. Eddy, C.E. Sylvie, et al., Rational design of SiBCN microstructures
using direct photolithography of patternable preceramic photoresists, Mater.
Des. 223 (2022) 11234, https://doi.org/10.1016/j.matdes.2022.111234.
[8] B. Sha, S. Dimov, C. Griffiths, et al., Investigation of micro-injection moulding:
Factors affecting the replication quality, J. Mater. Process. Technol. 183 (2–3)
(2007) 284–296, https://doi.org/10.1016/j.jmatprotec.2006.10.019.
[9] T. Nathan-Walleser, I.M. Lazar, M. Fabritius, et al., 3D micro-extrusion of
graphene-based active electrodes: towards high-rate AC line filtering
performance electrochemical capacitors, Adv. Funct. Mater. 24 (29) (2014)
4706-4716. 10.1002/ad fm.201304151.
[10] W.L. Chan, M. Fu, B. Yang, Study of size effect in micro-extrusion process of
pure copper, Mater. Des. 32 (7) (2011) 3772–3782, https://doi.org/10.1016/
j.matdes. 2011.03.045.
[11] A. Ambrosi, M. Pumera, 3D-printing technologies for electrochemical
applications, Chem. Soc. Rev. 45 (10) (2016) 2740–2755, https://doi.org/
10.1039/C5CS00714C.
[12] X. Li, R. Li, Z. Yu, et al., Deepening of nanograting structures on Si by a two-step
laser spatial-selective amorphization strategy combined with chemical
etching, Appl. Surf. Sci. 589 (2022), https://doi.org/10.1016/j.
apsusc.2022.152965 152965.
[13] B. Oktem, I. Pavlov, S. Ilday, et al., Nonlinear laser lithography for indefinitely
large-area nanostructuring with femtosecond pulses, Nat. Photonics 7 (11)
(2013) 897–901, https://doi.org/10.1038/nphoton.2013.272.
[14] M.A. Meitl, Z.T. Zhu, V. Kumar, et al., Transfer printing by kinetic control of
adhesion to an elastomeric stamp, Nat. Mater. 5 (1) (2006) 33–38, https://doi.
org/10.1038/nmat1532.
[15] S.Y. Chou, P.R. Krauss, P.J. Renstrom, Imprint lithography with 25-nanometer
resolution, Science 272 (5258) (1996) 85–87, https://doi.org/10.1126/science.
272.5258.85.
[16] L.J. Guo, Nanoimprint lithography: methods and material requirements, Adv.
Mater. 19 (4) (2007) 495–513, https://doi.org/10.1002/adma.200600882.
[17] G. Kumar, H.X. Tang, J. Schroers, Nanomoulding with amorphous metals,
Nature 457 (7231) (2009) 868–872, https://doi.org/10.1038/nature07718.
[18] H. Gao, Y. Hu, Y. Xuan, et al., Large-scale nanoshaping of ultrasmooth 3D
crystalline metallic structures, Science 346 (6215) (2014) 1352–1356, https://
doi.org/10.1126/science.1260139.
[19] N. Yu, P. Genevet, M.A. Kats, et al., Light propagation with phase
discontinuities: Generalized laws of reflection and refraction, Science 334
(6054) (2011) 333–337, https://doi.org/10.1126/science.1210713.
[20] J. Lin, J.P.B. Mueller, Q. Wang, et al., Polarization-controlled tunable directional
coupling of surface plasmon polaritons, Science 340 (6130) (2013) 331–334,
https://doi.org/10.1126/science.123374.
[21] W. Zhou, T.W. Odom, Tunable subradiant lattice plasmons by out-of-plane
dipolar interactions, Nat. Nanotechnol. 6 (7) (2011) 423–427.
[22] P. Nagpal, N.C. Lindquist, S.H. Oh, et al., Ultrasmooth patterned metals for
plasmonics and metamaterials, Science 325 (5940) (2009) 594–597, https://
doi.org/10.1126/science.117465.
[23] J.Z. Lu, L. Zhang, A.X. Feng, et al., Effects of laser shock processing on
mechanical properties of Fe-Ni alloy, Mater. Des. 30 (9) (2009) 3673–3678,
https://doi.org/10.1016/j.matdes.2009.02.015.
[24] H. Yang, F. Xiong, Y. Wang, et al., Manufacturing profile-free copper foil using
laser shock flattening, Int. J. Mach. Tools Manuf 152 (2020), https://doi.org/
10.1016/j.ijmachtools.2020.103542 103542.
[25] D. Devaux, R. Fabbro, L. Tollier, et al., Generation of shock waves by laser-
induced plasma in confined geometry, J. Appl. Phys. 74 (4) (1993) 2268–2273,
https://doi.org/10.1063/1.354710.
[26] B.C. Zhang, H.F. Yang, H. Liu, et al., Crystallographic features and
microstructure evolution of sandwich warm laser polishing: The case of
aluminum foil, Appl. Surf. Sci. 573 (2022), https://doi.org/10.1016/j.
apsusc.2021.151557 151557.
[27] P.F. Moonen, I. Yakimets, J. Huskens, Fabrication of transistors on flexible
substrates: from mass-printing to high-resolution alternative lithography
strategies, Adv. Mater. 24 (41) (2012) 5526–5541, https://doi.org/10.1002/
adma.201202949.
[28] H. Lan, Soft UV nanoimprint lithography and its applications, in: S. Hosaka
(Ed.), Updates in Advanced Lithography, InTech, New York, 2013.
[29] G.L. Cross, B.S. O’Connell, J.B. Pethica, Influence of elastic strains on the mask
ratio in glassy polymer nanoimprint, Appl. Phys. Lett. 86 (8) (2005), https://
doi.org/10.1063/1.1868074.
[30] S. Landis, N. Chaix, C. Gourgon, et al., Quantitative characterizations of a
nanopatterned bonded wafer: force determination for nanoimprint
lithography stamp removal, Nanotechnology 19 (12) (2008), https://doi.org/
10.1088/0957-4484/19/12/125305 125305.
[31] A. Amirsadeghi, J.J. Lee, S. Park, Surface adhesion and demolding force
dependence on resist composition in ultraviolet nanoimprint lithography,
Appl. Surf. Sci. 258 (3) (2011) 1272–1278, https://doi.org/10.1016/j.
apsusc.2011.09.090.
[32] S.H. Ahn, L.J. Guo, High-speed roll-to-roll nanoimprint lithography on flexible
plastic substrates, Adv. Mater. 20 (11) (2008) 2044–2049, https://doi.org/
10.1002/adma.200702650.
[33] H. Schift, Nanoimprint Lithography, in: B. Bhushan (Ed.), Springer Handbook of
Nanotechnology, Springer, Berlin, 2017, pp. 113–142.
[34] M. Li, Y. Chen, W. Luo, et al., Demolding force dependence on mold surface
modifications in UV nanoimprint lithography, Microelectron. Eng. 236 (2021),
https://doi.org/10.1016/j.mee.2020.111470 111470.