Next Article in Journal
Low-Cost Manufacturing of Monolithic Resonant Piezoelectric Devices for Energy Harvesting Using 3D Printing
Next Article in Special Issue
The Influence of the Mechanical Compliance of a Substrate on the Morphology of Nanoporous Gold Thin Films
Previous Article in Journal
Studies on the Functional Properties of Titanium Dioxide Nanoparticles Distributed in Silyl–Alkyl Bridged Polyaniline-Based Nanofluids
Previous Article in Special Issue
Microsecond All-Optical Modulation by Biofunctionalized Porous Silicon Microcavity
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Nanomaterials
Volume 13
Issue 16
10.3390/nano13162335
nanomaterials-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

High-Resolution Nanotransfer Printing of Porous Crossbar Array Using Patterned Metal Molds by Extreme-Pressure Imprint Lithography

by
Tae Wan Park
,
Young Lim Kang
,
Yu Na Kim
and
Woon Ik Park
*
Department of Materials Science and Engineering, Pukyong National University (PKNU), Busan 48513, Republic of Korea
*
Author to whom correspondence should be addressed.
Nanomaterials 2023, 13(16), 2335; https://doi.org/10.3390/nano13162335
Submission received: 20 June 2023 / Revised: 10 August 2023 / Accepted: 11 August 2023 / Published: 14 August 2023
(This article belongs to the Special Issue Design, Fabrication and Applications of Nanoporous Materials)
Browse Figures
Review Reports Versions Notes

Abstract

:
High-resolution nanotransfer printing (nTP) technologies have attracted a tremendous amount of attention due to their excellent patternability, high productivity, and cost-effectiveness. However, there is still a need to develop low-cost mold manufacturing methods, because most nTP techniques generally require the use of patterned molds fabricated by high-cost lithography technology. Here, we introduce a novel nTP strategy that uses imprinted metal molds to serve as an alternative to a Si stamp in the transfer printing process. We present a method by which to fabricate rigid surface-patterned metallic molds (Zn, Al, and Ni) based on the process of direct extreme-pressure imprint lithography (EPIL). We also demonstrate the nanoscale pattern formation of functional materials, in this case Au, TiO2, and GST, onto diverse surfaces of SiO2/Si, polished metal, and slippery glass by the versatile nTP method using the imprinted metallic molds with nanopatterns. Furthermore, we show the patterning results of nanoporous crossbar arrays on colorless polyimide (CPI) by a repeated nTP process. We expect that this combined nanopatterning method of EPIL and nTP processes will be extendable to the fabrication of various nanodevices with complex circuits based on micro/nanostructures.

1. Introduction

High-resolution nanofabrication methods are essential for the realization of well-arranged nanostructures with specific functionalities applicable to various advanced future device systems, such as lithium-ion batteries (LIBs) [1,2,3,4], high-performance energy harvesting devices [5,6,7], nonvolatile memories [8,9,10], solar/fuel cells [11,12,13,14], and next-generation electric vehicles (EVs) [15,16]. In particular, photolithography is currently a technology widely exploited to achieve high-level device integrations in various modern electronics [17,18,19,20]. Over the past several decades, photolithography has been important in the production of micro/nanostructures with dynamically controlled surface topographic integrated circuit (IC) structures in electronic devices [21,22]. The photolithography process is also compatible with flexible substrates, such as polyethylene terephthalate (PET) and polyimide (PI), to fabricate wearable or stretchable device systems [23,24,25]. However, despite the merits of patternability, productivity, and scalability, they have critical challenges related to their process price per unit area and the resolution limitation of approximately 50 nm. In particular, the development of a simple and new lithographic process for realizing nanoscale pattern formation at low cost is still needed.
To overcome these issues, several alternative lithography techniques, such as extreme ultraviolet (EUV) lithography [26,27], nanoimprint lithography (NIL) [28,29], dip-pen nanolithography (DPN) [30,31], atomic force microscope (AFM) lithography [32], electron-beam lithography (EBL) [33,34], and directed self-assembly (DSA) of block copolymers (BCPs) [35,36,37,38,39,40], have been consistently developed and reported for the purpose of cost-effectiveness and ultra-high-resolution pattern formation. Among these outstanding lithography techniques, nanotransfer printing (nTP) techniques have attracted much attention due to their excellent pattern resolution, patternability, and for their ability effectively to form two-dimensional (2D) and three-dimensional (3D) structures on arbitrary substrates [41,42,43,44]. On the basis of these reasons, papers on a range of unconventional transfer printing methods, including kinetically controlled nTP [45], water-assisted nTP [46], solvent-assisted nTP [47], laser-assisted nTP [48], and immersion transfer printing [49], have been continuously published. We also reported a thermally assisted nanotransfer printing (T-nTP) technique capable of producing functional nanostructures effectively over the eight-inch wafer level [50]. The fabrication of the initial mold, which is the basis of the process, is considered a very important core step in most nTP methods. However, a low-cost mold fabrication method is still required as, currently, molds manufactured by a high-cost lithography process, including photolithography, are generally used.
Herein, we introduce a new concept of the nTP process that uses surface-patterned metal master molds by extreme-pressure imprint lithography (EPIL). EPIL enables precise nanogeometries on a metallic substrate through the nanoscopic plastic deformation of the metal surface by a high load or high pressure using a Si stamp. The approach of fabricating numerous metal molds using a Si stamp can bring long-term economic feasibility in terms of the initial mold-based nTP process, which involves infinitely repeated replication steps. We also show how to fabricate various metal molds with nanopatterns by controlling the pressure based on the EPIL method. In addition, we explain how to obtain the replicated polymer patterns from the imprinted metal mold using an adhesive PI tape. Moreover, we demonstrate the reliable nanoscale pattern formation of functional materials on various surfaces via the T-nTP process.

2. Materials and Methods

2.1. Fabrication of Surface-Patterned Metal Master Molds

To create the surface nanopatterns on metallic materials, extreme-pressure imprint lithography, which can directly generate multiscale periodic micro/nanoscale pattern structures, was experimentally employed. A Si stamp fabricated by photolithography with a width/space of 250 nm was mounted onto the RAM head of press equipment capable of injecting a high load onto metal substrates. The Si mold with a depth of 250 to 350 nm used for the EPIL process was produced by conventional KrF photolithography and the reactive ion etching (RIE) process. Spin-coated positive photoresist (PR, Dongjin Semichem Co., Ltd., Republic of Korea) with a thickness of ~400 nm on the 8-inch Si wafer was exposed using a KrF scanner (Nikon, Tokyo, Japan, NSR-S203B). Then, exposed PR was developed using a developer solution (tetramethylammonium hydroxide, Dongjin Semichem Co., Ltd.). The remaining PR patterns were used as an etch mask to produce the Si pattern with plasma treatment by means of RIE (gas: CF4, working pressure: 7 mTorr, power: 250 W). After the removal of the residual PR areas from the dry-etched Si substrate using an RIE system, the nanopatterned Si mold with nanoscale line structures was finally obtained. All chip-level Si stamps used in this study were used by cutting an 8-inch wafer fabricated by photolithography. Zn (annealed, 99.5% metals basis, 0.25 mm, Alfa Aesar, Haverhill, MI, USA) and Al (99.99%, 0.13 mm, Sigma Aldrich Co., Ltd., St. Louis, MI, USA) substrates were directly pressed at extreme pressures of 6 and 6.5 tons, respectively, using a Si stamp fabricated by conventional photolithography. A Ni (99.9%, 0.125 mm, Sigma Aldrich Co., Ltd.) substrate was imprinted at approximately 13 tons.

2.2. Replication of Polymer Patterns Using Imprinted Metal Molds

During the replication step, solid poly(methyl methacrylate) (PMMA) particle with a molecular weight of 100 kg/mol (Sigma Aldrich Co., Ltd.) and liquid hydroxyl-terminated polydimethylsiloxane (PDMS-OH) with a molecular weight of 5 kg/mol (Polymer Source Inc., Dorval, QC, Canada) were used. PMMA granules were dissolved in a mixed solvent of toluene (99.5%, Junsei Co., Tokyo, Japan), acetone (99.5%, Junsei Co.), and heptane (99.0%, Junsei Co.) (Vtol:Vace:Vhep = 4:4:2) to yield a 4 wt%. The solubility parameters (δ, MPa1/2) of PMMA, toluene, and acetone are 19.0, 18.3, and 19.7, respectively. Toluene and acetone are good solvents for dissolving solid PMMA. To impart a hydrophobic state on the surface of the imprinted metal substrates, the PDMS solution dissolved in toluene yielding a 2.5 wt% was spin-cast for 23 s at a speed of 5000 rpm. This step was followed by annealing at 150 °C for 2 h using a vacuum oven (OV4-30, Jeio Tech. Co., Ltd., Republic of Korea). After the spin-casting of the PMMA solution on the hydrophobic surface of the imprinted metal mold, the PMMA film was attached and detached with mild pressure (~25 kPa) using a PI adhesive tape (PIT-10050S, Isoflex, Republic of Korea). A heptane (δ = 15.3 MPa1/2), which has a poor solubility parameter for brush-treated PDMS material, can help spin-coated PMMA film to separate well from the PDMS-coated metal molds. In the replication process, a laminator system that can provide uniform pressure on the replication area was used.

2.3. Pattern Transfer Printing

To transfer the nanoscale pattern structures, we utilized a heat-rolling-press system (LAMIART-470 LSI, GMP Corp., Busan, Republic of Korea). This system has four rolls composed of elastic silicone rubber that can effectively provide both uniform pressure and heat. The speed of the rolls is controllable from 200 to 1500 mm/min. The rolling speed and temperature for pattern transfer printing in this study were set to 1000 mm/min and 150 °C. Deposited functional materials, in this case Au, TiO2, and Ge2Se2Te5 (GST), on PMMA replica pattern were contacted on the target substrate and passed between heated rolls. The deposition processes were implemented by physical vapor deposition (PVD) using a direct-current (DC) and radio-frequency (RF) sputtering system (DC/RF Sputtering System, KVS-T1009640, Korea Vacuum Tech. Co., Ltd., Gimpo-si, Republic of Korea). The working pressure of the main chamber was constantly maintained at 5 × 10−3 torr during the PVD process (applied power: 200 W). An adhesive PI tape was manually removed from the target substrate after the bonded substrate-patterning medium-PI tape passed over the rolls.

2.4. Characterization

The nanoscale pattern structures were observed using a field emission scanning electron microscope (FE-SEM, MIRA3, TESCAN) at an acceleration voltage of 10 kV and a working distance of 5–8 mm.

3. Results

3.1. Nanotransfer Printing Using an Imprinted Metal Mold

The process sequence for the formation of the nanoscale pattern structure using an imprinted metal mold is schematically depicted in Figure 1. This conceptual strategy has three steps: metal mold fabrication (step 1), pattern replication (step 2), and pattern transfer printing (step 3). In step 1, the metal master substrates for the core materials of the patterning process are imprinted by EPIL using a Si stamp fabricated by conventional photolithography [51]. During the EPIL process, the planar surface of the metal substrate is modified through precise plastic deformation at room temperature without the use of heat, ultraviolet (UV) light, laser, or electrical sources. In step 2, the replica pattern is produced by peeling off the polymer film from the metal master mold using an adhesive PI tape (see Section 2, Materials and Methods, for the details of the replication step). A sticky layer of PI tape (Kapton tape) helps to decouple the polymeric thin film with nanoscale surface patterns after it has been cast onto the imprinted metal mold. In step 3, nanopatterned structures can be formed on the target substrate by the T-nTP process. The functional materials are evenly deposited on the protruding surfaces of replica polymer patterns by physical vapor deposition (PVD). The functional nanoscale patterns are then transferred onto an arbitrary substrate using a heat-rolling-press system.

3.2. Fabrication of Surface-Patterned Metal Molds via EPIL

To produce the master molds with metallic materials, the reliable top-down hard lithography of the EPIL process was employed. Several imprinted metal molds, which can be produced using one Si stamp, serve as a viable alternative with economic value to a Si mold during the T-nTP process for the fabrication of high-resolution nanostructures. Figure 2 shows various surface-patterned metallic master molds realized by EPIL. Figure 2a displays a replicated Al substrate from an original Si stamp. An imprinted Al substrate with a width/space of 250 nm presents the reverse phase of the Si stamp. A high load or high pressure (6.5 tons) was imposed on the surface of the Al substrate during the EPIL process. Scanning electron microscope (SEM) and the inset images in the figure clearly show the replicated high-resolution nanoscale pattern structures through the plastic deformation of the Al material. Figure 2b shows the imprinted Al substrate with a width of 1 µm and space of 250 nm. This pattern structure also presents a reverse phase with the original Si stamp (line width: 250 nm, line space: 1 µm). It should be noted that precise surface patterning with different line width/space patterns can be realized by the reliable EPIL method. Figure 2c shows cross-sectional-view SEM images of a Si stamp fabricated by photolithography and various metallic substrates surface-patterned by the EPIL process. To obtain excellent pattern resolutions of Ni and Zn materials, different loads of thirteen tons and six tons were injected on the target substrates, respectively. The patterning load for the successful pattern formation of nanoscopic geometries may vary depending on the manufactured hardness based on the intrinsic characteristics of the metallic materials used.

3.3. Replication Using Imprinted Metal Master Molds

Figure 3 shows the replication results of a polymer material when using an imprinted metal mold. The entire process of replication is schematically illustrated in Figure 3a. Prior to pattern replication, the imprinted metal molds were pretreated with a hydroxyl-terminated polydimethylsiloxane (PDMS-OH) brush to impart a hydrophobic surface on all molds. This surface modification step facilitates the separation of the replica polymer layer from the mold. During the replication process, the coated polymer layer cannot be separated without brush treatment. We prepared three master molds (Zn, Al, and Ni) with a width/space of 250 nm via the EPIL process (Figure 3b). Photographic and SEM images of each mold indicate that the EPIL process enables nanoscale patterning on the surfaces of the metal substrates. A PMMA solution dissolved in a mixed solvent of toluene, acetone, and heptane was then spin-cast onto the surface-patterned metal master molds. Replica patterns were successfully obtained after peeling off the functional PMMA film using an adhesive PI tape. Figure 3c shows the PMMA surface patterns replicated from the metal molds. High-resolution nanoscopic line structures were successfully obtained without any defects and/or cracks compared to the surface-patterned original metal molds. These results strongly support the claim that these imprinted three metal molds can be produced from one Si stamp and can sufficiently replace a Si stamp fabricated by photolithography in terms of nanoscale pattern formation by T-nTP. Here, we should emphasize that the imprinted metal molds can be used repeatedly to duplicate PMMA patterns.

3.4. Formation of Functional Nanopatterns on Various Surfaces via T-nTP

Figure 4 shows the formation of periodic nanoscale patterns on various substrates via the T-nTP process using an imprinted metal master mold. Figure 4a presents transfer-printed functional line patterns with a width of 250 nm. Au lines with a width of 250 nm were reliably transferred onto the surface of SiO2/Si substrate. TiO2 and GST nanostructures were also successfully printed on the surfaces of polished metal and glass substrates, respectively. Figure 4b shows schematic illustrations of the formation of a crossbar pattern structure. The multiple transfer printing process of the T-nTP technique enables the formation of hierarchical 3D nanogeometric structures. Figure 4c shows a transfer-printed TiO2 nanoporous crossbar on a flexible and transparent colorless polyimide (CPI) film, indicating stable attachments even after the substrate was bent. These results clearly demonstrate that the generation of nanoscale patterns on diverse surfaces and materials can be realized via the versatile T-nTP method when using surface-patterned metal molds imprinted by EPIL.
On the basis of these results for the combined method of EPIL and nTP, the possibility of applications in device systems that require the formation of high-resolution nanostructures on the surface of various substrates was confirmed. For the low-cost combined patterning method using an imprinted metal mold to become highly competitive compared to conventional lithographic technologies, such as photolithography, nanoimprint lithography, and inkjet printing, further research on shape control of the surfaces of metal molds and selective mirror polishing of surface-patterned metal substrates should be needed. Moreover, the development of a high-throughput automatic equipment system for the combined patterning technique will improve the reliability of the findings presented in this study.

4. Conclusions

In summary, a novel nanopatterning method that combines the EPIL and nTP processes to obtain well-ordered functional nanostructures was proposed. We fabricated various metallic nanomolds, in this case Zn, Al, and Ni, with periodic line structures from a Si stamp using the EPIL process without the use of an imprint resist or heat, laser, UV light, or electrical sources. The surface-patterned metal substrates were utilized as a master mold that can replace the Si stamps typically used during pattern transfer printing processes. We successfully replicated polymer patterns from the imprinted metal molds, and obtained well-ordered nanoscale line patterns with different line widths using PMMA replica patterns. We also demonstrated nanoscale pattern formation with functional materials, specifically, Au, TiO2, and GST, on various surfaces including SiO2/Si, polished metal, and slippery glass via the T-nTP process. Furthermore, we undertook the pattern generation of a TiO2 nanoporous crossbar structure on CPI film by the multiple T-nTP technique. We expect that this approach can be applied to other emerging device fabrication processes that involve complex functional nanostructures.

Author Contributions

Conceptualization, T.W.P. and W.I.P.; methodology, T.W.P.; validation, T.W.P. and W.I.P.; formal analysis, T.W.P., Y.L.K. and Y.N.K.; investigation, T.W.P.; resources, T.W.P. and W.I.P.; data curation, T.W.P.; writing—original draft preparation, T.W.P.; writing—review and editing, T.W.P. and W.I.P.; visualization, T.W.P.; supervision, W.I.P.; project administration, W.I.P. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT, Ministry of Science and ICT) (NRF-2022R1A4A1034312 and NRF-2021R1A2C1004119).

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Chen, H.; Shen, Z.; Pan, Z.; Kou, Z.; Liu, X.; Zhang, H.; Gu, Q.; Guan, C.; Wang, J. Hierarchical micro-nano sheet arrays of nickel–cobalt double hydroxides for high-rate Ni–Zn batteries. Adv. Sci. 2019, 6, 1802002. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  2. Zhang, B.; Zhang, Y.; Miao, Z.; Wu, T.; Zhang, Z.; Yang, X. Micro/nano-structure Co3O4 as high capacity anode materials for lithium-ion batteries and the effect of the void volume on electrochemical performance. J. Power Sources 2014, 248, 289–295. [Google Scholar] [CrossRef]
  3. Huang, G.; Xu, S.; Xu, Z.; Sun, H.; Li, L. Core–shell ellipsoidal MnCo2O4 anode with micro-/nano-structure and concentration gradient for lithium-ion batteries. ACS Appl. Mater. Interfaces 2014, 6, 21325–21334. [Google Scholar] [CrossRef] [PubMed]
  4. Palacin, M.R. Recent advances in rechargeable battery materials: A chemist’s perspective. Chem. Soc. Rev. 2009, 38, 2565–2575. [Google Scholar] [CrossRef]
  5. Jung, Y.; Ahn, J.; Kim, J.S.; Ha, J.H.; Shim, J.; Cho, H.; Oh, Y.S.; Yoon, Y.J.; Nam, Y.; Oh, I.K. Spherical Micro/Nano Hierarchical Structures for Energy and Water Harvesting Devices. Small Methods 2022, 6, 2200248. [Google Scholar] [CrossRef]
  6. Muthu, M.; Pandey, R.; Wang, X.; Chandrasekhar, A.; Palani, I.; Singh, V. Enhancement of triboelectric nanogenerator output performance by laser 3D-Surface pattern method for energy harvesting application. Nano Energy 2020, 78, 105205. [Google Scholar] [CrossRef]
  7. Shi, Q.; He, T.; Lee, C. More than energy harvesting–Combining triboelectric nanogenerator and flexible electronics technology for enabling novel micro-/nano-systems. Nano Energy 2019, 57, 851–871. [Google Scholar] [CrossRef]
  8. Park, T.W.; Park, W.I. Switching-Modulated Phase Change Memory Realized by Si-Containing Block Copolymers. Small 2021, 17, 2105078. [Google Scholar] [CrossRef]
  9. Noé, P.; Vallée, C.; Hippert, F.; Fillot, F.; Raty, J.-Y. Phase-change materials for non-volatile memory devices: From technological challenges to materials science issues. Semicond. Sci. Technol. 2017, 33, 013002. [Google Scholar] [CrossRef]
  10. Su, M.; Yang, Z.; Liao, L.; Zou, X.; Ho, J.C.; Wang, J.; Wang, J.; Hu, W.; Xiao, X.; Jiang, C. Side-Gated In2O3 Nanowire Ferroelectric FETs for High-Performance Nonvolatile Memory Applications. Adv. Sci. 2016, 3, 1600078. [Google Scholar] [CrossRef] [Green Version]
  11. Miyake, J.; Ogawa, Y.; Tanaka, T.; Ahn, J.; Oka, K.; Oyaizu, K.; Miyatake, K. Rechargeable proton exchange membrane fuel cell containing an intrinsic hydrogen storage polymer. Comm. Chem. 2020, 3, 138. [Google Scholar] [CrossRef] [PubMed]
  12. Atanasov, V.; Lee, A.S.; Park, E.J.; Maurya, S.; Baca, E.D.; Fujimoto, C.; Hibbs, M.; Matanovic, I.; Kerres, J.; Kim, Y.S. Synergistically integrated phosphonated poly (pentafluorostyrene) for fuel cells. Nat. Mater. 2020, 20, 370–377. [Google Scholar] [CrossRef] [PubMed]
  13. Orilall, M.C.; Wiesner, U. Block copolymer based composition and morphology control in nanostructured hybrid materials for energy conversion and storage: Solar cells, batteries, and fuel cells. Chem. Soc. Rev. 2011, 40, 520–535. [Google Scholar] [CrossRef]
  14. Kim, Y.S.; Wang, F.; Hickner, M.; McCartney, S.; Hong, Y.T.; Harrison, W.; Zawodzinski, T.A.; McGrath, J.E. Effect of acidification treatment and morphological stability of sulfonated poly (arylene ether sulfone) copolymer proton-exchange membranes for fuel-cell use above 100 C. J. Polym. Sci. Pt. B-Polym. Phys. 2003, 41, 2816–2828. [Google Scholar] [CrossRef]
  15. Sun, Y.-K.; Chen, Z.; Noh, H.-J.; Lee, D.-J.; Jung, H.-G.; Ren, Y.; Wang, S.; Yoon, C.S.; Myung, S.-T.; Amine, K. Nanostructured high-energy cathode materials for advanced lithium batteries. Nat. Mater. 2012, 11, 942–947. [Google Scholar] [CrossRef]
  16. Kumar, P.; Kim, K.-H.; Bansal, V.; Kumar, P. Nanostructured materials: A progressive assessment and future direction for energy device applications. Coord. Chem. Rev. 2017, 353, 113–141. [Google Scholar]
  17. Rühe, J. And there was light: Prospects for the creation of micro-and nanostructures through maskless photolithography. ACS Nano 2017, 11, 8537–8541. [Google Scholar]
  18. Wu, M.-H.; Whitesides, G.M. Fabrication of two-dimensional arrays of microlenses and their applications in photolithography. J. Micromech. Microeng. 2002, 12, 747. [Google Scholar] [CrossRef]
  19. Levenson, M.D.; Viswanathan, N.; Simpson, R.A. Improving resolution in photolithography with a phase-shifting mask. IEEE Trans. Electron Devices 1982, 29, 1828–1836. [Google Scholar] [CrossRef]
  20. Zhang, N.; Sun, W.; Rodrigues, S.P.; Wang, K.; Gu, Z.; Wang, S.; Cai, W.; Xiao, S.; Song, Q. Highly reproducible organometallic halide perovskite microdevices based on top-down lithography. Adv. Mater. 2017, 29, 1606205. [Google Scholar] [CrossRef]
  21. Li, L.; Liu, X.; Pal, S.; Wang, S.; Ober, C.K.; Giannelis, E.P. Extreme ultraviolet resist materials for sub-7 nm patterning. Chem. Soc. Rev. 2017, 46, 4855–4866. [Google Scholar] [CrossRef]
  22. Magin, C.M.; Anseth, K.S. In situ control of cell substrate microtopographies using photolabile hydrogels. Small 2013, 9, 578–584. [Google Scholar] [CrossRef]
  23. Yao, Y.; Zhang, L.; Leydecker, T.; Samorì, P. Direct photolithography on molecular crystals for high performance organic optoelectronic devices. J. Am. Chem. Soc. 2018, 140, 6984–6990. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  24. Acuautla, M.; Bernardini, S.; Gallais, L.; Fiorido, T.; Patout, L.; Bendahan, M. Ozone flexible sensors fabricated by photolithography and laser ablation processes based on ZnO nanoparticles. Sens. Actuator B-Chem. 2014, 203, 602–611. [Google Scholar] [CrossRef]
  25. Guo, C.; Liu, K.; Zhang, T.; Sun, P.; Liang, L. Development of flexible photothermal superhydrophobic microarray by photolithography technology for anti-icing and deicing. Prog. Org. Coat. 2023, 182, 107675. [Google Scholar] [CrossRef]
  26. Torretti, F.; Sheil, J.; Schupp, R.; Basko, M.; Bayraktar, M.; Meijer, R.; Witte, S.; Ubachs, W.; Hoekstra, R.; Versolato, O. Prominent radiative contributions from multiply-excited states in laser-produced tin plasma for nanolithography. Nat. Commun. 2020, 11, 9235. [Google Scholar] [CrossRef]
  27. Mojarad, N.; Gobrecht, J.; Ekinci, Y. Beyond EUV lithography: A comparative study of efficient photoresists’ performance. Sci. Rep. 2015, 5, 2334. [Google Scholar] [CrossRef] [Green Version]
  28. Gao, H.; Hu, Y.; Xuan, Y.; Li, J.; Yang, Y.; Martinez, R.V.; Li, C.; Luo, J.; Qi, M.; Cheng, G.J. Large-scale nanoshaping of ultrasmooth 3D crystalline metallic structures. Science 2014, 346, 1352–1356. [Google Scholar] [CrossRef]
  29. Kim, D.H.; Lee, D.W.; Oh, J.Y.; Won, J.; Seo, D.-S. Nanopatterning of Polymer/gallium oxide thin films by UV-curing nanoimprint lithography for liquid crystal alignment. ACS Appl. Nano Mater. 2022, 5, 1435–1445. [Google Scholar] [CrossRef]
  30. Lee, S.W.; Oh, B.K.; Sanedrin, R.G.; Salaita, K.; Fujigaya, T.; Mirkin, C.A. Biologically active protein nanoarrays generated using parallel dip-pen nanolithography. Adv. Mater. 2006, 18, 1133–1136. [Google Scholar]
  31. Lee, K.-B.; Park, S.-J.; Mirkin, C.A.; Smith, J.C.; Mrksich, M. Protein nanoarrays generated by dip-pen nanolithography. Science 2002, 295, 1702–1705. [Google Scholar] [CrossRef] [Green Version]
  32. Chen, J.; Sun, Y.; Zhong, L.; Shao, W.; Huang, J.; Liang, F.; Cui, Z.; Liang, Z.; Jiang, L.; Chi, L. Scalable fabrication of multiplexed plasmonic nanoparticle structures based on AFM lithography. Small 2016, 12, 5818–5825. [Google Scholar] [CrossRef]
  33. Hu, S.; Chen, J.; Yu, T.; Zeng, Y.; Wang, S.; Guo, X.; Yang, G.; Li, Y. A novel dual-tone molecular glass resist based on adamantane derivatives for electron beam lithography. J. Mater. Chem. C 2022, 10, 9858–9866. [Google Scholar] [CrossRef]
  34. Dieleman, C.D.; van der Burgt, J.; Thakur, N.; Garnett, E.C.; Ehrler, B. Direct patterning of CsPbBr3 nanocrystals via electron-beam lithography. ACS Appl. Energy Mater. 2022, 5, 1672–1680. [Google Scholar] [CrossRef]
  35. Park, T.W.; Kang, Y.L.; Byun, M.; Hong, S.W.; Ahn, Y.-S.; Lee, J.; Park, W.I. Controlled self-assembly of block copolymers in printed sub-20 nm cross-bar structures. Nanoscale Adv. 2021, 3, 5083–5089. [Google Scholar] [CrossRef]
  36. Park, T.W.; Jung, H.; Park, J.; Ahn, Y.-S.; Hong, S.W.; Lee, J.; Lee, J.-H.; Park, W.I. Topographically designed hybrid nanostructures via nanotransfer printing and block copolymer self-assembly. Nanoscale 2021, 13, 11161–11168. [Google Scholar] [CrossRef]
  37. Jung, H.; Shin, W.H.; Park, T.W.; Choi, Y.J.; Yoon, Y.J.; Park, S.H.; Lim, J.-H.; Kwon, J.-D.; Lee, J.W.; Kwon, S.-H.; et al. Hierarchical multi-level block copolymer patterns by multiple self-assembly. Nanoscale 2019, 11, 8433–8441. [Google Scholar] [CrossRef]
  38. Ross, C.A.; Berggren, K.K.; Cheng, J.Y.; Jung, Y.S.; Chang, J.B. Three-dimensional nanofabrication by block copolymer self-assembly. Adv. Mater. 2014, 26, 4386–4396. [Google Scholar] [CrossRef]
  39. Bosworth, J.K.; Paik, M.Y.; Ruiz, R.; Schwartz, E.L.; Huang, J.Q.; Ko, A.W.; Smilgies, D.-M.; Black, C.T.; Ober, C.K. Control of self-assembly of lithographically patternable block copolymer films. ACS Nano 2008, 2, 1396–1402. [Google Scholar] [CrossRef]
  40. Jung, D.S.; Bang, J.; Park, T.W.; Lee, S.H.; Jung, Y.K.; Byun, M.; Cho, Y.-R.; Kim, K.H.; Seong, G.H.; Park, W.I. Pattern formation of metal–oxide hybrid nanostructures via the self-assembly of di-block copolymer blends. Nanoscale 2019, 11, 18559–18567. [Google Scholar] [CrossRef]
  41. Tiefenauer, R.F.; Tybrandt, K.; Aramesh, M.; Voros, J. Fast and versatile multiscale patterning by combining template-stripping with nanotransfer printing. ACS Nano 2018, 12, 2514–2520. [Google Scholar] [CrossRef] [PubMed]
  42. Stuart, C.; Park, H.K.; Chen, Y. Fabrication of a 3D nanoscale crossbar circuit by nanotransfer-printing lithography. Small 2010, 6, 1663–1668. [Google Scholar] [CrossRef] [PubMed]
  43. Jiao, L.; Fan, B.; Xian, X.; Wu, Z.; Zhang, J.; Liu, Z. Creation of nanostructures with poly (methyl methacrylate)-mediated nanotransfer printing. J. Am. Chem. Soc. 2008, 130, 12612–12613. [Google Scholar] [CrossRef]
  44. Hines, D.; Mezhenny, S.; Breban, M.; Williams, E.; Ballarotto, V.; Esen, G.; Southard, A.; Fuhrer, M. Nanotransfer printing of organic and carbon nanotube thin-film transistors on plastic substrates. Appl. Phys. Lett. 2005, 86, 163101. [Google Scholar] [CrossRef] [Green Version]
  45. Meitl, M.A.; Zhu, Z.-T.; Kumar, V.; Lee, K.J.; Feng, X.; Huang, Y.Y.; Adesida, I.; Nuzzo, R.G.; Rogers, J.A. Transfer printing by kinetic control of adhesion to an elastomeric stamp. Nat. Mater. 2006, 5, 33–38. [Google Scholar] [CrossRef]
  46. Aghajamali, M.; Cheong, I.T.; Veinot, J.G. Water-Assisted Transfer Patterning of Nanomaterials. Langmuir 2018, 34, 9418–9423. [Google Scholar] [CrossRef]
  47. Jeong, J.W.; Yang, S.R.; Hur, Y.H.; Kim, S.W.; Baek, K.M.; Yim, S.; Jang, H.-I.; Park, J.H.; Lee, S.Y.; Park, C.-O. High-resolution nanotransfer printing applicable to diverse surfaces via interface-targeted adhesion switching. Nat. Commun. 2014, 5, 5387. [Google Scholar] [CrossRef] [Green Version]
  48. Li, R.; Li, Y.; Lü, C.; Song, J.; Saeidpouraza, R.; Fang, B.; Zhong, Y.; Ferreira, P.M.; Rogers, J.A.; Huang, Y. Thermo-mechanical modeling of laser-driven non-contact transfer printing: Two-dimensional analysis. Soft Matter 2012, 8, 7122–7127. [Google Scholar] [CrossRef]
  49. Nam, T.W.; Kim, M.; Wang, Y.; Kim, G.Y.; Choi, W.; Lim, H.; Song, K.M.; Choi, M.-J.; Jeon, D.Y.; Grossman, J.C. Thermodynamic-driven polychromatic quantum dot patterning for light-emitting diodes beyond eye-limiting resolution. Nat. Commun. 2020, 11, 3040. [Google Scholar] [CrossRef] [PubMed]
  50. Park, T.W.; Byun, M.; Jung, H.; Lee, G.R.; Park, J.H.; Jang, H.-I.; Lee, J.W.; Kwon, S.H.; Hong, S.; Lee, J.-H.; et al. Thermally assisted nanotransfer printing with sub–20-nm resolution and 8-inch wafer scalability. Sci. Adv. 2020, 6, eabb6462. [Google Scholar] [CrossRef]
  51. Park, W.I.; Park, T.W.; Choi, Y.J.; Lee, S.; Ryu, S.; Liang, X.; Jung, Y.S. Extreme-Pressure Imprint Lithography for Heat and Ultraviolet-Free Direct Patterning of Rigid Nanoscale Features. ACS Nano 2021, 15, 10464–10471. [Google Scholar] [CrossRef] [PubMed]
Nanomaterials 13 02335 g001
Figure 1. Process sequence of nanoscale pattern formation using imprinted metal molds. (Step 1: Fabrication of the metal master mold) The metal substrate is patterned by the extreme-pressure imprint lithography (EPIL) process. A metal substrate was directly patterned as a submicron-scale feature using a Si stamp fabricated by conventional photolithography. (Step 2: Pattern replication) The replica pattern is formed by attaching and detaching the spin-cast polymeric film on the imprinted metal master mold using an adhesive polyimide (PI) tape with a sticky side. (Step 3: Nanotransfer printing) The functional material is deposited onto the protruding parts of the replica pattern by the physical vapor deposition (PVD) process. The functional nanoscale patterns are then transferred onto an arbitrary substrate via the thermally assisted nanotransfer printing (T-nTP) process.
Figure 1. Process sequence of nanoscale pattern formation using imprinted metal molds. (Step 1: Fabrication of the metal master mold) The metal substrate is patterned by the extreme-pressure imprint lithography (EPIL) process. A metal substrate was directly patterned as a submicron-scale feature using a Si stamp fabricated by conventional photolithography. (Step 2: Pattern replication) The replica pattern is formed by attaching and detaching the spin-cast polymeric film on the imprinted metal master mold using an adhesive polyimide (PI) tape with a sticky side. (Step 3: Nanotransfer printing) The functional material is deposited onto the protruding parts of the replica pattern by the physical vapor deposition (PVD) process. The functional nanoscale patterns are then transferred onto an arbitrary substrate via the thermally assisted nanotransfer printing (T-nTP) process.
Nanomaterials 13 02335 g001
Nanomaterials 13 02335 g002
Figure 2. Surface-patterned metallic master molds by the direct EPIL process. (a) Replicated Al substrate with a width/space of 250 nm from the original Si stamp via the EPIL process. Surface-patterned Al substrate showing the reverse phase of the original Si stamp. (b) Imprinted Al substrate with different line-space widths of 1 µm–250 nm. (c) Various imprinted metal molds with Ni and Zn materials from the Si stamp. The cross-sectional-view SEM images clearly show the nanopatterned Si stamp and imprinted surfaces of Ni and Zn by EPIL. Scale bars, 1 µm (a–c).
Figure 2. Surface-patterned metallic master molds by the direct EPIL process. (a) Replicated Al substrate with a width/space of 250 nm from the original Si stamp via the EPIL process. Surface-patterned Al substrate showing the reverse phase of the original Si stamp. (b) Imprinted Al substrate with different line-space widths of 1 µm–250 nm. (c) Various imprinted metal molds with Ni and Zn materials from the Si stamp. The cross-sectional-view SEM images clearly show the nanopatterned Si stamp and imprinted surfaces of Ni and Zn by EPIL. Scale bars, 1 µm (a–c).
Nanomaterials 13 02335 g002
Nanomaterials 13 02335 g003
Figure 3. Replication of PMMA line patterns obtained from various imprinted metallic molds. (a) Procedure of the replication process. Before the pattern replications, the surfaces of metal molds are treated with a PDMS brush for easy separation of the replica material from the mold. (b) Imprinted metal (Zn, Al, and Ni) substrates via EPIL. Scale bars, 1 µm. (c) The replica patterns from the surface-patterned metal master molds. The insets show photographic images of the replica pattern from the imprinted metal molds. Scale bars, 1 µm. (d) Cross-sectional SEM images of replicated high-resolution PMMA patterns (line-width/space-width: 250 nm) from the Zn, Al, and Ni molds. Scale bars, 1 µm.
Figure 3. Replication of PMMA line patterns obtained from various imprinted metallic molds. (a) Procedure of the replication process. Before the pattern replications, the surfaces of metal molds are treated with a PDMS brush for easy separation of the replica material from the mold. (b) Imprinted metal (Zn, Al, and Ni) substrates via EPIL. Scale bars, 1 µm. (c) The replica patterns from the surface-patterned metal master molds. The insets show photographic images of the replica pattern from the imprinted metal molds. Scale bars, 1 µm. (d) Cross-sectional SEM images of replicated high-resolution PMMA patterns (line-width/space-width: 250 nm) from the Zn, Al, and Ni molds. Scale bars, 1 µm.
Nanomaterials 13 02335 g003
Nanomaterials 13 02335 g004
Figure 4. Various functional line structures and nanoporous crossbar array by the reliable nTP process. (a) Photographic and SEM images of line patterns with a 250 nm width printed with Au, TiO2, and GST materials onto SiO2/Si, polished metal, and slippery glass substrates, respectively. Scale bars, 1 µm. (b) Schematic illustration of the formation of the crossbar pattern structure. A multiple nTP process on a target substrate can effectively generate nanoscale 3D porous structures. (c) Transfer-printed TiO2 crossbar with a width of 250 nm on a colorless polyimide (CPI) substrate.
Figure 4. Various functional line structures and nanoporous crossbar array by the reliable nTP process. (a) Photographic and SEM images of line patterns with a 250 nm width printed with Au, TiO2, and GST materials onto SiO2/Si, polished metal, and slippery glass substrates, respectively. Scale bars, 1 µm. (b) Schematic illustration of the formation of the crossbar pattern structure. A multiple nTP process on a target substrate can effectively generate nanoscale 3D porous structures. (c) Transfer-printed TiO2 crossbar with a width of 250 nm on a colorless polyimide (CPI) substrate.
Nanomaterials 13 02335 g004
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Park, T.W.; Kang, Y.L.; Kim, Y.N.; Park, W.I. High-Resolution Nanotransfer Printing of Porous Crossbar Array Using Patterned Metal Molds by Extreme-Pressure Imprint Lithography. Nanomaterials 2023, 13, 2335. https://doi.org/10.3390/nano13162335

AMA Style

Park TW, Kang YL, Kim YN, Park WI. High-Resolution Nanotransfer Printing of Porous Crossbar Array Using Patterned Metal Molds by Extreme-Pressure Imprint Lithography. Nanomaterials. 2023; 13(16):2335. https://doi.org/10.3390/nano13162335

Chicago/Turabian Style

Park, Tae Wan, Young Lim Kang, Yu Na Kim, and Woon Ik Park. 2023. "High-Resolution Nanotransfer Printing of Porous Crossbar Array Using Patterned Metal Molds by Extreme-Pressure Imprint Lithography" Nanomaterials 13, no. 16: 2335. https://doi.org/10.3390/nano13162335

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop