Search

Directed self-assembly (DSA) of block copolymers is one of the most promising patterning techniques for patterning sub-10 nm features. However, at such small feature sizes, it is becoming increasingly difficult to fabricate the guiding pattern for the DSA process, and it is necessary to explore alternative guiding methods for DSA to achieve long-range ordered alignment. Here, we report the self-aligned assembly of a triblock copolymer, poly(2-vinylpyridine)-b-polystyrene-b-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) on neutral graphene nanoribbons with the gap consisting of a P2VP-preferential silicon oxide (SiO2) substrate via solvent vapor annealing. The assembled P2VP-b-PS-b-P2VP demonstrated long-range, one-dimensional alignment on the graphene substrate in a direction perpendicular to the boundary of the graphene and substrate with a half-pitch size of 8 nm, which greatly alleviates the lithography resolution required for traditional chemoepitaxy DSA. A wide processing window is demonstrated with the gap between graphene stripes varying from 10 to 100 nm, overcoming the restriction on widths of guiding patterns to have commensurate domain spacing. When the gap was reduced to 10 nm, P2VP-b-PS-b-P2VP formed a straight-line pattern on both the graphene and the substrate. Monte Carlo simulations showed that the self-aligned assembly of the triblock copolymer on the graphene nanoribbons is guided at the boundary of parallel and perpendicular lamellae on graphene and SiO2, respectively. Simulations also indicate that the swelling of a system allows for rapid rearrangement of chains and quickly anneal any misaligned grains and defects. The effect of the interaction strength between SiO2 and P2VP on the self-assembly is systematically investigated in simulations.

Directed self-assembly of block copolymers on chemical patterns is of considerable interest for sublithographic patterning. The concept of pattern interpolation, in which a subset of features patterned on a substrate is multiplied through the inherent morphology of an ordered block copolymer, has enabled fabrication of extremely small, defect-free features over large areas. One of the central challenges in design of pattern interpolation strategies is that of identifying system characteristics leading to ideal, defect-free directed assembly. In this work we demonstrate how a coarse-grained many-body model of block copolymers, coupled to an evolutionary computation (EC) strategy, can be used to design and optimize substrate-copolymer combinations for use in lithographic patterning. The proposed approach is shown to be significantly more effective than traditional algorithms based on random searches, and its results are validated in the context of recent experimental observations. The coupled simulation-evolution method introduced here provides a general and efficient method for potential design of complex device-oriented structures.

Graphene is one of the most promising nanomaterials with many extraordinary properties and numerous exciting applications. In this work, a green, facile, and rapid method was developed to prepare graphene directly from common biomass materials such as banana peels, cantaloupe peels, coconut peels, and orange peels by using concentrated solar radiation. The basic principle of this method is photothermal conversion. On a sunny day, the sunlight was concentrated by a biconvex lens to form a focused light spot with a high temperature above 1000 °C, which can directly convert fruit peels into graphene nanosheets within 2-3 s. The product is named concentrated-solar-induced graphene (CSIG) based on the process employed to generate it. The resulting CSIG was characterized using a range of analytical techniques. The Raman spectrum of the CSIG displayed two distinct peaks corresponding to the D and G bands at ∼1343 and ∼1568 cm

The emergence of near-eye displays, such as head-mounted displays, is triggering a requirement for highly enhanced display resolution. High-resolution micro-displays with micro-organic light-emitting diodes (micro-OLEDs) can be a preferential candidate, owing to the mature industrialization of OLEDs along with the advantages of flexibility, light weight, and ease of processing. However, micro-OLEDs with pixel sizes down to micrometers are difficult to be achieved using conventional techniques such as fine metal mask evaporation and lithography. Here, a solution-processing approach to pattern organic semiconductors (OSCs) for micro-OLED arrays with the assistance of templated dewetting is demonstrated. Solvents containing organic functional materials are dewetted on the surface with hydrophobic/hydrophilic patterns to form ordered droplet arrays using dip-coating. Subsequently, patterned OSC films are produced by effectively controlling solvent evaporation. Micro-OLED arrays with a pixel size down to 1 µm are successfully fabricated by further deposition of emitting/electron transport layers and top electrodes. This approach can open an avenue for low-cost manufacturing of flexible and high-resolution micro-displays.

Directed self-assembly (DSA) of block copolymers is one of the most promising patterning techniques for patterning sub-10 nm features. However, at such small feature sizes, it is becoming increasingly difficult to fabricate the guiding pattern for the DSA process, and it is necessary to explore alternative guiding methods for DSA to achieve long-range ordered alignment. Here, we report the self-aligned assembly of a triblock copolymer, poly(2-vinylpyridine)

Molecular ferroelectrics (MFs) have been proven to demonstrate excellent properties even comparable to those of inorganic counterparts usually with heavy metals. However, the validation of their device applications is still at the infant stage. The polycrystalline feature of conventionally obtained MF films, the patterning challenges for microelectronics and the brittleness of crystalline films significantly hinder their development for organic integrated circuits, as well as emerging flexible electronics. Here, a large-area flexible memory array is demonstrated of oriented molecular ferroelectric single crystals (MFSCs) with nearly saturated polarization. Highly-uniform MFSC arrays are prepared on large-scale substrates including Si wafers and flexible substrates using an asymmetric-wetting and microgroove-assisted coating (AWMAC) strategy. Resultant flexible memory arrays exhibit excellent nonvolatile memory properties with a low-operating voltage of5 V, i.e., nearly saturated ferroelectric polarization (6.5 µC cm

We report on the use of a selective, non-volatile ionic liquid (IL) to enhance the self-assembly via solvent annealing of a low molecular weight block copolymer (BCP) of styrene and 2-vinylpyridine (2VP) suitable for generating sub-10 nm features. Diblock and triblock copolymers of different molecular weights of styrene and 2VP are individually blended with the IL and then solvent annealed in acetone, a non-preferential solvent for the BCPs. Differential scanning calorimetry indicates that the IL selectively resides in the 2VP block of the BCP, resulting in a decrease of the block's Tg and an increase of the effective Flory-Huggins parameter (χeff) of the BCP. The influence of the IL on the non-preferential window of a random copolymer brush used to treat the substrate for self-assembly of the BCPs is also analyzed. Well-defined lamellar patterns form when the optimal weight ratio of IL (∼1%) is added to the BCPs. A detailed analysis of the orientational correlation length and pitch size of the BCPs quantitatively shows that the addition of the IL enhanced the microphase separation of the low molecular weight version of the BCP. Subsequent treatment of the self-assembled BCP with sequential infiltration synthesis yields sub-10 nm AlOx lines.

Recent progress in artificial intelligence is largely attributed to the rapid development of machine learning, especially in the algorithm and neural network models. However, it is the performance of the hardware, in particular the energy efficiency of a computing system that sets the fundamental limit of the capability of machine learning. Data-centric computing requires a revolution in hardware systems, since traditional digital computers based on transistors and the von Neumann architecture were not purposely designed for neuromorphic computing. A hardware platform based on emerging devices and new architecture is the hope for future computing with dramatically improved throughput and energy efficiency. Building such a system, nevertheless, faces a number of challenges, ranging from materials selection, device optimization, circuit fabrication and system integration, to name a few. The aim of this Roadmap is to present a snapshot of emerging hardware technologies that are potentially beneficial for machine learning, providing the Nanotechnology readers with a perspective of challenges and opportunities in this burgeoning field., Nanotechnology, 32 (1)

Directed self-assembly of block copolymers (BCPs) enables nanofabrication at sub-10 nm dimensions, beyond the resolution of conventional lithography. However, directing the position, orientation, and long-range lateral order of BCP domains to produce technologically-useful patterns is a challenge. Here, we present a promising approach to direct assembly using spatial boundaries between planar, low-resolution regions on a surface with different composition. Pairs of boundaries are formed at the edges of isolated stripes on a background substrate. Vertical lamellae nucleate at and are pinned by chemical contrast at each stripe/substrate boundary, align parallel to boundaries, selectively propagate from boundaries into stripe interiors (whereas horizontal lamellae form on the background), and register to wide stripes to multiply the feature density. Ordered BCP line arrays with half-pitch of 6.4 nm are demonstrated on stripes >80 nm wide. Boundary-directed epitaxy provides an attractive path towards assembling, creating, and lithographically defining materials on sub-10 nm scales., Directing the position, orientation, and long-range lateral order of block copolymer domains to produce technologically-useful, sublithographic patterns is a challenge. Here, the authors present a promising approach to overcome the challenge by directing assembly using spatial boundaries between planar, low-resolution regions on a surface with different composition.

Graphene-based MoS2 nanocomposites are expected to be promising anode materials for lithium ion batteries because of their large specific capacity and high conductivity. However, the aggregation of graphene and the weak interaction between the two components hinder their practical application. Inspired by the sandwich structure, novel three-dimensional flower-like MoS2-PrGO sandwich composites were proposed as an advanced anode material for lithium-ion batteries. The separated 2D ultrathin rGO nano-sheets were connected by PEO chains and assembled into a well-organized 3D layered spatial structure, which not only avoids the aggregation of graphene but also accommodates a high mass loading of the micro-scale MoS2 nano-flowers. MoS2 nano-flowers with open architecture deliver large specific area. The rGO interlayers act as a conductive framework, making all flower-like MoS2 nano-stuffing electrochemically active. The ultra-thin 2D nano-sheets provide excellent cycle stability due to their neglectable volume changes during cycling. The 3D flower-like MoS2-PrGO sandwich composites deliver high energy density, excellent conductivity and stable cyclic performance during charge-discharge process. With a nearly 100% coulombic efficiency, their reversible capacity is retained at 1,036 mA h g−1 even after 500 cycles at current densities of 100 mA g−1. This novel design strategy provides a broad prospect for the development of advanced anode materials for superior lithium storage.

Using a combination of systematic experiments and Monte Carlo simulations, this report demonstrates that the distribution of neutral solvent has a strong impact on the quality and kinetics of the self-assembly of block copolymers in thin films. Both methyl ethyl ketone (MEK, a good solvent) and acetone (a relatively poor solvent) were used for the solvent vapor annealing (SVA) of thin films of poly(2-vinylpyridine)-block-polystyrene-block-poly(2-vinylpyridine) (VSV) triblock copolymer. Acetone, the poorer solvent, accumulated at the interface of the VSV domains, while MEK was distributed more uniformly throughout the VSV. As a result, acetone screened the interactions between the blocks of the copolymer more than MEK. Because MEK afforded less screening of the different blocks, solvent annealing with MEK led to self-assembly of lower molecular weight VSV triblock copolymers than was possible with acetone. Solvent annealing with MEK also led to slower self-assembly kinetics and smaller correlation lengths ...

Directed self-assembly (DSA) of the domain structure in block copolymer (BCP) thin films is a promising approach for sub-10-nm surface patterning. DSA requires the control of interfacial properties on both interfaces of a BCP film to induce the formation of domains that traverse the entire film with a perpendicular orientation. Here we show a methodology to control the interfacial properties of BCP films that uses a polymer topcoat deposited by initiated chemical vapour deposition (iCVD). The iCVD topcoat forms a crosslinked network that grafts to and immobilizes BCP chains to create an interface that is equally attractive to both blocks of the underlying copolymer. The topcoat, in conjunction with a chemically patterned substrate, directs the assembly of the grating structures in BCP films with a half-pitch dimension of 9.3 nm. As the iCVD topcoat can be as thin as 7 nm, it is amenable to pattern transfer without removal. The ease of vapour-phase deposition, applicability to high-resolution BCP systems and integration with pattern-transfer schemes are attractive properties of iCVD topcoats for industrial applications. A thin topcoat that grafts directly to block copolymer films does not need to be removed prior to further fabrication steps.

Directed self-assembly (DSA) of block copolymers (BCPs) combines advantages of conventional photolithography and polymeric materials and shows competence in semiconductors and data storage applications. Driven by the more integrated, much smaller and higher performance of the electronics, however, the industry standard polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) in DSA strategy cannot meet the rapid development of lithography technology because its intrinsic limited Flory–Huggins interaction parameter (χ). Despite hundreds of block copolymers have been developed, these BCPs systems are usually subject to a trade-off between high χ and thermal treatment, resulting in incompatibility with the current nanomanufacturing fab processes. Here we discover that polystyrene-b-poly(propylene carbonate) (PS-b-PPC) is well qualified to fill key positions on DSA strategy for the next-generation lithography. The estimated χ-value for PS-b-PPC is 0.079, that is, two times greater than PS-b-PMMA (χ = 0.029 at ...

Characterization of the three-dimensional (3D) structure in directed self-assembly (DSA) of block copolymers is crucial for understanding the complex relationships between the guiding template and the resulting polymer structure so DSA could be successfully implemented for advanced lithography applications. Here, we combined scanning transmission electron microscopy (STEM) tomography and coarse-grain simulations to probe the 3D structure of P2VP-b-PS-b-P2VP assembled on prepatterned templates using solvent vapor annealing. The templates consisted of nonpreferential background and raised guiding stripes that had PS-preferential top surfaces and P2VP-preferential sidewalls. The full 3D characterization allowed us to quantify the shape of the polymer domains and the interface between domains as a function of depth in the film and template geometry and offered important insights that were not accessible with 2D metrology. Sidewall guiding was advantageous in promoting the alignment and lowering the roughness of the P2VP domains over the sidewalls, but incommensurate confinement from the increased topography could cause roughness and intermittent dislocations in domains over the background region at the bottom of the film. The 3D characterization of bridge structures between domains over the background and breaks within domains on guiding lines sheds light on possible origins of common DSA defects. The positional fluctuations of the PS/P2VP interface between domains showed a depth-dependent behavior, with high levels of fluctuations near both the free surface of the film and the substrate and lower fluctuation levels in the middle of the film. This research demonstrates how 3D characterization offers a better understanding of DSA processes, leading to better design and fabrication of directing templates.

Directed self-assembly of block copolymers and self-aligned double patterning are two commonly used pitch scaling techniques to increase the density of lithographic features. In this work, both of these pitch scaling techniques were combined, enabling patterning at even higher densities. In this process, directed self-assembly of a high-? block copolymer was used to form a line/space pattern, which served as a template for mandrels. Via these mandrels, atomic layer deposition was used to deposit a thin aluminium oxide spacer. By this method, a total pitch scaling factor of 8, equivalent to a 10.5 nm full pitch, was reached. The types of defects and the line roughness at the different steps of the process were discussed.

NiO-based flexible anodes have provoked great interest due to their high theoretical capacity, benign redox reactivity, and chemical and thermal stability. However, the issues of their poor cyclability, low rate capability, and mechanical instability limit their practical applications. To approach the high-performance flexible devices, 3D NiO/TiO2 nanotube network arrays on flexible carbon cloth substrates are fabricated through a simple two-step, seed-free solvothermal method. The ultrathin NiO nanosheets provide remarkable charge-discharge cycle performance due to their slight volume expansion during the charge-discharge process. The flexible carbon cloth provides a conductive and bendable matrix. TiO2 nanotube arrays not only deliver a fast electron transfer path, but also excellent mechanical stability during bending. The porous network architecture results in a remarkable reduction in the irreversible capacity loss without sacrificing specific surface area. This unique structure creates a reversible capacity of 592.2 mAh g−1 after 1000 cycles at a current density of 200 mA g−1, and has a rate capacity of 439 mAh g−1 even at high current densities of 2000 mA g−1. Their full cells maintain excellent electrochemical performance and mechanical stability after multiple folds. The convenient synthetic process creates a window of opportunity for bringing flexible, high-performance energy storage devices to markets.

Directed self-assembly (DSA) emerges as one of the most promising new patterning techniques for single digit miniaturization and next generation lithography. DSA achieves high-resolution patterning by molecular assembly that circumvents the diffraction limit of conventional photolithography. Recently, the International Roadmap for Devices and Systems listed DSA as one of the advanced lithography techniques for the fabrication of 3–5 nm technology node devices. DSA can be combined with other lithography techniques, such as extreme ultra violet (EUV) and 193 nm immersion (193i), to further enhance the patterning resolution and the device density. So far, DSA has demonstrated its superior ability for the fabrication of nanoscale devices, such as fin field effect transistor and bit pattern media, offering a variety of configurations for high-density integration and low-cost manufacturing. Over 1 T in−2 device density can be achieved either by direct templating or coupled with nanoimprinting to improve the throughput. The development of high χ block copolymer further enhances the patterning resolution of DSA. In addition to its superiority in high-resolution patterning, the implementation of DSA on a 300 mm pivot line fully demonstrates its potential for large-scale, high-throughput, and cost-effective manufacturing in industrial environment.

Three-dimensional (3D) mesoporous thin films with sub-100 nm periodic lattices are of increasing interest as templates for a number of nanotechnology applications, yet are hard to achieve with conventional top-down fabrication methods. Block copolymer self-assembly derived mesoscale structures provide a toolbox for such 3D template formation. In this work, single (alternating) gyroidal and double gyroidal mesoporous thin-film structures are achieved via solvent vapor annealing assisted co-assembly of poly(isoprene-block-styrene-block-ethylene oxide) (PI-b-PS-b-PEO, ISO) and resorcinol/phenol formaldehyde resols. In particular, the alternating gyroid thin-film morphology is highly desirable for potential template backfilling processes as a result of the large pore volume fraction. In situ grazing-incidence small-angle X-ray scattering during solvent annealing is employed as a tool to elucidate and navigate the pathway complexity of the structure formation processes. The resulting network structures are resistant to high temperatures provided an inert atmosphere. The thin films have tunable hydrophilicity from pyrolysis at different temperatures, while pore sizes can be tailored by varying ISO molar mass. A transfer technique between substrates is demonstrated for alternating gyroidal mesoporous thin films, circumventing the need to re-optimize film formation protocols for different substrates. Increased conductivity after pyrolysis at high temperatures demonstrates that these gyroidal mesoporous resin/carbon thin films have potential as functional 3D templates for a number of nanomaterials applications. Accepted version

The pathway of interfacial self-assembly of large-scale, highly ordered 2D nanoparticle/polymer monolayer or bilayer arrays from a toluene solution at an air/water interface was investigated using grazing-incidence small-angle scattering at a synchrotron source. Interfacial-assembly of the ordered nanoparticle/polymer array was found to occur through two stages: formation of an incipient randomly close-packed interfacial monolayer followed by compression of the monolayer to form a close-packed lattice driven by solvent evaporation from the polymer. Because the nanoparticles are hydrophobic, they localize exclusively to the polymer-air interface during self-assembly, creating a through thickness asymmetric film as confirmed by X-ray reflectivity. The interfacial self-assembly approach can be extended to form binary NP/polymer arrays. It is anticipated that by understanding the interfacial self-assembly pathway, this simple evaporative procedure could be conducted as a continuous process amenable to large area nanoparticle-based manufacturing needed for emerging energy technologies.

We report the formation of nanoimprint master templates that can be used for the fabrication of bit patterned media (BPM). The template was formed by directed self-assembly, with solvent annealing, of a symmetric ABA triblock copolymer to form perpendicularly oriented lamellae on chemical patterns. We used a high-χ block copolymer, poly(2-vinyl pyridine)-block-polystyrene-block-poly(2-vinyl pyridine) to achieve smaller feature sizes than are possible with polystyrene-block-poly(methyl methacrylate). The work shows that triblock copolymers can provide a large processing window in terms of pitch commensurability. Using block-selective infiltration (atomic layer deposition with sequential long soaking/purge cycles), an alumina composite with high etch resistance was specifically incorporated into the polar and hydrophilic P2VP domains. Subsequently, the surface pattern was successfully transferred into underlying Si substrates by etching with a fluorine-containing plasma to create a nanoimprint master. The line/space pattern of the nanoimprint master met the BPM fabrication requirement of defectivity

Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyrene-block-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. The rapid assembly kinetics, minimal topography and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces.

Directed self-assembly (DSA) of block copolymers (BCPs) is a leading strategy to pattern at sublithographic resolution in the technology roadmap for semiconductors and is the only known solution to fabricate nanoimprint templates for the production of bit pattern media. While great progress has been made to implement block copolymer lithography with features in the range of 10-20 nm, patterning solutions below 10 nm are still not mature. Many BCP systems self-assemble at this length scale, but challenges remain in simultaneously tuning the interfacial energy atop the film to control the orientation of BCP domains, designing materials, templates, and processes for ultra-high-density DSA, and establishing a robust pattern transfer strategy. Among the various solutions to achieve domains that are perpendicular to the substrate, solvent annealing is advantageous because it is a versatile method that can be applied to a diversity of materials. Here we report a DSA process based on chemical contrast templates and solvent annealing to fabricate 8 nm features on a 16 nm pitch. To make this possible, a number of innovations were brought in concert with a common platform: (1) assembling the BCP in the phase-separated, solvated state, (2) identifying a larger process window for solvated triblock vs diblock BCPs as a function of solvent volume fraction, (3) employing templates for sub-10-nm BCP systems accessible by lithography, and (4) integrating a robust pattern transfer strategy by vapor infiltration of organometallic precursors for selective metal oxide synthesis to prepare an inorganic hard mask.