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 ...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 x block copolymer further enhances the patterning resolution of DSA.In addition to its superiority in high-resolution patterning,the implementation ofDSA on a 300 mm pivot line fully demonstrates its potential for large-scale,high-throughput,and cost-effective manufacturing in industrial environment.展开更多
Wettability transition is a significant responsive mechanism which is widely applied to construct smart materials and systems.The broad-spectrum responsiveness of the wettability transition makes it a promising way to...Wettability transition is a significant responsive mechanism which is widely applied to construct smart materials and systems.The broad-spectrum responsiveness of the wettability transition makes it a promising way to expand innovative applications.Here,we develop a track-guided self-transportation system mediated by sequential wettability transition accompanied with capillary transportation.Alkaline fuel is loaded into polydimethylsiloxane(PDMS)cuboid to trigger the wettability transition of distributed superhydrophobic tracks laid in shallow water.After the wettability transition,the induced capillary force can propel the repetitive track-to-track transportation of PDMS.Importantly,the spacing between adjacent tracks is rationally designed based on multiple factors including threshold of wettability transition,diffusion kinetics and capillary interaction.Furthermore,the track-guided transportation system is applied to realize directed self-assembly of multiple PDMS building blocks for designated configuration,which increases the complexity and intelligence of self-assembly systems.展开更多
We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field t...We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field theory and derive,in a non-parametric setting,the sensitivity of the dissimilarity between the desired and the actual morphologies to arbitrary perturbations in the guiding pattern shape.The sensitivity is then used for the optimization of the confining pattern shapes such that the dissimilarity between the desired and the actual morphologies is minimized.The efficiency and robustness of the proposed gradient-based algorithm are demonstrated in a number of examples related to templating vertical interconnect accesses(VIA).展开更多
Layer-by-layer polyelectrolyte self-assembly, a common method for preparing high-quality ultra-thin films, was employed to direct the self-assembly behavior of polystyrene-block-poly(methyl methacrylate)(PS-b-PMMA) bl...Layer-by-layer polyelectrolyte self-assembly, a common method for preparing high-quality ultra-thin films, was employed to direct the self-assembly behavior of polystyrene-block-poly(methyl methacrylate)(PS-b-PMMA) block copolymer for the first time. Differing from the previous neutral polymer brushes anchored to silicon substrates via chemical modification, polyelectrolyte multilayers(PEMs) were anchored by electrostatic interaction and provided a stable, smooth, and neutral interface. In the present study, PS-b-PMMA was deposited on poly(acrylamide hydrochloride)/poly(acrylic acid)(PAH/PAA) PEMs prepared by layer-by-layer self-assembly to successfully yield vertical nanodomains after thermal annealing. Seven layered PEMs revealed an excellent, smooth surface, with a low roughness of 0.6 nm. The periodic structure with interlamellar spacing of 47 nm was determined by grazing-incidence small-angle X-ray scattering(GISAXS). The morphology of the PS-b-PMMA nanodomains depended on the polyanion-to-polycation concentration ratio, which is related to the interaction between the block copolymer and the substrate. Our results demonstrate that layer-by-layer self-assembly is a helpful method for the phase separation of block polymers and the fabrication of vertical, ordered nanodomains.展开更多
Directed self-assembly has been used to create micro-nano scale patterns,including chiral periodic structures of organic molecules,for potential applications in optics,photonics,metamaterials,and medical and sensing t...Directed self-assembly has been used to create micro-nano scale patterns,including chiral periodic structures of organic molecules,for potential applications in optics,photonics,metamaterials,and medical and sensing technologies.This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques.The solution of tetrakis(4-sulfonatophenyl)porphyrin(TPPS)was induced by chiral amino acids(L/D-arginine and L/D-serine)to selfassemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate(SDS).The structures show precise line widths(5.5μm)and gaps(18μm).Using in situ optical microscopy and second harmonic generation(SHG)microscopy,the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated.It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies.This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.展开更多
The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-drive...The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-driven self-assembly strategy by half-sandwich Cp^(*)Rh units was employed to construct diverse molecular links.The pyridyl ligand,adorned with thiophene moieties,assembles into[2]catenanes(2_(1)^(2)links),whereas the isoquinolinyl ligand produces molecular Borromean links(6_(2)^(3)links).Intriguingly,when utilizing extended bithiophene segments,the pyridyl ligand forms Borromean rings(6_(2)^(3)links),while isoquinolinyl counterparts produced a rare low-symmetry cyclic[3]catenane(6_(3)^(3)topology).The results were confirmed through single-crystal X-ray diffraction analysis,nuclear magnetic resonance(NMR)spectroscopy,and electrospray ionization time-of-flight mass spectrometry(ESI-TOF/MS)experiments.Synergistic π-π stacking,C-H···π interactions,and solvophobic effects governed the complex self-assembly system,with independent gradient model(IGM)analyses and solventaccessible surface area(SASA)calculations providing atomistic insights into the pathway selectivity of distinct topological links.展开更多
Hierarchical plasmonic biomaterials constructed from small nanoparticles(NPs)that combine into larger micron-sized structures exhibit unique properties that can be harnessed for various applications.Using diffusion-li...Hierarchical plasmonic biomaterials constructed from small nanoparticles(NPs)that combine into larger micron-sized structures exhibit unique properties that can be harnessed for various applications.Using diffusion-limited aggregation(DLA)and defined peptide sequences,we developed fractal silver biomaterials with a Brownian tree structure.This method avoids complex redox chemistry and allows precise control of interparticle distance and material morphology through peptide design and concentration.Our systematic investigation revealed how peptide charge,length,and sequence impact biomaterial morphology,confirming that peptides act as bridging motifs between particles and induce coalescence.Characterization through spectroscopy and microscopy demonstrated that arginine-based peptides are optimal for fractal assembly based on both quantitative and qualitative measurements.Additionally,our study of diffusion behavior confirmed the effect of particle size,temperature,and medium viscosity on nanoparticle mobility.This work also provides insights into the facet distribution in silver NPs and their assembly mechanisms,offering potential advancements in the design of materials for medical,environmental,and electronic applications.展开更多
The fatigue crack growth rate of a novel Ti-6Al-4V-1Mo titanium alloy,which is developed for laser directed energy deposition technique,was investigated before and after cyclic heat treatment(CHT).Changes in microstru...The fatigue crack growth rate of a novel Ti-6Al-4V-1Mo titanium alloy,which is developed for laser directed energy deposition technique,was investigated before and after cyclic heat treatment(CHT).Changes in microstructure,fracture surfaces,and crack growth paths were analyzed before and after CHT.Results indicate that in the stable crack growth region,the growth rates for the as-deposited and cyclic heat-treated specimens follow the relationships da/dN=1.8651×10^(−8)(ΔK)^(3.2271)and da/dN=1.4112×10^(−8)(ΔK)^(3.1125),respectively.Compared with that at the as-deposited state,the microstructure after CHT is transformed from a uniform basket-weave microstructure to a dual-phase microstructure consisting of near-sphericalαandβ-transformed matrix phases.The cyclic process also disrupts the continuity of the grain boundaryα(αGB)at the primaryβ-phase grain boundary.The coarsening of primaryαand the disruption ofαGB continuity are the primary factors to release stress concentration and promote crack deflection,thereby decreasing the fatigue crack growth rate.Additionally,the increased occurrence of crack branching,secondary cracking,and crack bridging in cyclic heat-treated specimens further reduces the crack driving force and slows the fatigue crack growth rate.展开更多
The Cooling-Storage-Ring External-target Experiment(CEE)at the Heavy Ion Research Facility in Lanzhou(HIRFL)is designed to study the properties of nuclear matter created in heavy-ion collisions at beam energies from a...The Cooling-Storage-Ring External-target Experiment(CEE)at the Heavy Ion Research Facility in Lanzhou(HIRFL)is designed to study the properties of nuclear matter created in heavy-ion collisions at beam energies from a few hundred MeV/u up to 1 GeV/u.It aims to facilitate research on the quantum chromodynamics(QCD)phase structure in the high-baryondensity region.Collective flow is a fundamental observable in heavy-ion collision experiments,providing information on the bulk properties of the produced matter.Although the standard event plane method has been widely used to measure collective flow,it is still important to validate and optimize this method for the CEE spectrometer.In this paper,we study the experimental procedures for measuring directed flow in^(238)U+^(238)U collisions at 500 MeV/u,using event planes reconstructed by Multi-Wire Drift Chamber and Zero Degree Calorimeter,respectively.Jet AA Microscopic(JAM)transport generator is used to generate events,and the detector response is simulated by the CEE Fast Simulation(CFS)package.Finally,the optimal kinematic region for proton directed flow measurements is discussed for the future CEE experiment.展开更多
Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a s...Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a significant challenge and has not yet been reported.In this work,we develop a hydrogen bond self-assembly(HBSA)strategy that is triggered by the acidic tumor microenvironment to enable the photodynamic transition of tetra(4-carboxylphenyl)porphyrin(TCPP)PSs from type Ⅱ to type Ⅰ reactions.Upon self-assembly of TCPP monomers into TCPP assemblies(TCPP-ass),the generated reactive oxygen species shift from singlet oxygen to superoxide anions,which induces caspase-3/GSDME-mediated programmed pyroptosis,enabling rapid and complete solid tumor elimination with minimized adverse effects and enhanced therapeutic efficacy.Crucially,the HBSA process occurs exclusively within tumor cells,and this tumor-specific self-assembly strategy not only utilizes high tissue penetration of TCPP molecular-PSs,but also avoids phototoxicity caused by the formation and accumulation of TCPP-ass nano-PSs in normal tissue,providing an innovative approach for precise cancer therapy.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
Since the discovery of a surfactant directed self-assembly approach for the fabrication of mesoporous silica in 1992,increasing attention has been focused on the design and synthesis of mesostructured functional mater...Since the discovery of a surfactant directed self-assembly approach for the fabrication of mesoporous silica in 1992,increasing attention has been focused on the design and synthesis of mesostructured functional materials.Organic functionalization is becoming a major topic in this research field,since highly ordered mesostructured organic-inorganic hybrids offer novel functionalities and enhanced performance over their individual components.We begin with a brief overview of the three fundamental methods(post-synthetic grafting technique,co-condensation method,and preparation of periodic mesoporous organosilicas) for the preparation of organically functionalized mesostructured silica,and focus on one of the most promising approaches,which herein was named as functional-template directed self-assembly(FTDSA) approach,and in the eyes of the authors it has a special position in the preparation of this class of hybrid materials.A comprehensive overview of the state of research in the area of FTDSA and its potential applications will be given.展开更多
The exciton-plasmon interaction between fluorescent colloidal semiconductor quantum dots and plasmonic metal nanoparticles may lead to emission quenching or enhancement of quantum dots, which have potential appli- cat...The exciton-plasmon interaction between fluorescent colloidal semiconductor quantum dots and plasmonic metal nanoparticles may lead to emission quenching or enhancement of quantum dots, which have potential appli- cations in renewable energy, nanophotonics, and biosensing. Semiconductor quantum dots and metal nanoparticles hybrids with controlled geometry, distance, and stoichiometry are crucial for the potential applications. While DNA nanotechnology, based on Watson-Crick base-pairing interactions between two single-stranded DNAs, has provided unique opportunities to generate fully programmable, functional metal nanoparticles and semiconductor quantum dots hybrid nanomaterials, and offers precisely control over the spacing, orientation, and chirality of the compo- nents. This review provides the highlights of the recent progresses in DNA directed self-assembly of colloidal sem- iconductor quantum dots and metallic nanoparticles heterogeneous nanomaterials. We also discuss the challenges and the trends in DNA directed self-assembly of semiconductor quantum dots and metallic nanoparticles hybrid nanomaterials.展开更多
While enol-keto tautomerism has attracted great interest in Schiff bases and related compounds in solution and crystal states,the self-assembly of energy-unfavored keto form were scarcely investigated.Here,we report a...While enol-keto tautomerism has attracted great interest in Schiff bases and related compounds in solution and crystal states,the self-assembly of energy-unfavored keto form were scarcely investigated.Here,we report a keto-form directed self-assembly of a naphthalene-attached enantiomeric N-salicylideneanil analog L/DGG-Nap accompanied with a significantly amplified circularly polarized luminescence(CPL).It was found that LGG-Nap exists as a mixture of enol and keto form in monomer at a diluted toluene solution.The increment of the concentrations leads to the formation of predominated keto form,which subsequently triggers the self-assembly.Cryo-transmission electron microscopy(Cryo-TEM)revealed that a hierarchical assembly process happened upon increasing the concentration of LGG-Nap in toluene.Individual nanofibers formed at 1×10-4 mol/L and transferred into helical nanofiber bundles in 5×10-3 mol/L.Interestingly,while these is nearly no circular dichroism(CD)or CPL in the monomeric solution,the assembly showed strong CD and CPL.Remarkably,the dissymmetry factor(glum)was significantly amplified from zero in solution through the 0.005 in individual nanofiber to 0.1 in nanofiber bundles.This work demonstrates that the enol-keto tautomerism can be broken and trigger the self-assembly upon increasing the concentration,which can subsequently direct the chiral self-assembly and significantly amplify the dissymmetry factor of assembled CPL materials.展开更多
Highly intricate surface architectures derived from patterned polymer microstructures have received increasing concern in recent years.Directional photo-manipulation(DPM)of azopolymers is one of the effective strategi...Highly intricate surface architectures derived from patterned polymer microstructures have received increasing concern in recent years.Directional photo-manipulation(DPM)of azopolymers is one of the effective strategies to tune the patterned polymer microstructures through directional mass migration(DMM)upon polarized light illumination.In this feature article,we emphasize the latest advances of DPM on azopatterns created by self-assembly.The mechanism of DMM,the photo-manipulation performance,and functions of manipulated patterns are introduced in sequence.As presented,DPM can manipulate the as-prepared microstructures feasibly by taking the advantages of non-contacting and nondestructive characters.Moreover,the challenges and opportunities of DPM strategy are discussed in conclusion.展开更多
Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practica...Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.展开更多
The layer-by-layer deposition strategy of additive manufacturing makes it ideal to fabricate dissimilar alloy components with varying functionality,which has promising application potential in a large number of indust...The layer-by-layer deposition strategy of additive manufacturing makes it ideal to fabricate dissimilar alloy components with varying functionality,which has promising application potential in a large number of industrial areas.In this study,two components composed of ERCuAl-A2 aluminum bronze(CuAl9)and Inconel 718 nickel-based superalloy were fabricated with different deposition orders by wire-arc directed energy deposition.Subject to changes in heat input and thermophysical properties of the substrate,the transition region of the deposited Cu-Ni component with the bottom half of CuAl9 and the top half of Inconel 718 is narrow and serrated.This region features a laminated intermetallic compound layer due to the convection and rapid cooling in the molten pool.In contrast,the Ni-Cu component deposited in the opposite order exhibits a 2 mm gradient transition zone.Within this region,a large number of diverse precipitates were found as well as regional variations in grain size due to the multi-layer partial remelting.Both two components show strong bonds and their tensile specimens tested along the vertical direction always fracture at the softer CuAl9 side.Excellent tensile properties along the horizontal direction were obtained for Cu-Ni(Ultimate tensile strength:573 MPa,yield stress:302 MPa,elongation:22%),while those of Ni-Cu are much lower due to the existence of the solidification cracks in the transition zone.The results from this study provide a reference for the additive manufacturing of Cu/Ni dissimilar alloy components,as well as their microstructure and mechanical properties control.展开更多
Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,whic...Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.展开更多
Solution and aging treatment were conducted on the laser directed energy deposition(LDED)-prepared carbon nanotubes(CNTs)-reinforced WE43(CNTs/WE43)layers to optimize their microstructure and surface properties in thi...Solution and aging treatment were conducted on the laser directed energy deposition(LDED)-prepared carbon nanotubes(CNTs)-reinforced WE43(CNTs/WE43)layers to optimize their microstructure and surface properties in this study.The microstructure of the WE43 and CNTs/WE43 layers was systematically compared.The dissolution of divorced eutectics at the grain boundaries was retarded by CNTs during solution treatment.The spot segregation composed of Mg_(24)Y_(5),CNTs,and Zr cores in the solution treated CNTs/WE43 layer presented a slight decreasing in Y content.The grain growth of both types of layers underwent three stages:slow,rapid,and steady-state.The significant inhibitory effect of CNTs on the grain growth of the LDED WE43 matrix was more pronounced than the promoting effect of temperature,resulting in a 47%increase at 510℃ and a 35%increase at 540℃ in the grain growth exponent compared to the WE43 layers at 510℃.During the subsequent aging treatment at 225℃,the precipitation sequences from plate-shaped β″to plate-shaped and globular β′ were observed in both types of layers.CNTs can facilitate an increase in the nucleation rate of precipitates,but without accelerating precipitation hardening rate.The long and short diameters of the precipitates in peak-aged state were decreased by 48.5%and 43.1%by addition of CNTs,respectively.The wear resistance of both the WE43 and CNTs/WE43 layers can be significantly enhanced through solution and aging treatment.The enhancement in wear resistance for the CNTs/WE43 layers is considerably greater than that of the WE43 layers.展开更多
Under the laser directed energy deposition(LDED)process,the rapid melting and solidification usually lead to the emergence of pores and coarse columnar dendrites,which in turn compromise the properties of the deposite...Under the laser directed energy deposition(LDED)process,the rapid melting and solidification usually lead to the emergence of pores and coarse columnar dendrites,which in turn compromise the properties of the deposited alloys.This study introduced in-situ ultrasonic rolling(UR)as an innovative method to enhance the corrosion resistance of LDED specimens,and the microstructural characteristics and their correlation with corrosion resistance were deeply investigated.The findings reveal that the LDED-UR specimen exhibits a reduction in both the fraction and size of pores.Under the influence of severe plastic deformation generated by LDED-UR process,fully equiaxed grains appear with a reduced average size of 28.61μm(compared to63.98μm for the LDED specimen with columnar grains).The electrochemical corrosion resistance of the LDED-UR specimen is significantly enhanced compared to the LDED specimen.This enhanced corrosion resistance can be attributed to the low fraction of small-sized pores,the fine and uniformly distributed Cr-enriched ferrite phase,and the formation of a compact and thick passive film due to dense grain boundaries.The insight of the correlation between microstructure and corrosion behavior opens up a new pathway to enhance the corrosion resistance of LDED specimens.展开更多
文摘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 x block copolymer further enhances the patterning resolution of DSA.In addition to its superiority in high-resolution patterning,the implementation ofDSA on a 300 mm pivot line fully demonstrates its potential for large-scale,high-throughput,and cost-effective manufacturing in industrial environment.
基金supported by the National Natural Science Foundation of China(Nos.52122315,21972008)Beijing Nova Program(No.Z201100006820021).
文摘Wettability transition is a significant responsive mechanism which is widely applied to construct smart materials and systems.The broad-spectrum responsiveness of the wettability transition makes it a promising way to expand innovative applications.Here,we develop a track-guided self-transportation system mediated by sequential wettability transition accompanied with capillary transportation.Alkaline fuel is loaded into polydimethylsiloxane(PDMS)cuboid to trigger the wettability transition of distributed superhydrophobic tracks laid in shallow water.After the wettability transition,the induced capillary force can propel the repetitive track-to-track transportation of PDMS.Importantly,the spacing between adjacent tracks is rationally designed based on multiple factors including threshold of wettability transition,diffusion kinetics and capillary interaction.Furthermore,the track-guided transportation system is applied to realize directed self-assembly of multiple PDMS building blocks for designated configuration,which increases the complexity and intelligence of self-assembly systems.
文摘We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field theory and derive,in a non-parametric setting,the sensitivity of the dissimilarity between the desired and the actual morphologies to arbitrary perturbations in the guiding pattern shape.The sensitivity is then used for the optimization of the confining pattern shapes such that the dissimilarity between the desired and the actual morphologies is minimized.The efficiency and robustness of the proposed gradient-based algorithm are demonstrated in a number of examples related to templating vertical interconnect accesses(VIA).
基金financially supported by the National Natural Science Foundation of China (Nos. 11605149, 11405259, U1932118, and U1732123)the Natural Science Foundation of Hunan Province (No. 2017JJ3309)+3 种基金the China Postdoctoral Science Foundation (No. 2017 M622595)the Zhejiang Public Service Technology Research Program/Analytical Test (No. LGC19F040001)the National Key R&D Program of China (No. 2017YFA0403000)the Science and Technology Commission of Shanghai Municipality (No. 17JC1400802)
文摘Layer-by-layer polyelectrolyte self-assembly, a common method for preparing high-quality ultra-thin films, was employed to direct the self-assembly behavior of polystyrene-block-poly(methyl methacrylate)(PS-b-PMMA) block copolymer for the first time. Differing from the previous neutral polymer brushes anchored to silicon substrates via chemical modification, polyelectrolyte multilayers(PEMs) were anchored by electrostatic interaction and provided a stable, smooth, and neutral interface. In the present study, PS-b-PMMA was deposited on poly(acrylamide hydrochloride)/poly(acrylic acid)(PAH/PAA) PEMs prepared by layer-by-layer self-assembly to successfully yield vertical nanodomains after thermal annealing. Seven layered PEMs revealed an excellent, smooth surface, with a low roughness of 0.6 nm. The periodic structure with interlamellar spacing of 47 nm was determined by grazing-incidence small-angle X-ray scattering(GISAXS). The morphology of the PS-b-PMMA nanodomains depended on the polyanion-to-polycation concentration ratio, which is related to the interaction between the block copolymer and the substrate. Our results demonstrate that layer-by-layer self-assembly is a helpful method for the phase separation of block polymers and the fabrication of vertical, ordered nanodomains.
基金funding from the National Natural Science Foundation of China(NSFC,Nos.22173112 and 91856121)Chinese Academy of Sciences for support(No.YJKYYQ20180014)。
文摘Directed self-assembly has been used to create micro-nano scale patterns,including chiral periodic structures of organic molecules,for potential applications in optics,photonics,metamaterials,and medical and sensing technologies.This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques.The solution of tetrakis(4-sulfonatophenyl)porphyrin(TPPS)was induced by chiral amino acids(L/D-arginine and L/D-serine)to selfassemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate(SDS).The structures show precise line widths(5.5μm)and gaps(18μm).Using in situ optical microscopy and second harmonic generation(SHG)microscopy,the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated.It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies.This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.
基金supported by the Department of Chemistry,Fudan Universitythe National Natural Science Foundation of China(22031003,21720102004)the Shanghai Science Technology Committee(19DZ2270100)。
文摘The 6-isoquinolinyl system was incorporated into mechanically interlocked molecules(MIMs)syntheses for comparative analysis of its assembly behavior with 4-pyridyl-based coordination ligands,where a coordination-driven self-assembly strategy by half-sandwich Cp^(*)Rh units was employed to construct diverse molecular links.The pyridyl ligand,adorned with thiophene moieties,assembles into[2]catenanes(2_(1)^(2)links),whereas the isoquinolinyl ligand produces molecular Borromean links(6_(2)^(3)links).Intriguingly,when utilizing extended bithiophene segments,the pyridyl ligand forms Borromean rings(6_(2)^(3)links),while isoquinolinyl counterparts produced a rare low-symmetry cyclic[3]catenane(6_(3)^(3)topology).The results were confirmed through single-crystal X-ray diffraction analysis,nuclear magnetic resonance(NMR)spectroscopy,and electrospray ionization time-of-flight mass spectrometry(ESI-TOF/MS)experiments.Synergistic π-π stacking,C-H···π interactions,and solvophobic effects governed the complex self-assembly system,with independent gradient model(IGM)analyses and solventaccessible surface area(SASA)calculations providing atomistic insights into the pathway selectivity of distinct topological links.
基金University of California,San Diego-Cellular and Molecular Medicine Electron Microscopy Core,Grant/Award Number:SCR_022039National Institutes of Health,Grant/Award Numbers:S10 OD023527,R21 DE029917,R01 DE031307,S10OD023555-A1National Science Foundation,Grant/Award Numbers:DMR-2242375,DMR-2011924,ECCS-2025752。
文摘Hierarchical plasmonic biomaterials constructed from small nanoparticles(NPs)that combine into larger micron-sized structures exhibit unique properties that can be harnessed for various applications.Using diffusion-limited aggregation(DLA)and defined peptide sequences,we developed fractal silver biomaterials with a Brownian tree structure.This method avoids complex redox chemistry and allows precise control of interparticle distance and material morphology through peptide design and concentration.Our systematic investigation revealed how peptide charge,length,and sequence impact biomaterial morphology,confirming that peptides act as bridging motifs between particles and induce coalescence.Characterization through spectroscopy and microscopy demonstrated that arginine-based peptides are optimal for fractal assembly based on both quantitative and qualitative measurements.Additionally,our study of diffusion behavior confirmed the effect of particle size,temperature,and medium viscosity on nanoparticle mobility.This work also provides insights into the facet distribution in silver NPs and their assembly mechanisms,offering potential advancements in the design of materials for medical,environmental,and electronic applications.
基金National Key Research and Development Program of China(2024YFB4610803)。
文摘The fatigue crack growth rate of a novel Ti-6Al-4V-1Mo titanium alloy,which is developed for laser directed energy deposition technique,was investigated before and after cyclic heat treatment(CHT).Changes in microstructure,fracture surfaces,and crack growth paths were analyzed before and after CHT.Results indicate that in the stable crack growth region,the growth rates for the as-deposited and cyclic heat-treated specimens follow the relationships da/dN=1.8651×10^(−8)(ΔK)^(3.2271)and da/dN=1.4112×10^(−8)(ΔK)^(3.1125),respectively.Compared with that at the as-deposited state,the microstructure after CHT is transformed from a uniform basket-weave microstructure to a dual-phase microstructure consisting of near-sphericalαandβ-transformed matrix phases.The cyclic process also disrupts the continuity of the grain boundaryα(αGB)at the primaryβ-phase grain boundary.The coarsening of primaryαand the disruption ofαGB continuity are the primary factors to release stress concentration and promote crack deflection,thereby decreasing the fatigue crack growth rate.Additionally,the increased occurrence of crack branching,secondary cracking,and crack bridging in cyclic heat-treated specimens further reduces the crack driving force and slows the fatigue crack growth rate.
基金supported in part by the National Key R&D Program of China(No.2024YFA1610700)the National Natural Science Foundation of China(No.12475147)。
文摘The Cooling-Storage-Ring External-target Experiment(CEE)at the Heavy Ion Research Facility in Lanzhou(HIRFL)is designed to study the properties of nuclear matter created in heavy-ion collisions at beam energies from a few hundred MeV/u up to 1 GeV/u.It aims to facilitate research on the quantum chromodynamics(QCD)phase structure in the high-baryondensity region.Collective flow is a fundamental observable in heavy-ion collision experiments,providing information on the bulk properties of the produced matter.Although the standard event plane method has been widely used to measure collective flow,it is still important to validate and optimize this method for the CEE spectrometer.In this paper,we study the experimental procedures for measuring directed flow in^(238)U+^(238)U collisions at 500 MeV/u,using event planes reconstructed by Multi-Wire Drift Chamber and Zero Degree Calorimeter,respectively.Jet AA Microscopic(JAM)transport generator is used to generate events,and the detector response is simulated by the CEE Fast Simulation(CFS)package.Finally,the optimal kinematic region for proton directed flow measurements is discussed for the future CEE experiment.
基金supported by the National Natural Science Foundation of China(22176058)the Science and Technology Commission of Shanghai Municipality(24DX1400200,23ZR1416100,25ZR1401082)+1 种基金the Program of Introducing Talents of Discipline to Universities(B16017)the Fundamental Research Funds for the Central Universities(222201717003)。
文摘Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a significant challenge and has not yet been reported.In this work,we develop a hydrogen bond self-assembly(HBSA)strategy that is triggered by the acidic tumor microenvironment to enable the photodynamic transition of tetra(4-carboxylphenyl)porphyrin(TCPP)PSs from type Ⅱ to type Ⅰ reactions.Upon self-assembly of TCPP monomers into TCPP assemblies(TCPP-ass),the generated reactive oxygen species shift from singlet oxygen to superoxide anions,which induces caspase-3/GSDME-mediated programmed pyroptosis,enabling rapid and complete solid tumor elimination with minimized adverse effects and enhanced therapeutic efficacy.Crucially,the HBSA process occurs exclusively within tumor cells,and this tumor-specific self-assembly strategy not only utilizes high tissue penetration of TCPP molecular-PSs,but also avoids phototoxicity caused by the formation and accumulation of TCPP-ass nano-PSs in normal tissue,providing an innovative approach for precise cancer therapy.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 20821091 and 20771009)
文摘Since the discovery of a surfactant directed self-assembly approach for the fabrication of mesoporous silica in 1992,increasing attention has been focused on the design and synthesis of mesostructured functional materials.Organic functionalization is becoming a major topic in this research field,since highly ordered mesostructured organic-inorganic hybrids offer novel functionalities and enhanced performance over their individual components.We begin with a brief overview of the three fundamental methods(post-synthetic grafting technique,co-condensation method,and preparation of periodic mesoporous organosilicas) for the preparation of organically functionalized mesostructured silica,and focus on one of the most promising approaches,which herein was named as functional-template directed self-assembly(FTDSA) approach,and in the eyes of the authors it has a special position in the preparation of this class of hybrid materials.A comprehensive overview of the state of research in the area of FTDSA and its potential applications will be given.
文摘The exciton-plasmon interaction between fluorescent colloidal semiconductor quantum dots and plasmonic metal nanoparticles may lead to emission quenching or enhancement of quantum dots, which have potential appli- cations in renewable energy, nanophotonics, and biosensing. Semiconductor quantum dots and metal nanoparticles hybrids with controlled geometry, distance, and stoichiometry are crucial for the potential applications. While DNA nanotechnology, based on Watson-Crick base-pairing interactions between two single-stranded DNAs, has provided unique opportunities to generate fully programmable, functional metal nanoparticles and semiconductor quantum dots hybrid nanomaterials, and offers precisely control over the spacing, orientation, and chirality of the compo- nents. This review provides the highlights of the recent progresses in DNA directed self-assembly of colloidal sem- iconductor quantum dots and metallic nanoparticles heterogeneous nanomaterials. We also discuss the challenges and the trends in DNA directed self-assembly of semiconductor quantum dots and metallic nanoparticles hybrid nanomaterials.
基金National Natural Science foundation of China(Nos.21861132002,21773043,21973020 and 21890734).
文摘While enol-keto tautomerism has attracted great interest in Schiff bases and related compounds in solution and crystal states,the self-assembly of energy-unfavored keto form were scarcely investigated.Here,we report a keto-form directed self-assembly of a naphthalene-attached enantiomeric N-salicylideneanil analog L/DGG-Nap accompanied with a significantly amplified circularly polarized luminescence(CPL).It was found that LGG-Nap exists as a mixture of enol and keto form in monomer at a diluted toluene solution.The increment of the concentrations leads to the formation of predominated keto form,which subsequently triggers the self-assembly.Cryo-transmission electron microscopy(Cryo-TEM)revealed that a hierarchical assembly process happened upon increasing the concentration of LGG-Nap in toluene.Individual nanofibers formed at 1×10-4 mol/L and transferred into helical nanofiber bundles in 5×10-3 mol/L.Interestingly,while these is nearly no circular dichroism(CD)or CPL in the monomeric solution,the assembly showed strong CD and CPL.Remarkably,the dissymmetry factor(glum)was significantly amplified from zero in solution through the 0.005 in individual nanofiber to 0.1 in nanofiber bundles.This work demonstrates that the enol-keto tautomerism can be broken and trigger the self-assembly upon increasing the concentration,which can subsequently direct the chiral self-assembly and significantly amplify the dissymmetry factor of assembled CPL materials.
基金financially supported by the National Natural Science Foundation of China(Nos.51622301 and 51573046)Projects of Shanghai Municipality(Nos.14SG29 and 17JC400700)Fundamental Research Funds for the Central Universities(No.222201718002)
文摘Highly intricate surface architectures derived from patterned polymer microstructures have received increasing concern in recent years.Directional photo-manipulation(DPM)of azopolymers is one of the effective strategies to tune the patterned polymer microstructures through directional mass migration(DMM)upon polarized light illumination.In this feature article,we emphasize the latest advances of DPM on azopatterns created by self-assembly.The mechanism of DMM,the photo-manipulation performance,and functions of manipulated patterns are introduced in sequence.As presented,DPM can manipulate the as-prepared microstructures feasibly by taking the advantages of non-contacting and nondestructive characters.Moreover,the challenges and opportunities of DPM strategy are discussed in conclusion.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.2020R1C1C1003375)。
文摘Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^(-2)and long cycle life(1000 h,1 mA·cm^(-2),and 1.0 mAh·cm^(-2)).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.
基金supported by the Key Research and Development Program of Shaanxi Province(2023-YBGY361)the National Natural Science Foundation of China(52275374 and 52205414)+1 种基金the Postdoctoral Fellowship Program of CPSF(GZC20232098)as well as the Xiaomi Foundation through Xiaomi Young Scholar Program。
文摘The layer-by-layer deposition strategy of additive manufacturing makes it ideal to fabricate dissimilar alloy components with varying functionality,which has promising application potential in a large number of industrial areas.In this study,two components composed of ERCuAl-A2 aluminum bronze(CuAl9)and Inconel 718 nickel-based superalloy were fabricated with different deposition orders by wire-arc directed energy deposition.Subject to changes in heat input and thermophysical properties of the substrate,the transition region of the deposited Cu-Ni component with the bottom half of CuAl9 and the top half of Inconel 718 is narrow and serrated.This region features a laminated intermetallic compound layer due to the convection and rapid cooling in the molten pool.In contrast,the Ni-Cu component deposited in the opposite order exhibits a 2 mm gradient transition zone.Within this region,a large number of diverse precipitates were found as well as regional variations in grain size due to the multi-layer partial remelting.Both two components show strong bonds and their tensile specimens tested along the vertical direction always fracture at the softer CuAl9 side.Excellent tensile properties along the horizontal direction were obtained for Cu-Ni(Ultimate tensile strength:573 MPa,yield stress:302 MPa,elongation:22%),while those of Ni-Cu are much lower due to the existence of the solidification cracks in the transition zone.The results from this study provide a reference for the additive manufacturing of Cu/Ni dissimilar alloy components,as well as their microstructure and mechanical properties control.
文摘Four glycoluril-based amphiphilic molecular clips(AMCs)M1~M4 have been prepared for intracellular delivery of short DNA.M1~M4 have two methyl groups on its convex surface and four cations on its aromatic side arm,which can be used to construct self-assembled nanoparticles in aqueous solution driven by hydrophobic interaction.Dynamic light scattering experiments show that M1 and M2 can be driven hydrophobically to aggregate into extremely stable nanoparticles in water at the micromolar concentrations.Fluorescence titration and zeta potential experiments support that the nanoparticles formed by M1 and M2 are able to efficiently encapsulate short DNA(sDNA).Fluorescence imaging and flow cytometry studies reveal that their nano sizes enable intracellular delivery of the encapsulated sDNA into both normal and cancer cells,with delivery percentage reaching up to 94%,while in vitro experiments indicate that the two compounds have excellent biocompatibility and low cytotoxicity.
基金supported by the National Natural Science Foundation of China(52005264).
文摘Solution and aging treatment were conducted on the laser directed energy deposition(LDED)-prepared carbon nanotubes(CNTs)-reinforced WE43(CNTs/WE43)layers to optimize their microstructure and surface properties in this study.The microstructure of the WE43 and CNTs/WE43 layers was systematically compared.The dissolution of divorced eutectics at the grain boundaries was retarded by CNTs during solution treatment.The spot segregation composed of Mg_(24)Y_(5),CNTs,and Zr cores in the solution treated CNTs/WE43 layer presented a slight decreasing in Y content.The grain growth of both types of layers underwent three stages:slow,rapid,and steady-state.The significant inhibitory effect of CNTs on the grain growth of the LDED WE43 matrix was more pronounced than the promoting effect of temperature,resulting in a 47%increase at 510℃ and a 35%increase at 540℃ in the grain growth exponent compared to the WE43 layers at 510℃.During the subsequent aging treatment at 225℃,the precipitation sequences from plate-shaped β″to plate-shaped and globular β′ were observed in both types of layers.CNTs can facilitate an increase in the nucleation rate of precipitates,but without accelerating precipitation hardening rate.The long and short diameters of the precipitates in peak-aged state were decreased by 48.5%and 43.1%by addition of CNTs,respectively.The wear resistance of both the WE43 and CNTs/WE43 layers can be significantly enhanced through solution and aging treatment.The enhancement in wear resistance for the CNTs/WE43 layers is considerably greater than that of the WE43 layers.
基金financial supports from the National Natural Science Foundation of China (No.52305440)the Natural Science Foundation of Changsha City (Nos.kq2208272,kq2208274)+1 种基金the Tribology Science Fund of the State Key Laboratory of Tribology in Advanced Equipment (SKLTKF22B09)the National Key Research and Development Program of China (2022YFB3706902)。
文摘Under the laser directed energy deposition(LDED)process,the rapid melting and solidification usually lead to the emergence of pores and coarse columnar dendrites,which in turn compromise the properties of the deposited alloys.This study introduced in-situ ultrasonic rolling(UR)as an innovative method to enhance the corrosion resistance of LDED specimens,and the microstructural characteristics and their correlation with corrosion resistance were deeply investigated.The findings reveal that the LDED-UR specimen exhibits a reduction in both the fraction and size of pores.Under the influence of severe plastic deformation generated by LDED-UR process,fully equiaxed grains appear with a reduced average size of 28.61μm(compared to63.98μm for the LDED specimen with columnar grains).The electrochemical corrosion resistance of the LDED-UR specimen is significantly enhanced compared to the LDED specimen.This enhanced corrosion resistance can be attributed to the low fraction of small-sized pores,the fine and uniformly distributed Cr-enriched ferrite phase,and the formation of a compact and thick passive film due to dense grain boundaries.The insight of the correlation between microstructure and corrosion behavior opens up a new pathway to enhance the corrosion resistance of LDED specimens.
