A Non-parametric Gradient-Based Shape Optimization Approach for Solving Inverse Problems in Directed Self-Assemblyof Block Copolymers

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).

Directed self-assembly of block copolymers for sub-10 nm fabrication

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.

Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy

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.

Interfacial self-transportation via controlled wettability transition for directed self-assembly

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.

Electrostatic Interaction-directed Construction of Hierarchical Nanostructured Carbon Composite with Dual Electrical Conductive Networks for Zinc-ion Hybrid Capacitors with Ultrastability

Metal-organic framework(MOF)-derived carbon composites have been considered as the promising materials for energy storage.However,the construction of MOF-based composites with highly controllable mode via the liquid-liquid synthesis method has a great challenge because of the simultaneous heterogeneous nucleation on substrates and the self-nucleation of individual MOF nanocrystals in the liquid phase.Herein,we report a bidirectional electrostatic generated self-assembly strategy to achieve the precisely controlled coatings of single-layer nanoscale MOFs on a range of substrates,including carbon nanotubes(CNTs),graphene oxide(GO),MXene,layered double hydroxides(LDHs),MOFs,and SiO_(2).The obtained MOF-based nanostructured carbon composite exhibits the hierarchical porosity(V_(meso)/V_(micro)∶2.4),ultrahigh N content of 12.4 at.%and"dual electrical conductive networks."The assembled aqueous zinc-ion hybrid capacitor(ZIC)with the prepared nanocarbon composite as a cathode shows a high specific capacitance of 236 F g^(-1)at 0.5 A g^(-1),great rate performance of 98 F g^(-1)at 100 A g^(-1),and especially,an ultralong cycling stability up to 230000 cycles with the capacitance retention of 90.1%.This work develops a repeatable and general method for the controlled construction of MOF coatings on various functional substrates and further fabricates carbon composites for ZICs with ultrastability.

Review on laser directed energy deposited aluminum alloys

Lightweight aluminum(Al)alloys have been widely used in frontier fields like aerospace and automotive industries,which attracts great interest in additive manufacturing(AM)to process high-value Al parts.As a mainstream AM technique,laser-directed energy deposition(LDED)shows good scalability to meet the requirements for large-format component manufacturing and repair.However,LDED Al alloys are highly challenging due to their inherent poor printability(e.g.low laser absorption,high oxidation sensitivity and cracking tendency).To further promote the development of LDED high-performance Al alloys,this review offers a deep understanding of the challenges and strategies to improve printability in LDED Al alloys.The porosity,cracking,distortion,inclusions,element evaporation and resultant inferior mechanical properties(worse than laser powder bed fusion)are the key challenges in LDED Al alloys.Processing parameter optimizations,in-situ alloy design,reinforcing particle addition and field assistance are the efficient approaches to improving the printability and performance of LDED Al alloys.The underlying correlations between processes,alloy innovation,characteristic microstructures,and achievable performances in LDED Al alloys are discussed.The benchmark mechanical properties and primary strengthening mechanism of LDED Al alloys are summarized.This review aims to provide a critical and in-depth evaluation of current progress in LDED Al alloys.Future opportunities and perspectives in LDED high-performance Al alloys are also outlined.

Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Chitosan/Sodium Alginate Multilayer pH-Sensitive Films Based on Layer-by-Layer Self-Assembly for Intelligent Packaging

The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.

Hollow tubes constructed by carbon nanotubes self-assembly for CO_(2) capture

Carbon nanotubes(CNTs)have garnered significant attention in the fields of science,engineering,and medicine due to their numerous advantages.The initial step towards harnessing the potential of CNTs involves their macroscopic assembly.The present study employed a gentle and direct self-assembly technique,wherein controlled growth of CNT sheaths occurred on the metal wire’s surface,followed by etching of the remaining metal to obtain the hollow tubes composed of CNTs.By controlling the growth time and temperature,it is possible to alter the thickness of the CNTs sheath.After immersing in a solution containing 1 g/L of CNTs at 60℃for 24 h,the resulting CNTs layer achieved a thickness of up to 60μm.These hollow CNTs tubes with varying inner diameters were prepared through surface reinforcement using polymers and sacrificing metal wires,thereby exhibiting exceptional attributes such as robustness,flexibility,air tightness,and high adsorption capacity that effectively capture CO_(2) from the gas mixture.

Printability disparities in heterogeneous material combinations via laser directed energy deposition:a comparative study

Additive manufacturing provides achievability for the fabrication of bimetallic and multi-material structures;however,the material compatibility and bondability directly affect the parts’formability and final quality.It is essential to understand the underlying printability of different material combinations based on an adapted process.Here,the printability disparities of two common and attractive material combinations(nickel-and iron-based alloys)are evaluated at the macro and micro levels via laser directed energy deposition(DED).The deposition processes were captured using in situ high-speed imaging,and the dissimilarities in melt pool features and track morphology were quantitatively investigated within specific process windows.Moreover,the microstructure diversity of the tracks and blocks processed with varied material pairs was comparatively elaborated and,complemented with the informative multi-physics modeling,the presented non-uniformity in mechanical properties(microhardness)among the heterogeneous material pairs was rationalized.The differences in melt flow induced by the unlike thermophysical properties of the material pairs and the resulting element intermixing and localized re-alloying during solidification dominate the presented dissimilarity in printability among the material combinations.This work provides an in-depth understanding of the phenomenological differences in the deposition of dissimilar materials and aims to guide more reliable DED forming of bimetallic parts.

Spontaneous Recovery in Directed Dynamical Networks

Complex networked systems,which range from biological systems in the natural world to infrastructure systems in the human-made world,can exhibit spontaneous recovery after a failure;for example,a brain may spontaneously return to normal after a seizure,and traffic flow can become smooth again after a jam.Previous studies on the spontaneous recovery of dynamical networks have been limited to undirected networks.However,most real-world networks are directed.To fill this gap,we build a model in which nodes may alternately fail and recover,and we develop a theoretical tool to analyze the recovery properties of directed dynamical networks.We find that the tool can accurately predict the final fraction of active nodes,and the prediction accuracy decreases as the fraction of bidirectional links in the network increases,which emphasizes the importance of directionality in network dynamics.Due to different initial states,directed dynamical networks may show alternative stable states under the same control parameter,exhibiting hysteresis behavior.In addition,for networks with finite sizes,the fraction of active nodes may jump back and forth between high and low states,mimicking repetitive failure-recovery processes.These findings could help clarify the system recovery mechanism and enable better design of networked systems with high resilience.

Layer by Layer Self-assembly Fiber-based Flexible Electrochemical Transistor

Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface morphology and electric property was investigated.The results confirmed the dense membrane of PEDOT:PSS and the lamellar structure of PDDA-rGO on the fibers.It has excellent electrical conductivity and mechanical properties.The fiber based electrochemical transistor(FECTs)prepared by the composite conductive fiber has a maximum output current of 8.7 mA,a transconductance peak of 10 mS,an on time of 1.37 s,an off time of 1.6 s and excellent switching stability.Most importantly,the devices by layer by layer self-assembly technology opens a path for the true integration of organic electronics with traditional textile technologies and materials,laying the foundation for their later widespread application.

Effect of hot isostatic pressure on the microstructure and tensile properties of γ'-strengthened superalloy fabricated through induction-assisted directed energy deposition

The microstructure characteristics and strengthening mechanism of Inconel738LC(IN-738LC) alloy prepared by using induction-assisted directed energy deposition(IDED) were elucidated through the investigation of samples subjected to IDED under 1050℃ preheating with and without hot isostatic pressing(HIP,1190℃,105 MPa,and 3 h).Results show that the as-deposited sample mainly consisted of epitaxial columnar crystals and inhomogeneously distributed γ’ phases in interdendritic and dendritic core regions.After HIP,grain morphology changed negligibly,whereas the size of the γ’ phase became increasingly even.After further heat treatment(HT,1070℃,2 h + 845℃,24 h),the γ’ phase in the as-deposited and HIPed samples presented a bimodal size distribution,whereas that in the as-deposited sample showed a size that remained uneven.The comparison of tensile properties revealed that the tensile strength and uniform elongation of the HIP + HTed sample increased by 5% and 46%,respectively,due to the synergistic deformation of bimodal γ’phases,especially large cubic γ’ phases.Finally,the relationship between phase transformations and plastic deformations in the IDEDed sample was discussed on the basis of generalized stability theory in terms of the trade-off between thermodynamics and kinetics.

Functional-template directed self-assembly(FTDSA) of mesostructured organic-inorganic hybrid materials

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.

Directed Self-assembly of Vertical PS-b-PMMA Nanodomains Grown on Multilayered Polyelectrolyte Films

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.

DNA Directed Self-Assembly of Fluorescent Colloidal Semiconductor Quantum Dots and Plasmonic Metal Nanoparticles Heterogeneous Nanomaterials

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.

Combination therapy to overcome ferroptosis resistance by biomimetic self-assembly nano-prodrug

Ferroptosis has emerged as a potent form of no-apoptotic cell death that offers a promising alternative to avoid the chemoresistance of apoptotic pathways and serves as a vulnerability of cancer.Herein,we have constructed a biomimetic self-assembly nano-prodrug system that enables the co-delivery of gefitinib(Gefi),ferrocene(Fc)and dihydroartemisinin(DHA)for the combined therapy of both ferroptosis and apoptosis.In the tumor microenvironment,this nano-prodrug is able to disassemble and trigger drug release under high levels of GSH.Interestingly,the released DHA can downregulate GPX4 level for the enhancement of intracellular ferroptosis from Fc,further executing tumor cell death with concomitant chemotherapy by Gefi.More importantly,this nano-prodrug provides highly homologous targeting ability by coating related cell membranes and exhibits outstanding inhibition of tumor growth and metastasis,as well as no noticeable side-effects during treatments.This simple small molecular self-assembled nano-prodrug provides a new reasonably designed modality for ferroptosis-combined chemotherapy.

Efficient conversion of lignin waste and self-assembly synthesis of C@MnCo_(2)O_(4)for asymmetric supercapacitors with high energy density

Lignin waste from the papermaking and biorefineries industry is a significantly promising renewable resource to prepare advanced carbon materials for diverse applications,such as the electrodes of supercapacitors;however,the improvement of their energy density remains a challenge.Here,we design a green and universal approach to prepare the composite electrode material,which is composed of lignin-phenolformaldehyde resins derived hierarchical porous carbon(LR-HPC)as conductive skeletons and the self-assembly manganese cobaltite(MnCo_(2)O_(4))nanocrystals as active sites.The synthesized C@MnCo_(2)O_(4)composite has an abundant porous structure and superior electronic conductivity,allowing for more charge/electron mass transfer channels and active sites for the redox reactions.The composite shows excellent electrochemical performance,such as the maximum specific capacitance of~726 mF cm^(-2)at 0.5 mV s^(-1),due to the significantly enhanced interactive interface between LR-HPC and MnCo_(2)O_(4)crystals.The assembled all-solid-state asymmetric supercapacitor,with the LR-HPC and C@MnCo_(2)O_(4)as cathode and anode,respectively,exhibits the highest volumetric energy density of 0.68 mWh cm^(-3)at a power density of 8.2 mW cm^(-3).Moreover,this device shows a high capacity retention ratio of~87.6%at 5 mA cm^(-2)after 5000 cycles.

Formation mechanism of inherent spatial heterogeneity of microstructure and mechanical properties of NiTi SMA prepared by laser directed energy deposition

Ni51Ti49 at.%bulk was additively manufactured by laser-directed energy deposition(DED)to reveal the microstructure evolution,phase distribution,and mechanical properties.It is found that the localized remelting,reheating,and heat accumulation during DED leads to the spatial heterogeneous distribution of columnar crystal and equiaxed crystal,a gradient distribution of Ni4Ti3 precipitates along the building direction,and preferential formation of Ni4Ti3 precipitates in the columnar zone.The austenite transformation finish temperature(Af)varies from-12.65℃(Z=33 mm)to 60.35℃(Z=10 mm),corresponding to tensile yield strength(σ0.2)changed from 120±30 MPa to 570±20 MPa,and functional properties changed from shape memory effect to superelasticity at room temperature.The sample in the Z=20.4 mm height has the best plasticity of 9.6%and the best recoverable strain of 4.2%.This work provided insights and guidelines for the spatial characterization of DEDed NiTi.