Combinatorial Particle Patterning

The unique properties of solid particles make them a promising element of micro‐ and nanostructure technologies. Solid particles can be used as building blocks for micro and nanostructures, carriers of monomers, or catalysts. The possibility of patterning different kinds of particles on the same substrate opens the pathway for novel combinatorial designs and novel technologies. One of the examples of such technologies is the synthesis of peptide arrays with amino acid particles. This review examines the known methods of combinatorial particle patterning via static electrical and magnetic fields, laser radiation, patterning by synthesis, and particle patterning via chemically modified or microstructured surfaces.     

Laser‐fired contact for n‐type crystalline Si solar cells

Laser‐fired contacts to n‐type crystalline silicon were developed by investigating novel metal stacks containing Antimony (Sb). Lasing conditions and the structure of metals stacks were optimized for lowest contact resistance and minimum surface damage. Specific contact resistance for firing different metal stacks through either silicon nitride or p‐type amorphous silicon was determined using two different models and test structures. Specific contact resistance values of 2–7 mΩcm² have been achieved. Recombination loss due to laser damage was consistent with an extracted local surface recombination velocity of ~20 000 cm/s, which is similar to values for laser‐fired base contact for p‐type crystalline silicon. Interdigitated back contact silicon heterojunction cells were fabricated with laser‐fired base contact and proof‐of‐concept efficiencies of 16.9% were achieved. This localized base contact technique will enable low cost back contact patterning and innovative designs for n‐type crystalline solar cell. Copyright © 2014 John Wiley & Sons, Ltd.     

“Clinging‐Microdroplet” Patterning Upon High‐Adhesion,Pillar‐Structured Silicon Substrates

The rapidly increasing research interest in nanodevices, including nanoelectronics, nano‐optoelectronics, and sensing, requires the development of surface‐patterning techniques to obtain large‐scale arrays of nanounits (mostly nanocrystals and/or nanoparticles) on a silicon substrate. Herein, we demonstrate a “clinging‐microdroplet” method to fabricate patterning crystal arrays based on the employment of high‐adhesion, superhydrophobic, pillar‐structured silicon substrates. Different from the previous hydrophilic/hydrophobic patterned self‐assembly monolayer technique, this method provides a novel strategy to fabricate patterning crystal arrays upon pillar‐structured silicon substrates of homogenous superhydrophobicity and high adhesion, which greatly simplifies the modification process of the supporting substrates. Ordered crystal arrays with a tunable size and distribution density were successfully generated, and individual crystals grew on the top of each micropillar. Besides soluble inorganic materials, protein microspheres and suspending Ag‐nanoparticle or polystyrene‐microsphere aggregations could also be patterned in regular arrays, showing the wide adaptation of such an adhesive patterning technique. This novel and low‐cost technique for patterning crystal arrays upon silicon substrates could yield breakthroughs in areas ranging from nanodevices to nanoelectronics.     

Fabrication of Multifaceted Micropatterned Surfaces with Laser Scanning Lithography

The implementation of engineered surfaces presenting micrometer‐sized patterns of cell adhesive ligands against a biologically inert background has led to numerous discoveries in fundamental cell biology. While existing surface patterning strategies allow patterning of a single ligand, it is still challenging to fabricate surfaces displaying multiple patterned ligands. To address this issue we implemented laser scanning lithography (LSL), a laser‐based thermal desorption technique, to fabricate multifaceted, micropatterned surfaces that display independent arrays of subcellular‐sized patterns of multiple adhesive ligands with each ligand confined to its own array. We demonstrate that LSL is a highly versatile “maskless” surface patterning strategy that provides the ability to create patterns with features ranging from 460 nm to 100 μm, topography ranging from ‐1 to 17 nm, and to fabricate both stepwise and smooth ligand surface density gradients. As validation for their use in cell studies, surfaces presenting orthogonally interwoven arrays of 1 μm × 8 μm elliptical patterns of Gly‐Arg‐Gly‐Asp‐terminated alkanethiol self‐assembled monolayers and human plasma fibronectin are produced. Human umbilical vein endothelial cells cultured on these multifaceted surfaces form adhesion sites to both ligands simultaneously and utilize both ligands for lamella formation during migration. The ability to create multifaceted, patterned surfaces with tight control over pattern size, spacing, and topography provides a platform to simultaneously investigate the complex interactions of extracellular matrix geometry, biochemistry, and topography on cell adhesion and downstream cell behavior.     

Arrays of Inorganic Nanodots and Nanowires Using Nanotemplates Based on Switchable Block Copolymer Supramolecular Assemblies

Here, a novel and simple route to fabricate highly dense arrays of palladium nanodots and nanowires with sub‐30 nm periodicity using nanoporous templates fabricated from supramolecular assemblies of a block copolymer, polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) and a low molecular weight additive, 2‐(4′‐hydroxybenzeneazo) benzoic acid (HABA) is demonstrated. The palladium nanoparticles, which are directly deposited in the nanoporous templates from an aqueous solution, selectively migrate in the pores mainly due to their preferential attraction to the P4VP block covering the pore wall. The polymer template is then removed by oxygen plasma etching or pyrolysis in air resulting in palladium nanostructures whose large scale morphology mirrors that of the original template. The method adopted in this work is general and versatile so that it could easily be extended for patterning a variety of metallic materials into dot and wire arrays.     

High‐Density Periodically Ordered Magnetic Cobalt Ferrite Nanodot Arrays by Template‐Assisted Pulsed Laser Deposition

A novel nanopatterning method using pulsed laser deposition through an ultrathin anodic aluminium oxide (AAO) membrane mask is proposed to synthesize well‐ordered nanodot arrays of magnetic CoFe₂O₄ that feature a wide range of applications like sensors, drug delivery, and data storage. This technique allows the adjustment of the array dimension from ～35 to ～300 nm in diameter and ～65 to ～500 nm in inter‐dot distance. The dot density can be as high as 0.21 Terabit in.^?2. The microstructure of the nanodots is characterized by SEM, TEM, and XRD and their magnetic properties are confirmed by well‐defined magnetic force microscopy contrasts and by hysteresis loops recorded by a superconducting quantum interference device. Moreover, the high stability of the AAO mask enables the epitaxial growth of nanodots at a temperature as high as 550 °C. The epitaxial dots demonstrate unique complex magnetic domains such as bubble and stripe domains, which are switchable by external magnetic fields. This patterning method creates opportunities for studying novel physics in oxide nanomagnets and may find applications in spintronic devices.     

Peptides for the Biofunctionalization of Silicon for Use in Optical Sensing with Porous Silicon Microcavities

Addressing the surface chemistry of silicon is of fundamental scientific and technical significance due to the wide use of this material in electronics and optics. A novel method of functionalizing silicon (Si) via short peptides with binding specificity for Si is presented. The peptide presenting the highest affinity for Si is identified via phage display technology, and the 12‐mer LLADTTHHRPWT and SPGLSLVSHMQT peptides were found to be specific for the n⁺‐Si and p⁺‐Si surfaces, respectively. In our sensing application, the obtained peptides are used as functionalizing linkers to allow porous silicon microcavities to bind biotin and then capture streptavidin. Molecular detection is monitored via reflectometric interference spectra as shifts in the resonance peaks of the cavity structure. An improved streptavidin sensing (21 times lower detection limit) with peptide‐functionalized porous silicon microcavities is demonstrated, compared to sensing performed with devices functionalized with the commonly used silanization method, suggesting that the modification of Si via Si‐specific peptides provides better interface layers for molecular detection. High‐resolution atomic force microscopy images corroborate this result and reveal the formation of ordered nanometer‐sized molecular layers when peptide‐route functionalization is performed.     

Multifaceted and Nanobored Particle Arrays Sculpted Using Colloidal Lithography

A novel method of fabricating multifaceted and nanobored particle arrays via colloidal lithography using colloidal‐crystal layers as masks for anisotropic reactive‐ion etching (RIE) is reported. The shape of the sculpted particles is dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, the RIE conditions, and the matrix (or mask) structure in colloidal lithography. Arrays of non‐spherical particles with sculpted shapes, which to date could not otherwise be produced, are fabricated using a tilted anisotropic RIE process and the layer‐by‐layer growth of a colloidal mask. These non‐spherical particles and their ordered arrays can be used for antireflection surfaces, biosensors, and nanopatterning masks, as well as non‐spherical building blocks for novel colloidal crystals. In addition, polymeric particles with patterned holes of controlled depths obtained by the present method can be applied to the fabrication of functional composite particles.     

Enhancing Ultrafast Lithium Ion Storage of Li4Ti5O12 by Tailored TiC/C Core/Shell Skeleton Plus Nitrogen Doping

It is of great importance to reinforce electronic and ionic conductivity of Li₄Ti₅O₁₂ electrodes to achieve fast reaction kinetics and good high‐power capability. Herein, for the first time, a dual strategy of combing N‐doped Li₄Ti₅O₁₂ (N‐LTO) with highly conductive TiC/C skeleton to realize enhanced ultrafast Li ion storage is reported. Interlinked hydrothermal‐synthesized N‐LTO nanosheets are homogeneously decorated on the chemical vapor deposition (CVD) derived TiC/C nanowires forming binder‐free N‐LTO@TiC/C core–branch arrays. Positive advantages including large surface area, strong mechanical stability, and enhanced electronic/ionic conductivity are obtained in the designed integrated arrays and rooted upon synergistic TiC/C matrix and N doping. The above appealing features can effectively boost kinetic properties throughout the N‐LTO@TiC/C electrodes to realize outstanding high‐rate capability at different working temperatures (143 mAh g^?1/10 C at 25 °C and 122 mAh g^?1/50 C at 50 °C) and notable cycling stability with a capacity retention of 99.3% after 10 000 cycles at 10 C. Moreover, superior high‐rate cycling life is also demonstrated for the full cells with N‐LTO@TiC/C anode and LiFePO₄ cathode. The dual strategy may provoke wide interests in fast energy storage areas and motivate the further performance improvement of power‐type lithium ion batteries (LIBs).     

Novel Patterning of Gold Using Spin‐Coatable Gold Electron‐Beam Resist

Conventional lithography methods of gold patterning are based on deposition and lift‐off or deposition and etching. In this letter, we demonstrate a novel method of gold patterning using spin‐coatable gold electron‐beam resist which is functionalized gold nanocrystals with amine ligands. Amine‐stabilized gold electron beam resist exhibits good sensitivity, 3.0 mC/cm², compared to that of thiol‐stabilized gold electron beam resists. The proposed method reduces the number of processing steps and provides greater freedom in the patterning of complex nanostructures.     

Direct UV Patterning of Electronically Active Fullerene Films

We utilize UV light for the attainment of high‐resolution, electronically active patterns in [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) films. The patterns are created by directly exposing selected parts of a solution‐cast PCBM film to UV light, and thereafter developing the film by immersing it in a tuned developer solution. We demonstrate that it is possible to attain complex, large‐area PCBM structures with a smallest demonstrated‐feature size of 1 μm by this method, and that the patterned PCBM material exhibits a high average electron mobility (1.2 × 10^?2 cm² V^?1 s^?1) in transistor experiments. The employment of UV light for direct patterning of PCBM for electronic applications is attractive, because PCBM exhibits high absorption in the UV range, and no sacrificial photoresist is needed. The patterning is achieved through the transformation by UV light of the soluble PCBM monomers into insoluble dimers with retained attractive electronic properties.     

Multicomponent Hierarchical Cu‐Doped NiCo‐LDH/CuO Double Arrays for Ultralong‐Life Hybrid Fiber Supercapacitor

Fiber supercapacitors have aroused great interest in the field of portable and wearable electronic devices. However, the restrained surface area of fibers and limited reaction kinetics of active materials are unfavorable for performance enhancement. Herein, an efficient multicomponent hierarchical structure is constructed by integrating the Cu‐doped cobalt copper carbonate hydroxide@nickel cobalt layered double hydroxide (CCCH@NiCo‐LDH) core–shell nanowire arrays (NWAs) on Cu fibers with highly conductive Au‐modified CuO nanosheets (CCCH@NiCo‐LDH NWAs@Au–CuO/Cu) via a novel in situ corrosion growth method. This multicomponent hierarchical structure contributes to a large accessible surface area, which results in sufficient permeation of the electrolyte. The Cu dopant could reduce the work function and facilitate fast charge transfer kinetics. Therefore, the effective ion diffusion and electron conduction will facilitate the electrochemical reaction kinetics of the electrode. Benefiting from this unique structure, the electrode delivers a high specific capacitance (1.97 F cm^?2/1237 F g^?1/193.3 mAh g^?1) and cycling stability (90.8% after 30 000 cycles), exhibiting superb performance compared with most oxide‐based fiber electrodes. Furthermore, the hybrid fiber supercapacitor of CCCH@NiCo‐LDH NWAs@Au–CuO/Cu//VN/carbon fibers is fabricated, providing a remarkable maximal energy density of 34.97 Wh kg^?1 and a power density of 13.86 kW kg^?1, exhibiting a great potential in high‐performance fiber‐shape energy‐related systems.     

Capillary‐Bridge Mediated Assembly of Conjugated Polymer Arrays toward Organic Photodetectors

Large‐scale patterning of high‐quality organic semiconductors is crucial for the fabrication of optoelectronic devices with high efficiency and low cost. Yet, owing to the uncontrollable dewetting dynamics of organic liquid in conventional solution patterning techniques, large defect density of organic architectures is inevitable, which is detrimental to the device performance. To address this challenge, herein a capillary‐bridge‐mediated assembly technique is developed for regulating the dewetting process, yielding large‐scale 1D microstructure ordered arrays. The 1D arrays organic photodetectors exhibit a high optoelectronic performance of light on/off ratio exceeding 100, responsivity of 3.24 A W^?1, detectivity of 3.20 × 10¹¹ Jones and fast response speed, showing a great improvement compared with spin‐coated membrane devices. In addition, the significant enhancement of the device photodetection under the electronic field modulation is investigated by applying a back‐gate voltage and explained with the photocurrent predominating in the OFF state and the neglected thermocurrent and tunneling current promoting in the ON state of the phototransistor devices. The research offers a new insight for the facile fabrication of large‐scale integrated photodetectors and other organic devices based on patterned conjugated polymers.     

Digital Plasmonic Patterning for Localized Tuning of Hydrogel Stiffness

The mechanical properties of the extracellular matrix (ECM) can dictate cell fate in biological systems. In tissue engineering, varying the stiffness of hydrogels—water‐swollen polymeric networks that act as ECM substrates—has previously been demonstrated to control cell migration, proliferation, and differentiation. Here, “digital plasmonic patterning” (DPP) is developed to mechanically alter a hydrogel encapsulated with gold nanorods using a near‐infrared laser, according to a digital (computer‐generated) pattern. DPP can provide orders of magnitude changes in stiffness, and can be tuned by laser intensity and speed of writing. In vitro cellular experiments using A7R5 smooth muscle cells confirm cell migration and alignment according to these patterns, making DPP a useful technique for mechanically patterning hydrogels for various biomedical applications.     

A Room‐Temperature High‐Conductivity Metal Printing Paradigm with Visible‐Light Projection Lithography

Fabricating electronic devices require integrating metallic conductors and polymeric insulators in complex structures. Current metal‐patterning methods such as evaporation and laser sintering require vacuum, multistep processes, and high temperature during sintering or postannealing to achieve desirable electrical conductivity, which damages low‐temperature polymer substrates. Here reports a facile ecofriendly room‐temperature metal printing paradigm using visible‐light projection lithography. With a particle‐free reactive silver ink, photoinduced redox reaction occurs to form metallic silver within designed illuminated regions through a digital mask on substrate with insignificant temperature change (<4 °C). The patterns exhibit remarkably high conductivity achievable at room temperature (2.4 × 10⁷ S m^?1, ≈40% of bulk silver conductivity) after simple room‐temperature chemical annealing for 1–2 s. The finest silver trace produced reaches 15 µm. Neither extra thermal energy input nor physical mask is required for the entire fabrication process. Metal patterns were printed on various substrates, including polyethylene terephthalate, polydimethylsiloxane, polyimide, Scotch tape, print paper, Si wafer, glass coverslip, and polystyrene. By changing inks, this paradigm can be extended to print various metals and metal–polymer hybrid structures. This method greatly simplifies the metal‐patterning process and expands printability and substrate materials, showing huge potential in fabricating microelectronics with one system.     

A Step‐Wise Approach for Dual Nanoparticle Patterning via Block Copolymer Self‐Assembly

A novel step‐wise approach for fabrication of periodic arrays of two different types of nanoparticles (NPs), selectively localized at different block copolymer phases is demonstrated. In the first step, pre‐synthesized ≈12 nm silver nanoparticles (AgNPs), stabilized with thiol‐terminated polystyrene, are mixed with poly(styrene‐block‐vinylpyridine) (PS‐b‐PVP) block copolymer in a common solvent. After film casting and consequent solvent vapor annealing the AgNPs are selectively localized within the PS phase of the block copolymer matrix due to the interaction with PS shell of the nanoparticles. In the second step, ≈2–5 nm gold, platinum, or palladium nanoparticles are directly deposited from their aqueous dispersion on the PVP domains of the self‐assembled block copolymer thin films. In such a way, thin films of nanostructured block copolymer with two types of nanoparticles, separated by the two distinct block copolymer phases, are prepared in a step‐wise manner. The presented method is very simple and can be applied for various combinations of pre‐synthesized nanoparticles where the characteristics of either type of nanoparticles are tuned accordingly in advance, which is more difficult to achieve for in situ synthesized nanoparticles.     

2D Material Enabled Offset‐Patterning with Atomic Resolution

Atomic‐precision patterning at large scale is a central requirement for nanotechnology and future electronics that is hindered by the limitations of lithographical techniques. Historically, imperfections of the fabrication tools have been compensated by multi‐patterning using sequential lithography processes. The realization of nanometer‐scale features from much larger patterns through offset stacking of atomically thin masks is demonstrated. A unique mutual stabilization effect between two graphene layers produces atomically abrupt transitions that selectively expose single‐layer covered regions. Bilayer regions, on the other hand, protect the underlying substrate from removal for several hours permitting transfer of atomic thickness variations into lateral features in various semiconductors. Nanoscopic offsets between two 2D materials layers could be introduced through bottom‐up and top‐down approaches, opening up new routes for high‐resolution patterning. A self‐aligned templating approach yields nanometer‐wide bilayer graphene nanoribbons with macroscopic length that produces high‐aspect‐ratio silicon nanowalls. Moreover, offset‐transfer of lithographically patterned graphene layers enables multipatterning of large arrays of semiconductor features whose resolution is not limited by the employed lithography and could reach <10 nm feature size. The results open up a new route to combining design flexibility with unprecedented resolution at large scale.     

3D Microfluidic Surface‐Enhanced Raman Spectroscopy (SERS) Chips Fabricated by All‐Femtosecond‐Laser‐Processing for Real‐Time Sensing of Toxic Substances

A novel all‐femtosecond‐laser‐processing technique is proposed for the fabrication of 2D periodic metal nanostructures inside 3D glass microfluidic channels, which have applications to real‐time surface‐enhanced Raman spectroscopy (SERS). In the present study, 3D glass microfluidic channels are fabricated by femtosecond‐laser‐assisted wet etching. This is followed by the space‐selective formation of Cu‐Ag layered thin films inside the microfluidic structure via femtosecond laser direct writing ablation and electroless metal plating. The Cu‐Ag films are subsequently nanostructured by irradiation with linearly polarized beams to form periodic surface structures. This work demonstrates that a double exposure to laser beams having orthogonal polarization directions can generate arrays of layered Cu‐Ag nanodots with dimensions as small as 25% of the laser wavelength. The resulting SERS microchip is able to detect Rhodamine 6G, exhibiting an enhancement factor of 7.3 × 10⁸ in conjunction with a relative standard deviation of 8.88%. This 3D microfluidic chip is also found to be capable of the real‐time SERS detection of Cd²⁺ ions at concentrations as low as 10 ppb in the presence of crystal violet. This technique shows significant promise for the fabrication of high performance microfluidic SERS platforms for the real‐time sensing of toxic substances with ultrahigh sensitivity.     

Fully Integrated Microscale Quasi‐2D Crystalline Molecular Field‐Effect Transistors

Monolithic integration of microscale organic field‐effect transistors (micro‐OFETs) is the only and inevitable path toward low‐cost large‐area electronics and displays. However, to date, such an ultimate technology has not yet evolved due to challenges in positioning and patterning highly crystalline microscale molecular layers as well as in developing micrometer scale integration schemes. In this work, by mastering the local growth of molecular semiconductors on pre‐defined terraces, single‐crystal quasi‐2D molecular layers tens of square micrometers in size are created in dense periodic arrays on a Si substrate. Nondestructive photolithographic processes are developed to pattern micro‐OFETs with mobilities up to 34.6 cm² V^?1 s^?1. This work demonstrates the feasibility to integrate arrays of short‐channel micro‐OFETs into electronic circuitry by highly parallel and size scalable fabrication technologies.     

Electrohydrodynamically Printed High‐Resolution Full‐Color Hybrid Perovskites

Hybrid perovskites show enormous potential for display due to their tunable emission, high color purity, strong photoluminescence and electroluminescence. For display applications, full‐color and high‐resolution patterning is compulsory, however, current perovskite processing such as spin‐coating fails to meet these requirements. Here, electrohydrodynamic (EHD) printing, with the unique advantages of high‐resolution patterning and large scalability, is introduced to fabricate full‐color perovskite patterns. Perovskite inks via simple precursor mixing are prepared to in situ crystallize tunable‐ and bright‐photoluminescence perovskite arrays without adding antisolvent. Through optimizing the EHD printing process, a high‐resolution dot matrix of 5 µm is achieved. The as‐printed patterns and pictures show full color and high controllability in micrometer dimension, indicating that the EHD printing is a competitive technique for future halide perovskite‐based high‐quality display.