Spontaneous Outcropping of Self‐Assembled Insulating Nanodots in Solution‐Derived Metallic Ferromagnetic La0.7Sr0.3MnO3 Films

A new mechanism is proposed for the generation of self‐assembled nanodots at the surface of a film based on spontaneous outcropping of the secondary phase of a nanocomposite epitaxial film. Epitaxial self‐assembled Sr–La oxide insulating nanodots are formed through this mechanism at the surface of an epitaxial metallic ferromagnetic La_0.7Sr_0.3MnO₃ (LSMO) film grown on SrTiO₃ from chemical solutions. TEM analysis reveals that, underneath the La–Sr oxide (LSO) nanodots, the film switches from the compressive out‐of‐plane stress component to a tensile one. It is shown that the size and concentration of the nanodots can be tuned by means of growth kinetics and through modification of the La excess in the precursor chemical solution. The driving force for the nanodot formation can be attributed to a cooperative effect involving the minimization of the elastic strain energy and a thermodynamic instability of the LSMO phase against the formation of a Ruddelsden–Popper phase Sr₃Mn₄O₇ embedded in the film, and LSO surface nanodots. The mechanism can be described as a generalization of the classical Stranski–Krastanov growth mode involving phase separation. LSO islands induce an isotropic strain to the LSMO film underneath the island which decreases the magnetoelastic contribution to the magnetic anisotropy.     

Large,Temperature‐Tunable Low‐Field Magnetoresistance in La0.7Sr0.3MnO3:NiO Nanocomposite Films Modulated by Microstructures

Magnetic properties and low‐field magnetoresistance (LFMR) in La_0.7Sr_0.3MnO₃ (LSMO):NiO nanocomposite films grown on SrTiO₃ (001) substrates, which are shown to be tunable with different microstructures, are investigated. The LSMO:NiO nanocomposite films with NiO volume ratio of 50% have a checkerboard‐like structure and show a large LFMR in a temperature range from 200 to 300 K (≈17% at 250 K with a magnetic field of 1 T). As the NiO volume ratio is increased to 70%, a nano‐columnar structure formed in the films. Their LFMR is significantly enhanced at a wide temperature range of 10–210 K. The highest value of LFMR with 41% is achieved at 10 K in a magnetic field of 1 T. The enhanced LFMR can be considered to result from the electron scattering at the ferromagnetic LSMO/NiO interfaces and magnetic tunnel junctions (MTJs) of LSMO/NiO/LSMO at the nanometer scale. These results demonstrate that large and tunable LFMR from low temperature to room temperature can be realized by controlling the microstructures in the epitaxial La_0.7Sr_0.3MnO₃:NiO nano­composite thin films, which will be expected to be applied in the devices using for a wide temperature range.     

Self‐Assembled Heteroepitaxial Oxide Nanocomposite Thin Film Structures: Designing Interface‐Induced Functionality in Electronic Materials

Achieving self‐assembling/self‐organizing systems is the holy grail of nanotechnology. Spontaneous organization is not unique to the physical sciences since nature has been producing such systems for millions of years. In biological systems global patterns emerge from numerous interactions among lower‐level components of the system. The same is true for physical systems. In this review, the self‐assembly mechanisms of oxide nanocomposite films, as well as the advantageous functionalities that arise from such ordered structures, are explored.     

A Three Component Self‐Assembled Epitaxial Nanocomposite Thin Film

A self‐assembled three phase epitaxial nanocomposite film is grown consisting of ≈3 nm diameter fcc metallic Cu nanorods within square prismatic SrO rocksalt nanopillars in a Sr(Ti,Cu)O_3‐δ perovskite matrix. Each phase has an epitaxial relation to the others. The core–shell‐matrix structures are grown on SrTiO₃ substrates and can also be integrated onto Si using a thin SrTiO₃ buffer. The structure is made by pulsed laser deposition in vacuum from a SrTi_0.75Cu_0.25O₃ target, and formed as a result of the limited solubility of Cu in the perovskite matrix. Wet etching removes the 3 nm diameter Cu nanowires leaving porous SrO pillars. The three‐phase nanocomposite film is used as a substrate for growing a second epitaxial nanocomposite consisting of CoFe₂O₄ spinel pillars in a BiFeO₃ perovskite matrix, producing dramatic effects on the structure and magnetic properties of the CoFe₂O₄. This three‐phase vertical nanocomposite provides a complement to the well‐known two‐phase nanocomposites, and may offer a combination of properties of three different materials as well as additional avenues for strain‐mediated coupling within a single film.     

Systematic Control of Nucleation Density in Poly(3‐Hexylthiophene) Thin Films

While molecular ordering via crystallization is responsible for many of the impressive optoelectronic properties of thin‐film semiconducting polymer devices, crystalline morphology and its crucial influence on performance remains poorly controlled and is usually studied as a passive result of the conditions imposed by film deposition parameters. A method for systematic control over crystalline morphology in conjugated polymer thin films by very precise control of nucleation density and crystal growth conditions is presented. A precast poly(3‐hexylthiophene) film is first swollen into a solution‐like state in well‐defined vapor pressures of a good solvent, while the physical state of the polymer chains is monitored using in situ UV–vis spectroscopy and ellipsometry. Nucleation density is selected by a controlled deswelling of the film or by a self‐seeding approach using undissolved crystalline aggregates that remain in the swollen film. Nucleation densities ranging successively over many orders of magnitude are achieved, extending into the regime of spherulitic domains 10 to 100 μm in diameter, a length scale highly relevant for typical probes of macroscopic charge transport such as field‐effect transistors. This method is presented as a tool for future systematic study of the structure‐function relation in semicrystalline semiconducting polymers in a broad range of applications.     

Electrochemically Triggered Selective Adsorption of Biotemplated Nanoparticles on Self‐Assembled Organometallic Diblock Copolymer Thin Films

The controlled adsorption of the iron‐containing cage protein ferritin at the nanoscale using stimuli‐responsive self‐assembled diblock copolymer thin‐film templates is reported. The diblock copolymer used study consists of a cylinder‐forming polystyrene‐block‐polyferrocenylsilane (PS‐b‐PFS), with PFS as the minor block, and shows reversible redox properties. To prevent any spontaneous protein adsorption on either block, the electrolyte pH is selected to leave the ferritin negatively charged, and the protein concentration and solution ionic strength are carefully tuned. Selective adsorption of ferritin on the PFS domains of the self‐assembled thin films is then triggered in situ by applying a positive potential, simultaneously oxidizing the PFS and attracting the ferritin electrostatically.     

Low‐Field Magnetoresistance in La0.67Sr0.33MnO3:ZnO Composite Film

A nanocomposite film of La_0.67Sr_0.33MnO₃ (LSMO):ZnO is synthesized by depositing LSMO solution on a vertical array of ZnO nanorods grown on (0001) Al₂O₃ substrate. The magnetic behavior of the composite film differs from that of a pure LSMO film, possibly due to smaller grain size in the composite, small amount of Zn doping, or the presence of nonmagnetic ZnO phase near the LSMO grain boundaries. Magnetotransport measurements show that the low‐field magnetoresistance (LFMR) of the nanocomposite film is significantly enhanced as compared to that observed for pure LSMO film. The highest value of the LFMR of the nanocomposite film at 10 K is –23.9% with a magnetic field of 0.5 T applied parallel to the current.     

Engineering Large Anisotropic Magnetoresistance in La0.7Sr0.3MnO3 Films at Room Temperature

The magnetoresistance (MR) effect is widely used in technologies that pervade the world, from magnetic reading heads to sensors. Diverse contributions to MR, such as anisotropic, giant, tunnel, colossal, and spin‐Hall, are revealed in materials depending on the specific system and measuring configuration. Half‐metallic manganites hold promise for spintronic applications but the complexity of competing interactions has not permitted the understanding and control of their magnetotransport properties to enable the realization of their technological potential. This study reports on the ability to induce a dominant switchable magnetoresistance in La_0.7Sr_0.3MnO₃ epitaxial films at room temperature (RT). By engineering an extrinsic magnetic anisotropy, a large enhancement of anisotropic magnetoresistance (AMR) is achieved which at RT leads to signal changes much larger than the other contributions such as the colossal magnetoresistance. The dominant extrinsic AMR exhibits large variation in the resistance in low field region, showing high sensitivity to applied low magnetic fields. These findings have a strong impact on the real applications of manganite‐based devices for the high‐resolution low field magnetic sensors or spintronics.     

Self‐Assembled Dense Colloidal Cu2Te Nanodisk Networks in P3HT Thin Films with Enhanced Photocurrent

The integration of colloidal nanocrystals with polymers adds optoelectronic functionalities to flexible and mechanically robust organic films. In particular, self‐assembled structures of nanocrystals in polymers can act as functional components enhancing, for instance, transport or optical properties of the hybrid material. This study presents Cu₂Te hexagonal nanodisks that assemble into ribbons with a face‐to‐face configuration in poly(3‐hexylthiophene‐2,5‐diyl) through a controlled solvent evaporation process. The ribbons form weaving patterns that create 3D networks fully embedded in the thin polymer film at high nanodisk concentration. The photoresponse of these composite films measured in a layered vertical geometry demonstrates increased photocurrent with increasing nanocrystal loading. This study attributes this behavior to the presence of networks of Cu₂Te nanodisks that form a bulk heterojunction with the semiconducting polymer, which improves exciton dissociation and the overall photoelectric response.     

Precise Tuning of (YBa2Cu3O7‐δ)1‐x:(BaZrO3)x Thin Film Nanocomposite Structures

Self‐assembled nanocomposite films and coatings have huge potential for many functional and structural applications. However, control and manipulation of the nanostructures is still at very early stage. Here, guidelines are established for manipulating the types of composite structures that can be achieved. In order to do this, a well studied (YBa₂Cu₃O_7‐δ)_1‐x:(BaZrO₃)_x ‘model’ system is used. A switch from BaZrO₃ nanorods in YBa₂Cu₃O_7‐δ matrix to planar, horizontal layered plates is found with increasing x, with a transitional cross‐ply structure forming between these states at x = 0.4. The switch is related to a release in strain energy which builds up in the YBa₂Cu₃O_7‐δ with increasing x. At x = 0.5, an unusually low strain state is observed in the planar composite structure, which is postulated to arise from a pseudo‐spinodal mechanism.     

Self‐Assembled Complexes of Horseradish Peroxidase with Magnetic Nanoparticles Showing Enhanced Peroxidase Activity

Bio‐nanocatalysts (BNCs) consisting of horseradish peroxidase (HRP) self‐assembled with magnetic nanoparticles (MNPs) enhance enzymatic activity due to the faster turnover and lower inhibition of the enzyme. The size and magnetization of the MNPs affect the formation of the BNCs, and ultimately control the activity of the bound enzymes. Smaller MNPs form small clusters with a low affinity for the HRP. While the turnover for the bound fraction is drastically increased, there is no difference in the H₂O₂ inhibitory concentration. Larger MNPs with a higher magnetization aggregate in larger clusters and have a higher affinity for the enzyme and a lower substrate inhibition. All of the BNCs are more active than the free enzyme or the MNPs (BNCs > HRP ? MNPs). Since the BNCs show surprising resilience in various reaction conditions, they may pave the way towards new hybrid biocatalysts with increased activities and unique catalytic properties for magnetosensitive enzymatic reactions.     

Molten‐Salt‐Assisted Self‐Assembly (MASA)‐Synthesis of Mesoporous Metal Titanate‐Titania,Metal Sulfide‐Titania,and Metal Selenide‐Titania Thin Films

New synthetic strategies are needed for the assembly of porous metal titanates and metal chalcogenite‐titania thin films for various energy applications. Here, a new synthetic approach is introduced in which two solvents and two surfactants are used. Both surfactants are necessary to accommodate the desired amount of salt species in the hydrophilic domains of the mesophase. The process is called a molten‐salt‐assisted self‐assembly (MASA) because the salt species are in the molten phase and act as a solvent to assemble the ingredients into a mesostructure and they react with titania to form mesoporous metal titanates during the annealing step. The mesoporous metal titanate (meso‐Zn₂TiO₄ and meso‐CdTiO₃) thin films are reacted under H₂S or H₂Se gas at room temperature to yield high quality transparent mesoporous metal chalcogenides. The H₂Se reaction produces rutile and brookite titania phases together with nanocrystalline metal selenides and H₂S reaction of meso‐CdTiO₃ yields nanocrystalline anatase and CdS in the spatially confined pore walls. Two different metal salts (zinc nitrate hexahydrate and cadmium nitrate tetrahydrate) are tested to demonstrate the generality of the new assembly process. The meso‐TiO₂‐CdSe film shows photoactivity under sunlight.     

Electric Field Controlled Self‐Assembly of Hierarchically Ordered Membranes

Self‐assembly in the presence of external forces is an adaptive, directed organization of molecular components under nonequilibrium conditions. While forces may be generated as a result of spontaneous interactions among components of a system, intervention with external forces can significantly alter the final outcome of self‐assembly. Superimposing these intrinsic and extrinsic forces provides greater degrees of freedom to control the structure and function of self‐assembling materials. In this work we investigate the role of electric fields during the dynamic self‐assembly of a negatively charged polyelectrolyte and a positively charged peptide amphiphile in water leading to the formation of an ordered membrane. In the absence of electric fields, contact between the two solutions of oppositely charged molecules triggers the growth of closed membranes with vertically oriented fibrils that encapsulate the polyelectrolyte solution. This process of self‐assembly is intrinsically driven by excess osmotic pressure of counterions and the electric field is found to modify the kinetics of membrane formation as well as membrane morphology and properties. Depending on the strength and orientation of the field we observe a significant increase or decrease of up to nearly 100% in membrane thickness, or the controlled rotation of nanofiber growth direction by 90 degrees which leads to a significant increase in mechanical stiffness. These results suggest the possibility of using electric fields to control structure in self‐assembly processes that involve the diffusion of oppositely charged molecules.     

Supramolecular Surface Chemistry: Substrate‐Independent,Phosphate‐Driven Growth of Polyamine‐Based Multifunctional Thin Films

The ability to engineer surfaces at the supramolecular level by controlled integration of specific chemical units through substrate‐independent methodologies represents one of the new paradigms of contemporary materials science. Here, a method is reported to form multifunctional supramolecular coatings through simple dip‐coating of substrates in an aqueous solution of polyamine in the presence of phosphate anions. The chemical richness and versatility of polyamines are exploited as phosphate receptors to form thin functional films on a broad variety of substrates, ranging from metal to carbonaceous surfaces. It is shown that the simple derivatization of pendant amino groups of polyallylamine precursors with different chemical groups can endow films with predefined responsiveness or multiple functions—this translates into one‐pot and one‐step preparation of substrate‐adherent films displaying built‐in functions. It is believed that the flexibility, speed, and versatility with which this method provides such robust functional films make it very attractive for preparing samples of fundamental and technological interest.     

Self‐Organized Single‐Walled Carbon Nanotube Conducting Thin Films with Honeycomb Structures on Flexible Plastic Films

Complex 1, synthesized from anionic shortened single‐walled carbon nanotubes and cationic ammonium lipid dissolved in organic solvents, is cast on pretreated transparent flexible poly(ethylene terephthalate) (PET) films under a higher relative humidity to form thin films with self‐organized honeycomb structures. The cell sizes are controllable by changing the experimental conditions. The lipid, which is the cationic part of complex 1, is easily removed by a simple ion‐exchange method, while maintaining the basic honeycomb structures. After the ion exchange, the nanotube honeycomb films on PET with thinner skeletons exhibit a dramatic decrease in the surface resistivity from insulating to conducting. Carbon nanotubes with honeycomb structures formed by the self‐organization on flexible polymer films are useful in many areas of nanoscience and technology including nanomaterials, nanoelectronics, nanodevices, catalysts, sensors, and so on.     

Engineering of Self‐Assembled Domain Architectures with Ultra‐high Piezoelectric Response in Epitaxial Ferroelectric Films

Substrate clamping and inter‐domain pinning limit movement of non‐180° domain walls in ferroelectric epitaxial films thereby reducing the resulting piezoelectric response of ferroelectric layers. Our theoretical calculations and experimental studies of the epitaxial PbZr_xTi_1–xO₃ films grown on single crystal SrTiO₃ demonstrate that for film compositions near the morphotropic phase boundary it is possible to obtain mobile two‐domain architectures by selecting the appropriate substrate orientation. Transmission electron microscopy, X‐ray diffraction analysis, and piezoelectric force microscopy revealed that the PbZr_0.52Ti_0.48O₃ films grown on (101) SrTiO₃ substrates feature self‐assembled two‐domain structures, consisting of two tetragonal domain variants. For these films, the low‐field piezoelectric coefficient measured in the direction normal to the film surface (d₃₃) is 200 pm V^–1, which agrees well with the theoretical predictions. Under external AC electric fields of about 30 kV cm^–1, the (101) films exhibit reversible longitudinal strains as high as 0.35 %, which correspond to the effective piezoelectric coefficients in the order of 1000 pm V^–1 and can be explained by elastic softening of the PbZr_xTi_1–xO₃ ferroelectrics near the morphotropic phase boundary.