Block copolymer self-assembly–directed synthesis of mesoporous gyroidal superconductors

Robbins, Spencer; Beaucage, Peter A.; Sai, Hiroaki; Tan, Kwan Wee; Werner, Jörg G.; Sethna, James P.; DiSalvo, Francis J.; Grüner, Sol M.; Dover, R. B. van; Wiesner, Ulrich

doi:10.1126/sciadv.1501119

Cited by 115 publications

(152 citation statements)

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“…From the magnetization test of the material, a superconducting transition with a critical temperature of 7.8 K and a broad transition down to 2.5 K were detected. The material exhibited a dramatic drop in electrical resistance at ≈7 K in the temperature‐dependent four‐point electrical resistance measurement ( Figure ) . This work demonstrated the possibility of finding new applications by combining unique periodic structures with different materials properties.…”

Section: Toward New Syntheses and Applicationsmentioning

confidence: 80%

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An Overview of Materials with Triply Periodic Minimal Surfaces and Related Geometry: From Biological Structures to Self‐Assembled Systems

2018

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Triply periodic minimal surface structures and related geometries are widely identified in many natural systems, such as biological membranes and biophotonic structures in butterfly-wing scales. Inspired by their marvelous and highly symmetrical structures and optimized physical properties, these structures have sparked immense interest for creating novel materials by extracting the design from nature. Significant progress has been made to understand these biological structures and fabricate artificial materials by top-down and bottom-up approaches for numerous applications in chemistry and materials science. Herein, research achievements, including theoretical and experimental discoveries, in both biological systems and the artificial synthesis of materials with triply periodic minimal surface structures and related materials are summarized. Recent developments in self-assembled lyotropic liquid crystal phases, block copolymer systems, and their inorganic replicas are discussed in detail.

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Section: Toward New Syntheses and Applicationsmentioning

confidence: 80%

Section: Toward New Syntheses and Applicationsmentioning

confidence: 99%

An Overview of Materials with Triply Periodic Minimal Surfaces and Related Geometry: From Biological Structures to Self‐Assembled Systems

2018

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“…The mesoscale porosity obviously raised the antiferromagnetic transition temperature of CoTiO 3 , compared to its bulk counterpart; [ 64 ] however, the details of mechanism are currently unclear. Among all porous CoTiO 3 , the T N of mCoTiO 3 ‐700 is lower than that of the other two samples.…”

Section: Resultsmentioning

confidence: 99%

Crystalline Mesoporous Complex Oxides: Porosity‐Controlled Electromagnetic Response

Liu

Shi

et al. 2020

Adv Funct Materials

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A colloidal-amphiphile-templated growth is developed to synthesize mesoporous complex oxides with highly crystalline frameworks. Organosilane-containing colloidal templates can convert into thermally stable silica that prevents the overgrowth of crystalline grains and the collapse of the mesoporosity. Using ilmenite CoTiO 3 as an example, the high crystallinity and the extraordinary thermal stability of its mesoporosity are demonstrated at 800 °C for 48 h under air. This synthetic approach is general and applicable to a series of complex oxides that are not reported with mesoporosity and high crystallinity, such as NiTiO . Those novel materials make it possible to build up correlations between mesoscale porosity and surfacesensitive physicochemical properties, e.g., electromagnetic response. For mesoporous CoTiO 3 , there is a 3 K increase of its antiferromagnetic ordering temperature, compared with that of nonporous one. This finding provides a general guideline to design mesoporous complex oxides that allow exploring their unique properties different from bulk materials.complex oxides, in general, has associated kinetic barriers from the slow diffusion in solids. [15] When there are two metal cations involved in crystallization of complex oxides like ABO 3 , their nonuniform distribution can result in spontaneous phase separation to form simple oxides. [16] A delicate balance of their sol-gel rates and the precautious control of thermal annealing procedure is needed. On the other hand, ordering competition between the crystallization of oxides and the mesoscale porosity brings profound difficulties to synthesize complex oxides (e.g., perovskites and ilmenites) with mesoporous structures. Crystallization usually leads to the formation of large crystalline grains that will create strong interfacial energies between crystalline walls and pores (e.g., air or templates). For any templated growth of mesoporous oxides using hydrocarbon-based surfactants or block copolymers (BCPs) as soft templates, [17][18][19] mesoscale nanostructures collapse prior to the crystallization of oxides, [20][21][22] because these soft templates are not mechanically strong and thermally stable under elevated temperatures (i.e., >500 °C).Nanostructures show a profound impact on the magnetic properties of materials as well and a few theoretical models have been proposed to understand magnetic behavior of nanoscale particles. [23][24][25][26][27][28][29][30] The magnetic ordering temperature (Curie temperature or Néel temperature) in magnetic materials

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“…As the A and C blocks are chemically distinguishable, the alternating gyroid is a useful technique for creating the thermodynamically unstable SG structure. This process can be performed either by infiltrating inorganic precursors into the polymer template, or by directly introducing the inorganic particles into the polymer self-assembly [20,118,119].…”

Section: Artificial Self-assembly Of Amphiphilic Moleculesmentioning

confidence: 99%

Bicontinuous cubic phases in biological and artificial self-assembled systems

2020

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Nature has created innumerable life forms with miraculous hierarchical structures and morphologies that are optimized for different life events through evolution over billions of years. Bicontinuous cubic structures, which are often described by triply periodic minimal surfaces (TPMSs) and their constant mean curvature (CMC)/parallel surface companions, are of special interest to various research fields because of their complex form with unique physical functionalities. This has prompted the scientific community to fully understand the formation, structure, and properties of these materials. In this review, we summarize and discuss the formation mechanism and relationships of the relevant biological structures and the artificial self-assembly systems. These structures can be formed through biological processes with amazing regulation across a great length scales; nevertheless, artificial construction normally produces the structure corresponding to the molecular size and shape. Notably, the block copolymeric system is considered to be an applicable and attractive model system for the study of biological systems due to their versatile design and rich phase behavior. Some of the phenomena found in these two systems are compared and discussed, and this information may provide new ideas for a comprehensive understanding of the relationship between molecular shape and resulting interface curvature and the selfassembly process in living organisms. We argue that the copolymeric system may serve as a model to understand these biological systems and could encourage additional studies of artificial self-assembly and the creation of new functional materials.

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Block copolymer self-assembly–directed synthesis of mesoporous gyroidal superconductors

Abstract: Block copolymer self-assembly is used to synthesize three-dimensionally continuous gyroidal mesoporous superconductors of niobium nitride.

Cited by 115 publications

References 55 publications

An Overview of Materials with Triply Periodic Minimal Surfaces and Related Geometry: From Biological Structures to Self‐Assembled Systems

An Overview of Materials with Triply Periodic Minimal Surfaces and Related Geometry: From Biological Structures to Self‐Assembled Systems

Crystalline Mesoporous Complex Oxides: Porosity‐Controlled Electromagnetic Response

Bicontinuous cubic phases in biological and artificial self-assembled systems

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