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Following nanoparticle self-assembly in real-time: Small-angle X-ray scattering and quartz crystal microbalance study of self-assembling iron oxide nanocubes
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0001-5435-2958
2020 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Self-assembly of nanoparticles is a widely used technique to produce nanostructured materials with crystallographic coherence on the atomic scale, i.e. mesocrystals, which can display useful collective properties. This thesis focusses on the underlying mechanism and dynamics of mesocrystal formation by using real-time techniques. Quartz-crystal microbalance with dissipation monitoring (QCM-D) as well as small-angle X-ray scattering (SAXS) in combination with optical microscopy were used to probe the temporal evolution of growing mesocrystals to elucidate the growth mechanism.

Time-resolved small-angle X-ray scattering was used to probe the formation and how the structure and defects of the growing mesocrystals in levitating droplets evolve with time. Probing self-assembly of oleate-capped iron oxide nanocubes during evaporation-driven poor-solvent enrichment (EDPSE) showed that a low particle concentration in combination with a short nucleation period can generate large and well-ordered mesocrystals. Information on the formation and transformation of defects in mesocrystals were obtained by analysis of the temporal evolution of crystal strain. A transition from a rapidly increasing isotropic strain to a decreasing anisotropic strain towards the end of the growth stage was observed. The occurrence of anisotropic strain was assigned to the formation of stress-relieving dislocations in the crystal, which were induced by large internal stresses caused by superlattice contraction.

Directed assembly of superparamagnetic iron oxide nanocubes, subjected to a weak magnetic field, produced one-dimensional mesocrystal fibers. Real-time SAXS as well as optical microscopy revealed a two-stage growth mechanism. The primary stage involved the growth of cuboidal mesocrystals by nanocube self-assembly. In a secondary stage, the cuboidal mesocrystals were assembled and aligned into fibers by the magnetic field. Evaluation of the magnetic dipole-dipole and van der Waals interactions showed that the dipolar forces arising between two nanocubes in a weak magnetic field are negligible compared to the van der Waals forces, but become the dominant force for larger mesocrystals, which drives the formation of fibers.

QCM-D combined with optical microscopy provided simultaneously information on the rheological properties as well as on the mass of an adsorbed self-assembled layer of iron oxide nanocubes. We show that the iron oxide nanocubes rapidly assembled into an array with primarily viscous characteristics. This fluid-like behaviour can be assigned to a layer of solvent surrounding the nanocubes inside the assembly. Expulsion of the thin solvent layer from the assembled array is responsible for the increase in rigidity observed shortly after the beginning of self-assembly.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University , 2020. , p. 94
Keywords [en]
self-assembly, mesocrystal, time-resolved, small-angle X-ray scattering, iron oxide nanocubes, QCM-D
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-180766ISBN: 978-91-7911-148-9 (print)ISBN: 978-91-7911-149-6 (print)OAI: oai:DiVA.org:su-180766DiVA, id: diva2:1423053
Public defence
2020-06-02, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript.

Available from: 2020-05-08 Created: 2020-04-13 Last updated: 2020-05-26Bibliographically approved
List of papers
1. Tunable assembly of truncated nanocubes by evaporation-driven poor-solvent enrichment
Open this publication in new window or tab >>Tunable assembly of truncated nanocubes by evaporation-driven poor-solvent enrichment
2019 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 10, article id 4228Article in journal (Refereed) Published
Abstract [en]

Self-assembly of nanocrystals is extensively used to generate superlattices with long-range translational order and atomic crystallographic orientation, i.e. mesocrystals, with emergent mesoscale properties, but the predictability and tunability of the assembly methods are poorly understood. Here, we report how mesocrystals produced by poor-solvent enrichment can be tuned by solvent composition, initial nanocrystal concentration, poor-solvent enrichment rate, and excess surfactant. The crystallographic coherence and mesoscopic order within the mesocrystal were characterized using techniques in real and reciprocal spaces, and superlattice growth was followed in real time by small-angle X-ray scattering. We show that formation of highly ordered superlattices is dominated by the evaporation-driven increase of the solvent polarity and particle concentration, and facilitated by excess surfactant. Poor-solvent enrichment is a versatile nanoparticle assembly method that offers a promising production route with high predictability to modulate and maximize the size and morphology of nanocrystal metamaterials.

National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-175083 (URN)10.1038/s41467-019-12237-y (DOI)000486138600003 ()31530817 (PubMedID)
Available from: 2019-10-23 Created: 2019-10-23 Last updated: 2020-04-19Bibliographically approved
2. Two-stage assembly in magnetic fields of iron oxide nanocubes into mesocrystal fibres
Open this publication in new window or tab >>Two-stage assembly in magnetic fields of iron oxide nanocubes into mesocrystal fibres
(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-180754 (URN)
Available from: 2020-04-09 Created: 2020-04-09 Last updated: 2020-04-25Bibliographically approved
3. Temporal Evolution of Superlattice Contraction and Defect-Induced Strain Anisotropy in Mesocrystals During Nanocube Self-Assembly
Open this publication in new window or tab >>Temporal Evolution of Superlattice Contraction and Defect-Induced Strain Anisotropy in Mesocrystals During Nanocube Self-Assembly
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-180753 (URN)
Available from: 2020-04-09 Created: 2020-04-09 Last updated: 2020-04-19Bibliographically approved
4. Time-resolved viscoelastic properties of self-assembling iron oxide nanocube superlattices probed by quartz crystal microbalance with dissipation monitoring
Open this publication in new window or tab >>Time-resolved viscoelastic properties of self-assembling iron oxide nanocube superlattices probed by quartz crystal microbalance with dissipation monitoring
2018 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 522, p. 104-110Article in journal (Refereed) Published
Abstract [en]

Self-assembly of nanoparticles into superlattices can be used to create hierarchically structured materials with tailored functions. We have used the surface sensitive quartz crystal microbalance with dissipation monitoring (QCM-D) technique in combination with video microscopy (VM) to obtain time-resolved information on the mass increase and rheological properties of evaporation-induced self-assembly of nanocubes. We have recorded the frequency and dissipation shifts during growth and densification of superlattices formed by self-assembly of oleic acid capped, truncated iron oxide nanocubes and analyzed the time-resolved QCM-D data using a Kelvin-Voigt viscoelastic model. We show that the nanoparticles first assemble into solvent-containing arrays dominated by a viscous response followed by a solvent releasing step that results in the formation of rigid and well-ordered superlattices. Our findings demonstrate that QCM-D can be successfully used to follow self-assembly and assist in the design of optimized routes to produce well-ordered superlattices.

Keywords
Self-assembly, Anisotropic nanoparticles, Quartz crystal microbalance with dissipation monitoring (QCM-D), Viscoelastic modeling
National Category
Chemical Sciences
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-156767 (URN)10.1016/j.jcis.2018.03.034 (DOI)000431100000012 ()29579561 (PubMedID)
Available from: 2018-06-07 Created: 2018-06-07 Last updated: 2020-04-19Bibliographically approved

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