Abstract: An innovative biomimetic method has been developed to synthesize layered nanocomposite coatings using silica and sugar-derived carbon to mimic the formation of a natural seashell structure. The layered nanocomposites are fabricated through alternate coatings of condensed silica and sugar. Sugar-derived carbon is a cost-effective material as well as environmentally friendly. Pyrolysis of sugar will form polycyclic aromatic carbon sheets, i.e., carbon black. The resulting final nanocomposite coatings can survive temperatures of more than 1150 °C and potentially up to 1650 °C. These coatings have strong mechanical properties, with hardness of more than 11 GPa and elastic modulus of 120 GPa, which are 80% greater than those of pure silica. The layered coatings have many applications, such as shielding in the form of mechanical barriers, body armor, and space debris shields. Graphical abstract: [Figure not available: see fulltext.]
Abstract: Here, we report the high pressure phase and morphology behavior of ordered anatase titanium dioxide (TiO2) nanocrystal arrays. One-dimensional TiO2 nanorods and nanorices were synthesized and self-assembled into ordered mesostructures. Their phase and morphological transitions at both atomic scale and mesoscale under pressure were studied using in situ synchrotron wide- and small-angle x-ray scattering (WAXS and SAXS) techniques. At the atomic scale, synchrotron WAXS reveals a pressure-induced irreversible amorphization up to 35 GPa in both samples but with different onset pressures. On the mesoscale, no clear phase transformations were observed up to 20 GPa by synchrotron SAXS. Intriguingly, sintering of TiO2 nanorods at mesoscale into nano-squares or nano-rectangles, as well as nanorices into nanowires, were observed for the first time by transmission electron microscopy. Such pressure-induced nanoparticle phase-amorphization and morphological changes provide valuable insights for design and engineering structurally stable nanomaterials. Impact statement: The high pressure behavior of nanocrystals (NCs) continues to be of interest, as previous studies have demonstrated that an externally applied pressure can serve as an efficient tool to induce structural phase transitions of NC assemblies at both the atomic scale and mesoscale without altering any chemistry by manipulating NC interatomic and interparticle distances. In addition, the high pressure generated deviatoric stress has been proven to be able to force adjacent NCs to connect and fuse into new crystalline nanostructures. Although the atomic structural evolution of TiO2 NCs under pressure has been widely investigated in the past decades, open questions remain regarding the mesoscale phase transition and morphology of TiO2 NC assemblies as a function of pressure. Therefore, in this work, systemic high pressure experiments on ordered arrays of TiO2 nanorods and nanorices were conducted by employing wide/small angle x-ray scattering techniques. The sintering of TiO2 assemblies at mesoscale into various nanostructures under pressure were revealed by transmission electron microscopy. Overall, this high pressure work fills the current gap in research on the mesoscale phase behavior of TiO2 assemblies. The observed morphology tunability attained by applying pressure opens new pathways for engineering nanomaterials and optimizing their collective properties through mechanical compression stresses. Graphical abstract: [Figure not available: see fulltext.].
Pulsed-power generators using the magnetic loading technique are able to produce well-controlled continuous ramp compression of condensed matter for high-pressure equation-of-state studies. X-ray diffraction (XRD) data from dynamically compressed samples provide direct measurements of the elastic compression of the crystal lattice, onset of plastic flow, strength-strain rate dependence, structural phase transitions, and density of crystal defects such as dislocations. Here, we present a cost effective, compact X-ray source for XRD measurements on pulsed-power-driven ramp-loaded samples. This combination of magnetically-driven ramp compression of materials with single, short-pulse XRD diagnostic will be a powerful capability for the dynamic materials community. The success in fielding this new XRD diagnostic dramatically improves our predictive capability and understanding of rate-dependent behavior at or near phase transition. As Sandia plans the next-generation pulse-power driver platform, a key element needed to deliver new state-of-the-art experiments will be having the necessary diagnostic tools to probe new regimes and phenomena. These diagnostics need to be as versatile, compact, and portable as they are powerful. The development of a platform-independent XRD diagnostic gives Sandia researchers a new window to study the microstructure and phase dynamics of materials under load. This project has paved the way for phase transition research in a variety of materials with mission interest.
Self-assembly of anisotropic plasmonic nanomaterials into ordered superstructures has become popular in nanoscience because of their unique anisotropic optical and electronic properties. Gold nanorods (GNRs) are a well-defined functional building block for fabrication of these superstructures. They possess important anisotropic plasmonic characteristics that result from strong local electric field and are responsive to visible and near-IR light. There are recent examples of assembling the GNRs into ordered arrays or superstructures through processes such as solvent evaporation and interfacial assembly. In this Minireview, recent progress in the development of the self-assembled GNR arrays is described, with focus on the formation of oriented GNR arrays on substrates. Key driving forces are discussed, and different strategies and self-assembly processes of forming oriented GNR arrays are presented. The applications of the oriented GNR arrays in optoelectronic devices are also overviewed, especially surface enhanced Raman scattering (SERS).
Nanoparticle (NP) high pressure behavior has been extensively studied over the years. In this review, we summarize recent progress on the studies of pressure induced NP phase behavior, property, and applications. This review starts with a brief overview of high pressure characterization techniques, coupled with synchrotron X-ray scattering, Raman, fluorescence, and absorption. Then, we survey the pressure induced phase transition of NP atomic crystal structure including size dependent phase transition, amorphization, and threshold pressures using several typical NP material systems as examples. Next, we discuss the pressure induced phase transition of NP mesoscale structures including topics on pressure induced interparticle separation distance, NP coupling, and NP coalescence. Pressure induced new properties and applications in different NP systems are highlighted. Finally, outlooks with future directions are discussed.
Pressure-driven assembly of ligand-grafted gold nanoparticle superlattices is a promising approach for fabricating gold nanostructures, such as nanowires and nanosheets. Optimizing this fabrication method will require extending our understanding of superlattice mechanics to regimes of high pressures. We use molecular dynamics simulations to characterize the response of alkanethiol-grafted gold nanoparticle superlattices to applied hydrostatic pressures up to 15 GPa. At low applied pressures, intrinsic voids govern the mechanics of compaction. As applied pressures increase, the void collapse and ligand compression depend significantly on the ligand length. These microstructural observations correlate directly with trends in bulk modulus and elastic constants. For short ligands, core-core contact between gold nanoparticles is observed at high pressures, which augurs irreversible response and eventual sintering. This presintering behavior was unexpected under hydrostatic loading and is observed only for the shortest ligands.
Semiconductor nanomaterials with controlled morphologies and architectures are of critical importance for high-performance optoelectronic devices. However, the fabrication of such nanomaterials on polymer-based flexible electrodes is particularly challenging due to degradation of the flexible electrodes at a high temperature. Here we report the fabrication of nickel oxide nanopillar arrays (NiOx NaPAs) on a flexible electrode by vapor deposition, which enables highly efficient perovskite solar cells (PSCs). The NiOx NaPAs exhibit an enhanced light transmittance for light harvesting, prohibit exciton recombination, promote irradiation-generated hole transport and collection, and facilitate the formation of large perovskite grains. These advantageous features result in a high efficiency of 20% and 17% for the rigid and flexible PSCs, respectively. Additionally, the NaPAs show no cracking after 500 times of bending, consistent with the mechanic simulation results. This robust fabrication opens a new opportunity for the fabrication of a large area of high-performance flexible optoelectronic devices.
Due to remarkable electronic property, optical transparency, and mechanical flexibility, monolayer molybdenum disulfide (MoS 2 ) has been demonstrated to be promising for electronic and optoelectronic devices. To date, the growth of high-quality and large-scale monolayer MoS 2 has been one of the main challenges for practical applications. Here we present a MoS 2 -OH bilayer-mediated method that can fabricate inch-sized monolayer MoS 2 on arbitrary substrates. This approach relies on a layer of hydroxide groups (aOH) that are preferentially attached to the (001) surface of MoS 2 to form a MoS 2 -OH bilayer structure for growth of large-area monolayer MoS 2 during the growth process. Specifically, the hydroxide layer impedes vertical growth of MoS 2 layers along the [001] zone axis, promoting the monolayer growth of MoS 2 , constrains growth of the MoS 2 monolayer only in the lateral direction into larger area, and effectively reduces sulfur vacancies and defects according to density functional theory calculations. Finally, the hydroxide groups advantageously prevent the MoS 2 from interface oxidation in air, rendering high-quality MoS 2 monolayers with carrier mobility up to ∼30 cm 2 V -1 s -1 . Using this approach, inch-sized uniform monolayer MoS 2 has been fabricated on the sapphire and mica and high-quality monolayer MoS 2 of single-crystalline domains exceeding 200 μm has been grown on various substrates including amorphous SiO 2 and quartz and crystalline Si, SiC, Si 3 N 4 , and graphene This method provides a new opportunity for the monolayer growth of other two-dimensional transition metal dichalcogenides such as WS 2 and MoSe 2 .
We report there has been widespread recent interest in self-assembly and synthesis of porphyrin and its derivatives-based ordered arrays aiming to emulate natural light-harvesting processes and energy storage. However, technologies that leverage the structural advantages of individual porphyrins have not been fully realized and have been limited by available synthesis methods. This article provides general perspectives on porphyrin and derivative chemistry, and discussions on surfactant-assisted cooperative self-assembly using amphiphilic surfactants and functional porphyrins and derivatives. The cooperative self-assembly amplifies the intrinsic advantages of individual porphyrins by engineering them into well-defined one-dimensional–three-dimensional (1D–3D) nanostructures. Surfactant-assisted self-assembly of amphiphilic surfactants and porphyrins has been utilized to form well-defined “micelle-like” nanostructures. Lastly, driven by intermolecular interactions, subsequent nucleation and growth confined within these nanostructures lead to the formation of 1D–3D ordered optically and electrically active nanomaterials with structure and function on multiple length scales.
Nanoparticles; Supramolecular Chemistry; Materials Science Nanoparticles (NPs)of controlled size, shape, and composition are important building blocks for the next generation of devices. There are numerous recent examples of organizing uniformly sized NPs into ordered arrays or superstructures in processes such as solvent evaporation, heterogeneous solution assembly, Langmuir-Blodgett receptor-ligand interactions, and layer-by-layer assembly. This review summarizes recent progress in the development of surfactant-assisted cooperative self-assembly method using amphiphilic surfactants and NPs to synthesize new classes of highly ordered active nanostructures. Driven by cooperative interparticle interactions, surfactant-assisted NP nucleation and growth results in optically and electrically active nanomaterials with hierarchical structure and function. How the approach works with nanoscale materials of different dimensions into active nanostructures is discussed in details. Some applications of these self-assembled nanostructures in the areas of nanoelectronics, photocatalysis, and biomedicine are highlighted. Finally, we conclude with the current research progress and perspectives on the challenges and some future directions.
Controlling microscopic morphology of energetic materials is of significant interest for the improvement of their performance and production consistency. As an important insensitive high explosive material, triaminotrinitrobenzene (TATB) has attracted tremendous research effort for military grade explosives and propellants. In this study, a new, rapid and inexpensive synthesis method for monodispersed TATB microparticles based on micelle-confined precipitation was developed. Surfactant with proper hydrophilic-lipophilic balance value was found to be critical to the success of this synthesis. The morphology of the TATB microparticles can be tuned between quasi-spherical and faceted by controlling the speed of recrystallization.
Fan, Hongyou F.; Billstrand, Brian B.; Bian, Kaifu B.; Alarid, Leanne A.
Here, we present that lead iodide based perovskites are promising optoelectronic materials ideal for solar cells. Recently emerged perovskite nanocrystals (NCs) offer more advantages including improved size-tunable band gap, structural stability, and solvent-based processing. Here we report a simple surfactant-assisted two-step synthesis to produce monodisperse PbI2 NCs which are then converted to methylammonium lead iodide perovskite NCs. Based on electron microscopy characterization, these NCs showed competitive monodispersity. Additionally, combined results from X-ray diffraction patterns, optical absorption, and photoluminescence confirmed the formation of high quality methylammonium lead iodide perovskite NCs. More importantly, by avoiding the use of hard-to-remove chemicals, the resulted perovskite NCs can be readily integrated in applications, especially solar cells through versatile solution/colloidal-based methods.
Porphyrins are vital pigments involved in biological energy transduction processes. Their abilities to absorb light, then convert it to energy, have raised the interest of using porphyrin nanoparticles as photosensitizers in photodynamic therapy. A recent study showed that self- assembled porphyrin-silica composite nanoparticles can selectively destroy tumor cells, but detection of the cellular uptake of porphyrin-silica composite nanoparticles was limited to imaging microscopy. Here we developed a novel method to rapidly identify porphyrin-silica composite nanoparticles using Atmospheric Solids Analysis Probe-Mass Spectrometry (ASAP-MS). ASAP-MS can directly analyze complex mixtures without the need for sample preparation. Porphyrin-silica composite nanoparticles were vaporized using heated nitrogen desolvation gas, and their thermo-profiles were examined to identify distinct mass- to-charge (M/Z) signatures. HeLa cells were incubated in growth media containing the nanoparticles, and after sufficient washing to remove residual nanoparticles, the cell suspension was loaded onto the end of ASAP glass capillary probe. Upon heating, HeLa cells were degraded and porphyrin-silica composite nanoparticles were released. Vaporized nanoparticles were ionized and detected by MS. The cellular uptake of porphyrin-silica composite nanoparticles was identified using this ASAP-MS method.
The performance of energetic materials (EM) varies significantly across production lots due to the inability of current production methods to yield consistent morphology and size. Lot - to - lot variations and the inability to remake the needed characteristics that meet specification is costly, increases uncertainty, and creates additional risk in programs using these materials. There is thus a pressing need to more reliably formulate EMs with greater control of mor pholog y . The goal of this project is to use the surfactant - assisted self - assembly to generate EM particles with well - defined size and external morphologies using triaminotrinitrobenzene (TATB) and hexanitrohexaazaisowurtzitane (CL - 20) as these EMs are both prevalent in the stockpile and present interesting/urgent reprocessing challenges. W e intend to understand fundamental science on how molecular packing influences EM morphology. We develop scale up fabrication of EM particle s with controlled morphology, p romising to eliminate inconsistent performance by providing a trusted and reproducible method to improve EM s for NW applications.
Pressure-driven assembly of ligand-grafted gold nanoparticle superlattices is a promising approach for fabricating gold nanostructures, such as nanowires and nanosheets. However, optimizing this fabrication method requires an understanding of the mechanics of their complex hierarchical assemblies at high pressures. We use molecular dynamics simulations to characterize the response of alkanethiol-grafted gold nanoparticle superlattices to applied hydrostatic pressures up to 15 GPa, and demonstrate that the internal mechanics significantly depend on ligand length. At low pressures, intrinsic voids govern the mechanics of pressure-induced compaction, and the dynamics of collapse of these voids under pressure depend significantly on ligand length. These microstructural observations correlate well with the observed trends in bulk modulus and elastic constants. For the shortest ligands at high pressures, coating failure leads to gold core-core contact, an augur of irreversible response and eventual sintering. This behavior was unexpected under hydrostatic loading, and was only observed for the shortest ligands.
Wei, Wenbo; Wang, Yuru; Ji, Juanjuan; Zuo, Shanshan; Li, Wentao; Bai, Feng; Fan, Hongyou F.
Anisotropic nanoparticles, such as nanorods and nanoprisms, enable packing of complex nanoparticle structures with different symmetry and assembly orientation, which result in unique functions. Despite previous extensive efforts, formation of large areas of oriented or aligned nanoparticle structures still remains a great challenge. Here, we report fabrication of large-area arrays of vertically aligned gold nanorods (GNR) through a controlled evaporation deposition process. We began with a homogeneous suspension of GNR and surfactants prepared in water. During drop casting on silicon substrates, evaporation of water progressively enriched the concentrations of the GNR suspension, which induces the balance between electrostatic interactions and entropically driven depletion attraction in the evaporating solution to produce large-area arrays of self-assembled GNR on the substrates. Electron microscopy characterizations revealed the formation of layers of vertically aligned GNR arrays that consisted of hexagonally close-packed GNR in each layer. Benefiting from the close-packed GNR arrays and their smooth topography, the GNR arrays exhibited a surface-enhanced Raman scattering (SERS) signal for molecular detection at a concentration as low as 10-15 M. Because of the uniformity in large area, the GNR arrays exhibited exceptional detecting reproducibility and operability. This method is scalable and cost-effective and could lead to diverse packing structures and functions by variation of guest nanoparticles in the suspensions.
The use of nanoparticles as a potential building block for photosensitizers has recently become a focus of interest in the field of photocatalysis and photodynamic therapy. Porphyrins and their derivatives are effective photosensitizers due to extended π-conjugated electronic structure, high molar absorption from visible to near-infrared spectrum, and high singlet oxygen quantum yields as well as chemical versatility. In this paper, we report a synthesis of self-assembled porphyrin nanoparticle photosensitizers using zinc meso-tetra(4-pyridyl)porphyrin (ZnTPyP) through a confined noncovalent self-assembly process. Scanning electron microscopy reveals formation of monodisperse cubic nanoparticles. UV-vis characterizations reveal that optical absorption of the nanoparticles exhibits a red shift due to noncovalent self-assembly of porphyrins, which not only effectively increase intensity of light absorption but also extend light absorption broadly covering visible light for enhanced photodynamic therapy. Electron spin-resonance spectroscopy (ESR) studies show the resultant porphyrin nanoparticles release a high yield of singlet oxygen. Nitric oxide (NO) coordinates to central metal Zn ions to form stabilized ZnTPyP@NO nanoparticles. We show that under light irradiation ZnTPyP@NO nanoparticles release highly reactive peroxynitrite molecules that exhibit enhanced antibacterial photodynamic therapy (APDT) activity. The ease of the synthesis of self-assembled porphyrin nanoparticles and light-triggered release of highly reactive moieties represent a completely different photosensitizer system for APDT application.
Low dimensional lead halide perovskite particles are of tremendous interest due to their size-tunable band gaps, low exciton binding energy, high absorption coefficients, outstanding quantum and photovoltaic efficiencies. In this paper, we report a new solution-based synthesis of stabilized Cs4PbBr6 perovskite particles with high luminescence. This method requires only mild conditions and produces colloidal particles that are ideal for highly efficient solution-based device fabrications. The synthesized microstructures not only display outstanding luminescence quantum yield but also long term stability in atmospheric conditions. Partial halide substitutions were also demonstrated to extend photoluminescence spectra of the perovskite particles. Finally, this convenient synthesis and optical tunability of Cs4PbBr6 perovskite particles will be advantageous for future applications of optoelectronic advices.
There has been a widespread interest in the preparation of self-assembled porphyrin nanostructures and their ordered arrays, aiming to emulate natural light harvesting processes and energy storage and to develop new nanostructured materials for photocatalytic process. Here, we report controlled synthesis of one-dimensional porphyrin nanostructures such as nanorods and nanowires with well-defined self-assembled porphyrin networks that enable efficient energy transfer for enhanced photocatalytic activity in hydrogen generation. Preparation of these one-dimensional nanostructures is conducted through noncovalent self-assembly of porphyrins confined within surfactant micelles. X-ray diffraction and transmission electron microscopy results reveal that these one-dimensional nanostructures contain stable single crystalline structures with controlled interplanar separation distance. Optical absorption characterizations show that the self-assembly enables effective optical coupling of porphyrins, resulting in much more enhanced optical absorption in comparison with the original porphyrin monomers, and the absorption bands red shift to more extensive visible light spectrum. The self-assembled porphyrin network facilitates efficient energy transfer among porphyrin molecules and the delocalization of excited state electrons for enhanced photocatalytic hydrogen production under visible light.
Multiple-color-emissive carbon dots (CDots) have potential applications in various fields such as bioimaging, light-emitting devices, and photocatalysis. The majority of the current CDots to date exhibit excitation-wavelength-dependent emissions with their maximum emission limited at the blue-light region. Here, a synthesis of multiple-color-emission CDots by controlled graphitization and surface function is reported. The CDots are synthesized through controlled thermal pyrolysis of citric acid and urea. By regulating the thermal-pyrolysis temperature and ratio of reactants, the maximum emission of the resulting CDots gradually shifts from blue to red light, covering the entire light spectrum. Specifically, the emission position of the CDots can be tuned from 430 to 630 nm through controlling the extent of graphitization and the amount of surface functional groups, COOH. The relative photoluminescence quantum yields of the CDots with blue, green, and red emission reach up to 52.6%, 35.1%, and 12.9%, respectively. Furthermore, it is demonstrated that the CDots can be uniformly dispersed into epoxy resins and be fabricated as transparent CDots/epoxy composites for multiple-color- and white-light-emitting devices. This research opens a door for developing low-cost CDots as alternative phosphors for light-emitting devices.
In an effort to utilize their unique photoactive properties, porphyrin monomers were assembled into tetragonal microparticles by a surfactant-assisted neutralization method through the cooperative interactions between the porphyrin building blocks including π-π stacking, J-aggregation and metal-ligand coordination. Electron microscopy characterization in combination with X-ray diffraction confirmed the three-dimensional ordered tetragonal microstructures with stable crystalline frameworks and well defined external surface morphology. Optical absorption and fluorescence spectroscopy revealed enhanced absorbance properties as compared with the raw porphyrin material, favourable for chromophore excitation and energy transport. With active and responsive optical properties, these new porphyrin microparticles look to serve as promising components for a wide range of applications including sensing, diagnostics, solar cells, and optoelectronic devices.
We recently developed a vacuum assisted micelle confinement synthesis for spherical microparticles of CL-20 with outstanding monodispersity. These microparticles are promising energetic material for explosive devices with enhanced and predictable performances. In this work, to facilitate further development and application of this synthesis, the particle growth process was monitored by in-situ dynamic light scattering measurements. The result was interpreted by a finite element model to obtain critical parameters. These parameters were then used to predict the behavior and product quality of batch synthesis under various operation conditions.
A new quantum dot synthesis method based on metallic-block copolymer precursors was developed. The synthesis produced CdS QDs assembled into chains. This method provides a new model for the study of 1D QD chains to determine its effect on charge transport and optoelectronic coupling. This synthesis method was readily extended to other semiconductor materials including PbS and perovskites producing QDs of various shapes. It evidenced further promise of this synthesis method to assist in the assembly, shape and size control of various nanomaterials.
Structurally controlled nanoparticles, such as core-shell nanocomposite particles by combining two or more compositions, possess enhanced or new functionalities that benefited from the synergistic coupling of the two components. Here we report new nanocomposite particles with self-assembled porphyrin arrays as the core surrounded by amorphous silica as the shell. The synthesis of such nanocomposite nanoparticles was conducted through a combined surfactant micelle confined self-assembly and silicate sol-gel process using optically active porphyrin as a functional building block. Depending on kinetic conditions, these particles exhibit structure and function at multiple length scales and locations. At the molecular scale, the porphyrins as the building blocks provide well-defined macromolecular structures for noncovalent self-assembly and unique chemistry for high-yield generation of singlet oxygen for photodynamic therapy (PDT). On the nanoscale, controlled noncovalent interactions of the porphyrin building block result in an extensive self-assembled porphyrin network that enables efficient energy transfer and impressive fluorescence for cell labeling, evidenced by absorption and photoluminescence spectra. Finally, the thin silicate shell on the nanoparticle surface allows easy functionalization, and the resultant targeting porphyrin-silica nanocomposites can selectively destroy tumor cells upon receiving light irradiation.
Nanocrystals (NCs) can self-assemble into ordered superlattices with collective properties, but the ability for controlling NC assembly remains poorly understandable toward achievement of desired superlattice. This work regulates several key variables of PbS NC assembly (e.g., NC concentration and solubility, solvent type, evaporation rate, seed mediation and thermal treatment), and thoroughly exploits the nucleation and growth as well as subsequent superlattice transformation of NC assembles and underneath mechanisms. PbS NCs in toluene self-assemble into a single face-centered-cubic (fcc) and body-centered-cubic (bcc) superlattice, respectively, at concentrations ≤17.5 and ≥70 mg/mL, but an intermediate concentration between them causes the coexistence of the two superlattices. Differently, NCs in hexane or chloroform self-assemble into only a single bcc superlattice. Distinct controls of NC assembly in solvent with variable concentrations confirm the NC concentration/solubility mediated nucleation and growth of superlattice, in which an evaporation-induced local gradient of NC concentration causes simultaneous nucleation of the two superlattices. The observation for the dense packing planes of NCs in fast growing fcc rather than bcc reveals the difference of entropic driving forces responsible for the two distinct superlattices. Decelerating the solvent evaporation does not amend the superlattice symmetry, but improves the superlattice crystallinity. In addition to shrinking the superlattice volume, thermal treatment also transforms the bcc to an fcc superlattice at 175 °C. Through a seed-meditated growth, the concentration-dependent superlattice does not change lattice symmetry over the course of continuous growth, whereas the newly nucleated secondary small nuclei through a concentration change have relatively higher surface energy and quickly dissolve in solution, providing additional NC sources for the ripening of the primarily nucleated larger and stable seeds. The observations under multiple controls of assembly parameters not only provide insights into the nucleation and growth as well as transformation of various superlattice polymorphs but also lay foundation for controlled fabrication of desired superlattice with tailored property.