bluuebunny/crossref_metadata_2025_split huggingface dataset:
Understanding Corona Exchange Dynamics on Single-Walled Carbon Nanotubes with Multiplexed Fluorescence Monitoring
Authors: Pinals Rebecca L , Yang Darwin , Cao Wendy , Landry Markita P 
Published: February 2020

Adsorption of polymers on single-walled carbon nanotubes (SWCNTs) has enabled developments in molecular sensing, in vivo imaging, gene and drug delivery, and chirality sorting applications. Noncovalent functionalization offers a modification route that preserves the pristine atomic structure, thus retaining the intrinsic near-infrared fluorescence of the SWCNTs for sensing or imaging functions, and offers a reversible binding mode for cargo delivery or chirality separation processes. However, noncovalent adsorption is an inherently dynamic process, where exchange occurs between molecules in the bulk solution and molecules on the surface, into what is known as the ‘corona phase’. In the case of polymers on SWCNTs, the nature, strength, and kinetics of both the polymer binding and unbinding processes are important contributors to the success of polymer-SWCNT based technologies. Understanding this binding process is especially important for intended uses of functionalized SWCNTs in biological environments, where native biomolecules compete with the original polymer to occupy the SWCNT surface. Binding of proteins and other biomolecules to the SWCNT not only disrupts the intended functionality of the nanoparticle, but further leads to potentially adverse biocompatibility outcomes.
We present an assay to study the process of corona exchange dynamics between solution-phase and corona-phase polymers on SWCNTs. Real-time tracking of polymer and protein adsorption and desorption events are conducted with systematic variation of the molecular entities and solution conditions. This assay exploits the quenching property of fluorophores in close proximity to the SWCNT surface to monitor ligand binding and unbinding events. Binding profiles are thus extracted from the experimental assay and used to inform a kinetic model of the system. This study encompasses exchange of SWCNT-adsorbed ssDNA and either ssDNA, surfactant, or protein added to the bulk solution with multiplexed fluorescence tracking of all entities. Moreover, the kinetics of these binding profiles are validated against an orthogonal and more ubiquitously-used platform monitoring solvatochromic shifting of the near-infrared SWCNT spectrum as a proxy for SWCNT corona perturbations (Beyene et al., Nano Letters, 2018; Heller et al., PNAS, 2011; Jena et al., ACS Appl. Mater. Interfaces, 2017). The work presented herein develops an understanding of the fundamental corona exchange mechanism, contextualizes the nature of the ligand exchange process versus SWCNT solvatochromic shifting, and provides insight into performance of these designed SWCNT-based systems in biologically relevant, protein-rich conditions.
(Invited) Controlling the Inner Dielectric Environment of Carbon Nanotubes to Tune Their Optical Properties
Authors: Cambre Sofie , Campo Jochen , Botka Bea , van Werveke Wouter , Obrzut Jan , Wenseleers Wim , Fagan Jeffrey A. 
Published: February 2020

The optical properties of single-wall carbon nanotubes (SWCNTs) are extremely sensitive to their external and internal environment. For example, filling the endohedral cavity with water molecules results in characteristic shifts and broadening of both the SWCNTs’ radial breathing mode vibrational frequency and their optical (electronic) transitions, as well as a quenching of their emission.[1] Although mostly ignored in literature, solvent ingestion effects are substantial, and can also be used to passivate the nanotube interior, by controlled manipulation of the endohedral environment prior to dispersion.[2]
In this work, specific and tunable modification of the optical properties of SWCNTs is demonstrated through the direct encapsulation of guest molecules with widely varying dielectric constants. Over 30 different compounds with varying static dielectric constant have been encapsulated inside the SWCNTs and their spectroscopic analysis, in comparison to unfilled (empty) SWCNTs, demonstrates experimentally that the general effect of filler static dielectric constant on the SWCNTs’ optical properties corresponds to a monotonic energy reduction (red-shifting) of the optical transitions with increased magnitude for higher dielectric constants. In addition to these spectral shifts, the filling also reveals a general increase of fluorescence intensity with lower dielectric constants.
Our investigation hence demonstrates a new degree of modulation of the SWCNTs’ optical properties by simple endohedral ingestion of various guest molecules.
[1] S. Cambré et al. Phys. Rev. Lett. 104, 207401 (2010); W. Wenseleers et al. Adv. Mater. 19, 2274 (2007); S. Cambré et al. ACS Nano 6, 2649 (2012)
[2] J. Campo et al Nanoscale Horizons 1, 317 (2016)
(Invited) Perylene-Based Functionalization of Carbon Nanotubes
Authors: Setaro Antonio 
Published: February 2020

Functionalization aims at granting compounds with additional features. This is achieved by typically attaching novel groups to the original systems. The aftermath of such process yields complexes whose charcteristics often result in more than just the mere sum of the initial products. The specific character of the functionalized structure, moreover, depends upon the way the functionalization strategy has been pursued.
We will focus on the carbon nanotubes functionalization through perylene, an aromatic molecule emitting in the excitation window of most single-walled nanotubes commercially available. We have previously shown that the perylene core of custom surfactants was able to attach though pi-pi stacking interactions onto the sidewall of CNTs while ensuring efficient excitation transfer to the tubes [1,2]. Here we will show how starting from the same elements (perylene and nanotubes) and pursuing different functionalization routines, we achieve systems with different features and functions. In particular, we will compare the characteristics of perylene-comprising polymers wrapped around the tubes [3] with the peculiarities of perylene covalently attached to the nanotubes following a novel conjugation-preserving routine we recently developed [4]. We will highlight the difference among the properties of the final products as well as the applications they would be suitable for.
[1] F Ernst et al., Adv. Funct. Mat. 2012, 22, 3921.
[2] F Ernst et al., Appl. Phys. Lett. 2013, 102, 233105.
[3] K. Huth et al, Small 2018, 14, 1800796.
[4] A Setaro et al. Nat. Comm. 2017, 8, 14281.
(Invited) Carbon Nanotube Photoluminescence Solvatochromism in Biomedicine: Spectroscopy, Imaging, and Modulation
Authors: Heller Daniel A. , Baker Hanan , Budhathoki-Uprety Januka , Cupo Christian , Harvey Jackson , Jena Prakrit Vaibhav , Langenbacher Rachel E , Mittal Jeetain , Roxbury Daniel , Shah Janki , Williams Ryan M. , Zerze Gul , Zheng Ming 
Published: February 2020

Modulation of the carbon nanotube photoluminescence band position has implications for applications such as sensing and imaging. Carbon nanotube photoluminescence solvatochromism, the hypsochromic or bathochromic shifting of nanotube emission, can be induced via changes in the local dielectric environment. We developed methods to modulate nanotube solvatochromic behavior to improve sensor responses, and we developed tools to observe solvatochromism within live cells and, recently, live animals.
We found that nanotube solvatochromism extends to variations of local electrostatic charge, induced by adsorption/desorption of polyelectrolytes on the nanotube surface, such as proteins and nucleic acids. We also found that dielectric and charge-mediated solvatochromism can be compounded to exacerbate the response. Upon triggered desorption of a polyelectrolyte, such as upon desorption of RNA upon hybridization, for instance, amphiphilic molecules can adsorb to the recently-uncovered nanotube surface. The adsorption displaces water to result in hypsochromic shifting, which can be additive, as polyelectrolyte desorption will also cause a hypsochromic shift. We found that the amphiphile may be a surfactant but, recently, we found that proteins can result in a similar response, facilitating the detection of viruses.
We developed tools to image changes in nanotube emission in live cells (near-infrared hyperspectral microscopy) and, recently, live animals (preclinical, near-infrared hyperspectral imaging). Carbon nanotube solvatochromism-based sensors, in combination with spectral imaging tools, allow measurements of biomarkers, drugs, and metabolites in live cells and organisms, facilitating improvements in disease detection, drug development, and biomedical research.
Carbon Nanotube Compositie Based Sensor for Detecting Hydrogen Molecules
Authors: Lee Junyeop , Kim jae Keon , Kim Samhwan , Jung Daewoong 
Published: February 2020

Accuracy and precise measurement of gas values is crucial for recognizing many critical biological and physical signs, as gas values present significant signals for monitoring chemistry, biology, environments and medical industries. Many sensing materials such as metal compounds, composite, nanowires, and polymers, for detecting gas have been investigated, and the merits and demerits of each have been reported [1,2]. Recently, carbon-based nanomaterials, including zero-dimensional fullerenes, one-dimensional carbon nanotubes (CNT), and two-dimensional graphene, have shown probable in gas sensor applications. Many prior works have reported their superior properties, including higher electrical conductivity, mechanical durability and chemical stability, and a larger surface area.In particularly, CNTs are well known material for sensor applications due to their stable graphite configuration, structural endurance under chemical/physical treatment processes, and mechanical characteristics. Moreover, lots of efforts to realize CNTs as chemical sensor material were performed by many groups previously [3]. They reported that the concentrations of electrons and holes in CNTs play important role in sensitivity of the CNT-based gas sensor. However, although many techniques were introduced to fabricate the CNT-based gas sensors, such device manufacturing processes were intricate and have limited repeatability and reliability, which makes hard them to be commercialized.The CNT yarn was introduced, reported and characterized previously by group using simple dry spinning method [4]. The CNT yarn has good electrical property with a high conductivity, and flexible structural property, and chemical stability. In this work, we develop the ability of CNT yarn for detecting hydrogen and carbon monoxide concentrations. Furthermore, we demonstrate that metal nanoparticles on the surface of CNT yarn highly affect the sensitivity of the CNT yarn-based gas sensor. Therefore, this study focused on the analysis and characteristics of the gas sensor using binary composite as gas sensor.
References
[1] Liu et al., Sensors 12, 9635 (2012).

[2] Varghese et al., Sens. Actuators. B 218, 160 (2015).

[3] Llobet et al., Sens. Actuators. B 179, 32 (2013).

[4] Hwang et al., Puller. Nanotub. Car. N. 24, 305 (2016).
Nanocarbons through the Artist’s Lens
Authors: Cohen Joseph , Harvey Jackson , Chyan Yieu , Tour James M. , Heller Daniel A. 
Published: February 2020

Carbon nanomaterials have unique structural and optical properties that have been under-explored for the development of artistic applications. We developed pigments and fluorescent dyes using single-walled carbon nanotube and graphene to create visual art. We developed carbon nanotube-based pigments for application to paper and other solid substrates with optimal fluorescence in the infrared. The photoluminescence of these paints was used to generate artwork that illuminates the unique properties and opportunities inherent in the material. We developed several methods to visualize the near-infrared nanotube emission, including novel lighting solutions as well as imaging solutions, for use with large-scale visual art formats.
We also developed large-scale visual art using graphene as a pigment. Laser-induced graphene was synthesized in-situ on paper substrates with dimensions up to 20 x 30 inches. Machine-automated processes allowed the faithful reproduction of computer-generated artwork into graphene on an “artist’s canvas.”
Carbon Nanotube-Inorganic Hybrid Systems and Devices
Authors: Palma Matteo 
Published: February 2020

We present different strategies for the generation of multifunctional nanomaterials employing single-walled carbon nanotubes (SWCNTs). In particular, we will discuss the formation of nanohybrids via the in-solution assembly of inorganic nanomaterials to SWCNTs, employed as nanoelectrodes or as nanoscale vector templates. Notably, both static and dynamic heterostructures were assembled, as well as nanoscale electronic devices; this allowed us to study and tailor various systems for different applications.
We will first discuss the in-solution assembly of organic-inorganic heterostructures consisting of single Quantum Dots (QDs) univocally linked at the terminal ends of individual SWCNTs. Monofunctionalized SWCNT-QD heterostructures were obtained and photophysical investigations at the single nanohybrid level showed evidence of electronic coupling [1]. Additionally, DNA linkers of differing lengths were used as molecular rulers to control the distance, and hence tune the energy/charge transfer between the two nanostructures in these SWCNT-QD nanohybrids.[2] A dynamic SWCNT-QD hybrid was also designed and assembled using a G-quadruplex DNA aptamer linker, so that the distance between the SWCNT and QD could be dynamically modulated by the introduction and removal of potassium ions (K+);[2] the system was further found to be sensitive to K+ concentrations between 1pM and 25mM. By and large, this approach opens the possibility of assembling tailored optoelectronic and light harvesting systems with single-particle control.
Finally, we will present the direct synthesis of multiplexed metal nanowire based devices using carbon nanotubes as vector templates. SWCNTs were filled with specifically designed metal precursors and dispersed in aqueous solution, enabling solution processability. The filled SWNTs were immobilized from solution onto different pre-patterned electrodes via a low-cost dielectrophoresis methodology. Metal nanowires were then grown by a facile and low temperature annealing treatment, while the nanotubes were removed using an oxygen plasma once immobilized in a device configuration. Electrical characterizations demonstrated the successful fabrication of metal nanowire electronic devices (no gate dependence).[3] Overall the strategy presented allows for a facile, low-cost and direct synthesis of multiple metal nanowire based devices for nanoelectronic applications.
[1] Small, 2017,13, 1603042
[2] Advanced Science, 2018, 5, 1800596
[3] Submitted
Effect of Seed Layer on Grain Size of Electroplated Cu
Authors: Lin Yen-Chen , Chan Po-Fan , Dow Wei-Ping 
Published: February 2020

Copper is widely used as the wires of semiconductor. The grain size of copper has been approved to influence its strength, ductility and conductivity. The larger the grain size, the less the grain boundary. Accordingly, the copper conductivity increases because grain boundary is the resistance of electronic transfer. Hence, the larger the grain size is, the better the copper conductivity will be. In this work, we attempt to produce thick copper film with large grain size by means of electroplating.
We found that seed layers could influence the structure of electroplated copper. Hence, we employed various seed layer materials, such as titanium, copper. The cross-section of the electroplated copper was observed by optical microscope (OM), focused ion beam (FIB), scanning electron spectroscopy (SEM) and transmission electron microscope (TEM). The plating additives were characterized using potentiostatic.
(Invited) A Tutorial on Atomic Layer Deposition and Its Application in Lithium-Ion Batteries
Authors: Detavernier Christophe 
Published: February 2020

Atomic layer deposition (ALD) is a deposition technique where thin films are deposited from sequential gas-surface reactions. Thanks to the self-limiting nature of these reactions, ALD provides interesting deposition characteristics such as atomic scale thickness control and deposition onto complex shaped substrates (including powders) with excellent uniformity and conformality. These features have enabled ALD to become a well-established tool in semiconductor manufacturing, and there is a growing consensus that other domains such as catalysis and energy storage can also strongly benefit from these unique coating characteristics.
In this tutorial, two different types of potential applications of ALD in the field of lithium-ion batteries will be discussed:
- ALD of the active components of a lithium-ion battery (positive and negative electrodes, solid electrolytes), either as functional layers in thin film batteries, or as thin film model systems. Novel battery concepts such as the 3D thin-film lithium-ion microbattery are promising for applications such as on-chip energy storage, and ALD could play an important role in the deposition of critical components of these battery stacks onto 3D nanostructured substrates, in particular for the interfaces and solid-electrolyte layers. Moreover, the excellent film quality, control over composition and crystallinity provided by ALD enable the synthesis of thin, planar model systems. Such thin film model systems with well-controlled properties provide simplified one-dimensional currents and are unbothered by the complex interplay of various components of the classical battery, such as binder, conductive additive, particle size, solvent composition etc, and can thus reveal potentially beneficial battery chemistries which would otherwise be obscured, or provide insights into otherwise very complex systems.
- ALD modification of surfaces and interfaces. In particular, ALD of protective coatings onto electrode materials has been explored extensively to stabilise interfaces and thus enhance cell cycle life. As battery ageing for traditional lithium-ion batteries can already be problematic, novel architectures, battery concepts and material chemistries pose increasingly greater challenges in this direction, and surface/interface engineering have become important strategies to overcome ageing and improve battery performance. To obtain a high quality coating on the complex surface of battery electrodes, the low processing temperature in combination with the thickness control, uniformity and conformality provided by ALD can become key advantages.
(Invited) ALD and MLD of Functional Thin-Film Coatings for Enhanced Performance in Li-Ion and Li-Metal Solid-State Batteries
Authors: Vereecken Philippe M. , Gandrud Knut Bjarne , Put Brecht , Hollevoet Simon , Labyedh Nouha , Debucquoy Maarten , Mees Maarten , De Taeye Louis , Swamy Reddy Keerthi Dorai , Pitillas Martinez Andrea , Detavernier Christophe 
Published: February 2020

The key figures of merit for batteries are Energy density, charging time (C-rate) and cycling Life time. In this invited talk we will focus on the application of continuous closed thin films as artificial interfaces in large capacity batteries or for the fabrication of functional battery components in micro-batteries. We will deal mostly with the perspective of device performance where the ALD and MLD processes merely provide the films and enable their ultrathin, continuous and conformal nature. Nanoscale film thickness allows for low interface and cell resistance even when the materials themselves are poor conductors. For example. LiPON (N-doped Li3PO4) is a solid electrolyte interesting because it is stable against metallic lithium but, because of its poor ionic conductivity (<10-6 S/cm) only practically useful for thicknesses under few hundred nanometers. Even further, materials which are not solid electrolytes by their own merit (e.g. TiO2) still have ion-transparent properties up to several tens of nanometer and can be used as ion transparent artificial interfaces in contrast to alumina which is an insulator for Li-ions. For coating of individual particles, ideally coatings which have both electronic and ionic conducting (or transparent) properties. Doping is one approach to enhance either conductivity.
When scaling down of the film thickness also finite size effects have to be considered, for example, the thickness of the electrical double layer, diffusion layer thickness and the electric field over the dielectric.
ALD and MLD can be used also to fabricate functional nanomaterials; i.e. by harvesting nanoscale effects. For example, nanocomposite solid electrolyte films of a few tens of nanometers were fabricated by a combination of MLD of inorganic-organic hybrid alucone thin-films, etching the organic fraction in water and functionalization by ALD of Li2CO3 and Li3PO4. For the first time, enhanced ion conductivity is shown by harvesting the enhanced ion conductivity at oxide/ion conductor interfaces.
Finally, volume changes during charge and discharge are limiting the cycle life-time of batteries, especially for rigid solid-state batteries. Also ALD thin-films suffer from the mechanical strain and the benefits of the “closed” protective film are lost. Therefore, MLD of hybrid organic/inorganic coatings is explored to enable more elastic coatings for improved cycle life time.
(Invited) Vapor-Deposited MOFs As Gap-Filling Low-k Dielectrics
Authors: Ameloot Rob 
Published: February 2020

Metal-organic frameworks (MOFs) are an intriguing class of porous crystalline materials with record internal surface areas. There is tremendous potential for integrating MOFs into microelectronics, e.g. as active sensor coatings or low-k dielectrics.[1] A key enabling step in leveraging the properties of MOFs in microelectronics will be the development of robust thin film deposition methods. Most procedures for the deposition of MOF thin films are incompatible with microelectronic fabrication because of corrosion and contamination issues.
We recently demonstrated chemical vapor deposition (CVD) of MOF thin films.[2] The MOF-CVD process allows conformal growth of thin films and extends MOF processing to one of the most commonly used techniques in thin film research and manufacturing. Future directions and potential applications of MOF-CVD coatings will be discussed, with special attention to their integration as gap-filling low-k materials in on-chip interconnects.

References

[1] Stassen, I.; Burtch, N.; Talin, A. A.; Falcaro, P.; Allendorf, M. D.; Ameloot, R. Chem. Soc. Rev.
2017, 46, 3185–3241.
[2] Stassen, I.; Styles, M.; Grenci, G.; Van Gorp, H.; Vanderlinden, W.; De Feyter, S.; Falcaro, P.; De Vos, D. E.; Vereecken, P.; Ameloot, R. Nat. Mater.
2016, 15 (3), 304–310.

Figure 1