ACS Nanoscience AuPub Date : 2023-01-25DOI: 10.1021/acsnanoscienceau.2c00059
Yucai Chen, Yue Wu, Yu Qi* and Sijin Liu,
{"title":"Cell Death Pathways: The Variable Mechanisms Underlying Fine Particulate Matter-Induced Cytotoxicity","authors":"Yucai Chen, Yue Wu, Yu Qi* and Sijin Liu, ","doi":"10.1021/acsnanoscienceau.2c00059","DOIUrl":"10.1021/acsnanoscienceau.2c00059","url":null,"abstract":"<p >Recently, the advent of health risks due to the cytotoxicity of fine particulate matter (FPM) is concerning. Numerous studies have reported abundant data elucidating the FPM-induced cell death pathways. However, several challenges and knowledge gaps are still confronted nowadays. On one hand, the undefined components of FPM (such as heavy metals, polycyclic aromatic hydrocarbons, and pathogens) are all responsible for detrimental effects, thus rendering it difficult to delineate the specific roles of these copollutants. On the other hand, owing to the crosstalk and interplay among different cell death signaling pathways, precisely determining the threats and risks posed by FPM is difficult. Herein, we recapitulate the current knowledge gaps present in the recent studies regarding FPM-induced cell death, and propose future research directions for policy-making to prevent FPM-induced diseases and improve knowledge concerning the adverse outcome pathways and public health risks of FPM.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/e9/8f/ng2c00059.PMC10125306.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9355986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Nanoscience AuPub Date : 2023-01-10DOI: 10.1021/acsnanoscienceau.2c00050
Fabio Marcuccio, Dimitrios Soulias, Chalmers C. C. Chau, Sheena E. Radford, Eric Hewitt, Paolo Actis* and Martin Andrew Edwards*,
{"title":"Mechanistic Study of the Conductance and Enhanced Single-Molecule Detection in a Polymer–Electrolyte Nanopore","authors":"Fabio Marcuccio, Dimitrios Soulias, Chalmers C. C. Chau, Sheena E. Radford, Eric Hewitt, Paolo Actis* and Martin Andrew Edwards*, ","doi":"10.1021/acsnanoscienceau.2c00050","DOIUrl":"10.1021/acsnanoscienceau.2c00050","url":null,"abstract":"<p >Solid-state nanopores have been widely employed in the detection of biomolecules, but low signal-to-noise ratios still represent a major obstacle in the discrimination of nucleic acid and protein sequences substantially smaller than the nanopore diameter. The addition of 50% poly(ethylene) glycol (PEG) to the external solution is a simple way to enhance the detection of such biomolecules. Here, we demonstrate with finite-element modeling and experiments that the addition of PEG to the external solution introduces a strong imbalance in the transport properties of cations and anions, drastically affecting the current response of the nanopore. We further show that the strong asymmetric current response is due to a polarity-dependent ion distribution and transport at the nanopipette tip region, leading to either ion depletion or enrichment for few tens of nanometers across its aperture. We provide evidence that a combination of the decreased/increased diffusion coefficients of cations/anions in the bath outside the nanopore and the interaction between a translocating molecule and the nanopore–bath interface is responsible for the increase in the translocation signals. We expect this new mechanism to contribute to further developments in nanopore sensing by suggesting that tuning the diffusion coefficients of ions could enhance the sensitivity of the system.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.2c00050","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9390306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Nanoscience AuPub Date : 2022-12-27DOI: 10.1021/acsnanoscienceau.2c00046
Kent O. Kirlikovali, Sylvia L. Hanna, Florencia A. Son and Omar K. Farha*,
{"title":"Back to the Basics: Developing Advanced Metal–Organic Frameworks Using Fundamental Chemistry Concepts","authors":"Kent O. Kirlikovali, Sylvia L. Hanna, Florencia A. Son and Omar K. Farha*, ","doi":"10.1021/acsnanoscienceau.2c00046","DOIUrl":"10.1021/acsnanoscienceau.2c00046","url":null,"abstract":"<p >Over the past 25 years, metal–organic frameworks (MOFs) have developed into an increasingly intricate class of crystalline porous materials in which the choice of building blocks offers significant control over the physical properties of the resulting material. Despite this complexity, fundamental coordination chemistry design principles provided a strategic basis to design highly stable MOF structures. In this Perspective, we provide an overview of these design strategies and discuss how researchers leverage fundamental chemistry concepts to tune reaction parameters and synthesize highly crystalline MOFs. We then discuss these design principles in the context of several literature examples, highlighting both relevant fundamental chemistry principles and additional design principles required to access stable MOF structures. Finally, we envision how these fundamental concepts may offer access to even more advanced structures with tailored properties as the MOF field looks toward the future.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.2c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9356637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Nanoscience AuPub Date : 2022-12-24DOI: 10.1021/acsnanoscienceau.2c00048
Wei-Hsin Chen, Wenting Wang, Qianqi Lin, David-Benjamin Grys, Marika Niihori, Junyang Huang, Shu Hu, Bart de Nijs, Oren A. Scherman and Jeremy J. Baumberg*,
{"title":"Plasmonic Sensing Assay for Long-Term Monitoring (PSALM) of Neurotransmitters in Urine","authors":"Wei-Hsin Chen, Wenting Wang, Qianqi Lin, David-Benjamin Grys, Marika Niihori, Junyang Huang, Shu Hu, Bart de Nijs, Oren A. Scherman and Jeremy J. Baumberg*, ","doi":"10.1021/acsnanoscienceau.2c00048","DOIUrl":"10.1021/acsnanoscienceau.2c00048","url":null,"abstract":"<p >A liquid-based surface-enhanced Raman spectroscopy assay termed PSALM is developed for the selective sensing of neurotransmitters (NTs) with a limit of detection below the physiological range of NT concentrations in urine. This assay is formed by quick and simple nanoparticle (NP) “mix-and-measure” protocols, in which Fe<sup>III</sup> bridges NTs and gold NPs inside the sensing hotspots. Detection limits of NTs from <i>PreNP</i> PSALM are significantly lower than those of <i>PostNP</i> PSALM, when urine is pretreated by affinity separation. Optimized PSALM enables the long-term monitoring of NT variation in urine in conventional settings for the first time, allowing the development of NTs as predictive or correlative biomarkers for clinical diagnosis.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.2c00048","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9390304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Nanoscience AuPub Date : 2022-12-21DOI: 10.1021/acsnanoscienceau.2c00056
Raymond E. Schaak*,
{"title":"One Year of ACS Nanoscience Au","authors":"Raymond E. Schaak*, ","doi":"10.1021/acsnanoscienceau.2c00056","DOIUrl":"https://doi.org/10.1021/acsnanoscienceau.2c00056","url":null,"abstract":"I is hard to believe that a year has passed already since the first issue of ACS Nanoscience Au was published in December of 2021. In the six issues in Volume 2, which constitute the first full year, ACS Nanoscience Au has published 44 contributions, including 3 Editorials, 1 Perspective, 11 Reviews, and 29 Articles/Letters. In total, all of the content published thus far in ACS Nanoscience Au has been viewed more than 88,000 times! This large number of views is a testament to the journal’s outstanding content, as well as its visibility and reach, which are maximized by its open access status. The published papers have been authored and accessed by researchers from around the world, highlighting the global impact and visibility of ACS Nanoscience Au. These papers also span the breadth of topics that define the field of nanoscience. To highlight the topical diversity and impact of the first year of ACS Nanoscience Au, the papers highlighted below are among the most accessed and cited so far. They represent a collection of Reviews and Perspectives in nanomedicine, nanoelectronics, active matter, environmental remediation, 1-D and 2-D materials, and energy, as well as Articles and Letters in nanoclusters, nanomedicine, nanoagriculture, nanowires, halide perovskites, SERS imaging, nanophotonics, DNA nanotechnology, and MXenes. Luciferase-Based Biosensors in the Era of the COVID-19 Pandemic (ACS Nanosci. Au 2021, 1, 15−37). Our very first published Review, by Taha Azad, Carolina Ilkow, John Bell, and co-workers, holds the current record for the highest number of article views in the journal. Viruses and proteins are inherently nanoscopic systems, and this Review highlights the development and use of biosensors to study virus biology, including SARS-CoV-2. Design of Over-1000 nm Near-Infrared Fluorescent Polymeric Micellar Nanoparticles by Matching the Solubility Parameter of the Core Polymer and Dye (ACS Nanosci. Au 2021, 1, 61−68). This Article by Masakazu Umezawa, Kohei Soga, and co-workers demonstrated a strategy for designing polymeric nanoparticles for biological imaging. They showed how near-infrared fluorescent probes could be accessed by matching the solubility parameters of a core polymer and a dye molecule. Gold Nanoparticle Smartphone Platform for Diagnosing Urinary Tract Infections (ACS Nanosci. Au 2022, 2, 324− 332). The diagnosis of urinary tract infections is important in medicine. In this Article, Warren Chan and co-workers used a gold nanoparticle colorimetric approach to detect clinically relevant bacteria concentrations, finding it both inexpensive and fast. They then used this to develop a smartphone platform for detecting urinary tract infections. Ligand Ratio Plays a Critical Role in the Design of Optimal Multifunctional Gold Nanoclusters for Targeted Gastric Cancer Therapy (ACS Nanosci. Au 2021, 1, 47−60). This Article by Mariá Francisca Matus, Sami Malola, and Hannu Hak̈kinen was the first to be accepted for publication in ACS ","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.2c00056","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71565287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Talia Bergaglio, Shayon Bhattacharya, Damien Thompson, P. Nirmalraj
{"title":"Label-Free Digital Holotomography Reveals Ibuprofen-Induced Morphological Changes to Red Blood Cells","authors":"Talia Bergaglio, Shayon Bhattacharya, Damien Thompson, P. Nirmalraj","doi":"10.1101/2022.12.13.519447","DOIUrl":"https://doi.org/10.1101/2022.12.13.519447","url":null,"abstract":"Understanding the dose-dependent effect of over-the-counter drugs on red blood cells (RBCs) is crucial for hematology and digital pathology. Yet, it is challenging to continuously record the real-time, drug-induced nanoscopic shape changes of RBCs in a label-free manner. Here, we demonstrate digital holotomography (DHTM) enabled real-time, label-free concentration-dependent and time-dependent monitoring of ibuprofen on RBCs from a healthy donor. The RBCs are segmented based on 3D and 4D refractive index tomograms and their morphological and chemical parameters are retrieved with their shapes classified using machine learning. We directly observed the formation and motion of spicules on the RBC membranes when aqueous solutions of ibuprofen were drop cast on wet blood, creating rough-membraned echinocyte forms. At low concentrations of 0.25-0.50 mM, the ibuprofen-induced morphological change was transient but at high concentrations (1.5-3 mM) the spiculated RBC remained over a period of up to 1.5 hours. Molecular simulations confirmed that aggregates of ibuprofen molecules at high concentrations significantly disrupted the RBC membrane structural integrity and lipid order, but produced negligible effect at low ibuprofen concentrations. Control experiments on the effect of urea, hydrogen peroxide and aqueous solutions on RBCs showed zero spicule formation. Our work elucidates the dose-dependent chemical effects on RBCs using label-free microscopes that can be deployed for the rapid detection of overdosage of over-the-counter and prescribed drugs. Significance The interaction between drugs and blood cells is an important field of study in order to understand the risk for drug-induced haematological adverse effects. Using digital holo-tomographic microscopy (DHTM), we can resolve the real-time effect of medications on the morphological and chemical properties of red blood cells with high spatial and temporal resolution and in a label-free manner. We show that our approach can be used as a haematology platform for the diagnosis of blood disorders and for monitoring the dose-dependent effect of prescribed and over-the-counter medications in a cost-effective manner, with significant implications for its applicability in resource-limited settings and in the field of personalized medicine.","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45665549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Nanoscience AuPub Date : 2022-11-25DOI: 10.1021/acsnanoscienceau.2c00042
Yanming Sun, Renjie Pan, Yuduo Chen, Yong Wang, Lei Sun, Neng Wang, Xing Ma* and Guo Ping Wang*,
{"title":"Efficient Preparation of a Magnetic Helical Carbon Nanomotor for Targeted Anticancer Drug Delivery","authors":"Yanming Sun, Renjie Pan, Yuduo Chen, Yong Wang, Lei Sun, Neng Wang, Xing Ma* and Guo Ping Wang*, ","doi":"10.1021/acsnanoscienceau.2c00042","DOIUrl":"10.1021/acsnanoscienceau.2c00042","url":null,"abstract":"<p >The applications of nanomotors in the biomedical field have been attracting extensive attention. However, it remains a challenge to fabricate nanomotors in a facile way and effectively load drugs for active targeted therapy. In this work, we combine the microwave heating method and chemical vapor deposition (CVD) to fabricate magnetic helical nanomotors efficiently. The microwave heating method can accelerate intermolecular movement, which converts kinetic energy into heat energy and shortens the preparation time of the catalyst used for carbon nanocoil (CNC) synthesis by 15 times. Fe<sub>3</sub>O<sub>4</sub> nanoparticles are in situ nucleated on the CNC surface by the microwave heating method to fabricate magnetically driven CNC/Fe<sub>3</sub>O<sub>4</sub> nanomotors. In addition, we achieved precise control of the magnetically driven CNC/Fe<sub>3</sub>O<sub>4</sub> nanomotors through remote manipulation of magnetic fields. Anticancer drug doxorubicin (DOX) is then efficiently loaded onto the nanomotors via π–π stacking interactions. Finally, the drug-loaded CNC/Fe<sub>3</sub>O<sub>4</sub>@DOX nanomotor can accurately accomplish cell targeting under external magnetic field control. Under short-time irradiation of near-infrared light, DOX can be quickly released onto target cells to effectively kill the cells. More importantly, CNC/Fe<sub>3</sub>O<sub>4</sub>@DOX nanomotors allow for single-cell or cell-cluster-targeted anticancer drug delivery, providing a dexterous platform to potentially perform many medically relevant tasks in vivo. The efficient preparation method and application in drug delivery are beneficial for future industrial production and provide inspiration for advanced micro/nanorobotic systems using the CNC as a carrier for a wide range of biomedical applications.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/20/d4/ng2c00042.PMC10125355.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9356633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Nanoscience AuPub Date : 2022-11-02DOI: 10.1021/acsnanoscienceau.2c00045
Ho Young Kim, Minki Jun, Sang Hoon Joo* and Kwangyeol Lee*,
{"title":"Intermetallic Nanoarchitectures for Efficient Electrocatalysis","authors":"Ho Young Kim, Minki Jun, Sang Hoon Joo* and Kwangyeol Lee*, ","doi":"10.1021/acsnanoscienceau.2c00045","DOIUrl":"10.1021/acsnanoscienceau.2c00045","url":null,"abstract":"<p >Intermetallic structures whose regular atomic arrays of constituent elements present unique catalytic properties have attracted considerable attention as efficient electrocatalysts for energy conversion reactions. Further performance enhancement in intermetallic catalysts hinges on constructing catalytic surfaces possessing high activity, durability, and selectivity. In this Perspective, we introduce recent endeavors to boost the performance of intermetallic catalysts by generating nanoarchitectures, which have well-defined size, shape, and dimension. We discuss the beneficial effects of nanoarchitectures compared with simple nanoparticles in catalysis. We highlight that the nanoarchitectures have high intrinsic activity owing to their inherent structural factors, including controlled facets, surface defects, strained surfaces, nanoscale confinement effects, and a high density of active sites. We next present notable examples of intermetallic nanoarchitectures, namely, facet-controlled intermetallic nanocrystals and multidimensional nanomaterials. Finally, we suggest the future research directions of intermetallic nanoarchitectures.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/06/0f/ng2c00045.PMC10125321.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9361876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Nanoscience AuPub Date : 2022-10-28DOI: 10.1021/acsnanoscienceau.2c00039
Harjot Kaur, Samarjeet Singh Siwal*, Reena V. Saini, Nirankar Singh and Vijay Kumar Thakur*,
{"title":"Significance of an Electrochemical Sensor and Nanocomposites: Toward the Electrocatalytic Detection of Neurotransmitters and Their Importance within the Physiological System","authors":"Harjot Kaur, Samarjeet Singh Siwal*, Reena V. Saini, Nirankar Singh and Vijay Kumar Thakur*, ","doi":"10.1021/acsnanoscienceau.2c00039","DOIUrl":"10.1021/acsnanoscienceau.2c00039","url":null,"abstract":"<p >A prominent neurotransmitter (NT), dopamine (DA), is a chemical messenger that transmits signals between one neuron to the next to pass on a signal to and from the central nervous system (CNS). The imbalanced concentration of DA may cause numerous neurological sicknesses and syndromes, for example, Parkinson’s disease (PD) and schizophrenia. There are many types of NTs in the brain, including epinephrine, norepinephrine (NE), serotonin, and glutamate. Electrochemical sensors have offered a creative direction to biomedical analysis and testing. Researches are in progress to improve the performance of sensors and develop new protocols for sensor design. This review article focuses on the area of sensor growth to discover the applicability of polymers and metallic particles and composite materials as tools in electrochemical sensor surface incorporation. Electrochemical sensors have attracted the attention of researchers as they possess high sensitivity, quick reaction rate, good controllability, and instantaneous detection. Efficient complex materials provide considerable benefits for biological detection as they have exclusive chemical and physical properties. Due to distinctive electrocatalytic characteristics, metallic nanoparticles add fascinating traits to materials that depend on the material’s morphology and size. Herein, we have collected much information on NTs and their importance within the physiological system. Furthermore, the electrochemical sensors and corresponding techniques (such as voltammetric, amperometry, impedance, and chronoamperometry) and the different types of electrodes’ roles in the analysis of NTs are discussed. Furthermore, other methods for detecting NTs include optical and microdialysis methods. Finally, we show the advantages and disadvantages of different techniques and conclude remarks with future perspectives.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.2c00039","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9361881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ACS Nanoscience AuPub Date : 2022-10-28DOI: 10.1021/acsnanoscienceau.2c00041
Manoel Alves Machado Filho, Ching-Lien Hsiao, Renato Batista dos Santos, Lars Hultman, Jens Birch and Gueorgui K. Gueorguiev*,
{"title":"Self-Induced Core–Shell InAlN Nanorods: Formation and Stability Unraveled by Ab Initio Simulations","authors":"Manoel Alves Machado Filho, Ching-Lien Hsiao, Renato Batista dos Santos, Lars Hultman, Jens Birch and Gueorgui K. Gueorguiev*, ","doi":"10.1021/acsnanoscienceau.2c00041","DOIUrl":"10.1021/acsnanoscienceau.2c00041","url":null,"abstract":"<p >By addressing precursor prevalence and energetics using the DFT-based synthetic growth concept (SGC), the formation mechanism of self-induced InAlN core–shell nanorods (NRs) synthesized by reactive magnetron sputter epitaxy (MSE) is explored. The characteristics of In- and Al-containing precursor species are evaluated considering the thermal conditions at a typical NR growth temperature of around 700 °C. The cohesive and dissociation energies of In-containing precursors are consistently lower than those of their Al-containing counterparts, indicating that In-containing precursors are more weakly bonded and more prone to dissociation. Therefore, In-containing species are expected to exhibit lower abundance in the NR growth environment. At increased growth temperatures, the depletion of In-based precursors is even more pronounced. A distinctive imbalance in the incorporation of Al- and In-containing precursor species (namely, AlN/AlN<sup>+</sup>, AlN<sub>2</sub>/AlN<sub>2</sub><sup>+</sup>, Al<sub>2</sub>N<sub>2</sub>/Al<sub>2</sub>N<sub>2</sub><sup>+</sup>, and Al<sub>2</sub>/Al<sub>2</sub><sup>+</sup> vs InN/InN<sup>+</sup>, InN<sub>2</sub>/InN<sub>2</sub><sup>+</sup>, In<sub>2</sub>N<sub>2</sub>/In<sub>2</sub>N<sub>2</sub><sup>+</sup>, and In<sub>2</sub>/In<sub>2</sub><sup>+</sup>) is found at the growing edge of the NR side surfaces, which correlates well with the experimentally obtained core–shell structure as well as with the distinctive In-rich core and vice versa for the Al-rich shell. The performed modeling indicates that the formation of the core–shell structure is substantially driven by the precursors’ abundance and their preferential bonding onto the growing edge of the nanoclusters/islands initiated by phase separation from the beginning of the NR growth. The cohesive energies and the band gaps of the NRs show decreasing trends with an increment in the In concentration of the NRs’ core and with an increment in the overall thickness (diameter) of the NRs. These results reveal the energy and electronic reasons behind the limited growth (up to ∼25% of In atoms of all metal atoms, i.e., In<sub><i>x</i></sub>Al<sub>1–<i>x</i></sub>N, <i>x</i> ∼ 0.25) in the NR core and may be qualitatively perceived as a limiting factor for the thickness of the grown NRs (typically <50 nm).</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.2c00041","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"9361880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}