bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structural Diversity Enables Dramatic Changes in Photocatalytic Efficiency of Porphyrinosilica Particles in Chem-Bio Binary Applications
Authors: Lee Suk Joong 
Published: August 2024

Because of their potential applications in catalysis, separation, and gas storage, porous materials such as metal–organic frameworks (MOFs), porous coordination polymers (PCPs), porous organic polymers (POPs), and polymers with intrinsic microporosity (PIMs) have received much attention. Various building blocks have been introduced with various functional groups. Among the various organic building blocks, porphyrin has become one of the most important building blocks for the construction of such materials witnessed by a wide range of molecular architectures using porphyrin derivatives with various applications. In addition, they are often used to modify the surface of porous silica materials such as SBA-15, MCM-41 and MCM-48, because these porous silica materials exhibit narrow pore size distributions, high thermal stability and easy accessibility.
In this presentation, a series of highly ordered mesoporous porphyrinosilicas akin to MCM-41 will be discussed, as novel recyclable heterogeneous photocatalysts, demonstrating their efficacy in the selective oxidation. Porphyrins are recognized as efficient photocatalysts for oxidation reactions, attributed to their capacity to generate reactive oxygen species (ROS). Integrating them into a mesoporous silica framework can mitigate self-degradation, thereby yielding an efficient catalytic system with an extended operational lifetime.
Morphology-Dependent Interaction between Tetraphenylporphyrins and a Metal Oxide Surface: Electronic Signature, Photo Physics, and Chemical Interaction
Authors: Bockstedte Michel 
Published: August 2024

Porphyrin-substrate hybrid systems are the building blocks in a series of materials, such as organic light-emitting diodes, chemical sensors, dye-sensitized solar cells and catalysts. Functional layers and 2D nanostructures on surfaces enable sensors, and nanoscale optical and magnetic materials. 3D porphyrin structures are for instance used in controlling and manipulating light at subwavelength dimensions. Understanding and correctly describing the way molecules interact with the substrate and in thin-film structures gives a handle on geometrical and electronic device properties. Indeed, adsorption and film-formation have a relevant effect on the molecular electronic structure even in the absence of strong covalent bonding, namely in terms of level-alignment with substrate states in the former and polarization-induced renormalization of molecular band gaps in the latter.
Using the case of Co(II)-tetraphenylporphyrin (CoTPP) on the MgO(100), we shine light on the adsorption at morphology-related low-coordinated surfaces sites and the effect of multilayer film formation from a theoretical perspective in a frame work of hybrid density functional theory and many-body perturbation theory. We simulate the photoemission spectra for relevant adsorption sites as a fingerprint with distinct site-related features in both valence and core-level regions of the electronic structure that are also observed in experiments on MgO(100) films on Ag(100) and thus aid the identification of sites. Effects of the formation of porphyrin films on the electronic and optical properties will be outlined for H2TPP and MgTPP.
We also highlight the self-metalation of H2TPP at morphology-related low-coordinated sites. Metalation is an important pathway for functionalization of porphyrin-based organic-inorganic structures. We address the self-metalation mechanism using ab initio molecular dynamics simulation at room temperature. While H2TPP is mobile on the pristine surface as the steric hindrance by phenyl rings prevents the physisorption of the macrocycle at a specific site, step edges or kink sites provide anchor points exposing low-coordinated, reactive oxygen-sites to hydrogens of the macrocycle. We report a spontaneous proton transfer at these sites forming an intermediate complex before the metalation occurs. This highlights the role of low-coordinated surface sites for the chemical interaction with the porphyrin.
Recent Fundamental Advances in Quality of High-Performance and Highly-Scaled Carbon Nanotube Transistors
Authors: Pitner Gregory 
Published: August 2024

Recently a number of breakthroughs have been reported by our team in the component qualities of transistors built on Carbon Nanotube (CNT) channels. However, any emerging channel material which seeks to outperform established semiconductors for transistor logic applications has a substantial hill to climb, given the incredible capabilities of advanced Si-based logic technology platforms. This talk will first aim to frame our progress on Carbon Nanotube CMOS technology in the broader context of the value proposition and desired component qualities needed to realize practical impact in computing applications. Next, we will share advances in the fundamental building blocks for Carbon Nanotube transistors towards these targets including channel, contact, doping, and gate-stack modules. Finally we will describe new record CNT MOSFET performance milestones achieved by integrating best available device components for first time, which gives insight into the remaining performance limiters and future directions.
[1] G. Pitner, et al., "Building High Performance Transistors on Carbon Nanotube Channel," VLSI 2023.
[2] S. Li, et al., "High-Performance and Low Parasitic Capacitance CNT MOSFET: 1.2 mA/um at Vds of 0.75 V by self-aligned doping in sub-20 nm spacer," IEDM 2023.
[3] N. Safron, et al., "Low N-type Contact Resistance to Carbon Nanotubes in Highly Scaled Contacts through Dielectric Doping," IEDM 2023.
[4] H.-Y. Chiu, et al., "Self-Aligned Contact Doping for Performance Enhancement of Low-Leakage Self-Alignment Method for High-Density Aligned CNT Array," Advanced Materials Interfaces, 2023.
[5] T.A. Chao, et al., "Small Molecule Additives to Suppress Bundling in Dimensional-Liminted Self-Alignment Method for High-Density Aligned CNT Array," Advanced Materials Interfaces, 2023.
[6] Q. Lin, et al., " Band-to-Band Tunneling Leakage Current Characterization and Projection in Carbon Nanotube Transistors," ACS Nano 2023.
[7] Z. Zhang, et al., "Complementary Carbon Nanotube Metal-Oxide-Semicondcutor Field-Effect Transistors with Localized Solid-State Extension DOping," Nature Electronics, 2023.
[8] S.K. Su, et al., " Perspective on Low-Dimensional Channel Materials for Extremely Scaled CMOS," VLSI 2022.
[9] Z. Zhang, et al., "Sub-Nanometer Interfacial Oxides on Highly Oriented Pyrolytic Graphite and Carbon Nanotubes Enabled by Lateral Oxide Growth," ACS Applied aterials & Interfaces, 2022.
[10] G. Pitner, et al., "Sub-0.5 nm Interfacial Dielectrics Enables Superior Electrostatics: 65 mV/dec top-gated Carbon Nanotube FETs at 15 nm gate length," IEDM 2020.
On-Surface Photopolymerization - What Does the Surface Do?
Authors: Ringel Eva , Grossmann Lukas , Lackinger Markus 
Published: August 2024

We attained the synthesis of mesoscale-ordered 2D polymers by the topochemical on-surface photopolymerization of fluorinated anthracene triptycene (fantrip) monomers. The underlying protocol is two-staged: (1) Self-assembly of the monomers into a photopolymerizable monolayer structure, where the photoactive anthracene moieties are face-to-face stacked; (2) cross-linking of the self-assembled monolayer into a covalent 2D polymer by photochemically excited [4+4] cycloadditions between the antiparallel aligned anthracene blades. Thereby, the long-range order attained in step (1) is transferred into the covalent state.
Yet, the topochemical approach depends crucially on achieving the reactive monomer packing with the appropriate mutual alignment of the anthracene blades. For this initial self-assembly, the underlying surface plays a decisive role, which also extends to the photopolymerization.
We show that the photoactive monolayer packing of fantrip monomers can be achieved on both alkane-passivated graphite and iodine-passivated Au(111) or Ag(111). Although the fantrip self-assembly appears essentially similar on these substrates, there are distinct differences in the subsequent photopolymerization. These can be rationalized by the photoexcitation of the substrate and the subsequent transfer of hot carriers to the molecular networks.
Nat. Chem. 13, 730-736 (2021)
Eur. J. Org. Chem. 2021, 5478–5490 (2021)
Trends Chem. 4, 471-474 (2022)
Angew. Chem. Int. Ed. 61, e202201044 (2022)
Mangenese Copper Selenide Nanosheet Arrays Derived from Metal-Organic Frameworks for Efficient Solid-State Asymmetric Supercapacitors
Authors: Alhammadi Ayoob , Bahaa Ahmed , Fetyan Abdulmonem , AlKindia Tawaddod , Susantyoko Rahmat Agung 
Published: August 2024

Metal chalcogenide nanostructures, particularly metal selenides, have unique properties, such as high electrical conductivity, large specific surface area, exclusive porous networks, and exceptional electrochemical properties compared to traditional nanostructures.1
2 A novel strategy is proposed to design and fabricate hierarchical Manganese copper selenide nanosheet (MnCuSe NS) arrays from metal-organic frameworks (MOFs). The hierarchical MnCuSe NS arrays can deliver enriched electroactive sites and shorten the ion/electron diffusion pathways. When evaluated as positive electrodes for supercapacitor (SC), the MnCuSe NS electrode displayed remarkable electrochemical properties with ultra-high specific capacity of ≈350.4 mA h g−
1 and an areal capacity of ≈0.94 mA h cm−
2 at a current density of 3 mA cm−
2, exceptional rate capability (≈79.5% of the capacity retention at a higher current density of 50 mA cm−
2), and outstanding cyclic stability (≈95.4 % of capacity retention after 10 000 cycles). Most importantly, the assembled MnCuSe NS//FeMnO/NG solid-state asymmetric SC exhibited a wide operating potential window of 1.6 V with an ultra-high volumetric capacity of ≈2.4 mA h cm−
3 at a current density of 3 mA cm−
2, an excellent energy density of ≈71.6 Wh Kg−
1 at a power density of ≈794 W Kg−
1, and ultra-long cycle life (≈93.4 % of capacity retention after 10 000 cycles). This proposed method provides a general protocol to design and fabricate metal selenide nanosheet arrays with superior electrochemical energy storage properties and exceptional cyclic stability, holding significant potential for future energy storage devices in commercial aspects.

Keywords: Hierarchical, Metal-organic frameworks, Metal chalcogenide, Energy density, Asymmetric supercapacitors
Reference:
(1) Han, J. H.; Kwak, M.; Kim, Y.; Cheon, J. Recent Advances in the Solution-Based Preparation of Two-Dimensional Layered Transition Metal Chalcogenide Nanostructures. Chem. Rev.
2018, 118 (13), 6151–6188. https://doi.org/10.1021/acs.chemrev.8b00264.
(2) Karuppasamy, K.; Vikraman, D.; Hussain, S.; Kumar Veerasubramani, G.; Santhoshkumar, P.; Lee, S.-H.; Bose, R.; Kathalingam, A.; Kim, H.-S. Unveiling a Binary Metal Selenide Composite of CuSe Polyhedrons/CoSe2 Nanorods Decorated Graphene Oxide as an Active Electrode Material for High-Performance Hybrid Supercapacitors. Chemical Engineering Journal
2022, 427, 131535. https://doi.org/10.1016/j.cej.2021.131535.
Corrosion Initiation on Reinforcing Steel with Mill Scale in Mortar
Authors: Doi Kotaro , Hiromoto Sachiko 
Published: August 2024

Corrosion of reinforcing steel rebar is the main cause of loss of the long-term reliability of concrete structures. When the rebar is corroded, the rust induces cracks and detachment of the cover concrete. The mill scale, a thick oxide film, is formed on the rebars when the rebar is hot rolled. The role of mill scale on the corrosion resistance of rebars in concrete has not been clarified, yet. This study studied the corrosion behavior of rebars with mill scale in mortar.
The samples are commercial rebars with 19 mm diameter, which have a mill scale of several tens of micrometers in thickness. The rebars without mill scale prepared by the electrolytic polishing were used as the comparison samples. A Hyperbaric-oxygen accelerated corrosion test (HOACT) [1] was carried out using the rebars embedded in the mortar with a 5.5 mm cover thickness. To prompt the breakdown of passive film on the rebars, 2.1 M NaCl solution was mixed with the mortar. In the HOACT, pressurized oxygen gas is supplied to the sample, and the oxygen reduction reaction on the steel surface is enhanced, leading to the steel's corrosion acceleration. The oxygen pressure was 0.6 MPa and the test period was 14 days. The corrosion of the rebar with a mill scale was more significant than that without a mill scale. This result shows that the mill scale reduces the corrosion resistance of the steel rebar in concrete [2].
To investigate the effect of the mill scale on the corrosion resistance of the rebar, anodic polarization measurements of the rebars with and without the mill scale were carried out in a saturated Ca(OH)2 solution containing Cl-. The pitting potential of the rebar with mill scale was more noble than that of the sample without mill scale. However, when the mill scale was scratched, the pitting potential was significantly shifted to the less noble direction, and it was below that of the rebar without the mill scale. These results show that the mill scale improves the corrosion resistance of the rebar in concrete, in contrast, the corrosion resistance of the rebar with a defective mill scale becomes even worse than that of the rebar without the mill scale [2].
[1] K. Doi, S. Hiromoto, H. Katayama, E. Akiyama, J. Electrochem. Soc., 165(9), C582-C589 (2018).
[2] K. Doi, S. Hiromoto, T. Shinohara, K. Tsuchiya, H. Katayama, E. Akiyama, Corrosion Science, 177, 108995 (2020).
(Invited) Visualizing Electrode Assembly Movement and Lithiation Gradients in Lithium-Metal Batteries
Authors: Abraham Daniel P. 
Published: August 2024

In this presentation we will introduce dilatometry and profilometry using Operando Energy Dispersive X-Ray Diffraction conducted at the Advanced Photon Source, Argonne National Laboratory. This approach is applied to a Li metal battery with a high-voltage NMC811 cathode but the method is suitable for any and all materials and electrodes.
In the technique, micrometer-wide collimated X-rays traverse the electrode assembly, and the Bragg peaks from different crystalline phases are used to track the hard edges of the solid materials as they move due to volume changes in the cell. We visualize, with submicron resolution, the movement of the oxide cathode and microporous separator: the latter is observed through the diffraction of X-rays off the lamellae in the polymer matrix. One can map movement of the cathode and also compression in the porous separator – a task that is beyond the capabilities of mechanical dilatometers. We use our approach to show periodic expansion and contraction of metallic lithium during delithiation and relithiation of the cathode and to quantify formation of mossy lithium on the metal surface. The method is universal, easy to implement in-operando, and is selective in distinguishing between different phases in materials.
Another dividend of this method is that it allows the profiling of lithiation gradients in the layered-oxide cathode. In our NMC811/Li cells, the cathode gradients are seen even with weak currents, they occur only during relithiation of the cathode, and they persist as the currents abate during constant-voltage discharge.
Other particulars of our experimental approach and observations will also be discussed during the talk.
Acknowledgement: This document has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357.
Next-Generation Batteries through Advanced 3D Electrode and Material Concepts
Authors: Falkowski Viktoria , Reinhold Carolyn , Rist Ulrich , Sterzl Yannic , Pfleging Wilhelm 
Published: August 2024

With the rise of renewable energy sources, energy storage solutions become increasingly important as they represent a key feature for secure and constant power supply. In this regard, battery systems play a crucial role in accelerating the transition towards sustainable and green energy sources. To meet the rising global demand, further advancement of the battery technology is imperative. One optimization pathway is to use battery materials that are more sustainable while also yielding improved electrochemical performance, contributing to both environmental and functional advancements. However, innovation must go beyond the material level, and new electrode design approaches for an efficient combination of high power and high energy systems are necessary.
In this context, the three-dimensional (3D) battery concept with its increased exposed electrode surface, shows a great promise for enhanced electrochemical performance compared to the conventional flat designs of state-of-the-art electrodes. Targeting at the bottleneck of high power/high energy density systems, the incorporation of micro-structured channels within the electrodes improves lithium-ion diffusion pathways and minimize strain from volume expansion during electrochemical cycling.
Our focus is the investigation of 3D electrode architectures generated by laser-processing techniques such as ultrafast laser ablation and laser-assisted printing. Working with ultrafast lasers offers the possibility to process materials while reducing thermal impact and allows the creation of well-designed and controllable electrode surface topographies. The adoption of this concept has already shown great impact in enhancing the high-rate capability and lifetime of conventional electrodes in lithium-ion batteries.[1-3]

Expanding the scope, this work explores the applicability of laser-generated 3D electrode architectures to next-generation battery active materials such as high-voltage lithium nickel manganese oxide (LNMO) composites. On anode side, silicon/graphite and amorphous carbon is extensively investigated for lithium-ion batteries and sodium-ion batteries, respectively. To understand the impact of the manufacturing process, electrochemical evaluations are complemented by findings from laser-induced breakdown spectroscopy, SEM-EDX, Raman measurements, and Auger electron spectroscopy.
In conclusion, this contribution highlights the promising advancements achieved by applying laser-generated 3D electrode architectures to next-generation battery materials and aims to provide valuable insights into this exciting frontier of battery research.
[1] W. Pfleging, Nanophotonics 7 (2018) 549–573.
[2] W. Pfleging, Int. J. Extrem.
Manuf. 3 (2021) 012002.
[3] M. Zaeh, Appl. Energy 303 (2021), 117693.
Interplay of Interphases in Lithium-Sulfur Cells
Authors: Bhargav Amruth , Robbins Victoria , Vanheusden Karel , Bugga Ratnakumar 
Published: August 2024

Lyten’s revolutionary 3D Graphene is enabling the transition to a greener future through its high energy density lithium-sulfur (Li-S) batteries. As with all battery chemistries, the electrolyte-electrode interphases formed in-situ during cell cycling not only regulate the redox processes but also strongly dictate the cycle life of the cells.
In this talk, we will describe the different interphases formed on the cathode and anode of a Li-S battery and their importance. A glimpse into how regulating these interphases using different additives affects the cycle life of cells will also be demonstrated.
Moore's Law Scaling and Chemical Mechanical Planarization (CMP)
Authors: Prince Matthew Jon 
Published: August 2024

Since the invention of the first integrated circuit in 1958, chemistry and materials have played a critical role in semiconductor process technologies, which has led to an exponential growth of transistors packed into circuits. Decades ago, Gordon Moore posited there would be a doubling of components every two years (revised from his original doubling every one-year prediction). This observation became known as Moore’s law.
As Denard scaling took on more complexity, the number of new materials used to build semiconductors increased at a torrid pace. The number of elements in the periodic table, used to fabricate devices, increased roughly five-fold from the 1980’s to the 2000’s.
In the earlier years, lithography, etch, thin films, implant, and diffusion were foundational technologies used to fabricate a silicon wafer into hundreds of microchips. In the late 1980’s a new technology Chemical Mechanical Planarization (CMP) was invented. It was developed out of necessity to reduce topography, critical for lithography’s depth of focus requirements. Without this key invention, patterning and building layer upon layer from front end transistors to back-end interconnects would not have been possible.
Intel implemented CMP into manufacturing in the early 1990’s on the 0.8 micron technology node which manufactured the 486 microprocessor. CMP was required to planarize dielectric oxide used to insulate the aluminum metal interconnects. Since then, the number of CMP applications over the last three decades has exploded, enabling the scaling of Moore’s Law.
CMP is not only used to improve lithography depth of focus. CMP also enables a method of metal interconnect and contact formation called damascene. Planarization is used to create dielectric isolation trenches, discrete plugs for insulation, aid advanced patterning architectures, build through silicon vias (TSVs), and enable complex wafer and chip bonding for die-to-die interconnects for disaggregated products.
Transistor scaling alone is no longer sufficient to meet device performance, power, and cost requirements. Complex material and architectural changes are required. And novel CMP applications continue to be added at each new technology node. This author will make an argument that CMP is critical to push scaling and enable future process nodes.

Figure 1
Evolving Preston’s Equation in Chemical Mechanical Planarization
Authors: Yang Jichul , Kobata Itsuki , Suzuki Kenichi , Kajita Shinji , Shiokawa Yoichi 
Published: August 2024

The evolution of semiconductor devices necessitates greater control parameters for enhancing CMP process controllability. Historically, CMP engineers have sought to improve polishing process performance by real-time control of time, pressure, and velocity using Preston’s equation. However, Preston’s equation has traditionally addressed blanket-wafer or non-patterned wafer’s vertical or horizontal scale controllability, such as wafer center to edge or the in-wafer non-uniformity expressed by percentage. However, limited control variables cannot determine patterning profile changes.
Upon closer examination of the basic Preston’s equation, other factors were considered constant or environmental parameters, excluding pressure and velocity. Current and future scaled-down devices demand additional control parameters to achieve nanometer-scale vertical controllability with patterned wafers. This presentation introduces an extended Preston’s equation by incorporating more control parameters, including temperature and slurry concentration. The study reveals that lowering and controlling the polishing temperature induces slurry selectivity changes by modulating the activation energy between the slurry and wafer. This temperature control also drives pad material changes that impact selectivity. Furthermore, the study evaluates in-situ slurry composition control to assess its real-time impact on wafer performance. When all five active parameters are combined into the extended Preston’s equation, it is demonstrated that real-time nanometer vertical scaling is achievable. The results of this study provide insights into the future design direction of CMP equipment, which will be communicated in this talk along with the concept of future CMP equipment.