bluuebunny/crossref_metadata_2025_split huggingface dataset:
New Perylene Diimide Dyes and Inks for Large Area Roll-Coated Organic Solar Cells
Authors: Welch Gregory Charles 
Published: December 2024

Polycyclic aromatic molecules, especially perylene diimide based dyes, are widely used as electronic materials in photovoltaic devices.1 Our team at the University of Calgary has been actively developing modified perylene diimides for use in a range of solution processed electronic devices including organic solar cells,2 organic light emitting diodes,3 transistors and sensors,4 electrochromic films,5 and photo/electro cathodes.6 This presentation will detail the design and synthesis of several classes of modified perylene diimides for specific use in large area organic solar cell devices and modules, primarily as cathode interlayers in both conventional and inverted type cells, but also as non-fullerene acceptors. Structure-property relationships, the formation of functional large area films via slot-die coating using green solvents, and utility both small area devices and flexible modules will be discussed. Applications as indoor light recycling devices and integration into operational greenhouses will be presented.
1 Journal of Materials Chemistry A, 2021, 9 6775-6789
2 Journal of Materials Chemistry C, 2020, 8, 13430-13438
3 Journal of Materials Chemistry C, 2020, 9, 2314-2319
4 Journal of Materials Chemistry C, 2021, 9, 13630-13634
5 Journal of Materials Chemistry C, 2024, 12, 1710-1717
6 Chemical Science, 2022, 13, 1049-1059
(Invited) Development of Fused Porphyrin Sensitizers for Efficient Dye-Sensitized Solar Cells
Authors: Higashino Tomohiro 
Published: December 2024

Dye-sensitized solar cells (DSSCs) have attracted considerable attention as an alternative to silicon-based solar cells due to their potential advantages in terms of power conversion efficiency, production cost, design flexibility, and indoor use. Because the photovoltaic performance of DSSCs strongly depends on sensitizers, various kinds of sensitizers have been developed. Among them, porphyrin sensitizers have made remarkable contribution to performance improvement in DSSCs. The push–pull type porphyrin sensitizers have displayed excellent light-harvesting ability and demonstrated high power conversion efficiencies more than 10% in DSSCs.
Meanwhile, incorporation of aromatic-fused structure into a porphyrin core is a fascinating option for highly efficient DSSCs because of direct π-expansion of the porphyrin core and resultant red-shifted absorption. However, aromatic-fused porphyrin sensitizers have suffered rather low cell performances due to their mismatch of HOMO-LUMO levels, high aggregation tendency, and short lifetime of the excited states. Bearing these in mind, we envisioned that the introduction of methylene-bridged fused structure into a porphyrin core would overcome these drawbacks, boosting the cell performance. In this context, we designed and synthesized a series of methylene-bridged thiophene-fused porphyrin sensitizers and revealed that the DSSC of thiophene-fused porphyrin sensitizer achieved the highest power conversion efficiency ever reported for DSSCs with aromatic-fused porphyrin sensitizers. Furthermore, rational molecular design can realize further enhancement of the photovoltaic performance of the DSSCs with thiophene-fused porphyrin sensitizers.
(Invited) Control of Elementary Processes in Semiconductor Process Plasmas
Authors: Shiratani Masaharu , Kamataki Kunihiro , Itagaki Naho , Yamashita Naoto , Okumura Takamasa , Koga Kazunori 
Published: December 2024

Low-temperature plasma technology is used in as much as 70% of the front-end processes of semiconductor fabrication, including etching, deposition, and surface modification [1-7]. In this talk, I focus on the importance of controlling elementary processes in semiconductor process plasmas. First of all, the choice of source gas is important. In hard carbon thin film deposition, for instance, the higher the C/H in the film, the harder the film tends to be. Therefore, it is easier to achieve a higher degree of hardness by using C2H2 as the raw material gas rather than CH4, which has a lower C/H. If the raw material molecules contain benzene rings, the benzene rings are more easily incorporated into the films, and the C/H tends to be lower. Next, it is important to select the type of radicals produced by electron impact dissociation of the source gas; in the case of CH4, four types of radicals, CH3, CH2, CH, and C, are produced by electron impact dissociation. The surface sticking probability is small for CH3 and large for C. To deposit films with high step coverage on complexly shaped surfaces such as trenches, it is desirable to use CH3, which has a small surface sticking probability, as the main precursor for film deposition. These two different directions make it difficult to form hard carbon thin films in trenches with a high step coverage. Therefore, other avenues are to be explored. One such approach is control of elementary processes by unconventional plasma generation, which includes pulsed plasmas, amplitude-modulated RF discharge plasmas, and arbitrary waveform excitation plasmas. In short, elementary process control is the key to success in low-temperature plasma technology.
Acknowledgements: This work was partly supported by JSPS KAKENHI (Grant Nos. JP20H00142, JP21H01372, JP21K18731, and JP23K03368), the JST ASPIRE, the NTT collaborative research, and the Murata Science Foundation.
[1] M. Morimoto, et al., Jpn. J. Appl. Phys. 62 (2023) SN1001.
[2] K. Kamataki, et al., Mater. Sci. Semicond. 164 (2023) 107613.
[3] M. N. Agusutrisno, et al., Mater. Sci. Semicond. 162 (2023) 107503.
[4] R. Narishige, et al., J. Mater. Res. 38 (2023) 1803.
[5] N. Yamashita, et al., J. Mater. Res. 38 (2023) 1178.
[6] I. Nagao, et al., Mater. Adv. 7 (2022) 918.
[7] S. H. Hwang, et al., Processes., 9 (2020) 2.
(Invited) Impact of CMOS Miniaturization on Digital and RF Applications and Its Future
Authors: Iwai Hiroshi 
Published: December 2024

Semiconductors, especially CMOS LSIs (Complementary Metal-Oxide-Semiconductor Large-Scale Integrated Circuits), are fundamental to our contemporary highly intelligent society, exemplified by technologies like artificial intelligence (AI). The exceptional performance and functionality of current CMOS LSIs are largely attributed to the ongoing miniaturization of their core components: MOSFETs (Metal-Oxide-Semiconductor Field-Effect Transistors). Since the inception of MOS LSI production in the early 1970s, MOSFETs have undergone regular size reductions every 2 to 3 years. The minimum linewidth, which was 10 μm in 1970, has now shrunk to nearly one-thousandth of that size, approaching 10 nm. Each phase of MOSFET miniaturization has encountered formidable technological challenges, overcome through innovative solutions.
However, we stand at a critical juncture. The relentless drive toward smaller MOSFETs is now approaching physical limits. The future trajectory of CMOS LSIs will veer away from further miniaturization and instead focus on channel stacking—a strategy to sustain progress. In this presentation, I delve into the history of CMOS LSI miniaturization, explore its impact on digital information processing and RF communication applications, and gaze into the post-miniaturization era, anticipating both opportunities and challenges.
Influence of Nanoscale Dielectric Gap on Electrical Characterization in Scanning Probe Microscopy
Authors: Eom Seongmun , Kavle Pravin , Kang Deokyoung , Kim Yeongyu , Martin Lane W. , Hong Seungbum 
Published: December 2024

Scanning Probe Microscopy (SPM) techniques, including Conductive-Atomic Force Microscopy (C-AFM), Kelvin Probe Force Microscopy (KPFM), and Piezoresponse Force Microscopy (PFM) or Electrochemical Strain Microscopy (ESM), are critical for the in situ, non-destructive analysis of material interfaces with high spatial resolution. Despite substantial advancements in SPM technologies, challenges related to their reliability and accuracy remain, primarily due to measurement artifacts and electrochemical reactions on the sample surface. These artifacts can significantly skew results, leading to misconceptions unless critically analyzed.
This study explores the influence of the dielectric gap on electric characterization, particularly focusing on how variations in permittivity affect the results obtained from C-AFM and PFM techniques. By adjusting the permittivity of the dielectric medium (air, water with εr = 79, and silicone oil with εr = 2.1-2.8), we demonstrate that high permittivity media can significantly correct the discrepancies commonly observed in coercive field measurements, aligning them closer to values obtained from conventional capacitor-based polarization methods.
Our findings illuminate the critical role of the dielectric gap in SPM, suggesting methodological adjustments for improved accuracy in the nanoscale electrical characterization of electrochemical materials. These insights offer significant implications for advancing the precision and reliability of SPM techniques in studying electronic materials.
Nucleation and Growth during Electrochemically Induced Deposition of Li3PO4
Authors: Saleh Ali Amir , De Taeye Louis , Patnaik Sai Gourang , Vanheusden Genis , Vereecken Philippe M. 
Published: December 2024

The field of electrochemically induced depositions has been gradually gaining a lot of attention in the last few decades due to the unique abilities it offers, namely the thin film deposition of insulating materials on a conductive surface [1]. While direct electrochemical methods can be used to deposit redox active species, their use in depositing insulating materials is limited as some insulating materials are redox inactive. One of these redox inactive insulating materials is Li3PO4. In the synthesis of Li3PO4 thin films a local pH increase near the electrode surface, by the electrochemical reduction of water, triggers the precipitation. Due to the surface confined nature of the diffusion layer, the OH- concentration near the surface will be significantly higher than in the bulk and phosphate near the surface will react with the hydroxides to form the deprotonated species, which in the presence of lithium ions will precipitate. This process can be visualized in Figure 1.
In this work, we have studied the nucleation and growth of electrochemically induced Li3PO4 deposition combining experiment and model. We developed a model to calculate the concentration profiles of the different species in the diffusion layer, which is then used to predict the point at which the solubility product is surpassed at the surface and in the near surface diffusion layer. This allows the prediction of the influence of the reaction parameters such as current density, bulk pH, lithium concentration, and initial phosphate concentration on the supersaturation. To further improve the accuracy of the model, turbidity experiments were performed to determine the effective solubility product of the system. The model was combined with the experiment to link supersaturation with seed density and understand the effect of current density and time on island density, size and precipitation rate. It is shown that, as for the case of direct electrodeposition where island density is function of overpotential (supersaturation), a direct correlation can be made between supersaturation and island density, supporting the classical nucleation and growth theories also for electrochemically induced deposition.

Figure 1
: Schematic representation of the electrochemically induced deposition of Li3PO4 with water as a probase.

References:

[1] Walcarius, A., Sibottier, E., Etienne, M. et al. Electrochemically assisted self-assembly of mesoporous silica thin films. Nature Mater
6, 602–608 (2007). https://doi.org/10.1038/nmat1951

Figure 1
Evaluation of Copper Sulfate Electroplating Solution and Film Quality Prediction Using Turbidity Measurement Method
Authors: Koga Toshiaki , Sakata Yoshitaro , Terasaki Nao 
Published: December 2024

Measuring and controlling the condition of the plating bath on the production line is important to achieve high quality plating and automation of the manufacturing process. Proper evaluation of plating solution degradation is one of the most pressing challenges in the copper sulfate electroplating process. However, constant monitoring and evaluation on the production line is difficult, and periodic sampling is used for evaluation. Optical measurement would be a simple and accurate method with which to achieve on-time and in-situ evaluation.
We have developed a method to optically measure monovalent copper (Cu(I)) in a copper sulfate electroplating solution to evaluate the deterioration of the solution. Bathocuproinedisulfonic acid, disodium salt (BCS) specifically reacts with Cu(I) and forms an absorption band in the visible light region. By measuring its absorbance, it becomes possible to quantify the Cu(I) concentration in the aqueous solution. Absorbance measurement using BCS is a technology that can easily quantify Cu(I), making immediate measurement possible at production sites.
Color reaction measurements are simple and suitable for production line applications, but like other methods, sampling is required. Furthermore, we proposed a method to evaluate plating solutions using fluorescence. This measurement detects the generation of fluorescence due to the decomposition of additives originally contained in the plating solution. There is no need to add special chemicals, and the state of the solution can be measured on the spot without sampling. However, this fluorescence is only effective when using Janus Green B (JGB) as an additive.
On the other hand, light scattering can detect the formation of microparticles in solution. It is known that the accumulation of copper fine particles due to disproportionation reactions affects the quality of copper sulfate electroplated films. This suggests that the production of copper fine particles in the plating solution increases the light scattering intensity and can serve as an indicator of the degree of turbidity of the solution.
In this study, we used a fluorometer to measure the intensity of light scattered in the direction perpendicular to the incident light as an indicator of the turbidity of the plating solution, and verified the relationship between the formation of fine particles due to energization and the increase in turbidity. This is equivalent to measuring turbidity using nephelometry. Furthermore, we will clarify the relationship between turbidity and Cu(I) accumulation and its effect on plating film quality, and consider its application to plating solution evaluation.

Figure 1
Towards the Electrodeposition of Graded Polymer / Metal Composites
Authors: McBride Michael , Rutledge Amanda , Hatfield Kendrich , Hooks Daniel E 
Published: December 2024

In high pressure physics applications, a shock wave can be modified by tuning the acoustic impedance of an impactor. The acoustic impedance is influenced by the sound speed of the material and the density. Forming structures that have a gradation in these properties enables a range of experiments to better understand materials under extreme conditions. Polymers are some of the lowest density materials with densities around 1 g/cc. The density of metals extends from ~1 g/cc to ~ 20 g/cc. Thus, being able to create graded polymer / metal structures maximizes the gradation of density.
Electropolymerization can be used to deposit polymer films on a surface. Polypyrrole can be synthesized from pyrrole in nitric acid via the electrochemical formation of the oxidizing nitrosyl ion. Metallic electrodeposition occurs via the reduction of metal salts. Therefore, careful control of the applied currents using pulse electrodeposition methods can be used to co-deposit both species. The challenge is in controlling the growth mechanisms.
Early observations indicated that polymers could nucleate from existing polymer chains or metallic surfaces. Metallic nucleation could only occur from metal sites, resulting in dendritic metallic structures decorated with polymers. Efforts to control the nucleation and growth dynamics to encourage more layer-by-layer growth are currently on-going. Herein, we will present our findings in controlling the microstructures of electrodeposited polymer / metal composites.
(Digital Presentation) Co-Nanocatalysts in the Reaction of Electrochemical Reduction of Nitrates to Ammonia
Authors: Kuznetsova Irina , Kultin Dmitry , Lebedeva Olga , Kalmykov Konstantin , Kustov Leonid 
Published: December 2024

Electrocatalytic methods for producing ammonia from nitrates represent a promising and environmentally friendly alternative to the traditional Haber-Bosch synthesis.
An important criterion for assessing the efficiency of a reduction reaction is the Faraday efficiency of the reaction. It is determined by the choice of catalyst electrode and its properties.
Nanocatalysts offer advantages over conventional metal catalysts by increasing catalyst activity by controlling particle size and reducing catalyst production costs.
Currently, the electrocatalytic activity of metal cobalt, its oxides, and mixed catalysts based on it are being actively studied. In this study, the electrocatalytic ability of electrodeposited and metallic cobalt in the reduction of nitrate to ammonia was investigated. The nanocatalysts were synthesized by electrodeposition of cobalt onto a graphite substrate from an aqueous solution of sodium sulfate at a deposition time of 5–30 min. The surface of the resulting catalysts represents a dense and thin layer of cobalt particles with a diameter of 20-100 nm.
The efficiency of nanocatalysts was assessed using Faraday efficiency (FE) data. The best results for electrodeposited cobalt were 50 to 60% FE. The electroreduction reaction of nitrates deserves further study and discussion of its prospects for industrial application.
Further research will be aimed at optimizing reaction conditions and developing new electrocatalysts with high efficiency and selectivity, including the addition of particles of other metals to cobalt (Fe, Cu, Ni).

Figure 1
The Mechanism of Redox-Mediated Li2O2 Oxidation and 1O2 Evolution in Li-Air Batteries
Authors: Dewar Daniel , Ahn Sunyhik , Zor Ceren , Yang Sixie , Nimmo Tammy , Kibler Alexander , Gao Xiangwen , Johnson Lee R , Bruce Peter 
Published: December 2024

The lithium-air (Li-O2) battery has the highest theoretical energy density (3500 Wh kg-1) of any rechargeable battery. Modelling has suggested more than 600 Wh kg-1 may be possible for the whole system, including air handling, making Li-O2 attractive for the electrification of aviation.(1) However, the development of the Li-O2 battery has faced many challenges since its inception, such as degradation and slow kinetics.(2) The discharge product at the cathode is Li2O2, which is electronically insulating and difficult to oxidise on re-charging.(3) To overcome the difficulties of direct electrochemical reactions involving an insulating solid, redox mediating molecules (RMs) were introduced such that the Li2O2 is formed and oxidised in the electrolyte solution in the pores of the cathode.(4) On charging the cell, the RM is oxidised at the surface of the cathode, and then diffuses to and oxidises Li2O2 within the cathode pores, releasing O2. It is desirable for the RM to operate at as low a voltage as possible, above the thermodynamic oxidation potential of Li2O2, to maximise energy efficiency during cycling.
In our recent work, we have investigated the mechanism by which RMs oxidise Li2O2 particles.(5) The trend of oxidation rate with mediator potential follows Marcus theory with a maximum rate at +3.74 V. We show that following the initial outer-sphere one-electron oxidation of Li2O2, the dominant subsequent step is the disproportionation of LiO2 to 3O2, and not the one-electron oxidation of LiO2 to 1O2 or 3O2 (Fig. 1). We also show how RMs with different potentials affect the 1O2 yield and that this does not correlate well with degradation, casting doubt on whether 1O2 is the major source of degradation during charge. Our mechanism not only explains why the current generation of mediators cannot deliver high charging rates at sufficiently low potentials for good round-trip energy efficiency but also points the way to designing mediators that can deliver high rates at low charge voltages.

W. J. Kwak, et al., Chem Rev, 2020, 120, 6626-6683.

S. A. Freunberger, et al., Angew Chem Int Ed Engl, 2011, 50, 8609-8613.

V. Viswanathan, et al., J Chem Phys, 2011, 135, 214704.

Y. Chen, et al., Nat Chem, 2013, 5, 489-494.

S. Ahn, et al., Nat Chem, 2023, 15, 1022-1029.

Figure 1
Small Molecule Aromatic Hydrocarbons: Powering Ultralong Cycle Life in Li-Ion Battery Anodes and Dual Chemical Prelithiation for Li-Ion Capacitors
Authors: Su Yu-Sheng , Arya Avi , Lai Kuan-Lin 
Published: December 2024

Exploring the potential of Small Molecule Aromatic Hydrocarbons (SMPAHs) such as naphthalene (Naph), biphenyl (BP), 9,9-dimethylfluorene (DiMF), phenanthrene (Phen), p-terphenyl (p-Ter), and pyrene (Py) reveals their exceptional performance as promising candidates for lithium-ion battery (LIB) anodes. These SMPAHs offer high specific capacities, remarkable cycle stability, and excellent rate capabilities. Investigation into their electrochemical behavior demonstrates superior long-term cyclability, with capacity retention exceeding 92% after 1500 cycles and a Coulombic efficiency approaching 100%. However, the study identifies the challenge of pyrene dissolution, which leads to poor capacity due to irreversible structural collapse caused by the vertical expansion of the pyrene dimer, resulting in the dissolution of pyrene into the electrolyte.
In parallel, SMPAHs drive advancements in lithium-ion capacitor (LIC) technology through a facile dual chemical prelithiation approach. Among them, the LIC cell with the Li-BP solution prelithiated hard carbon anode and activated cathode exhibits the highest energy density of 98 Wh/kg at 0.5C and retains 47% of reversible capacity at 20C, establishing it as one of the best-performing LICs reported to date. Notably, precise control of prelithiation level in AC cathodes is crucial to prevent unwanted lithiation and corrosion of aluminum. This integrated approach propels the evolution of electrochemical energy storage toward a greener and more efficient future.

Figure 1
Aging Analysis for Li Metal Batteries Exposed to Calendar and Non-Uniform Use Conditions
Authors: Dufek Eric J. , Barnes Pete , Kim Sangwook , Chen Bor-Rong , Zhang Hongxing , Efaw Corey M. , Wang Yulong , Park Bumjun , Li Bin , Evans Michael , Mak Bianca , Liaw Boryann , Olds Daniel , Khalifah Peter G. , Hodges Brittany 
Published: December 2024

Lithium metal batteries have seen dramatic advancement over the last 5 years. In realistic cell designs the ability to achieve both high energy and long cycle life have been demonstrated using constant current cycling. Based on the observed performance the timing is right for more detailed analysis of some of these promising systems in more realistic use cases including calendar aging and using interspersed charge and discharge pulses which mirror vehicle acceleration and regeneration. In a combination of studies it has been found that shifts to these use cases present both significant promise for the current technical approaches as well as distinct challenges which will need to be addressed for future implementation in long range, high performing electric vehicles.
This discussion will focus on a few of these key findings and present options to continue the advancement of high energy Li metal batteries.