bluuebunny/crossref_metadata_2025_split huggingface dataset:
Recent Advances in Zinc Anc Cooper Phthalocyanines As Hole Transporting Materials in Perovskite Solar Cells
Authors: Sastre-Santos Angela 
Published: July 2021

Recently, significant progresses have been achieved in the fabrication of highly efficient perovskite solar cells, while major challenges, such as commercial viablity of exotic materials and their instability, remain as an obstacle. Hole transporting materials (HTMs) represent a tricky choice for the fabrication of efficient solar cells and the cost uneffective Spiro-OMeTAD continue to be so far the most obvious candidate. Semiconductors molecules, such as metallophthalocyanines (MPcs)1 appeared as a promising class of p-type material, since they are less expensive and more stable.
In this communication, we will present the synthesis of novel ZnPcs,2 ZnPc dimers3 and CuPcs4 (see as examples Figure 1) as efficient, stable, and low cost HTMs in PSCs. The MPcs are substituted with functional groups that possesses a very good solubility in a wide range of organic solvents, adequate HOMO LUMO levels and thus can be applied from solution processing in a wide range of perovskite solar cell devices.
Figure 1. Different ZnPcs structures as HTMs in PSCs

References

M. Urbani, M. E. Ragoussi, M. K. Nazeeruddin, T. Torres, Coord. Chem. Rev.
2019, 381, 1-64.

P. Huang, A. Hernández, S. Kazim, J. Ortíz, Á. Sastre-Santos, S. Ahmad Sustainable Energy &Fuels.
2020, 4, 6188-6195.

a) D. Molina, M. A. Ruiz-Preciado, F. Sadegh, M. João Álvaro-Martins, M. Grätzel, A. Hagfeldt, Á. Sastre-Santos, J. Porphyr. Phthalocyanines, 2019, 23, 546–553. b) D. Molina, M. A. Ruiz‐Preciado, B. Carlsen, F. T. Eickemeyer, B. Yang, N. Flores‐Díaz, M. J. Álvaro‐Martins, K. Nonomura, A. Hagfeldt and Á. Sastre‐Santos, ChemPhotoChem, 2020, 4, 307–314.

a) L. Caliò, J. Follana-Berná, S. Kazim, M. Madsen, H. G. Rubahn, Á. Sastre-Santos, S. Ahmad, Sustainable Energy Fuels, 2017, 1, 2071-2077. b) P. Huang, A. Hernández, J. Follana-Berná, S. Kazim, J. Ortíz, Á. Sastre-Santos, S. Ahmad, submitted.
Supramolecular Architecturing of Quantum Box Arrays from Functionalized Porphyrins and Exploring Their Quantum States
Authors: Ahsan Aisha , Mousavi Fatemeh S. , Popova Olha , Nijs Thomas , Nowakowska Sylwia K. , Baljozovic Milos , Pasti Igor A. , Morari Cristian , Iarinca Luiza , Hill Jonathan P. , Liu Shi Xia , Decurtins Silvio , Thilgen Carlo , Gade Lutz , Lobo Checa Jorge , Diederich Francois , Stoehr Meike , Jung Thomas A. 
Published: July 2021

Our research is based on the analysis of structure-function correlations for a broad spectrum of functionalized porphyrins and phthalocyanines in their propensity to create increasingly complex and functional on surface architectures. [1] Thereby we use porphyrin and phthalocyanine functionalization and synthesis, ‘by design’, or ‘on-surface-supramolecular chemistry’ to create structures with specific physical properties towards e.g. future quantum devices.
By using a fluoro-bi-phenyl functionalized porphyrin to create a stable, porous organic network, we manufacture arrays of identical quantum boxes. These boxes contain a specific quantum well state arising from the confinement of the electronic (Shockley) surface state within the pores. We show that the electronic quantum box state as well as the interbox coupling can be modified locally by adsorbates, e.g. C60, interacting with the barrier. In view of the wealth of available and differently acting adsorbates, this approach allows for the engineering of quantum states in on-surface network architectures. Thus, by their dance on the nose of the ‘devil’ [3], porphyrins and phthalocyanines justify the emergence of ‘on-surface supramolecular physics’ as reflected by ongoing and future research work.
Fig. 1) Adsorbate-induced modification of the confining barriers in a quantum box array formed by a functionalized fluoro-bi-phenyl porphyrin on Ag(111). (Taken from [2])
[1] N. Wintjes et al. Two-dimensional phase behavior of a bimolecular porphyrin system at the solid-vacuum interface, J. Am. Chem. Soc. 2010, 132, 21, 7306-7311; N. Wintjes et al., Supramolecular synthons on surfaces: Controlling dimensionality and periodicity of tetraarylporphyrin assemblies by the interplay of cyano and alkoxy substituents Chem. Eur. J. 2008, 14, 5794.
[2] S. Nowakowska et al., Adsorbate-induced modification of the confining barriers in a quantum box array, ACS Nano 2018, 12, 768.
[3] W. Pauli “God made the bulk; surfaces were invented by the devil.” Quoted, e.g. in the Preface of A. Zangwill, Physics at Surfaces, Cambridge University Press, 1988. ISBN 978-0-521-34752-5

Figure 1
Unraveling Coordination Features of Hemihexaphyrazines - New Approach to Perspective Materials for Nanoelectronics
Authors: Islyaikin Mikhail K. , Koifman Oskar I. , Konarev Dmitri V. , Torres Tomas 
Published: July 2021

Hemihexaphyrazins are macrocycles containing three thiadiazole and three pyrrolecontaining subunits unified by an alternating fashion via six aza-bridges to form an expanded coordination cavity with 27-membered inner macroring bearing 9 nitrogen atoms. Due to such unusual structure to compare with porphyrins and phthalocyanines, hemihexaphyrazins have an enormous potential in coordination chemistry. It was established that they are able to hold 3 atoms of transition metals within inner cavity. Recently a clear evidence of such complexes formation was obtained by scanning tunneling microscopy (STM) [1]. Early using STM, unprecedented off-centered complexation motif of metal free hemihexaphyrazin (H3Hph) with dysprosium on Au(111) surface has been detected [2].
Moreover, it was showed that due to presence of 9 nitrogen atoms within coordination cavity, H3Hph in reduced state can act as an aza-crown ether to form a new type of double-decker complex [3]. Partial charge transfer and uniform distribution of the charge over two macrocycles make these as promising building blocks for designing compounds with potential conducting and magnetic properties.
Acknowledgement: this work was partially supported by Russian Foundation of Basic Research (project 19-03-00888) and Russian Science Foundation (project N 17-13-01215).
Literature

Bacilla Ana C. C., Okada Yusuke, Yoshimoto Soichiro, Islyaikin Mikhail K., Koifman Oskar I.; Kobayashi Nagao. Triangular Expanded Hemiporphyrazines: Electronic Structures and Nanoscale Characterization of Their Adlayers on Au(111). Bulletin of the Chemical Society of Japan. BCSJ. 2021, Vol.94, No.1, pp. 34 – 43. DOI: 10.1246/bcsj.20200188.

Borja Cirera, Olga Trukhina, Jonas Björk, Giovanni Bottari, Jonathan Rodriguez-Fernandez, Alberto Martín-Jiménez, Mikhail K Islyaikin, Roberto Otero, José M. Gallego, Rodolfo Miranda, Tomas Torres, and David Ecija. Long-range orientational self-assembly, spatially-controlled deprotonation and off-centered metallation of an expanded porphyrin. J. Am. Chem. Soc., 2017, 139 (40), pp 14129–14136. DOI: 10.1021/jacs.7b06406.

Dmitri Konarev, Salavat S. Khasanov, Mikhail K. Islyaikin, Akihiro Otsuka, Hideki Yamochi, Hiroshi Kitagawa, Rimma N. Lyubovskaya, Evgenii N. Ivanov, Oskar I. Koifman, Yuriy A. Zhabanov. Double-Decker Paramagnetic {(K)(H3Hhp)2}2- Radical Dianions Comprising Two [30]Trithia-2,3,5,10,12,13,15,20,22,23,25,30-Dodecaazahexaphyrins and a Potassium Ion. Chemistry – An Asian Journal. 2020, 15, 61 – 65. DOI: 10.1002/asia.201901518.
A Real Time Electrochemical Analysis of Co-Sputtered (Co-Cr) and (Co-Cr-Mo) Alloy Thin Film Libraries in Ringer’s Solution at 37 oc
Authors: Lone Shaukat Ali , Mardare Cezarina Cela , Mardare Andrei Ionut , Hassel Achim Walter 
Published: July 2021

Cobalt-based alloys are used as total hip replacement prostheses due to their exceptional tribocorrosion properties in the human physiological environment[1]. Due to continuous mechanical and corrosive conditions, the dissolution of Cr and Co in the body fluid is unavoidable. These metallic particles and ions can cause cancer and gene mutation in the body, therefore their leaching should be diminished by proper passivation[2].
In this work, two combinatorial thin film libraries namely a binary Co-Cr and a ternary Co-Cr-Mo were prepared by means of co-sputtering. Both libraries were characterized by state of the art high resolution scanning electron microscopy (SEM) and X-ray diffraction (XRD). The chromium content for binary Co-Cr library varied from 14-40 at.% (balanced Co) while for ternary Co-Cr-Mo library a compositional spread of Co (46-79 at.%), Cr (17-48 at.%) and Mo (3-11 at.%) was obtained. In both libraries roundish spike shaped grains were revealed at high cobalt content which gradually changed to refined and compact grains with the increment of Cr. Similarly, molybdenum (>-7 at.%) brought additional grain refinement. Furthermore, weak, and broad XRD peaks of rt HCP and ht FCC pure Co were disclosed at nearly all compositions. No intermetallic phase was determined in either library.
The real time electrochemical screening and corrosion stability were accomplished by a in house-built flow type scanning droplet cell microscope (FT-SDCM) in conjunction with an inductively couple plasma optical emission spectroscope (ICP-OES). Various electrochemical techniques i.e. open circuit potential, linear sweep voltammetry and Tafel extrapolation were utilized. No significant passive behavior was obtained for the alloys containing the Co content higher than (68-70 at.%) irrespective of Cr and Mo concentration. However, further increment in the Cr content significantly improved the alloy nobility and restricted the active to passive dissolution. The addition of Mo improved the transpassive dissolution. A graphical model was developed on the basis of this study and a composition range of (7-10) at.% Mo and (36-48) at.% Cr (complementary Co) is recommended as likely candidate for biomedical use.
References
[1] A. Aherwar, A. K. Singh, A. Patnaik, Cobalt Based Alloy: A Better Choice Biomaterial for Hip Implants, Trends Biomater. Artif. Organs, 30, 50–55, (2016); doi: 10.13140.2.1.2501.5284.
[2] E. N. Codaro, P. Melnikov, I. Ramires, A. C. Guastaldi, Corrosion Behavior of a Cobalt Chromium-Molybdenum Alloy, Russ. J. Electrochem., 36, pp. 1263-1267, (2000); doi: 10.1007/02757531
Electrodeposition of Zinc-Nickel Alloys from Ethylene Glycol for Corrosion Protection
Authors: Bernasconi Roberto , Firtin Fatma Godze , Kahyaoglu Buse , Nobili Luca , Magagnin Luca 
Published: July 2021

Zn rich ZnNi alloys electrodeposition have recently attracted the attention of researchers due to their interesting corrosion properties [1]. In particular, alloys containing Ni in the 15 - 25 % range find application in a number of industrial fields, like automotive and constructions. ZnNi is normally electrodeposited from aqueous solutions, in which plating takes place following a typical anomalous mechanism [2]. In the last few years, however, new deposition approaches have been attempted to improve ZnNi plating performances. Specifically, III generation deep eutectic solvents comprising choline chloride have been tested [3].
The present work investigates the use of non-aqueous ethylene glycol based electrolytes for the deposition of Zn rich ZnNi alloys. The use of ethylene glycol as solvent introduces many advantages with respect to aqueous solutions: low oxygen contamination, high deposits purity and no pH dependance [4]. ZnNi codeposition was studied employing cyclic voltammetry and layers were deposited under potentiostatic control. Deposition potential was varied and its influence on final composition and morphology was determined. Addition of an additive (NH4Cl) to enhance surface morphology was attempted as well [3]. Phase composition was investigated using XRD to determine the possible presence of a metastable γ-ZnNi phase, which has already been observed in the case of ZnNi plated from alkaline aqueous solution [5]. Finally, corrosion behavior of layers obtained from ethylene glycol was assessed and compared with equivalent coatings deposited from commercial aqueous solutions.
[1] M. Gavrila et al.; Surface and Coatings Technology, 123 (2-3), 164-172 (2000)
[2] G. Roventi et al.; Journal of Applied Electrochemistry 30 (2), 173–179 (2000)
[3] S Fashu et al.; Transactions of Nonferrous Metals Society of China 25 (6), 2054-2064 (2015)
[4] G. Panzeri et al.; Electrochimica Acta 271 (1), 576-581 (2018)
[5] S. Ieffa et al.; Transactions of the IMF 94, 321-324 (2014)
First Principles, Explicit Interface Studies of Oxygen Vacancyand Chloride in Al2O3 Films on Metal Surfaces for Metal Corrosion Applications
Authors: Leung Kevin 
Published: July 2021

Pitting corrosion is a much-studied and technologically relvant subject. However, the fundamental mechanisms responsible the breakdown of the passivating oxide layer are still subjects of debate. Chloride anions are known to accelerate corrosion; relevant hypotheses include Cl insertion into positively charged oxygen vacancies in the oxide film, and Cl adsorption on passivating oxide surfaces -- substituting for OH-. In this work, we conduct large scale first principles modeling of explicit metal/Al2O3 interfaces to investigate the energetics and electronic structure associated with these hypotheses in connection to atmospheric aluminum corrosion. The explicit interface models allow electron transfer that mimics electrochemical events, and the establishment of the relation between atomic structures at different interfaces and the electronic band alignment. For multiple model interfaces, we find that doubly charged oxygen vacancies, which are key ingredients of the point defect model (PDM) often used to analyze corrosion data, can only occur in the presence of a potential gradient that raises the voltage. Cl- insertion into oxide films can be energetically favorable in some oxygen vacancy sites, depending on the voltage. Cl- substitution of surface hydroxyl groups is energetically unfavorable. We also discuss the challenges associated with explicit DFT modeling of these complex interfaces.
Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the document do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

Figure 1
Effect of Applied Pressure on the Ceria Chemical Mechanical Planarization
Authors: Kwak Donggeon , Oh Seungjujn , Yun Junho , Kim Juhwan , Kim Taesung 
Published: July 2021

Ceria abrasive is widely used in the Inter layer dielectric (ILD) Chemical mechanical planarization (CMP) due to its high removal rate and high selectivity ability. Despite the relatively low hardness of the ceria, Ce-O-Si bonding between silicon oxide surface and ceria abrasive enables high removal rate of silicon oxide CMP. Therefore, it is important to investigate the Ce-O-Si bonding for further study of the post CMP cleaning as well as ceria CMP. In this study, the effect of the applied pressure on the ceria CMP was investigated. Dipping and polishing process was conducted to confirm the surface change with applied pressure. The Fourier-transform infrared spectroscopy was measured to compare between dipped wafer and polished wafer. Fig 1 showed FT-IR spectra of each samples. Bare wafer and dipped wafer show similar spectra. Meanwhile, polished wafer shows different spectra in the range of 1000-1200 cm-1 and 800-900cm-1 which were associate with the Si-O-SI and Si-O bonding. The intensity of the both peak decreased due to the Ce-O-Si bonding.
Zeta potential is a key factor for adsorption behavior of the ceria CMP. Generally, ceria particle can adsorb on the silicon oxide surface due to electrostatic attraction with opposite zeta potential. however, adsorption phenomenon was different as function of the applied pressure. The applied pressure plays an important role in the adsorption behavior of ceria as well as the zeta potential. This research suggests the importance of the applied pressure for the ceria CMP process.
Figure 1. FTIR spectra of the silicon oxide wafer in region of 600-1600 cm-1

Figure 1
Investigation of CMP Performance According to Pad Surface Condition and Abrasive Types
Authors: Jeon Sanghcuk , Lee Jungryul , Hong Seokjun , Kim Kyunghwun , Park Kihong , Kim Chang min , Kim Taesung 
Published: July 2021

Chemical mechanical planarization (CMP) is a planarization technique that combines mechanical and chemical factor for enhanced polishing and ﬁnishing. CMP process reduces the surface roughness to meet the requirements of semiconductors. The characteristics of CMP, such as material removal rate (RR), thickness uniformity and surface quality, are determined by various mechanical and chemical factors. CMP has many consumables. Slurry, conditioner, and pad are typically used in CMP process. These consumables’ interaction is very important in CMP process. The reason why, the other can affect each other. These factors are known to signiﬁcantly affect the results of CMP. During the process time, the lack of conditioner will block the pore and glazing on the pad surface. The longer process time, the lower pad cut rate is occurred because of poor conditioner performance [1]. And then pad glazing is occurred.
When the pad glazing occurred, RR is changed [2]. At this point, the RR has different value according to abrasive. The number of particles that can act on the wafer depends on the pad surface changed. This affects the local pressure acting on the wafer. As the amount of abrasive acting on the wafer increases, the local pressure on the wafer is decreased. As briefly think about the situation, reduction of local pressure should result in decreasing removal rate. However, when the pad glazing situation, the RR has difference phenomenon according to abrasive types. Normally, Fig.1 (a) shows RR using ceria abrasive. It has higher RR after pad glazing. Fig.1 (b) shows RR using silica abrasive. It has lower RR after pad glazing.
In this research, the difference in RR according to abrasive types generated during pad glazing was investigated. Based on these phenomena, I present the optimum pad land area each abrasive.

Reference

[1] C. Shin, H. Qin, S. Hong, S. Jeon, A. Kulkarni, and T. Kim, Journal of Mechanical Science and Technology, pp. 5659-5665, (2016).
[2] H. Kim et al., Wear, pp. 93-98, (2017).

Figure 1
Calendar Vs. Cycle Aging of Lithium-Ion Cells with Silicon Anode
Authors: Luo Mei , Rodrigues Marco-Tulio , Abraham Daniel P. , Shaw Leon 
Published: July 2021

Silicon has been investigated for decades, as an alternative to the graphite used in lithium-ion battery anodes, because of its high theoretical capacity. However, the large volume change of Si during electrochemical cycling (cycle-aging) deteriorates the solid electrolyte interphase (SEI) layer on the particles, resulting in increased electrolyte reduction reactions and associated capacity decay. Capacity fade is also observed in cells that are not cycled but simply held at voltage for extended periods of time (calendar-aging). [1]
Here we report the calendar and cycle-aging behavior of cells with a Si anode that is paired with a NMC532 cathode (Figure 1). The tests were conducted in coin cells and in cells with a reference electrode (prepared by in-situ lithiation of a 25 mm Cu wire). This reference electrode allowed us to determine changes in the individual electrode profiles during aging and to examine impedance changes that were monitored via hybrid pulse power characterization (HPPC) tests. [2]
Our various experiments have revealed the following: (i) capacity-fade is greater during cycle-aging than during calendar-aging; (ii) the capacity fade is associated with shifts in both positive and negative electrode potentials; (iii) parasitic currents are observed during the calendar-life hold, which indicate ongoing electrolyte reduction reactions at the silicon electrode; (iv)both electrodes contribute to the significant impedance rise observed during cell aging.
To further examine sources of the observed performance degradation we conducted experiments with cells with the Si paired with LiFePO4. These data, along with the probable mechanisms of cell aging, will also be discussed during the presentation.
References

Kalaga et al., Acta 2018, 280, 221-228.

Klett et al., Electrochem. Soc. 163 (2016) p. A875.

Acknowledgments: M.L. acknowledges the generous grants from the U.S. National Science Foundation with the award numbers of CMMI-1660572 and IIP-1918991 that enabled her research at Argonne National Laboratory. The electrodes and electrolytes used in this study are from Argonne’s Cell Analysis, Modeling and Prototyping (CAMP) Facility. We are grateful to Andrew Jansen, Bryant Polzin, and Steve Trask for their assistance during this study.

Figure 1
Characterization of Sn@TiO2 Anode Material for Li-Ion Battery Application
Authors: WANG Yun Hui , Shen Yu-Min , Chang Chia-Chin 
Published: July 2021

In this work, various phases of nanorod TiO2 were fabricated by hydrothermal process. Different crystalline phases of TiO2 nanowires will be analyzed by electrochemical analysis (CV, LSV, C-rate, charge and discharge, and EIS test) to investigate the influence of Li+ diffusion rate on specific capacitance. The in-situ XRD structure for charging and discharging will be carried out to explore the diffusion and structural behavior of Li+ in TiO2 was explored its fast charging, high capacitance and high safety characteristics, which will be a fundamental research of Sn modified on TiO2 nanowire. Transmission electron microscope image showed a range of 20 to 80 nm length TiO2 nanorods was success synthesized, and the XRD indicated the phase were rutile, anatase and rutile/anatase mixed by controlling the chelating agents (citric acid). The specific capacity of TiO2 nanorod was 120 mAh/g which the Columbic efficiency was ~ 99% under 0.1 C. A morphology of Sn@TiO2 was investigated as nano-capsule. The results are supposed to clarify the key factors of the fast charge, high specific capacitance and safety. It is expected that the Li+ ion influence on structure changes during the charge and discharge process by implementing this research. The fast charging, high specific capacity and high safety mechanism will be established as an index for material application and commercial products.
Keywords: TiO2 anode materials, Sn@TiO2 anode materials, Li-ion battery, In-operando XRD