Electron Spin Resonance Measurements Research Articles

Protonated g-C3N4/oxygen-doped g-C3N4 S-scheme homojunction fabricated by electrostatic self-assembly for photocatalytic hydrogen evolution and tetracycline hydrochloride degradation

S-scheme photocatalytic systems with high redox ability and separation efficiency of photoexcited charge carriers supply considerable prospects for environmental optimization and sustainable energy development. However, coupling well-suited reduction and oxidation components for target reactions remains a challenge worth exploring. Herein, an efficient S-scheme system for H2 generation and tetracycline hydrochloride (TCH) photodegradation based on protonated g-C3N4 (PCN) coupling with oxygen-doped g-C3N4 (OCN) is fabricated via a facile electrostatic self-assembly strategy. Intimate interfacial interactions originating from the ultrathin nanostructure and staggered energy band arrangement for the S-scheme charge transfer pathway provide compelling advantages for the highly efficient separation of photoinduced electron-hole pairs in the as-designed PCN/OCN homojunction. The in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) techniques and electron paramagnetic resonance (EPR) measurements are applied to confirm the successful construction and the validity of the S-scheme charge transfer pathway. The obtained PCN/OCN composites with optimal ratio achieve a decent H2 generation rate of 6184.7 μmol g−1 h−1 outpacing the single PCN by approximately 4.8-fold, and 90.5 % TCH photodegradation efficiency is also realized within 90 min. This work provides a delicate fresh round of elevation for the exploration of an effective photocatalytic system.

Latched detection of zeptojoule spin echoes with a kinetic inductance parametric oscillator.

When strongly pumped at twice their resonant frequency, nonlinear resonators develop a high-amplitude intracavity field, a phenomenon known as parametric self-oscillations. The boundary over which this instability occurs can be extremely sharp and thereby presents an opportunity for realizing a detector. Here, we operate such a device based on a superconducting microwave resonator whose nonlinearity is engineered from kinetic inductance. The device indicates the absorption of low-power microwave wavepackets by transitioning to a self-oscillating state. Using calibrated pulses, we measure the detection efficiency to zeptojoule energy wavepackets. We then apply it to measurements of electron spin resonance, using an ensemble of 209Bi donors in silicon that are inductively coupled to the resonator. We achieve a latched readout of the spin signal with an amplitude that is five hundred times greater than the underlying spin echoes.

Highly efficient peroxymonosulfate activation by CoFe2O4@attapulgite–biochar composites: Degradation properties and mechanism insights

Sulfate radical-based advanced oxidation processes (SR-AOPs) have been considered as a promising approach for degrading organic pollutants. Herein, CoFe2O4 anchored on attapulgite-biochar composites (CoFe2O4@ATP–BC) were synthesized by a sol-gel co-pyrolysis method and showed excellent catalytic performance, reusability and stability in activating peroxymonosulfate (PMS) for the degradation of Rhodamine B (RhB). The effects of PMS concentration, catalyst dosage, temperature, initial pH, NOM and inorganic ions on the removal of RhB were investigated. The radical quenching experiments and electron paramagnetic resonance (EPR) measurement confirmed that 1O2, O2∙− and surface-bound ∙OH and SO4∙− were major reactive oxygen species (ROS) in the RhB degradation by CoFe2O4@ATP–BC/PMS system, indicating that radical and non-radical degradation pathways were both involved. The possible catalytic mechanism of PMS by CoFe2O4@ATP–BC was proposed including the interface reaction and bulk reaction. The main degradation intermediates were identified by liquid chromatograph-mass spectrometry (LC-MS), and three possible degradation pathways of RhB were deduced accordingly. In general, the CoFe2O4@ATP–BC/PMS system provided fundamentals of theoretical and applied research to further develop supported bimetallic oxides for advanced oxidation treatment of organic wastewater.

Dihydropyrazine-reductant effects on band bending at PEDOT:PSS/perovskite interfaces in tin halide perovskite solar cells

This study investigates the effects of reducing treatment by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (TM-DHP) additives on band bending in the perovskite surface near poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole-selective contacts in tin-based-perovskite solar cells. We took electron spin resonance (ESR) spectroscopy measurements of PEDOT:PSS/tin perovskite stacks in the dark and under one-sun illumination. The findings indicate that downward band bending is formed in the tin perovskite layer near the PEDOT:PSS layer. This downward bending is not favorable in terms of surface passivation and hole selectivity. On the other hand, upward band bending occurs in stacks including tin perovskite layers with TM-DHP additives, indicating that TM-DHP prevents oxidation of tin perovskite, thus unfavorable downward band bending. ESR measurements of PEDOT:PSS/tin perovskite stacks without TM-DHP under illumination suggest reduction in the number of polarons caused by electron transport from perovskite layers toward PEDOT:PSS, which is driven by the unfavorable downward band bending. However, such electron transport toward PEDOT:PSS is prevented in PEDOT:PSS/tin perovskite stacks with TM-DHP. These findings, which demonstrate TM-DHP effects on interface band bending, are important for realizing highly efficient and stable tin perovskite solar cells.

Construction of Ideal One-Dimensional Spin Chains by Topochemical Dehydration/Rehydration Route.

One-dimensional (1D) Heisenberg antiferromagnets are of great interest due to their intriguing quantum phenomena. However, the experimental realization of such systems with large spin S remains challenging because even weak interchain interactions induce long-range ordering. In this study, we present an ideal 1D S = 5/2 spin chain antiferromagnet achieved through a multistep topochemical route involving dehydration and rehydration. By desorbing three water molecules from (2,2'-bpy)FeF3(H2O)·2H2O (2,2'-bpy = 2,2'-bipyridyl) at 150 °C and then intercalating two water molecules at room temperature (giving (2,2'-bpy)FeF3·2H2O 1), the initially isolated FeF3ON2 octahedra combine to form corner-sharing FeF4N2 octahedral chains, which are effectively separated by organic and added water molecules. Mössbauer spectroscopy reveals significant dynamical fluctuations down to 2.7 K, despite the presence of strong intrachain interactions. Moreover, results from electron spin resonance (ESR) and heat capacity measurements indicate the absence of long-range order down to 0.5 K. This controlled topochemical dehydration/rehydration approach is further extended to (2,2'-bpy)CrF3·2H2O with S = 3/2 1D chains, thus opening the possibility of obtaining other low-dimensional spin lattices.

Chitosan synergizes with bismuth-based metal-organic frameworks to construct double S-type heterojunctions for enhancing photocatalytic antimicrobial activity

In recent years, photocatalytic technology has been introduced to develop a new kind antimicrobial agents fighting antibiotic abusing and related drug resistance. The efforts have focused on non-precious metal photocatalysts along with green additives. In the present work, a novel bis-S heterojunctions based on the coupling of polysaccharide (CS) and bismuth-based MOF (CAU-17) s synthesized through a two-step method involving amidation reaction under mild conditions. The as prepared photocatalyst literally extended the light response to the near-infrared region. Owing to its double S-type heterostructure, the lifetime of the photocarriers is significantly prolonged and the redox capacity are enhanced. As a result, the as prepared photocatalyst indicated inhibition up to 99.9 % under 20 min of light exposure against Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria as well as drug-resistant bacteria (MRSA). The outstanding photocatalytic performance is attributed to the effective charge separation and migration due to the unique double S heterostructure. Such a double S heterostructure was confirmed through transient photocurrent response, electrochemical impedance spectroscopy tests and electron spin resonance measurements. The present work provides a basis for the simple synthesis of high-performance heterojunction photocatalytic inhibitors, which extends the application of CAU-17 in environmental disinfection and wastewater purification.

A Co-doped Ag3PO4 photocatalyst: Efficient degradation of organic pollutants and enhancement mechanism

In this study, an efficient Co-doped Ag3PO4 photocatalyst was prepared by the deposition method. Compared with Ag3PO4, the degradation efficiency of the optimal sample CAP-2 (the mole ratio of Co/Ag was 0.057 %) for MO (20 mgL−1) increased from 53.4 % to 95.0 % within 20 min, and the degradation efficiency for phenol (20 mgL−1) increased from 57.9 % to 91.8 % within 80 min. Moreover, the CAP-2 sample performed excellent mineralization ability and stable recycling capacity. Free radical capture experiments and electron spin resonance (ESR) measurements indicated that holes (h+) and superoxide radicals (⋅O2−) were the main active radicals. Doping Co ions broadened the optical absorption, introduced impurity level to promote the separation of carriers, and generated additional ⋅O2− owing to the mutual conversion of Co3+ and Co2+, thus considerably improving Ag3PO4 photocatalytic performance. This work provides a new reference for doping metal ions modified semiconductor photocatalysts to efficiently degrade organic pollutants.

Machine Learning Isotropic g Values of Radical Polymers.

Methods for electronic structure computations, such as density functional theory (DFT), are routinely used for the calculation of spectroscopic parameters to establish and validate structure-parameter correlations. DFT calculations, however, are computationally expensive for large systems such as polymers. This work explores the machine learning (ML) of isotropic g values, giso, obtained from electron paramagnetic resonance (EPR) experiments of an organic radical polymer. An ML model based on regression trees is trained on DFT-calculated g values of poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA) polymer structures extracted from different time frames of a molecular dynamics trajectory. The DFT-derived g values, gisocalc, for different radical densities of PTMA, are compared against experimentally derived g values obtained from in operando EPR measurements of a PTMA-based organic radical battery. The ML-predicted giso values, gisopred, were compared with gisocalc to evaluate the performance of the model. Mean deviations of gisopred from gisocalc were found to be on the order of 0.0001. Furthermore, a performance evaluation on test structures from a separate MD trajectory indicated that the model is sensitive to the radical density and efficiently learns to predict giso values even for radical densities that were not part of the training data set. Since our trained model can reproduce the changes in giso along the MD trajectory and is sensitive to the extent of equilibration of the polymer structure, it is a promising alternative to computationally more expensive DFT methods, particularly for large systems that cannot be easily represented by a smaller model system.

Exploring the Effect of V2O5 and Nb2O5 Content on the Structural, Thermal, and Electrical Characteristics of Sodium Phosphate Glasses and Glass-Ceramics.

Na-V-P-Nb-based materials have gained substantial recognition as cathode materials in high-rate sodium-ion batteries due to their unique properties and compositions, comprising both alkali and transition metal ions, which allow them to exhibit a mixed ionic-polaronic conduction mechanism. In this study, the impact of introducing two transition metal oxides, V2O5 and Nb2O5, on the thermal, (micro)structural, and electrical properties of the 35Na2O-25V2O5-(40 - x)P2O5 - xNb2O5 system is examined. The starting glass shows the highest values of DC conductivity, σDC, reaching 1.45 × 10-8 Ω-1 cm-1 at 303 K, along with a glass transition temperature, Tg, of 371 °C. The incorporation of Nb2O5 influences both σDC and Tg, resulting in non-linear trends, with the lowest values observed for the glass with x = 20 mol%. Electron paramagnetic resonance measurements and vibrational spectroscopy results suggest that the observed non-monotonic trend in σDC arises from a diminishing contribution of polaronic conductivity due to the decrease in the relative number of V4+ ions and the introduction of Nb2O5, which disrupts the predominantly mixed vanadate-phosphate network within the starting glasses, consequently impeding polaronic transport. The mechanism of electrical transport is investigated using the model-free Summerfield scaling procedure, revealing the presence of mixed ionic-polaronic conductivity in glasses where x < 10 mol%, whereas for x ≥ 10 mol%, the ionic conductivity mechanism becomes prominent. To assess the impact of the V2O5 content on the electrical transport mechanism, a comparative analysis of two analogue series with varying V2O5 content (10 and 25 mol%) is conducted to evaluate the extent of its polaronic contribution.

Heteropentanuclear {Ru(II)Cu(II)4} Kuratowski Complexes Assembled from a Ruthenium(II) Precursor Complex to Study Competing Exchange Interactions in M(II)(ta)2 Networks [ta(-) = 1,2,3-Triazolate

We report a directed two-step synthesis toward pentanuclear Kuratowski complexes. First, six 5,6-dimethylbenzo[1,2,3]triazole ligands (Me2btaH) are coordinated to a single Ru(II) ion, providing a topologically ideal template for the addition of further metal ions. The synthesis and crystal structures of [RuCu4X4(Me2bta)6] [X = acetylacetonate (acac) and tris(3,5-dimethyl-1-pyrazolyl)borate (Tp*)] are described. Both represent new members of the family of so-called Kuratowski (K3,3) complexes. The coordination units feature triazolato-bridged metal-centered {MM4} tetrahedra, which are known for frustrated magnetic interactions in both complexes and metal-organic frameworks. The novel Ru(II)-centered complexes were synthesized in order to investigate the influence of the presence or absence of a paramagnetic central metal ion in the Kuratowski complex. Superconducting quantum interference device and electron spin resonance measurements demonstrate that small deviations in bond lengths and valence angles can lead to the formation of pairs of magnetic exchange-coupled Cu(II) ions. Which Cu(II) ions pair up can be predicted in Jahn-Teller active compounds by the overlap of the respective orbitals. These data are compared with those gleaned for M(II)(ta)2 (ta = 1,2,3-triazolate) lattices, in which structurally similar {MM4} tetrahedra constitute the secondary building units.

Azomethine Fe3+ coordination compounds containing carbazole units: Synthetic approach, spectral characterization, and magnetic studies

The main aim of our study is to investigate various types of hybrid systems with a paramagnetic iron (III) ion as a core and photoactive derivatives of carbazole at the periphery. We have synthesized a variety of biligand coordination compounds with the composition [FeL2]A (where L is 2‐[2‐[(E)‐[4‐[4‐(3,6‐di‐tert‐butylcarbazol‐9‐yl)benzoyl]oxy‐2‐phenolate]methyleneamino]ethylamino]ethyl 4‐(3,6‐di‐tert‐butylcarbazol‐9‐yl)benzoate, A− is NO3− (I), Cl− (II), PF6− (III)). These systems were studied by superconducting quantum interference device (SQUID) magnetometry and X‐band electron paramagnetic resonance (EPR) spectroscopy. Magnetic measurements revealed mixed spin states (high spin [HS], low spin [LS]) of Fe (III) ions at room temperatures. Estimates of the corresponding spin contributions were made. It was found that all samples exhibit AFM exchange interactions between iron (III) ions. The ground spin state at 2.0 K was established and analyzed. EPR measurements confirmed the HS states of iron (III) and revealed two types of them: with weak distorted and strong low‐symmetry octahedral crystal fields.

Trap properties of novel UV-A persistent phosphor Sr3MgSi2O8:Ce3+

For the last few decades, there has been extensive research on the materials that persist to emit optical radiation long after any type of charging has stopped. Most of the established persistent luminescence (PersL) materials emit light in the visible part of the spectrum; however, in recent years, there has been a growing interest in UV-emitting persistent phosphors in recent years. These materials have been tested for various applications, such as photocatalysis, sterilization, and anti-counterfeiting, among others. Here, we report on the X-ray and UV-activated UV-A long PersL of Ce3+-doped Sr3MgSi2O8 material. We prepared samples with varied Ce3+ concentrations using solid–state reaction synthesis in an ambient atmosphere and conducted a thorough investigation using photoluminescence (PL), electron paramagnetic resonance (EPR), and thermally stimulated luminescence (TSL) spectroscopy methods. Our experiments show that the PersL signal of Ce3+ in the 300–450 nm range can be detected for at least 16 h when samples are irradiated with X-rays or UV. The TSL analysis reveals multiple discrete charge traps in the material with activation energies between 0.5 and 1.7 eV. Further EPR measurements confirm the presence of four paramagnetic centers. The thermal stability of these centers was analyzed, and it is established that one of these centers (g1 = 2.0056, g2 = 1.9981, and g3 = 1.9926) gradually decays at room temperature, which is correlated with the PersL processes.

Impact of tubing material on stability and filling accuracy of biologic drug product

This article is presenting completely new observations linked to Polysorbate 80 (PS80) oxidation in biologics drug product. Indeed, we observed that, in the drug product exposed to long contact time (∼ 1 h) in platinum-cured silicon tubing during the filling, the oxidation of PS80 is dramatically accelerated compared to short contact time. The phenomenon was observed in presence of iron traces (20 ppb), but not in absence of iron (< 2 ppb) or in presence of a chelator like EDTA. Electron Paramagnetic Resonance (EPR) measurements demonstrated the presence of radicals formed during the oxidation. It was deduced that platinum-cured silicon tubing is leaching some radical initiators, most probably peroxides decomposed by the iron. Alternative filling sets made of ThermoPlastic Elastomer (TPE) were investigated, both for the impact on PS80 stability and the filling performance using a peristaltic pump. The results showed that these filling sets were indeed not causing accelerated PS80 degradation but the process was not robust enough; these filling sets being too rigid for the constraints of the peristaltic pump rollers. These results show that there is no practical tubing alternative to platinum silicone cured tubing. To avoid the impact on PS80 oxidation the potential remediations presented in the article are to avoid any trace of iron or to add a chelating agent, or to discard the vials having experimented a filling stop (> 5 min).

The CW-EPR Capabilities of a Dual DNP/EPR Spectrometer Operating at 14 and 7 T

High-field electron paramagnetic resonance (EPR) measurements are indispensable for a better understanding of dynamic nuclear polarization (DNP), which relies on polarization transfer between electron and nuclear spins. DNP experiments are typically performed at high > 7 T magnetic fields and low ≤ 100 K temperatures, while EPR instrumentation capable of EPR measurements under these conditions is scarce. In this paper, we describe the CW EPR capabilities of a dual DNP/EPR spectrometer that is designed to carry out EPR experiments under “DNP conditions” at 14 and 7 T. In the first part, we present the design of this instrument, highlighting the choices made to allow for both DNP and EPR operations. The spectrometer uses a sweepable cryogen-free magnet with NMR-grade homogeneity, a closed-cycle cooling system, a quasi-optical induction mode bridge, and a superheterodyne receiver system. The probe design is optimized for low heat load and fast sample exchange under cryogenic conditions. The spectrometer can operate in frequency and field sweep modes, including wide field sweeps using the main coil of the magnet. In the second part, we present EPR spectra acquired over a wide range of samples and operating conditions, illustrating the CW EPR capabilities of the instrument.

{Ru(C6 H6 )}-Decorating Heteropolymolybdate for Highly Activity Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde.

An unclassical structure of {Ru(C6 H6 )}-based polyoxometalate, Cs6 H4 [Te2 Mo12 O46 {Ru(C6 H6 )}] ⋅ 16.5H2 O (1), has been successfully constructed from {Te2 Mo12 O46 }-type heteropolymolybdate and {Ru(C6 H6 )} group, which structure type was discovered for the first time. Compound 1 not only possesses strong light-harvesting ability, but also exhibits high carrier separation efficiency and lower charge transfer resistance. Under visible light irradiation, compound 1 displayed excellent catalytic activity and circularity in the conversion of benzyl alcohol to benzaldehyde (yield=94 %; turnover number=500; turnover frequency=20.8 h-1 ). Finally, the electron paramagnetic resonance measurement and energy level matching analysis provide theoretical basis for the derivation of the reaction mechanism.

Improved Placement Precision of Donor Spin Qubits in Silicon using Molecule Ion Implantation

AbstractDonor spins in silicon‐28 are among the best performing qubits in the solid state, offering unmatched coherence times, gate fidelities beyond 99% and the ability to fabricate arrays using deterministic ion implantation. Donor placement precision is improved upon, advantageous for qubit readout and coupling, by implanting molecule ions that carry bystander atoms to boost the detection confidence. Here, the suitability of phosphorus difluoride () molecule ions is demonstrated to fabricate donor qubits. Using secondary ion mass spectrometry, it is confirmed that (nuclear spin ) diffuses away from the implant site while remains close to its original location during a donor activation anneal. Electron spin resonance measurements are then performed on ‐implanted qubit devices. A pure dephasing time of and a coherence time of are extracted for the P donor electron‐ values comparable to those found in conventional atomic ‐implanted qubit devices. Additionally, the P donor electron is not found to hyperfine couple to any nuclear spins in its vicinity. Molecule ions therefore show great promise for producing high‐precision deterministically‐implanted arrays of long‐lived donor spin qubits.

Observation of the possible magnetic correction above the Curie temperature in Cr2Si2Te6 single crystals.

Intrinsic magnetic semiconductors hold great promise in the fields of fundamental magnetization and spintronics. One such semiconductor is Cr2Si2Ti6 (CST), a quasi two-dimensional (2D) magnetic semiconductor with potential applications in future magnetic devices. However, the origin of ferromagnetism in CST remains a mystery. To investigate this, ac/dc susceptibility and electronic spin resonance (ESR) measurements were conducted. Based on ac susceptibility scaling, the critical temperature (TC) for the ferromagnetic (FM) to paramagnetic (PM) phase transition was found to be ∼32.5 K, with a critical exponent of δ = 6.7 from the critical isotherm, β + γ = 1.72 from the temperature dependence of the crossover line, and γ = 1.43 from the temperature dependence of susceptibility along the same line. All critical exponents were found to be consistent with the dc magnetization scaling method. However, above and below TC, the origin of magnetism cannot be explained by a single theory. To explore the origin of abnormal magnetic critical behavior, ESR measurements were performed. Below T* ∼ 130 K, the ESR measurements revealed that the resonance field width (ΔH) tends to increase and decrease for the applied magnetic field H parallel and perpendicular to the c axis, respectively, indicating the onset of magnetic interaction even in the PM state. Meanwhile, the deviation from Curie-Weiss behavior below T* also confirmed the occurrence of magnetic correlation above the TC in CST. These observations suggest that the competition and cooperation among the direct and indirect interactions, the structural distortion and the van der Waals interaction at high temperature should be considered to investigate the origin of anomalous magnetism in CST. The present results provide valuable insights into the nature of ferromagnetism in 2D magnetic semiconductors.

CdS QDs grown on ellipsoidal BiVO4 for efficient photocatalytic degradation of tetracycline.

Designing efficient, inexpensive, and stable photocatalysts to degrade organic pollutants and antibiotics has become an effective way for environmental remediation. In this work, we successfully performed in situ growth of CdS QDs on the surface of elliptical BiVO4 to try to show the advantage of the binary heterojuncted photocatalyst (BVO@CdS) for the photocatalytic degradation of tetracycline (TC). The In situ growth of CdS QDs can provide a large number of reactive sites and also generate a larger contact area with BiVO4. In addition, compared with mechanical composite materials, in situ growth can significantly reduce the energy barrier at the interface between BiVO4 and CdS, providing more channels for the separation and migration of photogenerated charge carriers, and further improving reaction activity. As a result, BVO@CdS-0.05 shows the best degradation efficiency, with a degradation rate of 88% after 30 min under visible light. The TC photodegradation follows a pseudo-second-order reaction with a dynamic constant of 0.472 min-1, which is 6.47 times that of pure BiVO4, 7.24 times that of pure CdS QDs and 2 times that of the mechanical composite. The degradation rate of BVO@CdS-0.05 decreases to 77.8% with a retention rate of 88.5% after four cycles, demonstrating excellent stability. Through liquid chromatography-mass spectrometry (LC-MS) analysis, two possible pathways for TC degradation are proposed. Through free radical capture experiments, electron spin resonance measurements, and photoelectrochemical comprehensive analysis, it is confirmed that BVO@CdS composites have constructed an efficient Z-scheme heterojunction via in situ growth, thereby highly enhancing the separation and transport efficiency of charge carriers.

Hydrogen Termination Effect on SiO2/Si Interface State Density in CH3O-Molecular-Ion-Implanted Silicon Epitaxial Wafer for CMOS Image Sensors

The reduction in SiO2/Si interface state density (Dit) at the SiO2/Si interface region is important to improve the performance of complementary metal-oxide semiconductor (CMOS) image sensors. The CH3O-ion-implanted region stores hydrogen and releases the stored hydrogen during the subsequent heat treatment. This study demonstrates that a CH3O-ion-implanted epitaxial silicon wafer can reduce the Dit and Pb0 center density in SiO2/Si interface regions, as analyzed by quasi-static capacitance–voltage and electron spin resonance measurements, respectively. Both Dit and Pb0 center density in the CH3O-implanted wafer decreased with increasing heat treatment temperature. Moreover, the activation energy is estimated to be 1.57 eV for the hydrogen termination reactions induced by the CH3O-ion-implanted wafer. The activation energy is close to those of hydrogen molecules and Si dangling bonds at the SiO2/Si interface. This result means that Dit can be reduced by hydrogen from inside the silicon wafer, regardless of the heat treatment atmosphere. It has unique characteristics not found in conventional silicon wafers. The termination effect of the CH3O-molecular-ion-implanted epitaxial silicon wafers can contribute to the high electrical performance of CMOS image sensors.

AIE active fluorescent organic nanoparticles based optical detection of Cu2+ ions in pure water: a case of aggregation-disaggregation reversibility.

An AIE-active pyrene-terpyridine derivative, (4'-(pyren-1-yl)-2,2':6',2''-terpyridine) (1) was found to form nanoaggregate in an aqueous medium. The probe involved hydrogen bonding with solvent molecules that modulated the charge transfer behavior and consequently resulted in different spectroscopic behavior due to the formation of fluorescent organic nanoparticles (FONs). In the presence of Cu2+ ions, FONs displayed a ratiometric red shift of the absorption band (360 to 420 nm) accompanied by a prominent naked-eye color change from colorless to light yellow. With a gradual increase in water content, 1 displayed a huge red shift of the emission band (430 to 475 nm) denoting its switching from monomer to FONs. In the presence of Cu2+, the 475 nm emission band of FONs gradually diminished, facilitating the micromolar scale detection of Cu2+ (LOD = 8.57 μM) in a 100% aqueous medium with a fluorogenic color change from cyan to dark. The SEM and DLS data indicated the cation-induced disaggregation of FONs, which was further confirmed by mass spectral analysis and electron paramagnetic resonance measurement. In addition, the high selectivity of FONs towards Cu2+ ions over other potential cations and the 2 : 1 (1-Cu2+) binding stoichiometry were also determined. Moreover, the spectroscopic behavior of the monomeric amphiphilic probe was well supported by extensive DFT study. Such detection of Cu2+ ions in pure aqueous medium denoting an aggregation-disaggregation event is very rare in the literature.