X-ray Photoemission Spectra Research Articles

Growth of Ta-doped SnO2 on GaN as a UV-transparent conducting electrode and band alignment properties of the heterojunction

GaN-based ultraviolet light emitting diodes (UV LEDs) have attracted considerable attention in recent years and are required in various applications such as healthcare, light illumination, and optical communication. However, the limited UV transparency of the electrodes like indium-doped tin oxide has hindered the external quantum efficiency of current UV LEDs. In this work, we present the growth of UV-transparent Ta-doped SnO2 (TTO) thin films on GaN as a promising UV-transparent electrode for LEDs. TTO thin films with a thickness of 200 nm exhibit optical transmission exceeding 80% at the wavelength of 300 nm, with a low resistivity of 2.5 × 10−4 Ω·cm and a low contact resistance of 1.7 × 10−2 Ω cm2 to n-type GaN. High-resolution x-ray photoemission spectra were employed to reveal insight into the electronic structure of TTO and the interfacial band alignment of TTO/GaN heterojunction. The wide optical bandgap (∼4.6 eV) and high UV transparency of TTO films stem from a significant Burstein–Moss shift due to degenerate doping, giving rise to metal-like characteristics and a small barrier height at the interface of TTO/GaN. These findings imply the origin of low contact resistivity of TTO to n-type GaN and may be applicable to the development of UV-transparent electrodes of optoelectronic devices.

Annealing-induced transformation of nanocomposites based on Ni0.5Zn0.5Fe2O4 nanoparticles entangled with functionalized MWCNTs by ex-situ synthesis: Unveiling modified physical properties

The physicochemical properties of NZFO/f-MWCNTs composites based on 5 wt% of Ni0.5Zn0.5Fe2O4 (NZFO) nanoparticles and functionalized multi-walled carbon nanotubes (f-MWCNTs) synthesized via ex-situ method are presented. The influence of annealing on the as-received hybrids is discussed. The structural and microstructural analysis confirms the efficiency of the synthesis process. The slight redistribution of cations over tetrahedral and octahedral sites is noted by Raman and X-ray photoemission (XPS) studies. The NZFO crystallite size is almost stable over sample processing, but the presence of single particles, clusters and aggregates on the f-MWCNTs’ surface is proven. The XPS spectra comparison reveals the domination of nanotubes as designed. The deconvoluted Fe2p lines confirm the iron redistribution slightly modified by annealing. The magnetic properties analysis revealed the cluster-glass state of NZFO particles. The core-shell-like structure with a magnetic core and disordered layer is evidenced. The influence of Fe-based carbon matrix residues in all hybrids was detected.

Structure and optical properties of ZnxCd1-xS and Cu:ZnxCd1-xS templated on DNA molecules

One-dimensional ZnxCd1−xS and Cu: Zn x Cd1−x S nanostructures were prepared using DNA as a template to promote growth along the molecular axis. The formation of homogeneously alloyed nanocrystals with cubic zinc blende-type structures was verified using x-ray diffraction and Raman spectroscopy. X-ray photoemission spectra revealed the presence of Cu(I) in the doped Cu: Zn x Cd1−x S nanocrystals. The effectiveness of the DNA template to direct the semiconductor growth in one dimension was demonstrated by AFM and TEM. The nanostructures displayed a granular morphology comprising nanoparticles with an average diameter of 14 nm composed of assemblies of smaller crystallites of 2.0 nm in size. Rope-like assemblies with an average diameter of 48 nm and extending in length to several hundred micrometres were obtained by evaporation-induced self-assembly. UV-Vis absorption and emission spectra indicated that the optical bandgaps (2.89–4.00eV) and photoluminescence peaks (608–819 nm) of the DNA-templated nanocrystals could be precisely controlled by modifying the molar ratios of their Zn/Cd precursors. Doping with Cu(I) gave an increase in photoluminescence intensity and a composition-independent red-shift of 0.23 eV. The preparation of DNA-templated Zn x Cd1−x S and Cu: Zn x Cd1−x S provides a simple, low-temperature route to aqueous dispersions of inorganic materials with controlled optical gap.

Manganese substitution effect on physical properties of sol-gel derived DyFeO3 orthoferrite

A simple composite DyFe(1-x)MnxO3 (x = 0, 0.1, 0.3, 0.5) powders were successfully prepared by the sol–gel method. The effect of Mn modification on the structure, thermal and phase transition behaviour of DyFeO3 orthoferrite was investigated. Mn modification didn't show any structural change and all the samples confirmed the pure orthorhombic phase with Pbnm space group. However, a contradicting trend in the variation of lattice parameters were observed due to the presence of mixed oxidation state of Dy, Fe and Mn in the sample leading to oxygen vacancies. The presence of mixed oxidation state was confirmed through X-ray photoemission spectra (XPS). Scanning electron microscopy (SEM) and Williamson Hall (WH) plot confirmed a decrease in particle sizes with increasing Mn concentration leading to an increase in the specific surface area which suggested an inhibition of grain growth with Mn modification. The defects-initiated change in physical behaviour in terms of structural, thermal, microstructural and dielectric are analyzed and discussed in detail.

Probing electron–phonon coupling in magnetic van der Waals material NiPS3: A non-magnetic site-dilution study

NiPS3 is a van der Waals antiferromagnet which has been shown to exhibit spin-phonon and spin-charge coupling in the antiferromagnetically ordered state below TN = 155 K. It is also a rare Ni-based negative charge-transfer-type insulator with Ni valence in a linear superposition state ψ= αd8+ βd9L−+ γ d10L−2 , where L− is the ligand hole. Here, we study high-quality single-crystals of Ni1−x Zn x PS3 (0 < x < 0.2) using temperature-dependent specific heat and Raman spectroscopy probes. We show that in pristine NiPS3, the phonon mode at 176 cm−1 (P2), associated with the vibrations of Ni ions, exhibits a distinct Fano asymmetry. The Fano resonance is particularly pronounced in the paramagnetic phase above TN, which was further confirmed by temperature dependent Raman data on the Zn-doped crystals. In the Zn-doped crystals, while the magnetism weakens following the mean-field prediction for site-dilution in a honeycomb lattice, the Fano coupling |1/q| strengthens, increasing monotonically with increasing Zn-doping. The x-ray photoemission spectra suggest an increase in the weight of the d9 and d10 components in the Zn-doped crystals. These observations indicate the presence of strong electron–phonon coupling in Ni1−x Zn x PS3, in addition to the spin-phonon, and spin-charge coupling previously reported.

Exploring optical and electrochemical studies on thulium selenite (TmSeO3)

Abstract Thulium selenite (TmSeO3) has been synthesized by precipitation method. It shows interesting smooth surface with nearly non-symmetric texture similar to water droplets spreading on hydrophobic surface. TmSeO3 is found to be monoclinic structure with lattice parameters a = 5.919±0.01 Å, b = 12.422±0.01 Å, c = 8.717±0.01 Å, α = γ = 90°, β = 106.01° and V = 616.1 Å3. Fourier transform infrared spectroscopy confirms the presence of Tm–Se bonding. X-ray photo emission spectrum confirmed the presence of thulium, selenium and oxygen in the samples in oxide form. Magnetic study between 300 and 20 K, shows decrease of magnetic moment with temperature, then reaches saturation and aligns all thulium spins. This results cooperative interaction of thulium spins. M–H curve at 300 K confirms the paramagnetic nature of sample. Cyclic voltammogram of three electrode system, manifests electric double layer capacitance with a potential window of 0.55 V. Specific capacitance is 102 F/g. Chronopotentiometry analysis shows 75 F/g specific capacitance, 11 Wh kg−1 energy density, and 275 W kg−1 power density. Impedance analysis confirms electric double layer capacitor behavior. Hence, TmSeO3 electrode based symmetric supercapacitor device was successfully fabricated and tested by two electrode configuration in aqueous electrolyte of KOH. A specific capacitance of 64.60 F/g at 1 A/g within a potential window of 1.85 V was achieved. Impedance analysis also confirms electric double layer capacitor nature with low series resistance of 0.2596 Ω and charge transfer resistance of 1.6352 Ω. The improved cycling performance after 4000 cycles is 51.5 % specific capacitance retention. Thus, symmetric supercapacitor electrodes based TmSeO3 materials are expected to have good electrochemical properties and good stability for energy storage and conversion applications. Furthur, optical parameters 5.28 eV energy gap, 0.4924 eV Urbach energy value and 1.959 refractive index are determined.

Surface termination effects on Raman spectra of Ti3C2Tx MXenes: an in situ UHV analysis.

Ti3C2Tx MXenes have typically a mixed surface termination of oxygen, hydroxyl and fluorine groups (Tx). In this work, we investigate the influence of the surface termination on the vibrational properties of Ti3C2Tx by performing thermal desorption and in situ Raman spectroscopy in ultra-high-vacuum (UHV). Significant changes in the Raman spectra occur after annealing above 600 °C, correlated with the desorption of approximately 80% of the fluorine termination, as confirmed by mass spectrometry and X-ray photoemission spectra. In particular, the intense Raman mode at 203 cm-1, usually attributed to a Ti-C-layer stretching vibration, is strongly damped upon fluorine desorption, while the broad spectral features between 220 and 680 cm-1, usually attributed to surface group vibrations, are not changing significantly. We show that the Raman spectra and the change induced by fluorine desorption are well represented by the phonon density of states instead of zone-center phonon modes. Disorder-induced Raman scattering strongly contributes to the Raman spectra. Moreover, due to the metallic nature of MXenes, charge density fluctuation scattering contributes as well. We show that the two scattering mechanisms, deformation potential and charge density fluctuation, may lead to opposite interpretations concerning the symmetry of the fluorine-related mode at 203 cm-1. This study provides new insights into the interpretation of the Raman spectra of MXenes, especially regarding the relation between surface chemistry and vibrational spectroscopy.

Specific versus Nonspecific Solvent Interactions of a Biomolecule in Water.

Solvent interactions, particularly hydration, are vital in chemical and biochemical systems. Model systems reveal microscopic details of such interactions. We uncover a specific hydrogen-bonding motif of the biomolecular building block indole (C8H7N), tryptophan's chromophore, in water: a strong localized N-H···OH2 hydrogen bond, alongside unstructured solvent interactions. This insight is revealed from a combined experimental and theoretical analysis of the electronic structure of indole in aqueous solution. We recorded the complete X-ray photoemission and Auger spectrum of aqueous-phase indole, quantitatively explaining all peaks through ab initio modeling. The efficient and accurate technique for modeling valence and core photoemission spectra involves the maximum-overlap method and the nonequilibrium polarizable-continuum model. A two-hole electron-population analysis quantitatively describes the Auger spectra. Core-electron binding energies for nitrogen and carbon highlight the specific interaction with a hydrogen-bonded water molecule at the N-H group and otherwise nonspecific solvent interactions.

Visible light driven hydrogen peroxide production by oxygen and phosphorus co-doped CoP-C3N4 photocatalyst

Photocatalytic hydrogen peroxide (H2O2) by oxygen and phosphorus co-doped graphitic carbon nitride (C3N4) with cobalt phosphate (CoP) cocatalyst is investigated. The photocatalyst powder of CoP-C3N4 1:n, n = 0–4, n is the weight ratio of cyanuric acid added) was synthesized by melamine cyanurate template method. Characterization of the catalyst was performed by X-ray diffraction analysis, and scanning electron microscopy, X-ray photoemission spectra, and fluorescence decay spectra. Oxygen doping was performed by the melamine and cyanuric acid template method, followed by phosphorus doping of the C3N4 backbone by the introduction of CoP. Co-doping of O and P atom facilitated charge transfer on the C3N4 backbone, while CoP facilitated charge separation at the C3N4 interface. The CoP-C3N4 (1:4) photocatalyst increased H2O2 production rate by 293 % compared to that of the cyanuric acid-free photocatalyst and also achieved the photocatalytic oxygen evolution from water. These results indicate that O,P co-doped CoP-C3N4 can perform sacrificial agent-free hydrogen peroxide under visible light irradiation.

Quantitative analysis of energy loss processes for the core level intensities in hard X-ray photoemission

Hard X-ray Photoemission spectra (HAXPES) for Al films on Si substrates were measured, and thickness dependence of the Al and Si core level spectra was obtained. A quantitative analysis of the plasmon-loss processes and the continuous background was performed. Such loss process can be quantitatively understood using a HAXPES analysis, especially for the intensity analysis of the core levels. Si 1 s electrons excite extrinsic Al plasmons and continuous loss features as far as they propagate within the Al film. The results give us important information and enable us to separate the intrinsic, extrinsic and their interference effects in plasmon-loss processes. Even for the high energy excitation inherent to HAXPES, the interference effect between intrinsic and extrinsic plasmon-losses is shown to be not negligible. A stronger contribution from loss features than from the main peaks should be considered for quantitative analysis.

Effects of Post-UV/Ozone Treatment on Electrical Characteristics of Solution-Processed Copper Oxide Thin-Film Transistors.

To realize oxide semiconductor-based complementary circuits and better transparent display applications, the electrical properties of p-type oxide semiconductors and the performance improvement of p-type oxide thin-film transistors (TFTs) are required. In this study, we report the effects of post-UV/ozone (O3) treatment on the structural and electrical characteristics of copper oxide (CuO) semiconductor films and the TFT performance. The CuO semiconductor films were fabricated using copper (II) acetate hydrate as a precursor material to solution processing and the UV/O3 treatment was performed as a post-treatment after the CuO film was fabricated. During the post-UV/O3 treatment for up to 13 min, the solution-processed CuO films exhibited no meaningful change in the surface morphology. On the other hand, analysis of the Raman and X-ray photoemission spectra of solution-processed CuO films revealed that the post-UV/O3 treatment induced compressive stress in the film and increased the composition concentration of Cu-O lattice bonding. In the post-UV/O3-treated CuO semiconductor layer, the Hall mobility increased significantly to approximately 280 cm2 V-1 s-1, and the conductivity increased to approximately 4.57 × 10-2 Ω-1 cm-1. Post-UV/O3-treated CuO TFTs also showed improved electrical properties compared to those of untreated CuO TFTs. The field-effect mobility of the post-UV/O3-treated CuO TFT increased to approximately 6.61 × 10-3 cm-2 V-1 s-1, and the on-off current ratio increased to approximately 3.51 × 103. These improvements in the electrical characteristics of CuO films and CuO TFTs can be understood through the suppression of weak bonding and structural defects between Cu and O bonds after post-UV/O3 treatment. The result demonstrates that the post-UV/O3 treatment can be a viable method to improve the performance of p-type oxide TFTs.

Real-space Green's function approach for intrinsic losses in x-ray spectra

Intrinsic inelastic losses in x-ray spectra originate from excitations in an interacting electron system due to a suddenly created core-hole. These losses characterize the features observed in x-ray photoemission spectra (XPS), as well Here we present a complementary {\it ab initio} real-space Green's function (RSGF) generalization of the Langreth cumulant in terms of the dynamically screened core-hole interaction $W_c(\omega)$ and the independent particle response function. We find that the cumulant kernel $\beta(\omega)$ is analogous to XAS, but with the transition operator replaced by the core-hole potential with monopole selection rules. The behavior reflects the analytic structure of the loss function, with peaks near the zeros of the dielectric function, consistent with delocalized quasi-boson excitations. The approach simplifies when $W_c(\omega)$ is localized and spherically symmetric. Illustrative results and comparisons are presented for the electron gas, sodium, and some early transition metal compounds.

Band offsets of ITO/amorphous GaO x heterojunction determined by x-ray photoemission spectra

The band offsets of heterojunctions formed between indium tin oxide (ITO) and amorphous gallium oxide (a-GaO x ) of different stoichiometric ratios were measured by x-ray photoelectron spectroscopy using the Kraut method. a-GaO x films with different stoichiometric ratios were deposited on commercial ITO/quartz substrates using radio frequency magnetron sputtering by varying the Ar/O2 flux ratio. With the increase of oxygen flux in the reaction gas, the oxygen vacancy (VO) concentration of a-GaO x decreases and its bandgap increases from 5.2 eV to 5.32 eV, while the valence band offset of ITO/a-GaO x heterojunction changes from 0.29 ± 0.07 eV to −0.74 ± 0.06 eV and conduction band offset changes from 0.95 ± 0.085 to 2.10 ± 0.075 eV. The results indicate that the band alignment of ITO/a-GaO x heterojunction can change from type I to type II with the variation of Ga/O stoichiometric ratio, which can provide guidance for the design of their corresponding high-performance heterostructured devices.

Carbon-induced magnetic properties and anomalous Hall effect in Co2Mn2C thin films with L10 -like structures

${\mathrm{Co}}_{2}{\mathrm{Mn}}_{2}\mathrm{C}$ thin films were synthesized via vacuum carburization of the host CoMn alloy films based on a conventional gas-solid reaction to demonstrate the effect of C, a common light element, on the magnetic and spintronic materials. The crystal structure transitioned from the disordered face-centered-cubic CoMn to the $L{1}_{0}$-like ${\mathrm{Co}}_{2}{\mathrm{Mn}}_{2}\mathrm{C}$, for which the lattice constant increased from 0.356 to 0.378 nm. The C $1s$ x-ray photoemission spectra of the ${\mathrm{Co}}_{2}{\mathrm{Mn}}_{2}\mathrm{C}$ film indicated hybridization in C-Co and C-Mn and a homogeneous concentration of C in the film. The enhancement of both the saturation magnetization and the anomalous Hall conductivity (${\ensuremath{\sigma}}_{xy}$) was induced by C, attributing to the magnetic transition to the ferrimagnetic spin order. The surface flatness and high ${\ensuremath{\sigma}}_{xy}$ are promising characteristics for spintronic applications such as the spin-anomalous Hall effect. The atom- and spin-resolved density of states (DOS) via first-principles calculations revealed that face-centered Mn(II) and Co could be significantly influenced by C because of p-d hybridization, resulting in enhanced spin polarization of the DOS at the Fermi level of \ensuremath{\sim}0.82. These results demonstrate that the use of C could be an essential way to boost material properties in the future.

Weyl–Kondo semimetal behavior in the chiral structure phase of Ce3Rh4Sn13

The spin dynamics, crystalline-electric-field (CEF) level scheme, specific heat, and x-ray photoemission spectra (XPS) of ${\mathrm{Ce}}_{3}{\mathrm{Rh}}_{4}{\mathrm{Sn}}_{13}$ were investigated, which exhibits anomalous semimetal transport in the chiral crystallographic phase. CEF excitations observed at approximately 7 and 39 meV are consistent with the two inequivalent Ce-ion cites in the chiral structure. Because of broader CEF excitations and a strong $4{f}^{1}$ peak at the Fermi level in the Ce $4f$ on-resonance spectrum, the hybridized Ce $4f$ electrons contribute to the semimetal carriers. In addition, the spin fluctuation associated with the Kramers doublet ground state is characterized by the peak located at 0.15 meV. The electronic state involving the spin fluctuation causes the ${T}^{3}$ behavior of specific heat below 0.6 K, which is attributed to linear dispersion relations of electrons of the Weyl--Kondo semimetal in the chiral-lattice symmetry.

Coordination Chemistry of Uranyl Ions with Surface-Immobilized Peptides: An XPS Study.

The coordination chemistry of uranyl ions with surface immobilized peptides was studied using X-ray photoemission spectroscopy (XPS). All the peptides in the study were modified using a six-carbon alkanethiol as a linker on a gold substrate with methylene blue as the redox label. The X-ray photoemission spectra reveal that each modified peptide interacts differently with the uranyl ion. For all the modified peptides, the XPS spectra were taken in both the absence and presence of the uranium, and their comparison reveals that the interaction depends on the chemical group present in the peptides. The XPS results show that, among all the modified peptides in the current study, the (arginine)9 (R9) modified peptide showed the largest response to uranium. In the order of response to uranium, the second largest response was shown by the modified (arginine)6 (R6) peptide followed by the modified (lysine)6 (K6) peptide. Other modified peptides, (alanine)6 (A6), (glutamic acid)6 (E6) and (serine)6 (S6), did not show any response to uranium.

Investigation of lattice dynamics, magnetism, and electronic transport in β−Na0.33V2O5

We investigate the electronic and magnetic properties as well as lattice dynamics and spin-phonon coupling of $\beta$-Na$_{0.33}$V$_2$O$_5$ using temperature-dependent Raman scattering, dc-magnetization and dc-resistivity, x-ray photoemission, and absorption spectroscopy. The Rietveld refinement of XRD pattern with space group C2/m confirms the monoclinic structure. The analysis of temperature-dependent Raman spectra in a temperature range of 13--673~K reveals an anharmonic dependence of the phonon frequency and full width at half maximum, which is accredited to the symmetric phonon decay. However, below about 40 K, the hardening of the phonon frequency beyond anharmonicity is attributed to the spin-phonon coupling. Interestingly, the estimated effective magnetic moment $\mu_{\rm eff}=$ 0.63~$\mu_B$ from the magnetization data manifests a mixed-valence state of V ions in 4+ (18$\pm$1\%) and 5+ (82$\pm$1\%). A similar ratio of V$^{4+}$ to V$^{5+}$ is also observed in the x-ray photoemission and x-ray absorption near-edge spectra and that is found to be consistent with the sample stoichiometry. In addition, the V$^{4+}$ ions are distributed between different vanadium (V1 and V3) sites. The analysis of extended x-ray absorption fine structure at different V-sites gives the corresponding V--O bond lengths, which are utilized in the assignment of Raman modes. Moreover, the temperature-dependent resistivity resembles a semiconducting behavior where the charge carrier transport is facilitated by the band conduction at higher temperatures and via hopping $\le$260~K.

Charge-transfer effect in Fe 2p core-level x-ray photoemission spectra of trivalent Fe oxides: LDA + DMFT study

Motivated by recent hard x-ray photoemission spectroscopy (XPS) experiment for trivalent Fe oxides Sr2FeMoO6 (ferrimagnetic correlated metal) and LaFeO3 (antiferromagnetic Mott insulator) (Phuyal et al 2021 J. Phys. Chem. C 125 11249–56), we present a theoretical analysis of the Fe 2p core-level spectra using a computational method based on local density approximation combined with dynamical mean-field theory. We find that a nonlocal screening (NLS) effect in the XPS final states is crucial for interpreting the experimental XPS result of both the Fe oxides. A close relationship between the NLS feature in core-level spectra and a long-range magnetic ordering is emphasized.

Basis Set Selection for Molecular Core-Level GW Calculations.

The GW approximation has been recently gaining popularity among the methods for simulating molecular core-level X-ray photoemission spectra. Traditionally, Gaussian-type orbital GW core-level binding energies have been computed using either the cc-pVnZ or def2-nZVP basis set families, extrapolating the obtained results to the complete basis set limit, followed by an element-specific relativistic correction. Despite achieving rather good accuracy, it has been previously stated that these binding energies are chronically underestimated. In the present work, we show that those previous studies obtained results that were not well-converged with respect to the basis set size and that, once basis set convergence is achieved, there seems to be no such underestimation. Standard techniques known to offer a good cost-accuracy ratio in other theories demonstrate that the cc-pVnZ and def2-nZVP families exhibit contraction errors and might lead to unreliable complete basis set extrapolations for absolute binding energies, often deviating about 200-500 meV from the putative basis set limit found in this work. On the other hand, uncontracted versions of these basis sets offer vastly improved convergence. Even faster convergence can be obtained using core-rich property-optimized basis set families like pcSseg-n, pcJ-n, and ccX-nZ. Finally, we also show that the improvement observed for core properties using these specialized basis sets does not degrade their description of valence excitations: vertical ionization potentials and electron affinities computed with these basis sets converge as fast as the ones obtained with the aug-cc-pVnZ family, thus offering a balanced description of both core and valence regions.

A new polyoxometalate-based silver-organic framework as environmental-friendly catalyst for solvent-free cyanosilylation of aldehydes

A new polyoxometalate-based silver-organic framework Ag4(imbta)4(PWVWVI11O40) (1) (imbta=1-imidazol-1-ylmethyl-1H-benzotriazole) was synthesized as heterogeneous catalysts for cyanosilylation, and characterized by infrared spectroscopy, elemental analysis, single-crystal X-ray diffraction and X-ray photoemission spectra. The results of single crystal X-ray indicate that in compound 1, Ag ions, imbta ligands and PW12O403- construct a 2D layers by covalent bonds. The adjacent 2D layers are further connected together through numerous π‧‧‧π interactions and C–H‧‧‧O hydrogen bonding interactions to achieve a 3D supramolecular architecture. More importantly, compound 1 is able to act as a highly efficient heterogeneous Lewis acid-base catalyst for cyanosilylation of various aldehydes at room temperature under solvent-free condition. The conversion of anisaldehyde to the product of cyanohydrin trimethylsilyl ether reaches up to 99.9% within 4 h by catalyzing of compound 1. Also, it is observed that there is no obvious decrease of catalytic activity after three cycles. Therefore, the compound 1 has significant potential as environmental-friendly catalyst for widely practical application in cyanosilylation reactions.