A multinuclear solid state NMR study of the sol-gel formation of amorphous Nb2O5-SiO2 materials

Multinuclear 1H, 13C, 17O, 29Si MAS and 93Nb static NMR is reported from a series of sol-gel prepared (Nb2O5)x(SiO2)(1-x) materials with x=0.03, 0.075 or 0.30. 13C NMR shows that by 500 degrees C the organic precursor fragments have been removed although some residual carbon remains as a separate phase. The 29Si NMR typically shows three Q-species (Q2,3,4) in the initial gels, and that with increasing heat treatment the average n of the Qn-species increases as the organic fragments and hydroxyl groups are removed. 17O shows unequivocally that the x=0.03 and 0.075 samples are not phase separated, while at the much higher niobia-content of x=0.30 Nb-O-Nb signals are readily detected, a definite indication of the atomic scale phase separation of Nb2O5. The x=0.03 and 0.075 samples heated to 750 degrees C are thus representative of amorphous niobium silicates. Comparison is made to other sol-gel prepared metal silicates especially with another Group Va metal tantalum. The effects of tantalum and niobium on the silica network are very different and it is suggested here that most of the niobium is present as NbO4, forming part of the silicate network.     

The effects of different heat treatment and atmospheres on the NMR signal and structure of TiO2-ZrO2-SiO2 sol-gel materials

The effects of different heat treatment schemes (i.e. successively or directly heated to particular temperatures) and atmospheres (air or nitrogen) on the solid-state NMR spectra obtained from (TiO(2))(0.15)(ZrO(2))(0.05)(SiO(2))(0.80) sol-gel materials are investigated. A combination of 1H, 13C, 17O and 29Si NMR is used. 29Si MAS NMR indicates that the extent of condensation of the silica-based network strongly depends on the maximum temperature the sample has experienced, but the condensation is largely independent of the details of the heat treatment scheme and atmosphere used. For sol-gel produced silicate-based materials the results show that the equilibrium structure at each temperature is reached rapidly compared to the time (2h) spent at that temperature. The 17O NMR results confirm that a nitrogen atmosphere does significantly reduce loss of 17O from the structure but care must be taken since there could be differential loss of 17O from the regions having different local structural characteristics.     

The (29)Si T(1) and T(2) NMR relaxation in porous paramagnetic material SiO(2)-MnO-Al(2)O(3)

The (29)Si spin-lattice relaxation in porous silica-based material 1, doped by ions Mn(2+) at a Si/Mn ratio of 3.5, is non-exponential, independent of magic-angle spinning (MAS) rates and governed by direct dipolar coupling between electron and nucleus where an electron relaxation time is estimated to be about 10(-8)s. In the absence of mutual energy-conserving spin flips (spin diffusion) in 1, the (29)Si T(2) time increases linearly with spinning rates. None was observed in diamagnetic porous system 2. The unexpected (29)Si T(2) dependence has been interpreted in terms of the large bulk magnetic susceptibility (BMS) effects. It has been shown that editing the (29)Si Hahn-echo MAS NMR spectra eliminates wide lines, belonging to (29)Si nuclei in the proximity of paramagnetic centers, and reduces the BMS broadenings in sideband patterns for nuclei remote from these centers.     

17O NMR studies of a triangular-lattice superconductor NaxCoO2 x yH(2)O

We report the first 17O NMR studies of a triangular-lattice superconductor Na(1/3)CoO2 x 4/3H(2)O and the host material Na(x)CoO2 (x=0.35 and 0.72). Knight shift measurements reveal that p-d hybridization induces sizable spin polarization in the O triangular-lattice layers. Water intercalation makes CoO2 planes homogeneous and enhances low frequency spin fluctuations near T(c)=4.5 K at some finite wave vectors different from both the ferromagnetic and "120 degree" modes.     

Characterization of silicon sites in monoclinic zeolite ZSM-5 using 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) and molecular modelling

An attempt has been made to correlate the experimentally observed 29Si MAS NMR chemical shifts of monoclinic phase of highly siliceous ZSM-5 with their electronic properties. In order to incorporate the influence of next neighbor atoms on the 29Si chemical shielding of central SiO4, a pentameric cluster model (H12Si5O16) has been chosen. Each of the 24 crystallographically distinct Si sites, of ZSM-5 framework has been modelled by such cluster models. Based on semi-empirical quantum chemical calculations, a multiple linear regression analysis of the various electronic properties with the 29Si chemical shifts has been attempted. The relative difference in 29Si chemical shifts for the Si sites in ZSM-5 is reasonably accounted, although quantitative prediction may require non-empirical quantum chemical calculations.     

Origin of O 1s core-level shifts on oxygen adsorbed Si(111)-(7x7)

Density functional calculations are used to examine the chemical and structural origin of O 1s core-level shifts measured on the initial oxidation stage of Si(111)-(7x7). Our analysis of metastable core-level peaks leads to a conclusive identification of the long-sought metastable oxidation species as a tetrahedral SiO4 unit, formed by two successive O2 adsorptions on a Si adatom. The origin of a higher-binding core-level shoulder is clarified by the presence of a threefold-coordinated subsurface O atom, introduced as a decay product of the metastable SiO4 unit. The present study provides a detailed atomic-scale picture of the initial oxidation process of Si(111)-(7x7).     

Anomalous behavior of the dielectric constant of hafnium silicates: a first principles study

We present an extensive ab initio study of the structural and dielectric properties of hafnium silicates Hf(x)Si(1-x)O(2) that accounts for the observed anomalous dependence on composition of the static dielectric constant in the entire x range. The results reveal that this complex behavior reflects that of the structural development with x, from silica to hafnia, and clarify how different growth processes can also lead to scattered sets of data. Several simple models proposed thus far to explain part of the experimental data are shown to be inadequate. It is argued that silicate layers with low hafnium content form at the HfO(2)/Si interface and play a crucial role in preserving high electron mobility in the channel.     

Thermal decomposition of an ultrathin Si oxide layer around a Si(001)-(2 x 1) window

We examine the thermal decomposition of an ultrathin Si oxide layer around a Si(001)-(2 x 1) window opened by electron-beam-induced selective thermal decomposition. The decomposition progresses at the oxide/Si(001)-(2 x 1) boundary and follows two rate-limiting steps with activation energies of 4.0 and 1.7 eV. We propose that the former and latter energies correspond to the reaction of Si monomer with the oxide and the desorption of the SiO into the vacuum, respectively.     

New opportunities for high-resolution solid-state NMR spectroscopy of oxide materials at 21.1- and 18.8-T fields

We present here high-resolution solid state NMR spectra of several oxide and silicate materials that illustrate the improvements obtainable with very high external fields (18.8 and 21.1 T), with probes capable of tuning to a wide frequency range that allow observations of nuclides from high to low magnetogyric ratio. We discuss 27Al MAS spectra for the zeolite scolecite (CaAl2Si3O10 x 3H2O), 17O MAS data for analcime (NaAlSi2O6 x H2O), calcium monoaluminate (CaAI2O4), and titanite (CaTiSiO5), 39K spin-echo spectra for leucite (KAlSi2O6), microline (KAlSiO8), muscovite (KAl2(AlSi3O10)(OH2) and a potassium aluminosolicate glass, and preliminary 73Ge spin-echo MAS spectra for crystalline and glassy germanium dioxide (GeO2).     

Solid-state NMR characterisation of the thermal transformation of a Hungarian white illite

(1)H, (27)Al, (29)Si and (39)K solid-state NMR are reported from a Hungarian illite 2:1 clay for samples heated up 1600 degrees C. This single-phase sample has a small amount of aluminium substitution in the silica layer and very low iron-content ( approximately 0.4wt%). Thermal analysis shows several events that can be related to features in the NMR spectra, and hence changes in the atomic scale structure. As dehydroxylation occurs there is increasing AlO(4) and AlO(5)-contents. The silica and gibbsite layers become increasingly separated as the dehydroxylation progresses. Between 900 and 1000 degrees C the silica layer forms a potassium aluminosilicate glass. The gibbsite-layer forms spinel/gamma-Al(2)O(3) and some aluminium-rich mullite. Then on heating to 1600 degrees C changes in the (29)Si and (27)Al MAS NMR spectra are consistent with the aluminosilicate glass increasing its aluminium-content, the amount of mullite increasing probably with its silicon-content also increasing, and some alpha-Al(2)O(3) forming.     

X-[1H, 19F] triple resonance with a X-[1H] CP MAS probe and characterisation of a 29Si-19F spin pair

An economic approach for implementing X-[1H,19F] double-decoupling MAS NMR experiments with a conventional X-[1H] dual-channel CP MAS probe is demonstrated. The parameters characterising the isolated 29Si-19F spin pair in an organosilicon compound R(3)SiF (R = 9-anthryl) are determined. In addition, we discuss the optimum choice of experimental parameters for determining all 29Si-19F spin-pair parameters from straightforward 29Si MAS NMR spectra with only 1H decoupling applied during acquisition.     

Multinuclear (27Al, 29Si, 47,49Ti) solid-state NMR of titanium substituted zeolite USY

Multinuclear solid-state NMR spectroscopy, employing 29Si MAS,27Al MAS/3Q-MAS and (47,49)Ti wide-line experiments, has been used for the structural characterization of titanium substituted ultra-stable zeolite Y (Ti-USY). 27Al MAS experiments show the presence of aluminum in four (Al(IV)), five (Al(V)), and six (Al(VI)) coordination, whereas the multiplicity within Al(IV) and Al(VI) is revealed by 27Al 3Q-MAS experiments. Two different tetrahedral and octahedral Al environments are resolved and their isotropic chemical shifts (delta(CS)) and second-order quadrupole interaction parameters (P(Q)) have been determined by a graphical analysis of the 3Q-MAS spectra. The emergence of signal with higher intensity at -101 ppm in the 29Si MAS spectrum of Ti-USY samples indicates the possible occurrence of Q4(3Si,1Ti) type silicon environments due to titanium substitution in the faujasite framework. High-field (11.74T) operation, using a probehead specially designed to handle a large sample volume, has enabled the acquisition of 47,49Ti static spectra and identification of the titanium environment in the zeolite. The chemical shielding and electric field gradient tensors for the titanium environment in the zeolite have been determined by a computer simulation of the quadrupolar broadened static 47,49Ti NMR spectra.     

A Crystallographic and Mössbauer Spectroscopic Study of BaCo0.5x Zn0.5x Ti x Fe12−2x O19 (M-Type Hexagonal Ferrite)

Hyperfine Interactions - A series of pure polycrystalline M-type hexagonal ferrite with the formula BaCo0.5x Zn0.5x Ti x Fe12?2x O19 (x=0.0, 0.4, 0.8, 1.2, 1.6, 2.0) has been synthesized and...     

Structural investigations of the Yb  Si(111) - 2x1, 5x1 and 3x1 overlayers

The YbSi interface has been investigated in the sub-monolayer regime employing Ion Scattering Spectroscopy (ISS), Auger Electron Spectroscopy (AES) and Low Energy Electron Diffraction (LEED). Three different structures, YbSi(111) 2x1, YbSi(111) 5x1, and YbSi(111) 3x1, have been established by heat treatments of the interfaces. The structures consist of a stable overlayer of Yb atoms on the Si(111) surfaces. The distance of the Yb atoms to the uppermost layer of Si atoms has been estimated by comparing the YbSi ISS intensity ratio with the predictions of a model based on classical scattering theory and a Thomas-Fermi-Moliére potential. The height of the Yb atoms relative to the substrate toplayer was found to be 1.9 ± 0.3→.     

Solid-state NMR characterization of a controlled-pore glass and of the effects of electron irradiation

Controlled-pore glasses (CPGs) are silica-based materials which provide an adequate model system for a better understanding of the radiation chemistry of glasses, especially under nanoscopic confinement. This paper presents a characterization of a nanoporous CPG before and after electron irradiation using multinuclear solid-state magnetic resonance (NMR). 1H MAS NMR has been used for studying the surface proton sites and it is observed that the irradiation leads to a dehydration of the material. Accordingly, concerning the silicon sites near the surface, the observed variation of the Q4, Q3 and Q2 species from 1H-29Si CPMAS spectra shows an increase of the surface polymerization under irradiation, implying in majority a Q2 to Q3/Q4 conversion mechanism. Similarly, 1H-17 O CPMAS measurements exhibit an increase of Si-O-Si groups at the expenses of Si-OH groups. In addition, modifications of the environment of the residual boron atoms are also put in evidence from 11B MAS and MQMAS NMR These data show that MAS NMR methods provide sensitive tools for the characterization of these porous glasses and of the tiny modifications occurring under electron irradiation.     

<Superscript>29</Superscript>Si, <Superscript>27</Superscript>Al, <Superscript>1</Superscript>H and <Superscript>23</Superscript>Na MAS NMR Study of the Bonding Character in Aluminosilicate Inorganic Polymers

²⁹Si, ²⁷Al, ¹H and ²³Na solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to relate nominal composition, bonding character and compressive strength properties in aluminosilicate inorganic polymers (AIPs). The ²⁹Si chemical shift varies systematically with Si-to-Al ratio, indicating that the immediate structural environment of Si is altering with nominal composition. Fast ¹H MAS and ²⁹Si T _SiH/T _1ρ relaxation measurements demonstrated that occluded pore H₂O mobility within the disordered cavities is slow in comparison with H₂O mobility characteristics observed within the ordered channel structures of zeolites. The ²⁷Al MAS NMR data show that the Al coordination remains predominantly 4-coordinate. In comparison with the ²⁹Si MAS data, the corresponding ²⁷Al MAS line shapes are relatively narrow, suggesting that the AlO₄ tetrahedral geometry is largely unperturbed and the dominant source of structural disorder is propagated by large distributions of Si–O bond angles and bond lengths. Corresponding ²³Na MAS and multiple-quantum MAS NMR data indicate that Na speciation is dominated by distributions of hydration states; however, more highly resolved ²³Na resonances observed in some preparations supported the existence of short-range order. New structural elements are proposed to account for the existence of these Na resonances and an improved model for the structure of AIPs has also been proposed. Authors' address: John V. Hanna, NMR Facility, Institute of Materials and Engineering Science, Lucas Heights Research Laboratories, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Australia     

双掺杂铁基1111型超导体Nd1-xBaxFeAsO1-2xF2x的磁传输性能研究

采用两步固相反应法,在母相FeAs=1111结构的NdFeAsO中掺入BaF2,实现电子与空穴的双掺杂．该体系超导转变温度（Tc）在33-50K范围,取决于名义BaF2掺杂量x．在实验范围内,掺杂量越大,转变温度越高,当x=0．2时,Tc达到50K．磁电阻测量表明：高掺杂量样品（例如x=0．2）具有较高的上临界场（Hc...     

Microstructure evolution and passivation quality of hydrogenated amorphous silicon oxide(a-SiOx:H) on〈100〉- and 〈111〉-orientated c-Si wafers

Hydrogenated amorphous silicon oxide(a-SiOx:H) is an attractive passivation material to suppress epitaxial growth and reduce the parasitic absorption loss in silicon heterojunction(SHJ) solar cells. In this paper, a-SiOx:H layers on different orientated c-Si substrates are fabricated. An optimal effective lifetime(τ(eff)) of 4743 μs and corresponding implied opencircuit voltage(iV(oc)) of 724 mV are obtained on〈100〉-orientated c-Si wafers. While τ(eff) of 2429 μs and iV_oc of 699 mV are achieved on 111-orientated substrate. The FTIR and XPS results indicate that the a-SiOx:H network consists of SiOx(Si-rich), Si–OH, Si–O–SiHx, SiO2 ≡ Si–Si, and O3 ≡ Si–Si. A passivation evolution mechanism is proposed to explain the different passivation results on different c-Si wafers. By modulating the a-SiOx:H layer, the planar silicon heterojunction solar cell can achieve an efficiency of 18.15%.     

Sr3SiO5:Eu2+材料光谱特性研究

采用高温固相法制备了用于白光LED的Sr3SiO5:Eu2+材料.研究了合成温度及Sr/Si对样品光谱特性及结构的影响.结果显示,随合成温度的升高或Sr/Si的减小,样品的主发射峰均产生了明显的红移,同时,样品的晶体结构也受到了影响.利用InGaN管芯激发Sr3SiO5:Eu2+材料,表现出显色性较好的白光发射光谱,色坐标为(x=0.348,y=0.326).     

27Al multiple-quantum MAS NMR of mechanically treated bayerite (alpha-Al(OH)3) and silica mixtures

Two-dimensional 27Al multiple-quantum magic angle spinning (MQMAS) NMR experiments are used to study mixtures of bayerite (alpha-Al(OH)3) with either silicic acid (SiO2.nH2O) or silica gel (SiO2) that have been ground together for varying lengths of time. This mechanical treatment produces changes in the 27Al MAS and MQMAS NMR spectra that correspond to the formation of new Al species. Mean values of the quadrupolar interaction (PQ) and isotropic chemical shift (deltacs) are extracted from the two-dimensional 27Al NMR spectra for each of these species. The presence of significant distributions of both 27Al quadrupolar and chemical shift parameters is demonstrated and the effect of grinding duration on the magnitudes of these distributions is discussed.