Effect of codoping with C or N on electronic structures and magnetic properties of ZnO:Cu

Using first-principles calculations based on density functional theory, we investigated systematically the electronic structures and magnetic properties of ZnO:Cu. The results indicate that Cu-doped ZnO prefers a ferromagnetic ground state and behaves like a half-metallic ferromagnet. The magnetic moment mainly localizes at Cu atom and the rest mainly comes from the spin polarized O atoms. It has been found that the ferromagnetic stability can be enhanced slightly by substituting an oxygen atom with one N atom; while the ferromagnetic stability can be weakened by replacing one O atom with a C atom. Due to absence of magnetic ion and the 100% spin polarization of the carriers in ZnO:Cu, one can expect that Cu-doped ZnO would be a useful half-metallic ferromagnet both in practical application and in theoretical studies.     

Transformation of As-Grown Phosphorus-Related Centers in HPHT Treated Synthetic Diamonds

This communication presents new data on phosphorus-containing centers in synthetic diamonds grown in the P–C system by high-pressure high-temperature (HTHP) method and annealed in the temperature range of 2,073–2,573 K. The electron paramagnetic resonance (EPR) study has shown that as-grown at 1,873 K diamonds contain single substitutional nitrogen (P1) and single substitutional phosphorus (MA1) centers. The main part of the spin density in the MA1 center locates on the carbon atom C₁ separated from phosphorus by one carbon atom. HPHT annealing (7 GPa, 2,073–2,273 K) results in aggregating substitutional nitrogen and phosphorus atoms. On the first step of annealing (2,073 K) of as-grown diamonds nitrogen–phosphorus NIRIM8 (NP1) centers are created. It is supposed that nitrogen and phosphorus atoms in this center are separated by two carbons. Further temperature increasing shifts the nitrogen atom toward phosphorus and creates two new nitrogen–phosphorus centers NP2 and NP3 with the supposed structures C₁–N–C–P and N–P–C₁, respectively. The main part of the spin density in MA1, NIRIM8 (NP1), NP2 and NP3 is located on the carbon atom C₁. Annealing these samples in the temperature range of 2,073–2,273 K has shown vanishing of NIRIM8 and increasing of NP2 and NP3 centers. HPHT annealing of diamonds at 2,573 K significantly changes the electron paramagnetic resonance (EPR) spectra: all previous nitrogen–phosphorus centers disappear and two new phosphorus centers NP4 and NP5 are created. Features of these centers are g ≈ 2.001 and high spin density located on the phosphorus atoms. The NP5 center is sensitive to X-ray irradiation and low-temperature annealing. The EPR spectra of both these centers are due to the hyperfine structure of one phosphorus atom. The structures of all phosphorus-containing centers are discussed.     

Spin filtering and large magnetoresistance behaviors in carbon chain-zigzag graphene nanoribbon nanojunctions

Using the non-equilibrium Green's function method combined with the density functional theory, we investigate the electron and spin transport properties of carbon chains covalently connected with zigzag-edged graphene electrodes at finite bias with the parallel (P) and antiparallel (AP) magnetism configurations. When two zigzag-edged graphene electrodes are H2–ZGNR–H structures, spin filtering effect can be realized only with AP magnetism configuration. While one electrode is replaced with the H–ZGNR–H structure, we observe a dual spin filtering effect with above two magnetism configurations. But the spin transport properties of carbon chains can also be affected by the linking way of the carbon chain ends. Deeper analyses show that the spin-related properties are related to the electrodes, magnetism configurations, and the connection structure between electrodes and carbon chains.     

Spin transport in bimetallic pentalene complexes

Spin transport in bimetallic pentalene complexes (CpM(pentalene)M′Cp;M,M′=Fe,Co,Ni) between two gold electrodes was investigated, using a Green’s function formalism under density functional theory. Variation of the metal atom species in the complexes gives a considerable change in their spin properties, with hetero-bimetallic complexes containing an odd number of electrons exhibiting spin filter behaviour. In contrast, alternation in the contact condition, whether Cp-anchoring or adducting by sulphur-gold bonds, had almost no effect on spin filter behaviour, but did lead to variation in electrical conduction. We examined suitable bimetallic pentalene complexes in order to enhance their spin filter efficiency.     

Stability and Growth Modes of Ni--C Clusters: A Study based on All-Electron Density Function Theory

Growth modes of the free-standing NiCN （N ≤ 8） and Ni2CN （N ≤ 8） dusters are investigated by the allelectron density functional theory. The results reveal that there are two competing modes for the growth of these clusters： the linear chain and the ring structure without transannular bonds. The lowest-energy geometries of NiCN （N ≤ 8） are the linear chains with the Ni atom at one end, except for NiC2 and NiCT. The Ni2CN （N ≤ 8） clusters all prefer to the linear chains with the two Ni atoms at the two ends. Miilliken population analysis indicates that the total spin of the lowest-energy cluster show significant odd-even alternation. The NiMCN （M = 1,2） clusters with the even N are one and those with the odd-N are zero.     

Structural and electronic properties of endohedral phosphorus fullerene P@C60: an off-centre displacement of P inside the cage

Single P-doped endohedral P@C₆₀ is investigated via semiempirical and first-principles calculations. Unlike the encased N atom, which is situated on the centre of the C₆₀ cage and not covalently bound to the carbon atoms of the fullerene cage, static geometric optimization shows that the encased P atom occupies an off-centre position and is bound to the carbon atoms of the fullerene cage. The electronic ground state of the doped system is the spin quarter state, with spin density distribution significantly compressed by the cage.     

Influence of Interface Structure of Co/Cu （100） Superlattices on Electronic Structure and Giant Magnetoresistance

Electronic structures and magnetoresistance （MR） of Co3 Cu5 and Co3 Cur models as well as their interface atom exchange models Co2 CuCoCu4 and Co2 CuCoCu6 are investigated by the tlrst-principles pseudopotential planewave method based on density functional theory. Charge transfer, magnetic moment, density of states, spin asymmetry factor, and MR ratio are discussed. The results show that the values of charge transfer and spin asymmetry factor at the Fermi level of Co layers are closely related to the neighbouring background of the Co layer. The Co layer with two sides adjacent to the Cu layer would transfer more charge to the Cu layer than other neighbouring background and have the largest spin asymmetry factor at the Fermi level. The Co layer with two neighbouring Co layers （interior Co） would gain a little charge and have the smallest spin asymmetry factor at the Fermi level. Two-current model is used to evaluate the MR ratio of Co2CuCoCu4 （Co2CuCoCu6） to be larger than that of Co3 Cu5 （Co3 CUT）, which can be explained by the charge transfer and spin asymmetry factor.     

Structural stability and electronic properties of Ni-doped armchair graphene nanoribbons

The size dependent electronic properties of armchair graphene nanoribbons (AGNR) with Ni doped atoms have been investigated using spin-unrestricted density functional theory. We predict antiferromagnetic (AFM) ground states for Ni-termination and one edge Ni-doping. The computed formation energy reveals that one edge Ni-terminated AGNR are energetically more favourable as compared to pristine ribbons. One edge substitutional doping is energetically more favourable as compared to centre doping by ∼1 eV whereas both edge doping is unfavourable. The bond length of substitutional Ni atoms is shorter than that of Ni adsorption in GNR, implying a stronger binding for substitutional Ni atoms. It is evident that binding energy is also affected by the coordination number of the foreign atom. The results show that Ni-interaction perturbs the electronic structure of the ribbons significantly, causing enhanced metallicity for all configurations irrespective of doping site. The band structures reveal the separation of spin up and down electronic states indicating towards the existence of spin polarized current in Ni-terminated and one edge doped ribbons. Our calculation predicts that AGNR containing Ni impurities can play an important role for the fabrication of spin filters and spintronic devices.     

Spatially separated spin carriers in three-ports graphene nanoribbons

Exporting the different spin signals to different ports is of practical importance to graphene-based spintronic devices. In this work, we have designed a three-ports graphene nanoribbon (GNR) device by inserting square-shaped carbon tetragon (CT) into GNR symmetrically, and calculated the magnetic moment distribution and transmission spectrum by using first-principles calculation and quantum transport simulation. Our results show that CT can bring non-equivalent path for two spin transport channels resulting in one spin is easier to transport than the other in each output port. Overall whole model, the spin states would be separated in real space but degenerated in energy. After correcting the device with asymmetric edge hydrogenation, we can achieve spatially separated spin carriers in real space and stable spin transporting. Our results suggest this model can serve as the most basic logic device for applying in future spintronics.     

Adsorption of carbon monoxide on Si x Ge4– x (x = 0–4) nano-clusters: a hybrid meta density functional study

Theoretical study of carbon monoxide adsorption on Si _x Ge_{4 ? x} (x = 0–4) nano-clusters has been carried out using advanced hybrid meta density functional method of Truhlar (MPW1B95). MG3 semi-diffuse (MG3S) and correlation consistent valence basis sets with relativistic core potential were employed to improve the results. The agreement of the calculated ionization and dissociation energies with experimental values validates the reported structures of nano-clusters and justifies the use of hybrid meta density functional method. The geometry, adsorption energy, charge distribution, and vibrational frequency of CO adsorption on all possible structures were investigated. The maximum vibrational frequency changes occur in the bridge structures while the most stable structures occur when CO adsorbs on one silicon atom in a flat surface. The changes of spin densities arising through bridged structures with higher spin multiplicities were rationalized. Adsorption energies of CO on one Si atom are by far more negative than the corresponding value for on Ge atom, at the highest being nearly ?77 and ?35 kJ mol^?1. Comparison was made of adsorbed CO bridging neighbouring and diagonal Si atoms and the former was more stable, having adsorption energy of nearly ?77 kJ mol^?1. Flat surfaces adsorb CO more favourably. Exhaustive vibrational frequency analyses were performed to confirm the local minima energy of all optimized structures.     

Density functional theory study of the electronic and field emission properties of nitrogen- and boron-doped carbon nanocones

Using first-principles density functional theory, we have investigated the electronic and field emission properties of carbon nanocones (CNCs) doped with N or B with 60° disclination. Our findings are that the emission properties for the doped CNCs depend on the doping species, position, and concentration. Compared to pristine CNC, N-doped CNCs exhibit better field emission properties, in which as the doping concentration increases from 1.25% to 2.5% the maximum emission current at applied electric field of 0.3 V/Å increases from 0.94 μA (one N atom is doped at the position adjacent to the pentagon) to 2.90 μA (two N atoms are doped at pentagon). As for pristine CNC the emission current is only 0.21 μA. However, B-doping has no significant influence on the emission properties of CNCs. Our findings suggest that N-doped CNCs can be used as a candidate for cold-emission electron sources.     

E.S.R. of sulphur-substituted purines and nucleosides; carbon-centred radicals in mercaptopurine crystals at 77 K

Single crystals of the sulphur-containing DNA-base analogue 6-methylmercaptopurine (6MeMP) and its riboside 6-methylmercaptopurine riboside (6MeMPR) have been prepared and irradiated by 4·0 MeV electrons at 77 K. Electron spin resonance techniques have been used to study the radiation-induced radicals at 77 K. The primary carbon-centred radical, common to both molecules, has been identified as a species formed by hydrogen atom abstraction from the methyl group. The principal values of the two α-proton hyperfine coupling tensors and the g-tensors were almost the same for both molecules and for 6MeMPR were: α1, -28·8, -17·9 and -6·4 G; α2, -28·2, -15·7 and -9·8 G; and g, 2·0063, 2·0024 and 2·0018. These data indicate a spin density of 0·77 on the methyl carbon atom. Molecular orbitals determined from CNDO/2 methods were used in calculations of the directions and magnitude of the g-tensor principal values. Comparison of these calculated values and experimental data suggests that contribution of spin density in d-orbitals on the sulphur atom is important in describing the g-tensor. Methyl H-abstraction radicals trapped in pairs were also detected in 6MeMP and the data are consistent with an effective interspin distance of 4·67 Å.     

密度泛函方法研究NiSin(n=1~13)团簇

基于第一性原理,利用密度泛函理论中的广义梯度近似(GGA)系统研究了NiSin(n=1～13)团簇,在充分考虑自旋多重度的基础上讨论了这些团簇的生长行为,电子性质及其磁性,结果表明:NiSin 1的基态结构是在NiSin的基态结构上带帽一个Si原子而得到;随着团簇尺寸的增大,Ni原子逐渐从吸附在sin团簇的表面位置移动到Sin团簇笼内;掺杂Ni原子提高了硅团簇的稳定性;NiSi10团簇的稳定性在所有团簇中是最高的;电子总是从si向Ni转移,Ni原子所带的电荷数不仅与Ni原子的配位数有关,还与Nisin团簇的基态结构密切相关;n=1～2时,团簇的自旋总磁矩为2 μB,当n≥3时,团簇的磁性消失,这可能与Ni原子内部较强的sp-d杂化以及si原子内部的s-p杂化有关.     

The study of optical properties of amorphous thin films of mixed oxides In<Subscript>2</Subscript>O<Subscript>3</Subscript>—SnO<Subscript>2</Subscript> system,deposited by co-evaporation

A discussion of optical properties of mixed oxides In₂O₃—SnO₂ system is presented. Film thickness, substrate temperature, composition (in molar %) and annealing have a profound effect on the structure and optical properties of these films. Initially the increase in band gap with the increase of SnO₂ content in In₂O₃ is due to the increase in carrier density as a result of donor electrons from tin. The decrease in band gap above the critical Sn content is caused by the defects formed by Sn atoms, which act as carrier traps rather than electron donors. The increase in band gap with film thickness is caused by the increase in free carrier density which is generated by (i) Sn atom substitution of In atom, giving out one extra electron and (ii) oxygen vacancy acting as two electrons donor. The decrease in band gap with substrate temperature and annealing is due either to the severe deficiency of oxygen, which deteriorate the film properties and reduce the mobility of the carriers, or to the formation of indium species of lower oxidation state (In²⁺).     

Structural and electronic properties of carbon adsorbed on Fe(100)

Density functional theory within general gradient approximation (GGA) has been used to investigate sub-monolayer carbon atom adsorbed on Fe(100) as a function of coverage. The carbon atoms prefer to adsorb in the fourfold hollow site and bind strongly with the Fe surfaces. There is a substantial and strong coverage dependence of the carbon-induced expansion of the first interlayer spacing, reflecting a weakening of Fe–Fe bonds between the two outermost substrate layers. Some charge is found to transfer from substrate Fe to the adsorbate C atoms, which is responsible for the increase of work function. The density of states (DOS) analysis indicates the bonding of carbon with the first surface layer Fe atoms is primarily due to the interaction between Fe 3d_{x2-y2, xy} and C 2p_{x, y} orbitals, and the bonding of carbon with the second surface layer Fe atom that sits directly below the carbon atom is mainly from interaction between the minority spin Fe 3d_z2 and C 2p_z orbitals.     

FeO double-well potential as a result of spin density redistribution

According to the calculation of the electron structure of the FeO molecule performed by the ZINDO1 semi-empirical technique, the ground-state adiabatic potential has two close minima, each containing one vibration level. The states of the system in this minima differ in the spatial distribution of the spin density: the spin density is centered in the iron atom in the lowest well at 1.95 Å and a fraction of the spin with the opposite sign is transferred to oxygen in the other well at 1.8 Å. The temperature dependence of the fractions of molecules with the different bond lengths in the FeO gas has been found. The probability of switching the spin states has been shown to increase with pressure and temperature.     

CO2 motion in carbon dioxide deuterohydrate determined by applying maximum entropy method to neutron powder diffraction data

Crystal structures of carbon dioxide deuterohydrate were studied by neutron powder diffraction at temperatures from 10 to 200 K. Maps of scattering length density distribution were obtained using a maximum entropy method (MEM), which clarified the motion of CO₂ molecules in the hydrate. In small cages, the carbon atom of the CO₂ molecule is at the center of the cage, and the oxygen atoms of CO₂ revolve freely around the carbon atom. In large cages, the carbon atom also is at the center of the cage, but the oxygen atoms tend to revolve around the carbon atom along the plane parallel to the hexagonal facets of the cage.     

(110)-GaAs量子阱中光生载流子对电子自旋弛豫的影响

我们实验研究了(110)-GaAs量子阱中光生载流子对电子自旋弛豫的影响。通过测量量子阱的荧光寿命和光学吸收计算,我们能得到不同泵浦光功率下的带间吸收所产生的空穴浓度;相对应地,通过双色磁光科尔旋转技术,我们测量了该GaAs量子阱中电子自旋的动力学过程。结合两者,我们得到了电子自旋弛豫速率与空穴浓度的关系。实验结果表明电子自旋弛豫速率与空穴浓度呈线性依赖关系,验证了BirAronov-Pikus机制主导该体系的电子自旋弛豫。     

Ni(111)表面C原子吸附的密度泛函研究

基于密度泛函理论的第一性原理计算,对过渡金属Ni晶体与Ni (111)表面的结构和电子性质进行了研究, 并探讨了单个C原子在过渡金属Ni (111)表面的吸附以及两个C原子在Ni(111)表面的共吸附. 能带和态密度计算表明, Ni晶体及Ni (111)表面在费米面处均存在显著的电子自旋极化. 通过比较Ni (111)表面各位点的吸附能,发现单个C原子在该表面最稳定的吸附位置为第二层Ni原子上方所在的六角密排洞位, 吸附的第二个C原子与它形成碳二聚物时最稳定吸附位为第三层Ni原子上方所在的面心立方洞位. 电荷分析表明,共吸附时从每个C原子上各有1.566e电荷转移至相邻的Ni原子, 与单个C原子吸附时C与Ni原子间的电荷转移量(1.68e)相当. 计算发现两个C原子共吸附时在六角密排洞位和面心立方洞位的磁矩分别为0.059μ_B和 0.060μ_B,其值略大于单个C原子吸附时所具有的磁矩(0.017μ_B).     

Features of magnetic resonance in nanoporous carbon with pores filled with transition-metal atoms

Properties of nanoporous carbon (NPC) free of metal atoms and NPC containing atoms of Ni, Co and Pd in their pores are studied by electron spin resonance (ESR). The asymmetrical ESR line with the so-called Dyson line shape points out that charge carriers are responsible for the resonance spectrum in metal-free NPC. Although the amount of Ni, Co, and Pd introduced into nanopores is small, the NPC properties change significantly. A bulk ferromagnetism is observed in the case of NPC with Co and Pd, but not in NPC:Ni. Co atoms in pores of NPC cause the formation of a new material, namely, a disordered ferromagnetic medium with some features in the Co atom distribution. Magnetic properties are strongly temperature-dependent. The temperature dependences of the conductivity and ESR integral intensity in NPC:Ni reveal an exponential growth with the same activation energy. The magnetic resonance spectrum of NPC:Pd consists of four signals for NPC which is produced from SiC. There are one ferromagnetic and three paramagnetic signals belonging to the carbon dangle sp³- and sp²-bonds kind and to the paramagnetic clusters of Pd atoms.