In this work we have employed density-functional theory with hybrid functionals to investigate the atomic and electronic structure of bare and hydrogenated Co doped ZnO nanowires. We find that in the absence of passivation on the nanowire surface, the cobalt atoms segregate to the surface. On the other hand, under hydrogen passivation, the incorporation of Co is more favorable at inner sites. This suggests that the incorporation of Co in nanostructures has a dependence on the environment and may be facilitated by external atoms and relaxation of the surface.
Current voltage and Kelvin Probe Force Microscopy (KPFM) measurements were performed on single ZnO nanowires. Measurements are shown to be strongly correlated with the contact behavior, either ohmic or Schottky. The ZnO nanowires were obtained by metallo-organic chemical vapor deposition (MOCVD) and contacted using electronic-beam lithography. Depending on the contact geometry, good quality ohmic contacts (linear I V behavior) or non-linear (diode like) Schottky contacts were obtained. Current voltage and KPFM measurements on both types of contacted ZnO nanowires were performed in order to inv…
CdSe quantum dots (QDs) with different organic linker molecules are attached to ZnO nanowires (NWs) to study the luminescence dynamics and the electron tunneling from the QDs to the nanowires in time-resolved photoluminescence (PL) and photoconductivity measurements. The PL transients of the QD luminescence indicate two different recombination channels: the direct recombination inside the QD core and the recombination via QD surface defect states. After linking the QDs to the ZnO NW surface, photo-induced electron tunneling from an excited state of the QD into the conduction band of the nanowi…
Hexagonal [0001] nonpassivated ZnO nanowires are studied with density functional calculations. The band gap and Young's modulus in nanowires which are larger than those in bulk ZnO increase along with the decrease of the radius of nanowires. We find ZnO nanowires have larger effective piezoelectric constant than bulk ZnO due to their free boundary. In addition, the effective piezoelectric constant in small ZnO nanowires doesn't depend monotonously on the radius due to two competitive effects: elongation of the nanowires and increase of the ratio of surface atoms.
Single crystal ZnO nanowires doped with indium are synthesized via the laser-assisted chemical vapor deposition method. The conductivity of the nanowires is measured at low temperatures in magnetic fields both perpendicular and parallel to the wire axes. A quantitative fit of our data is obtained, consistent with the theory of a quasi-one-dimensional metallic system with quantum corrections due to weak localization and electron-electron interactions. The anisotropy of the magneto-conductivity agrees with theory. The two quantum corrections are of approximately equal magnitude with respective t…
As a potential solution for low-cost efficient solar cells, radial junctions consisting of ZnO nanowires arrays embedded in Cu2O thin films have been theoretically modeled. Calculations have been performed to explore the geometric dependence of performance of such wire-based solar cells. By properly setting material properties and cell dimensions, a reasonable power conversion efficiency of 19.7% can be expected in a material with 2 μm minority carrier diffusion length. The detrimental effects of bulk, interface and contact-related states on solar cell performance have also been studied, from …
Controlling the growth of zinc oxide nanowires is necessary to optimize the performances of nanowire-based devices such as photovoltaic solar cells, nano-generators, or light-emitting diodes. In this view, we investigate the nucleation and growth mechanisms of ZnO nanowires grown by metalorganic vapor phase epitaxy either on O-polar ZnO or on sapphire substrates. Whatever the substrate, ZnO nanowires are Zn-polar, as demonstrated by convergent beam electron diffraction. For growth on O-polar ZnO substrate, the nanowires are found to sit on O-polar pyramids. As growth proceeds, the inversion do…
Vertically aligned, beaded zinc germinate (Zn2GeO4)/ zinc oxide (ZnO) hybrid nanowire arrays were successfully synthesized by a vapor-solid process via a catalyst-free approach. The as-synthesized products were characterized using X-ray diffraction, scanning electron microscopy and transmission electron microscopy equipped with an energy-dispersive X-ray spectrometer. TEM studies revealed the beaded microstructures of the Zn2GeO4/ZnO nanowire. Furthermore, Zn2GeO4 nanotubes were synthesized after wet etching treatments on Zn2GeO4/ZnO hybrid nanowires.
The effect of applying an external electric field on doping-induced spin-orbit splitting of the lowest conduction-band states in a bismuth-doped zinc oxide nanowire is studied by performing electronic structure calculations within the framework of density functional theory. It is demonstrated that spin splitting in Bi-doped ZnO nanowires could be tuned and enhanced electrically via control of the strength and direction of the applied electric field, thanks to the nonuniform and anisotropic response of the ZnO:Bi nanowire to external electric fields. The results reported here indicate that a si…
The bending of a nonconducting piezoelectric ZnO nanowire is simulated by finite element method calculations. The top part is bent by a lateral force, which could be applied by an atomic force microscope (AFM) tip. The generated electrical potential is 0.3 V. This relatively high signal is, however, difficult to measure, due to the low capacitance of the ZnO nanowire (4x10^{-5} pF) as compared to the capacitance of most preamplifiers (5 pF). A further problem arises from the semiconducting properties of experimentally fabricated ZnO nanowires which causes the disappearance of the voltage signa…
Mn-doped ZnO was synthesized using a co-precipitation technique. X-ray diffraction (XRD) measurements and photoluminescence (PL) spectra show that Mn ions are doped into the lattice positions of ZnO. The modes at 202, 330, and 437 cm-1 in the Raman spectrum are assigned as 2E2 (low), E2 (high)-E2 (low), and E2 (high) modes of ZnO base, respectively. The mode at 528 cm-1 is ascribed to a local vibrational mode related to Mn. The mode at 580 cm-1 should be an intrinsic mode of ZnO and assigned to E1 longitudinal optical (LO). Its reinforcement should result from a combination of resonance at the…
This paper presents two first-principles calculations on the lattice- and electronic- structures of a small-diameter infinite and truncated ZnO nanowire. The two calculations show excellent agreement with each other. For the small diameter nanowire, the lattice and electronic properties are determined by the relaxed surface. We find a similarity between the nanowire surface and the surface of the bulk material, and discuss the assignment of the rotational quantum number m to the bands.
We perform molecular dynamics (MD) simulations to investigate the effect of polar surfaces on the thermal transport in zinc oxide (ZnO) nanowires. We find that the thermal conductivity in nanowires with free polar (0001) surfaces is much higher than in nanowires that have been stabilized with reduced charges on the polar (0001) surfaces, and also hexagonal nanowires without any transverse polar surfaces. From normal mode analysis, we show that the higher thermal conductivity is due to a shell-like reconstruction that occurs for the free polar surfaces. This shell-like reconstruction suppresses…
We performed density-functional calculations to investigate the electronic structure of ZnO/GaN core/shell heterostructured nanowires (NWs) orientating along <0001> direction. The build-in electric filed arising from the charge redistribution at the {1-100} interfaces and the band offsets were revealed. ZnO-core/GaN-shell NWs rather than GaN-core/ZnO-shell ones were predicted to exhibit natural charge spatial separation behaviors, which are understandable in terms of an effective mass model. The effects of quantum confinement on the band gaps and band offsets were also discussed.
In this work, ZnO nanowire arrays decorated with titanium nitride (TiN) nanoparticles as surface enhanced Raman scattering (SERS) substrates is demonstrated. ZnO nanowires were grown by hydrothermal synthesis while ~100 nm TiN nanoparticles were obtained by grinding commercial powders for several hours. They were then decorated on the ZnO nanowire arrays using acetone as the medium. Scanning electron microscopy confirmed the presence of TiN nanoparticles on the ZnO nanowires. TiN nanoparticles exhibited localized surface plasmon resonances at 430, 520 and 600 nm. SERS experiments using Nile Bl…
We investigated both numerically and experimentally the dynamics of individual ZnO nanowires immersed in an in-plane switching (IPS) 4-Cyano-4-pentylbiphenyl (5CB) liquid crystal cell under switching electric fields. Comparing the motion of nanowires captured by a high-speed CCD camera with the simulated results allows the interaction among nanowires, liquid crystals and external electric field to be studied. Our results show that in the nematic phase, the relaxation and response of a nanowire are both controlled by both the dielectrophoretic torque induced by the external electric field and t…
We analyse the morphological, structural and luminescence properties of self-assembled ZnO nanowires grown by chemical vapour transport on Si(001). The examination of nanowire ensembles by scanning electron microscopy reveals that a non-negligible fraction of nanowires merge together forming coalesced aggregates during growth. We show that the coalescence degree can be unambiguously quantified by a statistical analysis of the cross-sectional shape of the nanowires. The examination of the structural properties by X-ray diffraction evidences that the nanowires crystallize in the wurtzite phase, …
In this work we have employed density-functional theory with hybrid functionals to investigate the atomic and electronic structure of bare and hydrogenated Mn doped ZnO nanowires with small diameter. We determine changes in magnetic and electronic structure of Mn-doped ZnO nanowires due to surface effects, such as hydrogen adsorption on the surface, presence of oxygen vacancies and dangling bonds. In the absence of passivation on the nanowire surface, the manganese atoms segregate to the surface, whereas under hydrogen adsorption the incorporation of Mn is energetically more favourable at inne…
Plastic relaxation of the misfit stress in core-shell semi-conducting nanowires can lead to structural defects, detrimental to applications. Core-shell Zn{0.7}Mg{0.3}O/ZnO quantum well heterostructures were deposited on ZnO nanowires. Strain along the a and c axes of the wurtzite structure is relaxed through the glide of dislocation half-loops from the free surfaces, within pyramidal and prismatic planes. Some half-loops are closed up in the barriers to accommodate the misfit at two consecutive interfaces of the quantum well stack. Dislocations are also observed within the nanowire core: contr…
First principles calculations of the O surfaces of Co-ZnO show that substitutional Co ions develop large magnetic moments which long-range coupling depends on their mutual distance. The local spin polarization induced at the O atoms is three times larger at the surface than in the bulk, and the surface stability is considerably reinforced by Co. Moreover, a robust ferromagnetic state is predicted at the Oxygen (0001) surface even in the absence of magnetic atoms. The occurrence of surface magnetic moments correlates with the number of {\it p}-holes in the valence band of the oxide, and the dis…
Ion implantation is an interesting method to dope semiconducting materials such as zinc oxide provided that the implantation-induced defects can be subsequently removed. Nitrogen implantation followed by anneals under O2 were carried out on zinc oxide nanowires in the same conditions as in a previous study on bulk ZnO [J. Appl.Phys. 109, 023513 (2011)], allowing a direct comparison of the defect recovery mechanisms. Transmission electron microscopy and cathodoluminescence were carried out to assess the effects of nitrogen implantation and of subsequent anneals on the structural and optical pro…
We simulated and experimentally investigated the sputter yield of ZnO and GaAs nanowires, which were implanted with energetic Mn ions at room temperature. The resulting thinning of the nanowires and the dopant concentration with increasing Mn ion fluency were measured by accurate scanning electron microscopy (SEM) and nano-X-Ray Fluorescence (nanoXRF) quantification, respectively. We observed a clear enhanced sputter yield for the irradiated nanowires compared to bulk, which is also corroborated by iradina simulations. These show a maximum if the ion range matches the nanowire diameter. As a c…
Based on density functional theory calculations, we systematically investigate the behaviors of a H atom in Ag-doped ZnO, involving the preference sites, diffusion behaviors, the electronic structures and vibrational properties. We find that a H atom can migrate to the doped Ag to form a Ag-H complex by overcoming energy barriers of 0.3 - 1.0 eV. The lowest-energy site for H location is the bond center of a Ag-O in the basal plane. Moreover, H can migrate between this site and its equivalent sites with energy cost of less than 0.5 eV. In contrast, dissociation of such a Ag-H complex needs ener…
Our predictions, based on density-functional calculations, reveal that surface doping of ZnO nanowires with Bi leads to a linear-in-$k$ splitting of the conduction-band states, through spin-orbit interaction, due to the lowering of the symmetry in the presence of the dopant. This finding implies that spin polarization of the conduction electrons in Bi-doped ZnO nanowires could be controlled with applied electric (as opposed to magnetic) fields, making them candidate materials for spin-orbitronic applications. Our findings also show that the degree of spin splitting could be tuned by adjusting …
The fracture strength of ZnO nanowires vertically grown on sapphire substrates was measured in tensile and bending experiments. Nanowires with diameters between 60 and 310 nm and a typical length of 2 um were manipulated with an atomic force microscopy tip mounted on a nanomanipulator inside a scanning electron microscope. The fracture strain of (7.7 +- 0.8)% measured in the bending test was found close to the theoretical limit of 10% and revealed a strength about twice as high as in the tensile test. From the tensile experiments the Young's modulus could be measured to be within 30% of that o…
Precise control of morphologies of one-dimensional (1D) or 2D nanostructures during growth has not been easily accessible, usually degrading the device performance and therefore limiting applications to various advanced nanoscale electronics and optoelectronics. Graphene could be a platform to serve as a substrate for both morphology control and direct use of electrodes due to its ideal monolayer flatness with π electrons. Here, we report that by using graphene directly as a substrate, vertically well-aligned ZnO nanowires and nanowalls were obtained systematically by controlling Au catalyst t…
The synthesis, morphology and magneto-transport properties of nanostructure-engineered charge-ordered Pr0.5Ca0.5MnO3 grown on ZnO nanowires are reported. The stability of the charge-ordering can be tuned, but more interestingly the sign of the magnetoresistance is inverted at low temperatures. Coexistence of ferromagnetic clusters on the surface and antiferromagnetic phase in the core of the grains were considered in order to understand these features. This work suggests that such a process of growing on nanowires network can be readily extended to other transition metal oxides and open doors …
We utilize classical molecular dynamics to study surface effects on the piezoelectric properties of ZnO nanowires as calculated under uniaxial loading. An important point to our work is that we have utilized two types of surface treatments, those of charge compensation and surface passivation, to eliminate the polarization divergence that otherwise occurs due to the polar (0001) surfaces of ZnO. In doing so, we find that if appropriate surface treatments are utilized, the elastic modulus and the piezoelectric properties for ZnO nanowires having a variety of axial and surface orientations are a…
We develop an InAs nanowire gate-all-around field-effect transistor using a transparent conductive zinc oxide (ZnO) gate electrode, which is in-situ atomic layer deposited after growth of gate insulator of Al2O3. We perform magneto-transport measurements and find a crossover from weak localization to weak antilocalization effect with increasing gate voltage, which demonstrates that the Rashba spin-orbit coupling is tuned by the gate electrode. The efficiency of the gate tuning of the spin-orbit interaction is higher than those obtained for two-dimensional electron gas, and as high as that for …
We have grown nitrogen-doped ZnO films grown by two kinds of epitaxial methods on lattice-matched ScAlMgO$_4$ substrates. We measured the photoluminescence (PL) of the two kinds of ZnO:N layers in the donor-acceptor-pair transition region. The analysis of excitation-intensity dependence of the PL peak shift with a fluctuation model has proven that our observed growth-technique dependence was explained in terms of the inhomogeneity of charged impurity distribution. It was found that the inhomogeneity in the sample prepared with the process showing better electrical property was significantly sm…
The controlled modification of the electronic properties of ZnO nanorods via transition metal doping is reported. A series of ZnO nanorods were synthesized by chemical bath growth with varying Co content from 0 to 20 atomic % in the growth solution. Optoelectronic behavior was probed using cathodoluminescence, time-resolved luminescence, transient absorbance spectroscopy, and the incident photon-to-current conversion efficiency (IPCE). Analysis indicates the crucial role of surface defects in determining the electronic behavior. Significantly, Co-doping extends the light absorption of the nano…
We report room temperature ferromagnetism in as-implanted Eu doped ZnO (ZnO:Eu). To address the origin of ferromagnetism ab initio calculations of ZnO:Eu system are performed. Results show that the ferromagnetism is induced by ZnO point defects as Eu ions in perfect ZnO tend to align antiferromagnetically.
Native and hydrogen-plasma induced shallow traps in hydrothermally grown ZnO crystals have been investigated by charge-based deep level transient spectroscopy (Q-DLTS), photoluminescence and cathodoluminescence microanalysis. The as-grown ZnO exhibits a trap state at 23 meV, while H-doped ZnO produced by plasma doping shows two levels at 22 meV and 11 meV below the conduction band. As-grown ZnO displays the expected thermal decay of bound excitons with increasing temperature from 7 K, while we observed an anomalous behaviour of the excitonic emission in H-doped ZnO, in which its intensity incr…
We report persistently increased conduction in ZnO nanowires irradiated by ion beam with various ion energies and species. This effect is shown to be related to the already known persistent photo conduction in ZnO and dubbed persistent ion beam induced conduction. Both effects show similar excitation efficiency, decay rates, and chemical sensitivity. Persistent ion beam induced conduction will potentially allow countable (i.e., single dopant) implantation in ZnO nanostructures and other materials showing persistent photo conduction.
Recently the point defect responsible for the intra-3$d$ luminescence of cobalt in doped ZnO samples has been indentified\,\cite{pssb2019}. In this work we further extend our investigation to other point defects in Co-doped ZnO. We use density-functional theory and GW calculations to determined the orbital-resolved band structure of cobalt doped zinc oxide (ZnO). We show that mainly O-p and Co-d orbitals take part in the process and confirm that an oxygen interstitial nearby a cobalt atom is a likely defect to occur in Co-implanted ZnO samples. We also rule out that other common point defects …
The combination of x-ray spectroscopy methods complemented with theoretical analysis unravels the coexistence of paramagnetic and antiferromagnetic phases in the Zn_0.9Mn_0.1O shell deposited onto array of wurtzite ZnO nanowires. The shell is crystalline with orientation toward the ZnO growth axis, as demonstrated by X-ray linear dichroism. EXAFS analysis confirmed that more than 90% of Mn atoms substituted Zn in the shell while fraction of secondary phases was below 10%. The value of manganese spin magnetic moment was estimated from the Mn Kβ X-ray emission spectroscopy to be 4.3μB which is c…
Metal-oxide nanowires are showing a great interest in the domain of gas sensing due to their large response even at a low temperature, enabling low-power gas sensors. However their response is still not fully understood, and mainly restricted to the linear response regime, which limits the design of appropriate sensors for specific applications. Here we analyse the non-linear response of a sensor based on ZnO nanowires network, both as a function of the device geometry and as a response to oxygen exposure. Using an appropriate model, we disentangle the contribution of the nanowire resistance a…
In this paper Al doped ZnO (AZO) thin films with 0, 3, 6 and 12 at. % Al concentration were prepared by sol-gel method on glass substrates. The deposited films were annealed at different temperatures of 300, 350, 400, 450 and 500 °C for 1 h in air. X-ray diffraction (XRD) showed wurtzite crystalline structure for the films annealed above 400 °C. The films were subsequently irradiated by beams of excimer (KrF, λ=248 nm) laser. The evolution of crystal structure, surface morphology and optical properties were studied using XRD, filed emission scanning electron microscope (FE-SEM) and UV-Vis spec…
Cobalt-doped ZnO (Co2+:ZnO) films were studied by magnetic circular dichroism (MCD) spectroscopy. A broad 300 K ferromagnetic MCD signal was observed between 1.4 and 4.0 eV after introducing shallow donor states by exposure of paramagnetic Co2+:ZnO films to zinc vapor. The new sub-bandgap ferromagnetic MCD intensity is attributed to low-energy photoionization transitions originating from a spin-split donor impurity band in ferromagnetic Co2+:ZnO.
Preliminary results on the properties of transition-metal (Ti, V, Cr, Mn, Fe, Co, Ni) $δ$-doped ZnO are reported. Using \emph{ab-initio} electronic structure calculations the magnetic order is studied assuming both the cubic rock-salt and zinc-blende structures for ZnO. The ground state magnetic order is found to depend strongly on the transition-metal atom.
An emerging branch of electronics, the optospintronics, would be highly boosted if the control of magnetic order by light is implemented in magnetic semiconductors nanostructures being compatible with the actual technology. Here we show that the ferromagnetic magnetization of low Fe-doped ZnO nanowires prepared by carbothermal process is enhanced under illumination up to temperatures slightly below room temperature. This enhancement is related to the existence of an oxygen vacancy V$_{\rm O}$ in the neighbouring of an antiferromagnetic superexchange Fe$^{3+}$-Fe$^{3+}$ pair. Under illumination…
Long needle-shaped single crystals of Zn1-xCoxO were grown at low temperatures using a molten salt solvent technique, up to x=0.10. The conduction process at low temperatures is determined to be by Mott variable range hopping. Both pristine and cobalt doped crystals clearly exhibit a crossover from negative to positive magnetoresistance as the temperature is decreased. The positive magnetoresistance of the Zn1-xCoxO single crystals increases with increased Co concentration and reaches up to 20% at low temperatures (2.5 K) and high fields (>1 T). SQUID magnetometry confirms that the Zn1-xCoxO c…
We report a surfactant assisted synthesis of Mn doped ZnO polycrystalline samples showing robust room temperature ferromagnetism as characterized by X-ray diffraction analysis, Transmission Electron Microscopy, Electron Paramagnetic Resonance and DC magnetization mearurements. This surfactant assisted synthesis method, developed by us, is found to be highly reproducible. Further, it can also be extended to the synthesis of other transition metal doped ZnO.
The hydrogen interstitial and the substitutional Al_Zn, Ga_Zn and In_Zn are all shallow donors in ZnO and lead to n-type conductivity. Although shallow donors are expected to repel each other, we show by first principles calculations that in ZnO these shallow donor impurities attract and form a complex, leading to a donor level deep in the band gap. This puts a limit on the n-type conductivity of (Al,Ga,In)-doped ZnO in the presence of hydrogen.
Nanowire-based light-emitting devices require multi-quantum well heterostructures with high room temperature optical efficiencies. We demonstrate that such efficiencies can be attained through the use of ZnO/Zn(1-x)MgxO core shell quantum well heterostructures grown by metal organic vapour phase epitaxy. Varying the barrier Mg concentration from x=0.15 to x=0.3 leads to the formation of misfit induced dislocations in the multi quantum wells. Correlatively, temperature dependant photoluminescence reveals that the radial well luminescence intensity decreases much less rapidly with increasing tem…
In this study, we report the enhancement in field emission (FE) properties of ZnO nanostructure by Ni doping at the base pressure of ~1 x 10-8 mbar, which were grown by the simple wet chemical process. ZnO nanostructure shows single crystalline wurtzite structure up to Ni 10% doping. FESEM represents change in the nanostructure morphology from thick nanoneedles to nanoflakes via thin nanorods with increase in Ni doped ZnO. The turn-on field required to draw a field emission (FE) current density at 1μA/cm2 is found to be 2.5, 2.3, 1.8 and 1.7 V/μm for ZnO(Ni0%), ZnO(Ni5%), ZnO(Ni7.5%) and ZnO(N…
Cu doped transparent ZnO thin films were spin coated on conductive glass substrates. The samples were subsequently annealed in air for 1 hour at 500 0C in order to form the phase of ZnO. ZnO samples were doped with different Cu molar percentages up to 5%. The impedance and photovoltaic properties of sample were measured. Photocurrent and photovoltage of doped and undoped samples were measured in KI/I2 electrolyte. Adding a trace amount of Cu improved the conducting properties of ZnO samples without changing other basic properties of ZnO. The photocurrent gradually increases with the doping con…
We have studied the electronic structure and the magnetism of Cu-doped ZnO nanowires, which have been reported to show ferromagnetism at room temperature [G. Z. Xing ${et}$ ${al}$., Adv. Mater. {\bf 20}, 3521 (2008).], by x-ray photoemission spectroscopy (XPS), x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD). From the XPS and XAS results, we find that the Cu atoms are in the "Cu$^{3+}$" state with mixture of Cu$^{2+}$ in the bulk region ($\sim$ 100 nm), and that "Cu$^{3+}$" ions are dominant in the surface region ($\sim$ 5 nm), i.e., the surface electronic stru…
We report magnetism in carbon doped ZnO. Our first-principles calculations based on density functional theory predicted that carbon substitution for oxygen in ZnO results in a magnetic moment of 1.78 $μ_B$ per carbon. The theoretical prediction was confirmed experimentally. C-doped ZnO films deposited by pulsed laser deposition with various carbon concentrations showed ferromagnetism with Curie temperatures higher than 400 K, and the measured magnetic moment based on the content of carbide in the films ($1.5 - 3.0 μ_B$ per carbon) is in agreement with the theoretical prediction. The magnetism …
We investigated the optical and optoelectronic properties of vertically aligned Al:ZnO nanorod arrays synthesized by the hydrothermal technique at a considerably low temperature on a sputtered Al-ZnO seed layer. The nanorod arrays maintained remarkable alignment along the c-axis over a large area. The seed layers and nanorod arrays showed various optical band gaps. Investigation of the optoelectronic properties of nanorod arrays on
We have investigated the magnetic properties of non-doped ZnO nanostructures by using {\it ab initio} total energy calculations. Contrary to many proposals that ferromagnetism in non-doped semiconductors should be induced by intrinsic point defects, we show that ferromagnetism in nanostructured materials should be mediated by extended defects such as surfaces and grain boundaries. This kind of defects create delocalized, spin polarized states that should be able to warrant long-range magnetic interactions.
A novel sol-gel route to c-axis orientated undoped and Co, Fe, Mn and V doped ZnO films is reported. Sols were prepared from a hydrated zinc acetate precursor and dimethyl formamide (DMF) solvent. Films were spin-coated on to hydrophilic sapphire substrates then dried, annealed and post-annealed, producing almost purely uniaxial ZnO crystallites and a high degree of long-range structural order. Specific orientation of hexagonal crystallites is demonstrated both perpendicular and parallel to the substrate surface. Cobalt doping resulted in the formation of columnar ZnO nanocrystals. Vanadium do…
The formation energies and electronic structure of europium doped zinc oxide has been determined using DFT and many-body $GW$ methods. In the absence of intrisic defects we find that the europium-$f$ states are located in the ZnO band gap with europium possessing a formal charge of 2+. On the other hand, the presence of intrinsic defects in ZnO allows intraband $f-f$ transitions otherwise forbidden in atomic europium. This result coorroborates with recently observed photoluminescence in the visible red region [1].
Following the theoretical predictions of ferromagnetism in Mn- and Co-doped ZnO, several workers reported ferromagnetism in thin films as well as in bulk samples of these materials. While some observe room-temperature ferromagnetism, others find magnetization at low temperatures. Some of the reports, however, cast considerable doubt on the magnetism of Mn- and Co-doped ZnO. In order to conclusively establish the properties of Mn- and Co-doped ZnO, samples with 6 percent and 2 percent dopant concentrations, have been prepared by the low-temperature decomposition of acetate solid solutions. The …
We have developed a simple, surfactant assisted synthesis route for the preparation, in gram quantities, of Co and Li doped ZnO nanocrystalline samples showing robust room temperature ferromagnetism. Our studies show that RTF is intrinsic to Zn0.85Co0.05Li0.10O and not due to any segregated secondary phases. In addition, it has been shown that the defects play an important role in activating RTF in these oxide systems. This also provide an explanation for the widely varying results observed in the literature. The method can also be extended for the synthesis of other transition metal doped ZnO…
Structural and magnetic properties have been studied for polycrystalline Zn_1-xMn_xO (x=0.02, 0.03, 0.05). Low-temperature (~500 oC) synthesis leaves unreacted starting ZnO and manganese oxides. Contrary to a recent report, no bulk ferromagnetism was observed for single-phase materials synthesized in air at temperatures above 900 oC. Single-phase samples show paramagnetic Curie-Weiss behavior.
The thin film configuration presents obvious practical advantages over the 1D implementation in energy harvesting systems such as easily manufacturing and processing and long lasting and stable devices. However, most of the ZnO-based piezoelectric nanogenerators (PENGs) reported so far relay in the exploitation of single-crystalline ZnO nanowires because their self-orientation in the c-axis and ability to accommodate long deformations resulting in a high piezoelectric performance. Herein, we show an innovative approach aiming to produce PENGs by combining polycrystalline ZnO layers fabricated …
P mono-doped and (P, N) co-doped ZnO are investigated by the first-principles calculations. It is found that substitutive P defect forms a deep acceptor level at O site (PO) and it behaves as a donor at Zn site (PZn), while interstitial P (Pi) is amphoteric. Under equilibrium conditions, these defects contribute little to the p-type conductivity of ZnO samples since the formation energy of PZn is much lower than that of Pi or PO when EF is below mid-gap (a prerequisite p-type condition). Zinc vacancies (VZn) and PZn-2VZn complex are demonstrated to be shallow acceptors with ionization energies…
