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1.
The Cr-doped zinc oxide (Zn0.97Cr0.03O) nanoparticles were successfully synthesized by sol-gel method. The relationship between the annealing temperature (400 °C, 450 °C, 500 °C and 600 °C) and the structure, magnetic properties and the optical characteristics of the produced samples was studied. The results indicate that Cr (Cr3+) ions at least partially substitute Zn (Zn2+) ions successfully. Energy dispersive spectroscopy (EDS) measurement showed the existence of Cr ion in the Cr-doped ZnO. The samples sintered in air under the temperature of 450 °C had single wurtzite ZnO structure with prominent ferromagnetism at room temperature, while in samples sintered in air at 500 °C, a second phase-ZnCr2O4 was observed and the samples were not saturated in the field of 10000 Oe. This indicated that they were mixtures of ferromagnetic materials and paramagnetic materials. Compared with the results of the photoluminescence (PL) spectra, it was reasonably concluded that the ferromagnetism observed in the studied samples was originated from the doping of Cr in the lattice of ZnO crystallites.  相似文献   

2.
Transparent conducting indium doped zinc oxide was deposited on glass substrate by ultrasonic spray method. The In doped ZnO samples with indium concentration of 3 wt.% were deposited at 300, 350 and 400 °C with 2 min of deposition time. The effects of substrate temperature and annealing temperature on the structural, electrical and optical properties were examined. The DRX analyses indicated that In doped ZnO films have polycrystalline nature and hexagonal wurtzite structure with (0 0 2) preferential orientation and the maximum average crystallite size of ZnO: In before and annealed at 500 °C were 45.78 and 55.47 nm at a substrate temperature of 350 °C. The crystallinity of the thin films increased by increasing the substrate temperature up 350 °C, the crystallinity improved after annealing temperature at 500 °C. The film annealed at 500 °C and deposited at 350 °C show lower absorption within the visible wavelength region. The band gap energy increased from Eg = 3.25 to 3.36 eV for without annealing and annealed films at 500 °C, respectively, indicating that the increase in the transition tail width. This is due to the increase in the electrical conductivity of the films after annealing temperature.  相似文献   

3.
Valence-band and conduction-band the electronic structure of the CrS (δ=0) and Cr5S6 (δ=0.17) has been investigated by means of photoemission and inverse-photoemission spectroscopies. The bandwidth of the valence bands of Cr5S6 (8.5 eV) is wider than that of CrS (8.1 eV), though the Cr 3d partial density of states evaluated from the Cr 3p-3d resonant photoemission spectroscopy is almost unchanged between the two compounds concerning shapes as well as binding energies. The Cr 3d (t2g) exchange splitting energies of CrS and Cr5S6 are determined to be 3.9 and 3.3 eV, respectively.  相似文献   

4.
DC electrical conductivity (σdc) of electron-doped antiferromagnetic CaMn1−xCrxO3 (0?x?0.3) has been discussed elaborately in the light of polaron hopping conduction. The increase in Cr doping concentration increases the conductivity and decreases the activation energy. Non-adiabatic polaron hopping conduction is observed in all the manganites at high temperatures. The analysis of σdc data shows that small polarons are formed at lower concentrations (?5%) of Cr doping and undoped samples. However, large polarons are materialized at higher doping (?10%) concentrations. This is consistent with the fact that doped Cr3+ has larger ionic size compared to that of Mn4+. Again, strong electron-phonon (e-ph) interaction is perceived in undoped and 5% Cr-doped samples but not in manganites with larger doping concentration. This also confirms the formation of larger polarons with the increase of x. Mott's variable range hopping (VRH) model can elucidate the dc conductivity at very low temperatures. It has been detected that single phonon-assisted hopping is responsible for the dc conduction in the Cr-doped CaMnO3 manganites.  相似文献   

5.
Electron energy loss spectra (ELS) have been obtained from polycrystalline Cr and Cr2O3 before and after surface reduction by 2 keV Ar+ bombardment. The primary electron energy used in the ELS measurements was systematically varied from 100 to 1150 eV in order to distinguish surface versus bulk loss processes. Two predominant loss features in the ELS spectra obtained from Cr metal at 9.0 and 23.0 eV are assigned to the surface and bulk plasmon excitations, respectively, and a number of other features arising from single electron transitions from both the bulk and surface Cr 3d bands to higher-lying states in the conduction band are also present. The ELS spectra obtained from Cr2O3 exhibit features that originate from both interband transitions and charge-transfer transitions between the Cr and O ions as well as the bulk plasmon at 24.4 eV. The ELS feature at 4.0 eV arises from a charge-transfer transition between the oxygen and chromium ions in the two surface layers beneath the chemisorbed oxygen layer, and the ELS feature at 9.8 eV arises from a similar transition involving the chemisorbed oxygen atoms. The intensity of the ELS peak at 9.8 eV decreases after Ar+ sputtering due to the removal of chemisorbed oxygen atoms. Sputtering also increases the number of Cr2+ states on the surface, which in turn increases the intensity of the 4.0 eV feature. Furthermore, the ELS spectra obtained from the sputtered Cr2O3 surface exhibit features characteristic of both Cr0 and Cr2O3, indicating that Ar+ sputtering reduces Cr2O3. The fact that neither the surface- nor the bulk-plasmon features of Cr0 can be observed in the ELS spectra obtained from sputtered Cr2O3 while the loss features due to Cr0 interband transitions are clearly present indicates that Cr0 atoms form small clusters lacking a bulk metallic nature during Ar+ bombardment of Cr2O3.  相似文献   

6.
Pyramidal ZnO nanorods with hexagonal structure having c-axis preferred orientation are grown over large area silica substrates by a simple aqueous solution growth technique. The as-grown nanorods were studied using XRD, SEM and UV-vis photoluminescence (PL) spectroscopy for their structural, morphological and optical properties, respectively. Further, the samples have also been annealed under different atmospheric conditions (air, O2, N2 and Zn) to study the defect formation in nanorods. The PL spectra of the as-grown nanorods show narrow-band excitonic emission at 3.03 eV and a broad-band deep-level emission (DLE) related to the defect centers at 2.24 eV. After some mild air annealing at 200 °C, fine structures with peaks having energy separation of ∼100 meV were observed in the DLE band and the same have been attributed to the longitudinal optical (LO) phonon-assisted transitions. However, the annealing of the samples under mild reducing atmospheres of N2 or zinc at 550 °C resulted in significant modifications in the DLE band wherein high intensity green emission with two closely spaced peaks with maxima at 2.5 and 2.7 eV were observed which have been attributed to the VO and Zni defect centers, respectively. The V-I characteristic of the ZnO:Zn nanorods shows enhancement in n-type conductivity compared to other samples. The studies thus suggest that the green emitting ZnO:Zn nanorods can be used as low voltage field emission display (FED) phosphors with nanometer scale resolution.  相似文献   

7.
Pure and tin doped zinc oxide (Sn:ZnO) thin films were prepared for the first time by NSP technique using aqueous solutions of zinc acetate dehydrate, tin (IV) chloride fendahydrate and methanol. X-ray diffraction patterns confirm that the films are polycrystalline in nature exhibiting hexagonal wurtzite type, with (0 0 2) as preferred orientation. The structural parameters such as lattice constant (‘a’ and ‘c’), crystallite size, dislocation density, micro strain, stress and texture coefficient were calculated from X-ray diffraction studies. Surface morphology was found to be modified with increasing Sn doping concentration. The ZnO films have high transmittance 85% in the visible region, and the transmittance is found to be decreased with the increase of Sn doping concentration. The corresponding optical band gap decreases from 3.25 to 3.08 eV. Room temperature photoluminescence reveals the sharp emission of strong UV peak at 400 nm (3.10 eV) and a strong sharp green luminescence at 528 nm (2.34 eV) in the Sn doped ZnO films. The electrical resistivity is found to be 106 Ω-cm at higher temperature and 105 Ω-cm at lower temperature.  相似文献   

8.
Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E2 mode and longitudinal optical A1 (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10−6 Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.  相似文献   

9.
Uniform and flat single crystal ZnO:P nanobelts (NBs) were fabricated on Si (1 0 0) substrates by the thermal evaporation method. The growth process, free-catalyst self-assembly vapor-solid (V-S) mechanism, was described and investigated deeply in terms of thermodynamics and kinetics. Then, the photoluminescence (PL) properties of ZnO NBs were studied in a temperature range from 10 to 270 K. At 10 K the recombination of acceptor-bound exciton (A0X) was predominant in the PL spectrum, and was attributed to the transition of PZn−2VZn complex bound exciton. The active energy of A0X and acceptor binding energy were calculated to be 17.2 and 172 meV, respectively. The calculated acceptor binding energy of P doped ZnO nanostructure is in good agreement with that of P doped ZnO film.  相似文献   

10.
Heavily doped Zn1−xMnxO (x = 0.3) films were prepared by polymeric precursor method onto glass substrates and their structural, morphological, optical and magnetic properties carefully studied. Undoped ZnO films were also prepared for the purpose of comparison. The polymeric precursor method consists in preparing a coating solution from the Pechini process followed by a three-step thermal treatment of the as deposited films at temperatures up to 550 °C for 30 min. X-ray diffraction (XRD) analysis reveals the typical hexagonal wurtzite structure of the undoped ZnO film. The addition of Mn ions leads to a dramatic reduction of the crystalline quality of film although no evidence of affectation by secondary phases is found. The affectation of the ZnO structure may be due to the formation of Mn clusters and generation of defects such as vacancies and interstitials. Here, the solubility limit of the Mn ions in ZnO should play an important role and it is discussed in the framework of ionic radius and valence states. The scanning electron microscopy (SEM) analysis shows that the surface of the doped sample was affected by the presence of cracks due, probably, to the expansion of the lattice constant of Zn0.7Mn0.3O caused by the Mn incorporation in the ZnO lattice. The existence of cluster-type structures on the surface is corroborated by atomic force microscopy (AFM). The EDX analysis, carried out on some areas in the film, yielded Mn/Zn ratios of about 0.3, which points out to an effective Mn incorporation in the film. On the other hand, the absorption edge of the doped films is red shifted to 2.9 eV (3.24 eV for undoped ZnO film) and the absorption edge is less sharp due, probably, to amorphous states appearing in the band gap. No evidence of dilute magnetic semiconductor mean-field ferromagnetic behavior is observed. The temperature dependence of the magnetization follows a Curie law suggesting pure paramagnetic behavior. The very small s-shape behavior of M versus H (without hysteresis) observed at room temperature on selected areas would stem from Mn clusters which are easily formed in transition metal doped ZnO.  相似文献   

11.
ZnO-Al2O3 nanocomposite thin films were prepared by sol-gel technique. The room temperature synthesis was mainly based on the successful peptization of boehmite (AlO(OH)) and Al(OH)3 compounds, so as to use it as matrix to confine ZnO nanoparticles. The relative molar concentrations of xZnO to (1 − x) Al2O3 were varied as x = 0.1, 0.2 and 0.5. The optical absorption spectra of the thin films showed intense UV absorption peaks with long tails of variable absorption in the visible region of the spectra. The ZnO-Al2O3 nanocomposites thin films were doped with MgO by varying its molar concentrations as y = 0.05, 0.75, 0.1, 0.125, 0.15 and 0.2 with respect to the ZnO present in the composite. The MgO doped thin films showed suppression of the intense absorption peaks that was previously attained for undoped samples. The disappearance of the absorption peaks was analyzed in terms of the crystalline features and lattice defects in the nanocomposite system. The bulk absorption edge, which is reportedly found at 3.37 eV, was shifted to 5.44 eV (for y = 0.05), 5.63 eV (for y = 0.075) and maximum to 5.77 eV (for y = 0.1). In contrast, beyond the concentration, y = 0.1 the absorption edges were moved to 5.67 eV (for y = 0.125), 5.61 eV (for y = 0.15) and to 5.49 eV (for y = 0.2). This trend was explained in terms of the Burstein-Moss shift of the absorption edges.  相似文献   

12.
Cr-doped mullites were prepared from single-phase precursors containing up to 9.60 wt% Cr2O3 using a sol-gel technique followed by thermal treatment. Particle induced X-ray emission spectroscopy and X-ray powder diffraction were used to characterize the samples. Mullites were orthorhombic, space group Pbam. Cr doping caused the increase of unit-cell parameters. Strongest expansion was noticed along c-axis followed by a and bc/c=0.089, Δa/a=0.061, Δb/b=0.045% per mole Cr2O3). A second phase, namely θ-(Al,Cr)2O3, was revealed by XRD in the sample containing 9.60 wt% Cr2O3. The structure of mullites was refined by the Rietveld method, location of Cr3+ was performed by the EPR spectroscopy. At low chromium doping level (Cr2O3 content less than ∼5 wt%) Cr3+ ions were substituted for Al3+ in the AlO6 octahedra of the mullite structure (M1 site). For higher doping level, Cr3+ ions were additionally substituted for Al3+ in the AlO6 octahedra of the second phase [θ-(Al,Cr)2O3 at 1400 °C, or α-(Al,Cr)2O3 at 1600 °C] which segregated in the system. Substitution of Cr3+ for Al3+ on M1 site in the mullite structure resulted in increase of average distances in (M1)O6 octahedron and decrease of average distances in T*O4 tetrahedron, while average distances in TO4 tetrahedron stayed almost constant.  相似文献   

13.
P doped ZnO films were grown on quartz by radio frequency-magnetron sputtering method using a ZnO target mixed with 1.5 at% P2O5 in the atmosphere of Ar and O2 mixing gas. The as-grown P doped ZnO film showed n-type conductivity, which was converted to p-type after 800 °C annealing in Ar gas. The P doped ZnO has a resistivity of 20.5 Ω cm (p∼2.0×1017 cm−3) and a Hall mobility of 2.1 cm2 V−1 s−1. XRD measurement indicated that both the as-grown and the annealed P doped ZnO films had a preferred (0 0 2) orientation. XPS study agreed with the model that the PZn-2VZn acceptor complex was responsible for the p-type conductivity as found in the annealed P-doped ZnO. Temperature-dependent photoluminescence (PL) spectrum showed that the dominant band is located at 3.312 eV, which was attributed to the free electronic radiative transition to neutral acceptor level (FA) in ZnO. The PZn-2VZn acceptor complex level was estimated to be at EV=122 meV.  相似文献   

14.
In this work, we report on the effect of Cr incorporation on the microstructural and optical properties of TiO2:Cr thin films deposited by the RF-magnetron sputtering method. The structural, morphological, chemical bonding and optoelectronic properties of the sputter-deposited TiO2:Cr films were systematically investigated, as a function the incorporated Cr content, by means of various techniques including X-ray diffraction (XRD), atomic force microscopy (AFM), Fourier-Transform Infra-Red (FTIR) absorption, X-ray Photoelectron Spectroscopy (XPS) and ellipsometry. The Cr incorporation into the TiO2 films was controlled by adjusting the RF power (PCr) on the Cr target during the co-sputtering process of TiO2 and Cr. We were thus able to demonstrate that by varying PCr from 8 W to 150 W, the Cr content of the TiO2:Cr films can be fairly controlled from ∼2 at.% to ∼18 at.% and their associated bandgap engineered from 3.3 eV to 1.5 eV. The room-temperature deposited TiO2:Cr are mainly amorphous with the presence of some TiO2 nanocrystallites, and their density increases as their Cr content is increased. The Cr inclusions were found to coexist under both metallic and oxidized forms in the films. By subjecting the TiO2:Cr films to post-annealing treatment (at 550 °C), their crystalline structure was found to be sensitive to their Cr content. Indeed, an anatase-to-rutile phase transformation has been pointed out to occur at a Cr content of ∼7 at.%. Likewise, the Cr-content dependence of the bandgap of annealed TiO2:Cr films undergoes a transition around the 7 at.% of Cr. Our results demonstrate the ability to control the Cr-content of TiO2:Cr films, which leads to tune their optoelectronic properties, such as bandgap or optical absorption edge.  相似文献   

15.
Highly transparent and conducting Chromium doped ZnO (Cr:ZnO) thin films with preferential c-axis orientation were grown on (0 0 0 1) sapphire substrates using buffer assisted pulsed laser deposition. The resistivity of Cr:ZnO thin films was found to decrease to a minimum value of ∼1.13×10−3Ω cm with the increasing Cr concentration up to ∼1.9 at.% and then increase with further increase of Cr concentration. On the contrary, the band gap and carrier concentration of Cr:ZnO thin films increased up to ∼3.37 eV and ∼2×1020 cm−3, respectively, with the increase of Cr concentration up to ∼1.9 at.%, then decreased with further increase of Cr concentration. The increase of carrier concentration and conductivity with Cr doping at low Cr concentrations (<1.9 at.%) could be attributed to the presence of Cr in +3 valence state in ZnO thus acting as donor while decrease of carrier concentration beyond ∼1.9 at.% of Cr concentration could be attributed to the charge compensating effect due to the presence of acceptor like point defects such as oxygen interstitials. This was experimentally confirmed using x-ray photoelectron spectroscopy. The observed variation in the band gap of Cr:ZnO thin films with increasing Cr doping was attributed to the competing effects of the high free carrier concentration induced Burstein-Moss blue shift and band gap narrowing.  相似文献   

16.
Pure and Cobalt doped zinc oxide were deposited on glass substrate by Ultrasonic spray method. Zinc acetate dehydrate, Cobalt chloride, 4-methoxyethanol and monoethanolamine were used as a starting materials, dopant source, solvent and stabilizer, respectively. The ZnO samples and ZnO:Co with Cobalt concentration of 2 wt.% were deposited at 300, 350 and 400 °C. The effects of substrate temperature and presence of Co as doping element on the structural, electrical and optical properties were examined. Both pure and Co doped ZnO samples are (0 0 2) preferentially oriented. The X-ray diffraction results indicate that the samples have polycrystalline nature and hexagonal wurtzite structure with the maximum average crystallite size of ZnO and ZnO:Co were 33.28 and 55.46 nm. An increase in the substrate temperature and presence doping the crystallinity of the thin films increased. The optical transmittance spectra showed transmittance higher than 80% within the visible wavelength region. The band gap energy of the thin films increased after doping from 3.25 to 3.36 eV at 350 °C.  相似文献   

17.
We explore the effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles synthesized by the sol-gel method. X-ray diffraction and x-ray photoelectron spectroscopy data show evidence that Cr has been incorporated into the wurtzite ZnO lattice as Cr2+ ions substituting for Zn2+ ions without any detectable secondary phase in as-synthesized Zn0.97Cr0.03O nanopowders. The room temperature magnetization measurements reveal a large enhancement of saturation magnetization Ms as well as an increase of coercivity of H2-annealed Zn0.97Cr0.03O:H samples. It is found that the field-cooled magnetization curves as a function of temperature from 40 to 400 K can be well fitted by a combination of a standard Bloch spin-wave model and Curie–Weiss law. The values of the fitted parameters of the ferromagnetic exchange interaction constant a and the Curie constant C of H2-annealed Zn0.97Cr0.03O:H nanoparticles are almost doubled upon H2-annealing. Photoluminescence measurements show evidence that the shallow donor defect or/and defect complexes such as hydrogen occupying an oxygen vacancy Ho may play an important role in the origin of H2-annealing induced enhancement of ferromagnetism in Cr-H codoped ZnO nanoparticles.  相似文献   

18.
S. Funk 《Applied Surface Science》2007,253(17):7108-7114
We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr2O3(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO2 adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of Ei = 0.1-1.1 eV and adsorption temperatures of Ts = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy Ed = 33.3 kJ/mol, first order pre-exponential 1 × 1013 s−1). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (Ed = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S0, is independent of Ts for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing Ei, with S0 smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low Ei is approx. independent of coverage (Kisliuk-shape) and increases initially at large Ei with coverage (adsorbate-assisted adsorption). CO2 physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of Ed has been obtained by means of a Redhead analysis of the TDS curves.  相似文献   

19.
Transparent conductive Co-doped ZnO thin films were deposited by ultrasonic spray technique. Conditions of preparation have been optimized to get good quality. A set of cobalt (Co)-doped ZnO (between 0 and 3 wt%) thin films were grown on glass substrate at 350 °C. The thin films were annealed at 500 °C for improvement of the physical properties. Nanocrystalline films with hexagonal wurtzite structure and a strong (0 0 2) preferred orientation were obtained. The maximum value of grain size G = 63.99 nm is attained with undoped ZnO film. The optical transmissions spectra showed that both the undoped and doped ZnO films have transparency within the visible wavelength region. The band gap energy decreased after doping from 3.367 to 3.319 eV when Co concentration increased from 0 to 2 wt% with slight increase of electrical conductivity of the films from 7.71 to 8.33 (Ω cm)−1. The best estimated structure, optical and electrical results are achieved in Co-doped ZnO film with 2 wt%.  相似文献   

20.
Single crystalline ZnO films were grown on c-plane GaN/sapphire (0 0 0 1) substrates by molecular beam epitaxy. Cr+ ions were implanted into the ZnO films with three different doses, i.e., 1 × 1014, 5 × 1015, and 3 × 1016 cm−2. The implantation energy was 150 keV. Thermal treatment was carried out at 800 °C for 30 s in a rapid thermal annealing oven in flowing nitrogen. X-ray diffraction (XRD), atomic force microscopy, Raman measurements, transmission electron microscopy and superconducting quantum interference device were used to characterize the ZnO films. The results showed that thermal annealing relaxed the stress in the Cr+ ions implanted samples and the implantation-induced damage was partly recovered by means of the proper annealing treatment. Transmission electron microscopy measurements indicated that the first five monolayers of ZnO rotated an angle off the [0 0 0 1]-axis of the GaN in the interfacial layer. The magnetic-field dependence of magnetization of annealed ZnO:Cr showed ferromagnetic behavior at room temperature.  相似文献   

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