Correlation between electrical and optical properties of Cr:ZnO thin films grown by pulsed laser deposition

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.     

Synthesis of stable dispersion of ZnO quantum dots in aqueous medium showing visible emission from bluish green to yellow

Aqueous dispersion of 4-8 nm size stable ZnO quantum dots (QDs) exhibiting luminescence in the visible region have been synthesized by a simple solution growth technique at room temperature. Silica has been used as capping agent to control the particle size as well as to achieve uniform dispersion of QDs in aqueous medium. X-ray diffractometer (XRD) analysis reveals formation phase pure ZnO particles having wurzite (hexagonal) structure. Atomic force microscope (AFM) images show that the particles are spherical in shape, having average crystalline sizes ∼4, 5.5 and 8 nm for samples prepared at pH values of 10, 12 and 14, respectively. From the optical absorption studies, the band gap energy of QDs is found to be blue shifted as compared to bulk ZnO (3.36 eV) due to the quantum confinement effect and is consistent with the band gap calculated by using effective-mass approximation model. The photoluminescence (PL) observed in these QDs has been attributed to the presence of defect centers.     

Substrate temperature influence on the properties of nanostructured ZnO transparent ultrathin films grown by PLD

Zinc oxide films of 40 nm thickness have been deposited on glass substrates by pulsed laser deposition using an excimer XeCl laser (308 nm) at different substrate temperatures ranging from room temperature to 650 °C. Surface investigations carried out by using atomic force microscopy have shown a strong influence of temperature on the films surface topography. UV-VIS transmittance measurements have shown that our ZnO films are highly transparent in the visible wavelength region, having an average transmittance of ∼90%. The optical band gap of the films was found to be 3.26 eV, which is lower than the theoretical value of 3.37 eV. Besides the normal absorption edge related to the transition between the valence and the conduction band, an additional absorption band was also recorded in the wavelength region around 364 nm (∼3.4 eV). This additional absorption band may be due to excitonic, impurity, and/or quantum size effects. Photoreduction/oxidation in ozone of the ZnO films lead to larger conductivity changes for higher deposition temperature. In conclusion, the ozone sensing characteristics as well as the optical properties of the ZnO thin films deposited by pulsed laser deposition are strongly influenced by the substrate temperature during growth. The sensitivity of the films towards ozone might be enhanced significantly by the control of the films deposition parameters and surface characteristics.     

Density controllable growth of ZnO quantum dots by MOCVD

High quality self-assemble ZnO quantum dots (QDs) have been successfully grown on the Si(111) substrates by metalorganic chemical vapor deposition (MOCVD). The diameter of ZnO QDs is about 10 nm in average, and the densities and the sizes of ZnO QDs can be well controlled by adjusting the growth temperature, which were evident in the SEM images. The properties and stress involved in ZnO QDs are studied by X-ray diffraction. In addition, room temperature photoluminescence spectra reveal that the ZnO QDs exhibit a band gap blue shift because of the quantum confinement effects.     

Synthesis and optical properties of Co-doped ZnO nanofibers prepared by electrospinning

In this work, Co-doped ZnO nanofibers have been fabricated successfully by an electrospinning technique. The as-prepared nanofibers are characterized by themogravimetric analysis (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Raman spectra and photoluminescence spectroscopy (PL). Results have showed that a wurtzite ZnO nanofibers were obtained and the PL spectrum showed a red-shift by 10 nm due to narrowing of the ZnO band gap (∼3.29 eV) as a result of Co doping. Meanwhile, Raman scattering spectra exhibited an unusual peak at 540 cm⁻¹.     

Structural,optical and magnetic study of (1−x)ZnO–xMgO composites prepared through solid state reaction method

We report the study of structural, optical and magnetic properties of (1−x)ZnO–xMgO (x=0.35, 0.40, 0.45 and 0.50) composites prepared by solid state reaction method. X-ray diffraction pattern confirms the presence of both the phases associated with ZnO (hexagonal) and MgO (cubic), which is revealed through the existence of (1 1 1) and (2 0 0) peaks in addition to ZnO peaks. The lattice parameter c as calculated using X-ray analysis undergoes shrinkage with increasing content of MgO. Microstructural analysis suggests that there is no variation in spherical elongated shape of grains with increasing concentration of MgO, where the average grain size is found to be ∼600 nm. The band gap as calculated from optical absorption spectra obtained by diffuse reflectance method recorded at room temperature is tuned from 3.16 to 3.55 eV. Photoluminescence spectra consist of near band edge UV emission (389 nm) and defect level emission (503 nm). The increase of MgO concentration leads to blue shift of UV emission peaks. The magnetic measurements conducted using SQUID at 5 K temperature reveals ferromagnetism along with paramagnetic and superparamagnetic components. Saturation magnetisation (M_s) is observed to be enhanced with MgO doping.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

Chemical spray pyrolysis deposition and characterization of p-type CuCr1−xMgxO2 transparent oxide semiconductor thin films

A chemical spray pyrolysis technique for deposition of p-type Mg-doped CuCrO₂ transparent oxide semiconductor thin films using metaloorganic precursors is described. As-deposited films contain mixed spinel CuCr₂O₄ and delafossite CuCrO₂ structural phases. Reduction in spinel CuCr₂O₄ fraction and formation of highly crystalline films with single phase delafossite CuCrO₂ structure is realized by annealing at temperatures ?700 °C in argon. A mechanism of synthesis of CuCrO₂ films involving precursor decomposition, oxidation and reaction between constituent oxides in the spray deposition process is presented. Post-annealed CuCr_0.93Mg_0.07O₂ thin films show high (?80%) visible transmittance and sharp absorption at band gap energy with direct and indirect optical band gaps 3.11 and 2.58 eV, respectively. Lower (∼450 °C) substrate temperature formed films are amorphous and yield lower direct (2.96 eV) and indirect (2.23 eV) band gaps after crystallization. Electrical conductivity of CuCr_0.93 Mg_0.07O₂ thin films ranged 0.6-1 S cm⁻¹ and hole concentration ∼2×10¹⁹ cm⁻³ determined from Seebeck analysis. Temperature dependence of conductivity exhibit activation energies ∼0.11 eV in 300-470 K and ∼0.23 eV in ?470 K region ascribed to activated conduction and grain boundary trap assisted conduction, respectively. Heterojunction diodes of the structure Au/n-(ZnO)/p-(CuCr_0.93Mg_0.07O₂)/SnO₂ (TCO) were fabricated which show potential for transparent wide band gap junction device.     

Study on the structure and optical property of Zn1−xCuxO sol–gel thin films on quartz substrate

Zn_1−xCu_xO thin films (x=0, 1.0, 3.0, 5.0%) are prepared on quartz substrate by sol–gel method. The structure and morphology of the samples are investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results show that Cu ions were effectively penetrated into the ZnO crystal lattices with substitutional and interstitial impurities to form stable solid solutions without changing the polycrystalline wurtzite structure. Two peaks at 420 nm (2.95 eV, violet), 485 nm (2.56 eV, blue) have been observed from the photoluminescence (PL) spectra of the samples. It is concluded that the violet peak may correspond to the exciton emission; the blue emission corresponds to the electron transition from the bottom of the conduction band to the acceptor level of zinc vacancy. The optical test shows that the optical band gap E_g is decreased with the increase amount of Cu doping in ZnO. The band gap decrease from 3.40 eV to 3.25 eV gradually. It is also found that the transmission rate is increased rapidly with the increase of Cu ions concentration.     

Deposition and characterization of transparent and conductive sprayed ZnO:B thin films

Highly transparent and conductive Boron doped zinc oxide (ZnO:B) thin films were deposited using chemical spray pyrolysis (CSP) technique on glass substrate. The effect of variation of boron doping concentration in reducing solution on film properties was investigated. Low angle X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [002] direction. The films with resistivity 2.54×10⁻³ Ω-cm and optical transmittance >90% were obtained at optimized boron doping concentration. The optical band gap of ZnO:B films was found ∼3.27 eV from the optical transmittance spectra for the as-deposited films. Due to their excellent optical and electrical properties, ZnO:B films are promising contender for their potential use as transparent window layer and electrodes in solar cells.     

CdTe aggregates in KBr crystalline matrix

In this work, we report the experimental results on the fabrication and optical characterization of Czochralski (Cz) grown KBr single crystals doped with CdTe crystallites. The results of the optical absorption have shown two bands, the first one located at 250 nm demonstrates the incorporation of cadmium atoms in the KBr host followed by a partial chemical decomposition of CdTe, the second band located at 585 nm shows an optical response of CdTe aggregates. Photoluminescence spectra at room temperature before annealing showed a band located at 520 nm (2.38 eV), with a blue shift from the bulk gap of 0.82 eV (E_g (CdTe)=1.56 eV). While the photoluminescence spectra after annealing at 600 °C showed a band situated at 640 nm (1.93 eV), these bands are due to band-to-band transitions of CdTe nanocrystals with a blue shift from the bulk gap at 0.38 eV. Blue shift in optical absorption and photoluminescence spectra confirm nanometric size of dopant. X-ray diffraction (XRD) spectra have shown the incorporation of CdTe aggregates in KBr.     

Effect of Sn concentration on structural and optical properties of zinc oxide nanobelts

We investigated structural and optical properties of Sn-doped ZnO nanobelts with different Sn concentrations. X-ray diffraction and Raman spectra showed that the Sn-doped ZnO nanobelts have wurtzite structure at low Sn concentration (<2.1 at%) and over 2.1 at% a part of them starts to have the inverse spinel Zn₂SnO₄ structure phase. In addition, for Sn-doped ZnO nanobelts, the photoluminescence spectra indicate that ultraviolet emission peak appears first a blue shift with the increase of Sn concentration due to Burstein-Moss effect and then exhibits a red shift due to band gap renormalization effect.     

Structural, electrical and optical properties of Gd doped and undoped ZnO:Al (ZAO) thin films prepared by RF magnetron sputtering

The influence of the gadolinium doping on the structural features and opto-electrical properties of ZnO:Al (ZAO) films deposited by radio frequency (RF) magnetron sputtering method onto glass substrates was investigated. X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [0 0 2] direction. The Gd doped ZAO film with a thickness of 140 nm showed a high visible region transmittance of 90%. The optical band gap was found to be 3.38 eV for pure ZnO film and 3.58 eV for ZAO films while a drop in optical band gap of ZAO film was observed by Gd doping. The lowest resistivities of 8.4 × 10⁻³ and 10.6 × 10⁻³ Ω cm were observed for Gd doped and undoped ZAO films, respectively, which were deposited at room temperature and annealed at 150 °C.     

Blue luminescent silicon nanocrystals prepared by short pulsed laser ablation in liquid media

The pulsed laser processing in liquid media is an attractive alternative to produce room temperature luminescent silicon nanocrystals (Si-ncs). We report on a blue luminescent Si-ncs preparation by using nanosecond pulsed laser (Nd:YAG, KrF excimer) processing in transparent polymer and water. The Si-ncs fabrication is assured by ablation of crystalline silicon target immersed in liquids. During the processing and following aging in liquids, oxide based liquid media, induce shell formation around fresh nanocrystals that provides a natural and stable form of surface passivation. The stable room temperature blue-photoluminescent Si-ncs are prepared with maxima located around ∼440 nm with corresponding optical band gap around ∼2.8 eV (∼430 nm). Due to the reduction of surface defects, the Si-ncs preparation in water, leads to a narrowing of full-width-half-maxima of the photoluminescence spectra.     

Dependence of film thickness on the structural and optical properties of ZnO thin films

ZnO thin films are prepared on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) at room temperature. Optical parameters such as optical transmittance, reflectance, band tail, dielectric coefficient, refractive index, energy band gap have been studied, discussed and correlated to the changes with film thickness. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. Films with optical transmittance above 90% in the visible range were prepared at pressure of 6.5 × 10⁻⁴ Torr. XRD analysis revealed that all films had a strong ZnO (0 0 2) peak, indicating c-axis orientation. The crystal grain size increased from 14.97 nm to 22.53 nm as the film thickness increased from 139 nm to 427 nm, however no significant change was observed in interplanar distance and crystal lattice constant. Optical energy gap decreased from 3.21 eV to 3.19 eV with increasing the thickness. The transmission in UV region decreased with the increase of film thickness. The refractive index, Urbach tail and real part of complex dielectric constant decreased as the film thickness increased. Oscillator energy of as-deposited films increased from 3.49 eV to 4.78 eV as the thickness increased.     

Properties of sol-gel dip-coated zinc oxide thin films

Zinc oxide (ZnO) films were deposited on glass substrates by the sol-gel dip coating method using acrylamide route. The films were characterized by X-ray diffraction studies which indicated wurtzite structure. Optical absorption measurements indicated band gap in the range 3.17-3.32 eV. XPS studies indicated the formation of ZnO. The resistivity of the films were in the range 1000-10,000 ohm cm.     

Cu-doped ZnO nanoparticles: Synthesis, structural and electrical properties

Pure and Cu doped ZnO nanopowders (5, 10, 15, 20, 25 and 30 at% Cu) have been synthesized using co-precipitation method. Transmission Electron Microscopic analysis has shown the morphology of ZnO nanopowders to be quasi-spherical. Powder X-ray Diffraction studies have revealed the systematic doping of Cu into the ZnO lattice up to 10% Cu, though the peaks corresponding to CuO in 10% Cu are negligibly very small. Beyond this level, there was segregation of a secondary phase corresponding to the formation of CuO. Fourier Transform Infrared spectra have shown a broad absorption band at ∼490 cm⁻¹ for all the samples, which corresponds to the stretching vibration of Zn-O bond. DC electrical resistivity has been found to decrease with increasing Cu content. The activation energy has also been observed to decrease with copper doping i.e. from ∼0.67 eV for pure ZnO to ∼0.41 eV for 30 at% Cu doped ZnO.     

Low-temperature deposited ZnO thin films on the flexible substrate by cathodic vacuum arc technology

In this paper, un-doped zinc oxide (ZnO) films with various thicknesses (150, 250, 350, 450 and 550 nm) were successfully prepared onto PET substrates using cathodic vacuum arc technique at low-temperature (<40 °C). Their microstructure, optical and electrical properties were investigated and discussed. The films showed (0 0 2) peaks, an average transmittance over 80% in the visible region. Calculated values of the band gap are around 3.29-3.33 eV when the film thickness increased, indicating a slight blue shift of optical transmission spectra. The lowest resistivity about 5.26 × 10⁻³ Ω cm could be achieved for the un-doped ZnO film with thickness of 550 nm.     

The effect of heat treatment on the physical properties of sol-gel derived ZnO thin films

Zinc oxide (ZnO) thin films were deposited on microscope glass substrates by sol-gel spin coating method. Zinc acetate (ZnAc) dehydrate was used as the starting salt material source. A homogeneous and stable solution was prepared by dissolving ZnAc in the solution of monoethanolamine (MEA). ZnO thin films were obtained after preheating the spin coated thin films at 250 °C for 5 min after each coating. The films, after the deposition of the eighth layer, were annealed in air at temperatures of 300 °C, 400 °C and 500 °C for 1 h. The effect of thermal annealing in air on the physical properties of the sol-gel derived ZnO thin films are studied. The powder and its thin film were characterized by X-ray diffractometer (XRD) method. XRD analysis revealed that the annealed ZnO thin films consist of single phase ZnO with wurtzite structure (JCPDS 36-1451) and show the c-axis grain orientation. Increasing annealing temperature increased the c-axis orientation and the crystallite size of the film. The annealed films are highly transparent with average transmission exceeding 80% in the visible range (400-700 nm). The measured optical band gap values of the ZnO thin films were between 3.26 eV and 3.28 eV, which were in the range of band gap values of intrinsic ZnO (3.2-3.3 eV). SEM analysis of annealed thin films has shown a completely different surface morphology behavior.     

Structural and PL properties of Cu-doped ZnO films

Cu-doped ZnO films with hexagonal wurtzite structure were deposited on silicon (1 1 1) substrates by radio frequency (RF) sputtering technique. An ultraviolet (UV) peak at ∼380 nm and a blue band centered at ∼430 nm were observed in the room temperature photoluminescent (PL) spectra. The UV emission peak was from the exciton transition. The blue emission band was assigned to the Zn interstitial (Zn_i) and Zn vacancy (V_Zn) level transition. A strong blue peak (∼435 nm) was observed in the PL spectra when the α_Cu (the area ratio of Cu-chips to the Zn target) was 1.5% at 100 W, and ZnO films had c-axis preferred orientation and smaller lattice mismatch. The influence of α_Cu and the sputtering power on the blue band was investigated.