Formation of Precipitates in Si Implanted with <Superscript>64</Superscript>Zn<Superscript>+</Superscript> and <Superscript>16</Superscript>O<Superscript>+</Superscript> Ions

The results of studying the surface Si layer and precipitate formation in CZ n-Si(100) samples sequentially implanted with ⁶⁴Zn⁺ ions with a dose of 5 × 10¹⁶ cm² and energy of 100 keV and ¹⁶O⁺ ions with the same dose but an energy of 33 keV at room temperature so that their projection paths R_p = 70 nm would coincide are presented. The post-implantation samples are annealed for 1 h in an inert Ar medium in the temperature range of 400–900°C with a step of 100°C. The profiles of the implanted impurities are studied by time-of-flight secondary ion mass spectrometry. The Si surface is visualized using a scanning electron microscope, while the near-surface layer is visualized with the help of maps of elements formed by Auger electron spectroscopy with profiling over depth. The ZnO(002) texture is formed in an amorphized Si layer after the implantation of Zn and O ions. ZnO(102) crystallites of 5 nm in size are found in a recrystallized single-crystalline Si layer after annealing in Ar at 700°C.     

Atomic Layer Deposition of UV‐Absorbing ZnO Films on SiO2 and TiO2 Nanoparticles Using a Fluidized Bed Reactor

Atomic layer deposition (ALD) was used to apply conformal, nanothick ZnO coatings on particle substrates using a fluidized bed reactor. Diethylzinc (DEZ) and water were used as precursors at 177 °C. Observed growth rates were ca. 2.0 Å/cycle on primary particles as verified by HRTEM. ICP‐AES and XPS were used to quantify Zn:substrate ratios. Layers of 6, 18, and 30 nm were deposited on 550 nm SiO₂ spheres for UV blocking cosmetics particles. TiO₂ nanoparticles were coated in the second part of this work by ZnO shells of 2, 5, and 10 nm thickness as novel inorganic sunscreen particles. The specific surface area of powders changed appropriately after nanothick film deposition using optimized conditions, signifying that high SA particles can be functionalized without agglomeration. The ZnO layers were polycrystalline as deposited and narrowing of the FWHM occurred upon annealing. Annealing the ZnO‐TiO₂ nanocomposite powder to 600 °C caused the formation of zinc titanate (Zn₂TiO₄) in both oxygen‐rich and oxygen‐deficient environments. The non‐ideal surface behavior of the DEZ precursor became problematic for the much longer times required for high surface area nanoparticle processing and results in Zn‐rich films at this growth temperature. In situ mass spectrometry provides process control capability to functionalize bulk quantities of nano‐ and ultrafine particles without significant precursor waste or process overruns. ZnO overlayers can be efficiently deposited on the surfaces of primary particles using ALD processing in a scalable fluidized bed reactor.     

Specific features of the segregation-related redistribution of phosphorus during thermal oxidation of heavily doped silicon layers

A model of the diffusion-segregation redistribution of phosphorus in an SiO₂/Si system during thermal oxidation of highly doped silicon layers is developed taking into account the formation of a peak of surface impurity concentration at the interface. The formation of this surface concentration peak is attributed to a change in the free energy of the impurity atoms near the silicon surface. This process is simulated by a diffusion-segregation equation. It is shown that the developed diffusion-segregation model is quite adequate for describing the phosphorus redistribution occurring during the oxidation of uniformly doped silicon layers. For the oxidation of implanted silicon layers, it was found that the segregation coefficient of the phosphorus at the SiO₂/Si interface is not constant but depends on time in the same way as the efficiency of transient enhanced diffusion in silicon. This phenomenon is explained by the reactivity of the impurity segregation during the thermal oxidation of silicon, when excess point defects in the implanted silicon layer affect both the oxidation process and the capture of impurity atoms by the growing silicon dioxide.     

The Zn(S,O,OH)/ZnMgO buffer in thin‐film Cu(In,Ga)(Se,S)2‐based solar cells part II: Magnetron sputtering of the ZnMgO buffer layer for in‐line co‐evaporated Cu(In,Ga)Se2 solar cells

A ZnS/Zn_1‐xMg_xO buffer combination was developed to replace the CdS/i‐ZnO layers in in‐line co‐evaporated Cu(In,Ga)Se₂(CIGS)‐based solar cells. The ZnS was deposited by the chemical bath deposition (CBD) technique and the Zn_1‐xMg_xO layer by RF magnetron sputtering from ceramic targets. The [Mg]/([Mg] + [Zn]) ratio in the target was varied between x = 0·0 and 0·4. The composition, the crystal structure, and the optical properties of the resulting layers were analyzed. Small laboratory cells and 10 × 10 cm² modules were realized with high reproducibility and enhanced stability. The transmission is improved in the wavelength region between 330 and 550 nm for the ZnS/Zn_1‐xMg_xO layers. Therefore, a large gain in the short‐circuit current density up to 12% was obtained, which resulted in higher conversion efficiencies up to 9% relative as compared to cells with the CdS/i‐ZnO buffer system. Peak efficiencies of 18% with small laboratory cells and 15·2% with 10 × 10 cm² mini‐modules were demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of Thermal Annealing on the Characteristics of Phosphorus-Implanted ZnO Crystals

A P-doped ZnO surface layer on undoped ZnO wafers was prepared by phosphorus (P) ion implantation. Hall effect measurement revealed p-type conduction in such layers annealed at 800°C. This indicates that acceptor levels are present in P-doped ZnO, even though the ZnO is still n-type. Micro-Raman scattering in ?z(xy)z geometry was conducted on P-implanted ZnO. The E ₂ ^high mode shift observed toward the high-energy region was related to compressive stress as a result of P-ion implantation. This compressive stress led to the appearance of an A ₁(LO) peak, which is an inactive mode. This A ₁(LO) peak relaxed during thermal annealing in ambient oxygen at temperatures higher than 700°C. The P2p_3/2 peak observed at 135.6 eV by x-ray photoelectron spectroscopy is associated with chemical bond formation leading to 2(P₂O₅) molecules. This indicates that implanted P ions substituted Zn sites in the ZnO layer. In photoluminescence spectroscopy, the P-related peaks observed at energies ranging between 3.1 and 3.5 eV originated from (A⁰, X) emission, because of P_Zn-2V_Zn complexes acting as shallow acceptors. The acceptor level was observed to be 126.9 meV above the valence band edge. Observation of this P-related emission indicates that ion implantation results in acceptor levels in the P-doped ZnO layer. This suggests that the P₂O₅ bonds are responsible for the p-type activity of P-implanted ZnO.     

Suppression of Red Luminescence in Wire Explosion Derived Eu:ZnO

Europium oxide (Eu₂O₃) is coated on zinc (Zn) wire using the electrophoretic deposition process. The coated Zn wire is subjected to the wire explosion process (WEP) which is rapid (< 15 min), and chimie douce (soft chemical, low temperature), in nature; this results in the formation of Eu doped ZnO. The explosion chamber contains oxygen (99.9%) at atmospheric pressure. Electron micrographs indicate that the particle sizes are ～ 80 nm. Diffractogram-based analysis suggests that the crystallite size is ~ 18–20 nm in the as-prepared doped ZnO nanoparticles. Electron paramagnetic resonance shows the presence of Zn vacancies and the cryo-photoluminescence spectrum indicates that Eu exists in the + 3 state. A combined Williamson–Hall plot and Kisielowski’s model based analysis indicates that Eu is a substitutional dopant in WEP derived Eu:ZnO particles. It is estimated that this material has ～ 0.24 at.% doping. This analysis also shows that, unlike another popular material GaN, in the case of ZnO, Eu³⁺ strictly substitutes for Zn²⁺ (i.e., dopant replacing a cation–anion pair does not seem possible). It may be noted that Eu³⁺ in a suitable host is oftentimes reported to be an efficient luminophore. The IR spectra show a band shift from 486 cm^?1 to 493 cm^?1; with peak shifts from 436 cm^?1 to 430 cm^?1 in Raman spectra. These too indicate the presence of Eu in the samples. However, at room temperature, only green luminescence (centered at 534 nm) is observed from the sample indicating (1) high concentrations of O_Zn anti-site defects and Zn vacancies, and (2) concomitant quenching of the luminescence at room temperature. Our results suggest that WEP is viable for synthesizing rare earth doped ceramic materials. However, obtaining efficient phosphors using this approach will likely require, (1) reduction of defect densities, and (2) appropriate passivation using post-processing.     

Atomic layer deposition of Zn1−xMgxO buffer layers for Cu(In,Ga)Se2 solar cells

Fabrication of Zn_1−xMg_xO films by atomic layer deposition (ALD) has been studied for use as buffer layers in Cu(In,Ga)Se₂ (CIGS)‐based solar cell devices. The Zn_1−xMg_xO films were grown using diethyl zinc, bis‐cyclopentadienyl magnesium and water as precursors in the temperature range from 105 to 180°C. Single‐phase ZnO‐like films were obtained for x < 0·2, followed by a two phase region of ZnO‐ and MgO‐like structures for higher Mg concentrations. Increasing optical band gaps of up to above 3·8 eV were obtained for Zn_1−xMg_xO with increasing x. It was found that the composition of the Zn_1−xMg_xO films varied as an effect of deposition temperature as well as by increasing the relative amount of magnesium precursor pulses during film growth. Completely Cd‐free CIGS‐based solar cells devices with ALD‐Zn_1−xMg_xO buffer layers were fabricated and showed efficiencies of up to 14·1%, which was higher than that of the CdS references. Copyright © 2006 John Wiley & Sons, Ltd.     

Photocatalytic degradation of methyl orange and gas-sensing performance of nanosized ZnO

ZnO nanoparticles were synthesized by calcining composites of zinc nitrate and poly(vinyl pyrrolidone) (PVP, molecular weight 30 000) at a mass ratio of 1:2 at 500 °C for 2 h. X-Ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques were used to characterize the as-synthesized ZnO nanoparticles. The particles ranged in size from 30 to 50 nm. Infrared spectra of PVP and the PVP+Zn(NO₃)₂·6H₂O composite revealed coordination between the carbonyl (C=O) of PVP and Zn²⁺ of zinc nitrate, which led to a uniform nanoparticle morphology. The gas-sensing properties and photocatalytic performance of the final product were systematically investigated. The results show that the ZnO nanoparticles exhibit both a high response for ethanol detection and excellent photocatalytic activity for degradation of methyl orange under UV irradiation for 30 min.     

Abnormal Diffusion Behavior of Zn in Cu/Sn-9 wt.%Zn/Cu Interconnects During Liquid–Solid Electromigration

The diffusion behavior of Zn atoms and the interfacial reaction in Cu/Sn-9 wt.%Zn/Cu interconnects undergoing liquid–solid electromigration were investigated under a current density of 5.0 × 10³ A/cm² at 230°C. A reverse polarity effect was revealed, in which the interfacial intermetallic compounds (IMCs) at the cathode grew continuously and were remarkably thicker than those at the anode. This behavior resulted from the directional migration of Zn atoms from the anode towards the cathode, which was induced by the positive effective charge number (Z ^*) of the Zn atoms rather than by back-stress. Consequently, at the anode, dissolution and massive spalling of the Cu-Zn IMCs occurred, and the depletion of Zn atoms resulted in the transformation of initial interfacial Cu₅Zn₈ IMC into (Cu₆Sn₅ + CuZn); at the cathode, the interfacial Cu₅Zn₈ IMC gradually transformed into (Cu₅Zn₈ + CuZn); in the solder, the Zn content reduced continuously from 9 wt.% to 0.9 wt.%. A growth model is proposed to explain the reverse polarity effect, and the average Z ^* of Zn atoms in Cu₅Zn₈ was calculated to be +0.25 using this model.     

Stable Zinc Metal Anodes with Textured Crystal Faces and Functional Zinc Compound Coatings

The uneven electrodeposition and inferior corrosion resistance are the fundamental obstacles to achieve stable Zn metal anodes. The features of the electrode surface/interface are closely correlated with the properties. Herein, the Zn surface with more exposed (002)_Zn planes is modified through a simple acid-etching approach. The in situ generated zinc compounds form an interface layer with strong adhesion to the Zn electrode, which can enhance the Zn²⁺ ion kinetics and regulate the deposition/dissolution behaviors. A variety of acids with functional cations are selected, among which the phosphoric acid etches the Zn with a higher extent of texturing and generates a more compact layer. The obtained zinc phosphate@Zn electrode enables stable cycling and fast kinetics in symmetrical and full Zn metal batteries. This study provides a new example of combined surface and interface modification toward high-performance aqueous zinc metal anodes.     

Photoelectric properties of ZnO films doped with Cu and Ag acceptor impurities

The influence exerted by doping with Cu and Ag acceptor impurities at a content of 1, 3, and 5 at. % on the luminescence and photoconductivity of zinc oxide films has been studied. Electron-beam evaporation in optimal modes has been used to obtain films with predominant luminescence in the UV spectral range. It has been shown that the incorporation of copper yields three types of point defects in ZnO: Cu_Zn (3d¹⁰), Cu_Zn (3d⁹), and Cu_i; and in silver, a single type: Ag_Zn (3d¹⁰). Precipitation of a silver oxide phase at the highest impurity concentration has been observed. Impurity incorporation leads to a pronounced increase in the resistance and photosensitivity of films.     

Active Layer Thickness Effects on the On-State Current and Pulse Measurement at Room Temperature on Deposited Zinc Oxide Thin-Film Transistors

This study reports on the fabrication of thin-film transistors (TFTs) with transparent zinc oxide (ZnO) semiconductors serving as the active channel and silicon dioxide (SiO₂) serving as the gate insulator. The ZnO films were deposited by radiofrequency magnetron sputtering at room temperature. Moreover, the effects of channel thickness on the structural and pulse current?Cvoltage characteristics of ZnO TFTs using a bottom gate configuration were investigated. As the channel thickness increased, the crystalline quality and the channel conductance were enhanced. The electrical characteristics of TFTs exhibited field-effect mobilities of 8.36?cm²/Vs to 16.40?cm²/Vs and on-to-off current ratios of 10⁸ to 10⁷ for ZnO layer thickness of 45?nm and 70?nm, respectively. The threshold voltage was in the range of 10?V to 31?V for ZnO layer thicknesses from 35?nm to 70?nm, respectively. The low deposition and processing temperatures make these TFTs suitable for fabrication on flexible substrates.     

A Mössbauer study of a two-electron acceptor impurity of zinc in silicon

Mössbauer emission spectroscopy of the ⁶⁷Ga(⁶⁷Zn) isotope was used to show that the two-electron acceptor impurity of Zn is present in silicon only in the form of neutral (Zn⁰) or doubly ionized (Zn^2?) centers, depending on the Fermi-level position. Broadening of the spectra corresponding to the above centers indicates that the local symmetry of these centers is not cubic. The absence of the line corresponding to the singly ionized state (Zn^2?) of zinc in the Mössbauer spectra of partially compensated samples is regarded as evidence that the correlation energy is negative.     

Study of zinc impurity atoms in GaP, GaAs, and GaSb 67Ga(67Zn) and 67Cu(67Zn) by emission Mössbauer spectroscopy

The Mössbauer spectra of ⁶⁷Ga(⁶⁷Zn) and ⁶⁷Cu(⁶⁷Zn) impurity atoms in the bulk of GaP, GaAs, and GaSb samples correspond to isolated zinc centers at Ga sites. The observed shift of the spectral centers of gravity to higher positive velocities at the transition from p-to n-type samples corresponds to the recharging of a shallow zinc impurity center. Mössbauer spectra of ⁶⁷Cu(⁶⁷Zn) impurities at the surface of samples represent a superposition of spectra corresponding to isolated zinc centers at gallium sites with those corresponding to zinc associates with an arsenic vacancy.     

Electrochemical Activation of Manganese‐Based Cathode in Aqueous Zinc‐Ion Electrolyte

Low‐cost and highly safe zinc‐manganese batteries are expected for practical energy storage and grid‐scale application. The electrolyte adjustment is further combined to boost their performance output; however, the mechanism behind the electrochemical contrast caused by electrolyte composition remains unclear, which has held back the development of these systems. Hence, new insight into the electrochemical activation of manganese‐based cathodes, which is induced by the aqueous zinc‐ion electrolyte, is provided. The relationship between the desolvation of Zn²⁺ from [Zn(OH₂)₆]²⁺‐solvation shell and the electrolyte/electrode interfacial reaction to form Zn₄SO₄(OH)₆·4H₂O phase or its analogues is established, which is the key for the electrochemical activation. Further electrolyte optimization promotes the cycling stability of Zn/LiMn₂O₄ battery with a long life span over 2000 cycles. This work illuminates the confused direction in exploring electrolyte for zinc‐manganese batteries.     

Surface texture of single-crystal silicon oxidized under a thin V<Subscript>2</Subscript>O<Subscript>5</Subscript> layer

The process of surface texturing of single-crystal silicon oxidized under a V₂O₅ layer is studied. Intense silicon oxidation at the Si–V₂O₅ interface begins at a temperature of 903 K which is 200 K below than upon silicon thermal oxidation in an oxygen atmosphere. A silicon dioxide layer 30–50 nm thick with SiO₂ inclusions in silicon depth up to 400 nm is formed at the V₂O₅–Si interface. The diffusion coefficient of atomic oxygen through the silicon-dioxide layer at 903 K is determined (D ≥ 2 × 10^–15 cm² s^–1). A model of low-temperature silicon oxidation, based on atomic oxygen diffusion from V₂O₅ through the SiO₂ layer to silicon, and SiO _x precipitate formation in silicon is proposed. After removing the V₂O₅ and silicon-dioxide layers, texture is formed on the silicon surface, which intensely scatters light in the wavelength range of 300–550 nm and is important in the texturing of the front and rear surfaces of solar cells.     

The lattice position of diffused Zn in InP

We have measured the substitutional fraction (f_s) for Zn atoms diffused into InP crystals using the proton-induced x-ray excitation (PIXE) technique. Diffusion times ranged from 15–60 min at 425–650° C. For several samples with diffusion depths in the range 0.75-3.7 μm (as determined by SIMS analysis), we find that the Zn impurity atoms reside almost totally on lattice sites: f_s = 0.9 ± 0.1. Contrary to results of an earlier study, we find no evidence for precipitates in the diffused layers. However, only ∼10^-3-10^-1 of the Zn is electrically active, consistent with Tuck and Hooper’s suggestion of neutral V_p Zn_In V_p complexes.     

The annealing of Cd1−xZnxTe in CdZn vapors

As-grown CdZnTe usually contains defects, such as twins, subgrain boundaries, dislocations, and Te precipitates. It is always important to anneal CdZnTe slices in Cd vapor to eliminate these defects, especially Te precipitates. The exchange of Zn atoms between the slices and the vapor plays an important role during the annealing process. In this paper, the effects of Zn partial pressure on the properties of the annealed slices are studied carefully by measuring the concentration profiles, the infrared (IR) transmission spectra, and the x-ray rocking curves. It was found that a surface layer with different compositions and possibly different structure from the bulk crystal formed during the annealing of CdZnTe samples in the saturated Zn vapor. The accumulation of excess Te in the surface layer helps to increase the IR permeability of the bulk crystal greatly. To improve the crystallization quality, a lower Zn-pressure annealing should be used following the high Zn-pressure annealing. The diffusion of Zn in the bulk crystal has also been analyzed at the temperatures of 700°C and 500°C. Calculations determined that D_Zn (700°C)=4.02 × 10⁻¹² cm²s⁻¹ and D_Zn (500°C)=1.22 × 10⁻¹³ cm²s⁻¹.     

Highly Reversible Zn Anode Enabled by Controllable Formation of Nucleation Sites for Zn‐Based Batteries

Aqueous Zn batteries have drawn tremendous attention for their several advantages. However, the challenges of Zn anodes such as the corrosion and ZnO densification have compromised their application in rechargeable Zn‐based batteries. In this paper, a straightforward strategy is employed to facilitate the uniform Zn stripping/plating of the Zn anode through using a ZrO₂ coating layer, which contributes to the controllable nucleation sites for Zn²⁺ and fast Zn²⁺ transportation through the favorable Maxwell–Wagner polarization. As a result, the low polarization (24 mV at 0.25 mA cm^?2), high Coulombic efficiency (99.36% at 20 mA cm^?2), and long cycle life (over 3800 h at 0.25 mA cm^?2) can be obtained for the ZrO₂‐coated Zn anode. It is believed that the ZrO₂ coating layer can also act as an inert physical barrier to decrease the contact of the anode and electrolyte, thus reducing both the Zn corrosion and formation of ZnO densification, and then improve the reversibility of Zn anode. The results demonstrated in this work provide an appealing strategy for the future development of rechargeable Zn‐based batteries.     

Growth of Heteroepitaxial ZnO Thin Films on GaN‐Buffered Al2O3 (0001) Substrates by Low‐Temperature Hydrothermal Synthesis at 90 °C

Heteroepitaxial ZnO films are successfully grown on nondoped GaN‐buffered Al₂O₃ (0001) substrates in water at 90 °C using a two‐step process. In the first step, a discontinuous ZnO thin film (ca. 200 nm in thickness) consisting of hexagonal ZnO crystallites is grown in a solution containing Zn(NO₃)·6 H₂O and NH₄NO₃ at ca. pH 7.5 for 24 h. In the second step, a dense and continuous ZnO film (ca. 2.5 μm) is grown on the first ZnO thin film in a solution containing Zn(NO₃)·6 H₂O and sodium citrate at ca. pH 10.9 for 8 h. Scanning electron microscopy, X‐ray diffraction, UV‐vis absorption spectroscopy, photoluminescence spectroscopy, and Hall‐effect measurement are used to investigate the structural, optical, and electrical properties of the ZnO films. X‐ray diffraction analysis shows that ZnO is a monocrystalline wurtzite structure with an epitaxial orientation relationship of (0001)[11 0]_ZnO∥(0001)[11 0]_GaN. Optical transmission spectroscopy of the two‐step grown ZnO film shows a bandgap energy of 3.26 eV at room temperature. A room‐temperature photoluminescence spectrum of the ZnO film reveals only a main peak at ca. 380 nm without any significant defect‐related deep‐level emissions. The electrical property of ZnO film showed n‐type behavior with a carrier concentration of 3.5 × 10¹⁸ cm^–3 and a mobility of 10.3 cm² V^–1 s^–1.