Zinc Oxide Nanoparticles with Defects

Zinc oxide in the form of nanoscale materials can be regarded as one of the most important semiconductor oxides at present. However, the question of how chemical defects influence the properties of nanoscale zinc oxide materials has seldom been addressed. In this paper, we report on the introduction of defects into nanoscale ZnO, their comprehensive analysis using a combination of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption spectroscopy/extended X‐ray absorption fine structure (XAS/EXAFS), electron paramagnetic resonance (EPR), magic‐angle spinning nuclear magnetic resonance (MAS‐NMR), Fourier‐transform infrared (FTIR), UV‐vis, and photoluminescence (PL) spectroscopies coupled with ab‐initio calculations), and the investigation of correlations between the different types of defects. It is seen that defect‐rich zinc oxide can be obtained under kinetically controlled conditions of ZnO formation. This is realized by the thermolysis of molecular, organometallic precursors in which ZnO is pre‐organized on a molecular scale. It is seen that these precursors form ZnO at low temperatures far from thermodynamic equilibrium. The resulting nanocrystalline ZnO is rich in defects. Depending on conditions, ZnO of high microstructural strain, high content of oxygen vacancies, and particular content of heteroatom impurities can be obtained. It is shown how the mentioned defects influence the electronic properties of the semiconductor nanoparticles.     

脉冲激光沉积法制备ZnO基薄膜研究进展

作为一种新型的Ⅱ-Ⅵ半导体材料,ZnO具有优良的光学和电学性能,在紫外光发射器件、自旋功能器件、气体探测器、表面声波器件等领域有着广阔的应用前景.首先介绍了ZnO材料和脉冲激光溅射法的一些相关内容,然后从材料制备角度着重阐述了目前利用脉冲激光沉积法(PLD)制备ZnO基薄膜的若干重要研究方向,例如p型掺杂、p-n结的制备、Mg掺杂、Cd掺杂和磁性离子掺杂等.     

The effect of growth conditions,point defects and hydrogen on the electronic structure and properties of p-type (Al,N) codoped ZnO: A first principles study

The effects of point defects, hydrogen, and growth conditions on the electronic structure and properties of the (Al,N) codoped p-type ZnO have been investigated using the first principles method. The obtained results showed that the Al_Zn–N_O–V_Zn complex is a shallow acceptor that can play an important role in achieving the p-type conductivity in the (Al,N) codoped ZnO films. Our results showed also that the electrical conductivity type in the (Al,N) codoped ZnO films strongly depends on the donor/acceptor concentrations ratio. The codoped ZnO films prepared under both Zn-rich and O-rich growth conditions with a donors/acceptors ratio of 1:2 have a p-type conductivity, while those prepared with a ratio of 1:1 cannot be p-type unless if they are prepared under O-rich conditions. The achieved p-type quality depends also on the used nitrogen doping source. To prepare p-type ZnO film of high quality using the (Al,N) codoping method, the use of NO or NO₂ is recommended. The presence of donor defects such as oxygen vacancies and hydrogen will significantly affect the electronic properties of the (Al,N) codoped ZnO films, and if the concentration of these defects in the sample is high enough, the material can be easily converted to n-type.     

Co-doped ZnO dilute magnetic semiconductor

This paper reports on recent findings in the Co-doped ZnO system where as-deposited samples with n-type semiconductor properties display magnetic ordering above room temperature. Detailed atomic scale structural characterization has eliminated clustering and second-phase formation as the source of the magnetic behavior. Upon high-temperature annealing in oxygen, the samples become insulating and the magnetization drops. This suggests that the observed magnetic behavior of the oxide is directly related to the presence of intrinsic defects, notably oxygen vacancies and Zn interstitials. These defects are believed to mediate exchange coupling of the Co spins through electron doping of the matrix, and perhaps also the formation of bound magnetic polarons.     

p型ZnO薄膜制备的研究进展

ZnO是一种性能优异的"低温蓝光工程"宽带隙Ⅱ-Ⅵ族半导体材料,但因本征施主缺陷和施主杂质引起的自补偿效应等使ZnO很难有效地实现n型向p型导电的转变。为此,阐述了ZnO薄膜的p型掺杂机理,介绍了国内外研究者在抑制自补偿、提高受主掺杂元素固溶度及寻求合适的受主掺杂元素等方面p型ZnO薄膜的最新研究进展。研究表明:增加ZnO材料中N原子固溶度的各种办法如施主-受主共掺杂、超声雾化气相淀积及本征ZnO薄膜在NH3气氛下后退火等和选择IB族中的Ag为受主掺杂元素是实现ZnO薄膜p型导电的有效措施。期望通过本综述能为国内ZnO基器件应用的p型ZnO薄膜的制备提供新思路。     

Defects and Resistive Switching of Zinc Oxide Nanorods with Copper Addition Grown by Hydrothermal Method

Vertically aligned zinc oxide (ZnO) nanorods (NRs) were hydrothermally synthesized from 0.1 M zinc acetate solution on ZnO-seeded Si(100) substrates. ZnO NRs with copper addition were also synthesized by introducing copper acetate into the zinc acetate solution to investigate the effects of copper addition on the growth and resistive switching of the ZnO nanorods. The ZnO NRs had hexagonal wurtzite structure with preferential c-axis orientation. Copper was mainly present as copper oxide (CuO) secondary phase which produces many visible defects, and the lattice fringes of the ZnO NRs are thereby damaged. Copper addition quenches the ultraviolet emission of the ZnO NRs but enhances their green emission. Additionally, copper addition shifts the Zn 2p and O 1s peaks of the x-ray photoelectron spectra towards lower binding energy, which may result from an increase of oxygen vacancies. ZnO NRs with and without copper addition exhibit reversible bipolar resistive switching. The copper addition shrinks the deviations of programming voltages, with a decrease in the minimal set voltage and an increase in the minimal reset voltage, which can probably be attributed to the introduced oxygen vacancies and the copper-related defects.     

Electrical techniques for the measurement of deep states

When point defects, either intrinsic (such as vacancies or interstitials) or extrinsic (most impurities with the exception of shallow donors or acceptors) are introduced into a semiconductor, they can result in the occurrence of ‘deep states’. These are electronic levels that are not normally ionized at room temperature, but can affect both carrier concentrations and minority carrier lifetime. The purpose of this review is to provide an outline of the techniques that are commonly used to characterize deep defect states in terms of their electrical properties.     

ZnO spintronics and nanowire devices

ZnO is a very promising material for spintronics applications, with many groups reporting room-temperature ferromagnetism in films doped with transition metals during growth or by ion implantation. In films doped with Mn during pulsed laser deposition (PLD), we find an inverse correlation between magnetization and electron density as controlled by Sn-doping. The saturation magnetization and coercivity of the implanted single-phase films were both strong functions of the initial anneal temperature, suggesting that carrier concentration alone cannot account for the magnetic properties of ZnO:Mn and factors such as crystalline quality and residual defects play a role. Plausible mechanisms for ferromagnetism include the bound magnetic polaron model or exchange that is mediated by carriers in a spin-split impurity band derived from extended donor orbitals. The progress in ZnO nanowires is also reviewed. The large surface area of nanorods makes them attractive for gas and chemical sensing, and the ability to control their nucleation sites makes them candidates for microlasers or memory arrays. Single ZnO nanowire depletion-mode metal-oxide semiconductor field effect transistors exhibit good saturation behavior, threshold voltage of ∼−3 V, and a maximum transconductance of 0.3 mS/mm. Under ultraviolet (UV) illumination, the drain-source current increased by approximately a factor of 5 and the maximum transconductance was ∼5 mS/mm. The channel mobility is estimated to be ∼3 cm²/Vss, comparable to that for thin film ZnO enhancement mode metal-oxide semiconductor field effect transistors (MOSFETs), and the on/off ratio was ∼25 in the dark and ∼125 under UV illumination. The Pt Schottky diodes exhibit excellent ideality factors of 1.1 at 25°C, very low reverse currents, and a strong photoresponse, with only a minor component with long decay times thought to originate from surface states. In the temperature range from 25°C to 150°C, the resistivity of nanorods treated in H₂ at 400°C prior to measurement showed an activation energy of 0.089 eV and was insensitive to ambient used. By contrast, the conductivity of nanorods not treated in H₂ was sensitive to trace concentrations of gases in the measurement ambient even at room temperature, demonstrating their potential as gas sensors. Sensitive pH sensors using single ZnO nanowires have also been fabricated.     

The optical properties of rare earth Gd doped ZnO nanocrystals

We present a study of the light emission properties, from UV to blue spectral region, of Gd doped ZnO nanocrystals fabricated by means of a thermal evaporation vapor phase deposition process. The samples were grown from a mixed Zn/Gd source, with a molar percentage of Gd ranging from 0% (pure ZnO) to 5%, 10%, or 15%, in a constant O₂/Ar gas mixture flowing at 500° C. The pure ZnO nanocrystals exhibited a strong and predominant UV emission peaking at 375 nm. Besides the UV emission of ZnO nanocrystals, two strong blue emissions, located at 432 and 397 nm, are observed for the sample doped with 5% Gd. The strong blue emissions are mainly induced by the impurity levels of Gd introduced into the band gap of the ZnO nanocrystals. The UV emission of ZnO decreases as the doping concentration of Gd increases, and the blue emission is replaced by a broad defect emission due to the greater number of defects and impurities, as well as Gd₂O₃ on the surface. The results show that the optical properties of ZnO can be tuned by the doping concentration of Gd.     

Positron annihilation spectroscopy: Applications to Si,ZnO, and multilayer semiconductor structures

The potential of positron annihilation spectroscopy (PAS) for defect characterization at the atomic scale in semiconductors is demonstrated for Si, ZnO, and multilayer structures, such as an AlGaAs/GaAs solar cell. The types of defects discussed include: i) vacancy complexes, oxygen impurities and dopants, ii) the influence of cooling rates on spatial non-uniformities in defects, and iii) characterization of buried interfaces. In sev-eral instances, the results of the PAS investigations are correlated with data from other established semiconductor characterization techniques.     

UV‐Induced Multilevel Current Amplification Memory Effect in Zinc Oxide Rods Resistive Switching Devices

Zinc oxide (ZnO) devices represent an alternative in the semiconductor technology for their application in resistive switching memory devices and ultraviolet (UV) photodetectors due to their chemical and electrical properties. The multilevel current amplification of ZnO rods RRAM devices induced by UV light illumination is reported here for the first time. The resistive switching mechanism underlying in this type of devices is attributed to the formation of conductive filaments composed of oxygen vacancies. The analysis of the photodecay processes carried out on the devices fabricated with different electrodes shows that the type of interface (Ag/ZnO and Au/ZnO) affects the surface barrier height, which influences the photodecay rate. It is shown that by applying UV light, higher relaxation constants (slower photodecay rates) are obtained and lead to multilevel current amplification behavior.     

Self‐Compensated Insulating ZnO‐Based Piezoelectric Nanogenerators

Remarkable enhancement of piezoelectric power output from a nanogenerator (NG) based on a zinc oxide (ZnO) thin film is achieved via native defect control. A large number of unintentionally induced point defects that act as n‐type carriers in ZnO have a strong influence on screening the piezoelectric potential into a piezoelectric NG. Here, additional oxygen molecules bombarded into ZnO lead to oxygen‐rich conditions, and the n‐type conductivity of ZnO is decreased dramatically. The acceptor‐type point defects such as zinc vacancies created during the deposition process trap n‐type carriers occurring from donor‐type point defects through a self‐compensation mechanism. This unique insulating‐type ZnO thin film‐based NGs (IZ‐NGs) generates output voltage around 1.5 V that is over ten times higher than that of an n‐type ZnO thin film‐based NG (around 0.1 V). In addition, it is found that the power output performance of the IZ‐NG can be further increased by hybridizing with a p‐type polymer (poly(3‐hexylthiophene‐2,5‐diyl):phenyl‐C₆₁‐butyric acid methyl ester) via surface free carrier neutralization.     

The preparation of oxygen-deficient ZnO nanorod arrays and their enhanced field emission

Vertical and uniform zinc oxide (ZnO) nanorod arrays (NRAs) with sharp tips were fabricated on Zn substrate by a straightforward hydrothermal method without the assistance of seed layer, template or surfactant. Whereafter, the as-synthesized ZnO NRAs were successfully doped with oxygen vacancies by sodium borohydride (NaBH₄) solution reduction, aiming to generate donor energy levels below the conduction band. More importantly, the doped concentration of oxygen vacancies could be effectively controlled by adjusting the reduction temperature, and we have ultimately achieved the purpose of controllable tailoring the energy band structure of ZnO NRAs. As with design, the oxygen-deficient ZnO NRAs present a lower turn-on field of 0.67 V/μm, higher field enhancement factor of 64601 and better field emission stability. Such excellent FE performance of the as-prepared emitter should originate from the optimization of geometry, the efficient electron transport, as well as the decreased work function.     

Effect of system interactions on the removal of total oxidizablecarbon from DI water polishing loops

Ultra-pure water systems in semiconductor plants consist of many components. Although the operating principles behind each component are well-known, the interactions between system components, including cancellation and synergism, are not generally understood and taken into account. In this study, two examples of these interactions are studied and analyzed: UV interactions with membrane filters and UV interactions with ion exchange units. The results indicate that the sequencing of UV and filter affect the total oxidizable carbon removal efficiency and it is preferable to have filter before UV. UV followed by ion exchange is an effective configuration for some impurities but can be undesirable for some contaminants and particles     

The UV and blue light emission properties of Mn doped ZnO nanocrystals

We present a study of the light emission properties over wavelengths from UV to blue of Mn doped ZnO nanocrystals fabricated by means of a thermal evaporation vapor phase deposition process. The samples were grown with a Mn mole ratio in the Zn/Mn mixed source of 0% (pure ZnO sample, used as a reference), 5%, 10%, or 15% in a constant O₂/Ar gas mixture flowing at 500 °C. The pure ZnO nanocrystals exhibited a strong and predominantly UV emission peaking at 377 nm. In the photoluminescence spectra of mixed ZnO:Mn nanocrystals the major UV emission shifts from 377 to 408 nm, and a strong blue emission appears at 435 nm. The former is mainly induced by the impurity levels of Mn introduced in the band gap of the ZnO nanocrystals, while the latter is closely related to defect and Mn²⁺ ions. With increasing Mn concentration the blue emission is enhanced due to the strong exchange interaction in the short range spin system and the excess impurities on the surface. The results show that the optical properties of ZnO can be tuned by the doping concentration of Mn. Mn doped ZnO nanocrystals with strong blue emission can be used in the fabrication of blue light devices.     

Features of conductivity mechanisms in heavily doped compensated V<Subscript>1–<Emphasis Type="Italic">x</Emphasis> </Subscript>Ti<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>FeSb Semiconductor

The crystal and electronic structure and also the energy and kinetic properties of n-VFeSb semiconductor heavily doped with the Ti acceptor impurity are investigated in the temperature and Ti concentration ranges of T = 4.2–400 K and N_A^Ti ≈ 9.5 × 10¹⁹–3.6 × 10²¹ cm^–3 (x = 0.005–0.20), respectively. The complex mechanism of the generation of acceptor and donor structural defects is established. It is demonstrated that the presence of vacancies at Sb atomic sites in n-VFeSb gives rise to donor structural defects (“a priori doping”). Substitution of the Ti dopant for V in VFeSb leads simultaneously to the generation of acceptortype structural defects, a decrease in the number of donor defects, and their removal in the concentration range of 0 ≤ x ≤ 0.03 via the occupation of vacancies by Sb atoms, and the generation of donor defects due to the occurrence of vacancies and an increase in their number. The result obtained underlies the technique for fabricating new n-VFeSb-based thermoelectric materials. The results are discussed in the context of the Shklovsky–Efros model for a heavily doped compensated semiconductor.     

The neglected influence of zinc oxide light-soaking on stability measurements of inverted organic solar cells

Although zinc oxide (ZnO) is one of the most commonly used materials for electron transport layers in organic solar cells (OSCs), it also comes with disadvantages such as the so-called light-soaking issues, i.e., its need for exposure to UV light to reach its full potential in OSCs. Here, the impact of ZnO light-soaking issues on stability measurements of OSCs is investigated. It is found that in the absence of UV light a reversible degradation occurs, which is independent of the used active layer material and accelerates at higher temperatures but can be undone with a short UV exposure. This reversible aging is attributed to the re-adsorption of oxygen, which for manufacturing reasons is trapped at the interface of ZnO, even in an oxygen-free environment. This oxygen can be removed with a UV pretreatment of the ZnO but at the expense of device efficiency and production that has to take place in an oxygen-free environment. This study establishes that stability measurements of ZnO-containing OSCs must be performed exclusively with a light source including a UV part since the usage of a simple white light source – as often reported in the literature – can lead to erroneous results.     

Oxygen Deficiency and Hydrogen Turn ZnO Red

The effect of hydrogen on ZnO while annealing at 1370 K under oxygen-poor conditions with excess Zn vapor or Ti metal is studied. ZnO turns red only when hydrogen is present in a complex with oxygen vacancies. A practical method is described to remove hydrogen from ZnO in a sealed ampoule and to bind it to Ti metal. Hydrogen coupled to an oxygen vacancy is the simplest defect to explain the observations. The coloration is reversible at 1370 K by adding or removing hydrogen, consistent with an activation energy >1.5 eV. In red ZnO Hall data show a shallow donor level around 45 meV.     

ZnO薄膜紫外光敏特性及晶界势垒的研究

以二水合醋酸锌为原料,采用sol-gel法在石英衬底上制备了ZnO薄膜。用AFM观察表面形貌,通过测量真空条件下不同温度热处理后薄膜的I-V特性,拟合计算晶界势垒高度。研究了热处理温度对ZnO薄膜性能的影响。结果表明:经650℃热处理制备的ZnO薄膜样品具有较佳性能,结构均匀致密,粒径分布为20～32nm。在10V偏压和1.24×10–3W/cm2光强下,紫外光灵敏度为43.95;无光照条件下晶界势垒高度为0.079eV。紫外光照使晶界势垒高度下降为0.011eV,薄膜的紫外光灵敏度与势垒高度的相对变化密切相关。