First-principles study and electronic structures of Mn-doped ultrathin ZnO nanofilms

The first-principles density functional calculation is used to investigate the electronic structures and magnetic properties of Mn-doped and N-co-doped ZnO nanofilms.The band structure calculation shows that the band gaps of ZnO films with 2,4,and 6 layers are larger than the band gap of the bulk with wurtzite structure and decrease with the increase of film thickness.However,the four-layer ZnO nanofilms exhibit ferromagnetic phases for Mn concentrations less than 24% and 12% for Mn-doping performed in the whole layers and two layers of the film respectively,while they exhibit spin glass phases for higher Mn concentrations.It is also found,on the one hand,that the spin glass phase turns into the ferromagnetic one,with the substitution of nitrogen atoms for oxygen atoms,for nitrogen concentrations higher than 16% and 5% for Mn-doping performed in the whole layers and two layers of the film respectively.On the other hand,the spin-glass state is more stable for ZnO bulk containing 5% of Mn impurities,while the ferromagnetic phase is stable by introducing the p-type carriers into the bulk system.Moreover,it is shown that using the effective field theory for ferromagnetic system,the Curie temperature is close to the room temperature for the undamped Ruderman-Kittel-Kasuya-Yoshida（RKKY） interaction.

Oxygen vacancy and Mn2+induced ferromagnetism in Mn-doped ZnO thin films

With the purpose of investigating the origin of ferromagnetism(FM), Mn-doped Zn O thin films had been fabricated by radio frequency(rf) magnetron sputtering and subsequent anneal process. The characterization of the Mn-doped Zn O thin films was conducted by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), and superconducting quantum interference device(SQUID). With increasing the anneal temperature from 300°C to 700°C for 3 min, the influence on magnetism of the Mndoped ZnO thin films is slight. While extending the anneal time from 3 to 50 min at 300°C, the influence on magnetism is obvious and the Mn-doped ZnO thin films with 30 min clearly demonstrate FM. Compared with the effect of oxygen vacancy and substitutional Mn2+on the ferromagnetic behavior, OVplays the main role in inducing FM of the Mn-doped ZnO thin films with good crystal structure.

Tribological behavior of N-doped ZnO thin films by metal organic chemical vapor deposition under lubricated contacts

N-doped ZnO thin films were deposited on 304L stainless steel through the pyrolysis of zinc acetate and ammonium acetate in different ratios at a temperature of 420 ℃ using metal organic chemical vapor deposition.Compositional and structural analyzes of the films were performed by using Rutherford backscattering spectroscopy and X-ray diffraction.The frictional behavior of the thin films and 304L stainless steel substrate was evaluated using a ball-on-flat configuration with reciprocating sliding under marginally lubricated and fully flooded conditions.Al alloy (2017) was used as ball counterface,while basestock synthetic polyalfaolefin oil (PAO10) without additives was used as lubricant.The flat and ball counterface surfaces were examined to assess the wear dimension and failure mechanism.Under marginally lubricated condition,N-doped ZnO thin films provided significant reduction in friction,whereas the films have minimal or no effect in friction under fully flooded condition.N-doped ZnO thin films showed a significant effect in protecting the ball counterface as wear volume was reduced compared with that of the substrate under the marginally lubricated condition.Under the fully flooded condition,with the exception of one of the films,the wear volume of the N-doped ZnO thin films ball reduced compared with that of the substrate.In all the ball counterfaces for N-doped ZnO thin films under both conditions,wear occurred through abrasive mechanism of various degrees or mild polishing.Thus,superfluous lubrication of N-doped ZnO thin films is not necessary to reduce friction and wear.

P-Type Nitrogen-Doped ZnO Films Prepared by In-Situ Thermal Oxidation of Zn_3N_2 Films

P-type nitrogen-doped ZnO films are prepared successfully by in-situ thermal oxidation of Zn3N2 films. The prepared films are characterized by x-ray diffraction, non-Rutherford back.scattering （non-RBS） spectroscopy, x- ray photoelectron spectroscopy, and photoluminescence spectrum. The results show that the Zn3N1 films start to transform to ZnO at 400℃ and the total nitrogen content decreases with the increasing annealing temperature. The p-type fihns are achieved at 500℃ with a low resistivity of 6.33Ω.cm and a high hole concentration of ＋8.82 × 10^17 cm-3, as well as a low level of carbon contamination, indicating that the substitutional nitrogen （No） is an effective acceptor in the ZnO：N film. The photoluminescence spectra show clear UV emissions and also indicate the presence of oxygen vacancy （Vo） defects in the ZnO：N films. The p-type doping mechanism is briefly discussed.

Effect of Annealing Temperature on Structural and Optical Properties of N-Doped ZnO Films

Nitrogen-doped ZnO （ZnO：N） films are prepared by thermal oxidation of sputtered Zn3N2 layers on A1203 substrates. The correlation between the structural and optical properties of ZnO：N films and annealing temperatures is investigated. X-ray diffraction result demonstrates that the as-sputtered Zn3N2 films are transformed into ZnO：N films after annealing above 600℃. X-ray photoelectron spectroscopy reveals that nitrogen has two chemical states in the ZnO：N films： the No acceptor and the double donor （N2）o. Due to the No acceptor, the hole concentration in the film annealed at 700℃ is predicted to be highest, which is also confirmed by Hall effect measurement. In addition, the temperature dependent photoluminescence spectra allow to calculate the nitrogen acceptor binding energy.

Electrical and nonlinear optical properties of TGZO transparent conducting films deposited by magnetron sputtering

Thin transparent oxide conducting films(TCOFs)of titanium and gallium substituted zinc oxide(TGZO)were fabricated via radio frequency(RF)magnetron sputtering technique.The effects of RF power on electrical,linear and nonlinear optical characteristics were investigated by Hall tester,Ultraviolet(UV)-visible spectrophotometer and optical characterization method.The results indicate that RF power significantly influences the electrical and optical properties of the deposited films.As RF power raises,the resistivity and Urbach energy fall initially and then rise,while the figure of merit,mean visible transmittance and optical bandgap show the reverse variation trend.At RF power of 190 W,the TGZO sample exhibits the highest electro-optical properties,with the maximum figure of merit(1.14×10^(4)Ω^(-1)∙cm^(-1)),mean visible transmittance(86.9%)and optical bandgap(3.50 eV),the minimum resistivity(6.26×10^(-4)Ω∙cm)and Urbach energy(174.23 meV).In addition,the optical constants of the deposited films were determined by the optical spectrum fitting method,and the RF power dependence of nonlinear optical properties was studied.It is observed that all the thin films exhibit normal dispersion characteristics in the visible region,and the nonlinear optical parameters are greatly affected by the RF power in the ultraviolet region.

Multilevel optoelectronic hybrid memory based on N-doped Ge_(2)Sb_(2)Te_(5)film with low resistance drift and ultrafast speed

Multilevel phase-change memory is an attractive technology to increase storage capacity and density owing to its high-speed,scalable and non-volatile characteristics.However,the contradiction between thermal stability and operation speed is one of key factors to restrain the development of phase-change memory.Here,N-doped Ge_(2)Sb_(2)Te_(5)-based optoelectronic hybrid memory is proposed to simultaneously implement high thermal stability and ultrafast operation speed.The picosecond laser is adopted to write/erase information based on reversible phase transition characteristics whereas the resistance is detected to perform information readout.Results show that when N content is 27.4 at.%,N-doped Ge_(2)Sb_(2)Te_(5)film possesses high ten-year data retention temperature of 175℃and low resistance drift coefficient of 0.00024 at 85℃,0.00170 at 120℃,and 0.00249 at 150℃,respectively,owing to the formation of Ge–N,Sb–N,and Te–N bonds.The SET/RESET operation speeds of the film reach 520 ps/13 ps.In parallel,the reversible switching cycle of the corresponding device is realized with the resistance ratio of three orders of magnitude.Four-level reversible resistance states induced by various crystallization degrees are also obtained together with low resistance drift coefficients.Therefore,the N-doped Ge_(2)Sb_(2)Te_(5)thin film is a promising phase-change material for ultrafast multilevel optoelectronic hybrid storage.

Microstructure and optical properties of nitrogen-doped ZnO film

The nitrogen doping of ZnO film deposited by the magnetron sputtering method is subsequently realized by the hydrothermal synthesis method.The nitrogen-doped ZnO film is preferably（002） oriented.With the increase of hexamethylenetetramine（HMT） solution concentration,the average grain size of the film along the 002 direction almost immediately decreases and then monotonously increases,conversely,the lattice strain first increases and then decreases.The structural evolution of the film surface from compact and even to sparse and rough is attributed to the enhanced nitrogen doping content in the hydrothermal process.The transmission and photoluminescence properties of the film are closely related to grain size,lattice strain,and nitrogen-related defect arising from the enhanced nitrogen doping content with HMT concentration increasing.

Deposition and Characterisation of Nitrogen-Doped Zinc Oxide Thin Films by MOCVD Using Zinc Acetate—Ammonium Acetate Precursor

The synthesis and comprehensive analysis of nitrogen-doped zinc oxide thin films grown from a compound precursor of zinc acetate and ammonium acetate has been reported. The precursor was processed in different ratios of the zinc acetate-ammonium acetate additives, and each combination was used to deposit a thin film using metalorganic chemical vapour deposition (MOCVD) method. The produced thin films were characterised using Rutherford backscattering (RBS) spectroscopy, uv-visible spectrometry, x-ray diffractometry, four point probe measurements and optical microscopy. The deposited thin films showed a fairly consistent zinc:oxygen:nitrogen ratio of 4.4:3.7:1, the film structures were quasicrystalline and the sheet resistivities were high, while other familiar characteristics like optical transmittance, bandgap, thermal stability, etc. were maintained in the grown films. Applications in device fabrication and active sensor devices were hence envisaged as the emergent potentials of the thin films.

Structural,Morphological and Electrical Properties of In-Doped Zinc Oxide Nanostructure Thin Films Grown on p-Type Gallium Nitride by Simultaneous Radio-Frequency Direct-Current Magnetron Co-Sputtering

Zinc oxide （ZnO） is one of the most promising and frequently used semiconductor materials. In-doped nanos- tructure ZnO thin films are grown on p-type gallium nitride substrates by employing the simultaneous rf and dc magnetron co-sputtering technique. The effect of In-doping on structural, morphological and electrical properties is studied. The different dopant concentrations are accomplished by varying the direct current power of the In target while keeping the fixed radio frequency power of the ZnO target through the co-sputtering deposition technique by using argon as the sputtering gas at ambient temperature. The structural analysis confirms that all the grown thin films preferentially orientate along the c-axis with the wurtzite hexagonal crystal structure without having any kind of In oxide phases. The presenting Zn, 0 and In elements＇ chemical compositions are identified with EDX mapping analysis of the deposited thin films and the calculated M ratio has been found to decrease with the increasing In power. The surface topographies of the grown thin films are examined with the atomic force microscope technique. The obtained results reveal that the grown film roughness increases with the In power. The Hall measurements ascertain that all the grown films have n-type conductivity and also the other electrical parameters such as resistivity,mobility and carrier concentration are analyzed.

ZnO Films Synthesized by Solid-Source Chemical Vapor Deposition with c-Axis Parallel to Substrate

ZnO films with c -axis parallel to the substrate are reported.ZnO films are synthesized by solid-source chemical vapor deposition,a novel CVD technique,using zinc acetate dihydrate (solid) as the source material.The properties are characterized by X-ray diffraction,atomic force microscopy and transmission spectra.The parallel oriented ZnO films with mixed orientation for (100) and (110) planes are achieved on glass at the substrate temperature of 200℃ and the source temperature of 280℃,and a qualitative explanation is given for the forming of the mixed orientation.AFM images show that the surface is somewhat rough for the parallel oriented ZnO films.The transmission spectrum exhibits a high transmittance of about 85% in the visible region and shows an optical band gap about 3.25eV at room temperature.

A Novel Approach to Synthesizing Porous ZnO Films: Inorganic Chelating Sol-Gel Method

Porous ZnO films are synthesized by inorganic chelating sol-gel method,which is a novel sol-gel technique using zinc nitrate as starting materials and citric acid as the chelating reagent.The crystal structure,surface morphology,porous and optical properties of the deposited films are investigated.X-ray diffraction pattern analysis shows that crystal structure of the ZnO films is hexagonal wurtzite.Scanning electron microscopy (SEM) shows that the ZnO film is porous.The curve of pore size distribution has two peak values at about 2.02nm and 4.97nm and BET surface area of the ZnO film is 27.57m2/g.In addition,the transmittance spectrum gives a high transmittance of 85% in the visible region and optical bandgap of the ZnO film (fired at 500℃) is 3.25eV.

基于共溅射ZnO/SnO_(2)异质结薄膜的气体传感器研究

采用射频磁控共溅射法在叉指电极上制备了ZnO/SnO_(2)n-n异质结复合薄膜,系统测试了其气敏特性,并分析了其气敏机理。结果表明,与ZnO薄膜和SnO_(2)薄膜气体传感器相比,ZnO/SnO_(2)异质结薄膜气体传感器具有更低的工作温度、更高的灵敏度以及更快的响应和恢复速度。ZnO/SnO_(2)异质结薄膜气体传感器对乙醇具有较好的选择性,最低检测体积分数为1×10^(-6),最佳工作温度为250℃;对1×10^(-4)乙醇气体的灵敏度可达18.4,响应时间和恢复时间分别为10 s和19 s。

Growth and Optical Properties of ZnO Films and Quantum Wells

The growth characteristics during metalorganic chemical vapor deposition and optical properties of ZnO films on sapphire （Al2O3） （0001） and （1120） substrates are studied. For the former,the effects of two important growth parameters,i, e. temperature and pressure, are investigated in detail. Due to the large lattice mismatch between the film and the substrate, ZnO nanocrystals are usually obtained. The growth behavior at the film-substrate interface is found to be strongly dependent on the growth temperature,while the growth pressure determines the shape of the nanostructures as they grow. It is difficult to obtain ZnO films that have good quality and a smooth surface simultaneously. Due to the smaller lattice mismatch,the critical thickness of ZnO on the Al2O3 （1120） surface is found to be much larger than that on the Al2O3 （0001） surface. ZnO/MgZnO quantum wells with graded well thicknesses are grown on the Al2O3 （1120） surfaces,and their optical properties are studied. The built-in electric field in the well layer, generated by the piezoelectric effect, is estimated to be 3 × 10^5 V/cm. It is found that growth at low temperatures and low pressures may facilitate the incorporation of acceptor impurities in ZnO.

Effect of sputtering conditions on growth and properties of ZnO :Al films

Al-doped zinc oxide（AZO） films were deposited on glass substrates by mid-frequency magnetron sputtering. The effects of substrate rotation speed and target-substrate distance on the electrical, optical properties and microstructure and crystal structures of the resulting films were investigated by scanning electron microscopy（SEM）, atomic force microscopy（AFM）, X-ray diffraction（XRD）, spectrophotometer and Hall-effect measurement system, respectively. XRD results show that all AZO films exhibit a strong preferred c-axis orientation. However, the crystallinity of films decreases with the increase of substrate rotation speed, accompanying with the unbalanced grains grows. For the films prepared at different target-substrate distances, the uniform microstructure and morphology are observed. The highest carrier concentration of 5.9×1020 cm-3 and Hall mobility of 13.1 cm^2/（V·s） are obtained at substrate rotation speed of 0 and target-substrate distance of 7 cm. The results indicate that the structure and performances of the AZO films are strongly affected by substrate rotation speed.

双层结构对ZnO TFT稳定性的影响

室温下采用射频磁控溅射方法在SiO_(2)/Si衬底上沉积了单层ZnO薄膜和高氧/低氧双层ZnO薄膜,采用电子束蒸发设备蒸镀Al电极,制备单沟道ZnO TFTs和双层沟道ZnO TFTs。比较两种结构ZnO TFTs的各种性能参数,分析双层结构对TFTs产生的影响。实验结果表明,底部高含氧量ZnO层和顶部低含氧量ZnO层构成了DAL同质结且高氧/低氧薄膜存在载流子浓度产差,利用载流子从高浓度向低浓度扩散的性质,可以填补栅介电层和沟道层之间的界面态缺陷,使器件界面类受主陷阱减少,有效降低TFTs的滞回现象。与单有源层TFTs相比,双沟道层TFTs还具有电学调制作用,其电学性能和稳定性均有明显的提高,得到最佳TFTs的开/关电流比达到3.44×10^(9),亚阈值摆幅为0.68 V/dec,阈值电压偏移为1.2 V。

Crystallization Behavior and Properties of B-Doped ZnO Thin Films Prepared by Sol-Gel Method with Different Pyrolysis Temperatures

Boron-doped zinc oxide transparent （BZO） films were prepared by sol-gel method. The effect of pyrolysis temperature on the crystallization behavior and properties was systematically investigated. XRD patterns revealed that the BZO films had wurtzite structure with a preferential growth orientation along the c-axis. With the increase of pyrolysis temperature, the particle size and surface roughness of the BZO films increased, suggesting that pyrolysis temperature is the critical factor for determining the crystallization behavior of the BZO films. Moreover, the carrier concentration and the carrier mobility increased with increasing the pyrolysis temperature, and the mean transmittance for every film is over 90% in the visible range.

Low-Temperature Growth of ZnO Films on GaAs by Metal Organic Chemical Vapor Deposition

ZnO thin films were grown on GaAs （001） substrates by metal-organic chemical vapor deposition （MOCVD） at low temperatures ranging from 100 to 400℃. DEZn and 1-12 O were used as the zinc precursor and oxygen precursor, respectively. The effects of the growth temperatures on the growth characteristics and optical properties of ZnO films were investigated. The X-ray diffraction measurement （XRD） results indicated that all the thin films were grown with highly c- axis orientation. The surface morphologies and crystal properties of the films were critically dependent on the growth temperatures. Although there was no evidence of epitaxial growth, the scanning electron microscopy （SEM） image of ZnO film grown at 400℃ revealed the presence of ZnO microcrystallines with closed packed hexagon structure. The photoluminescence spectrum at room temperature showed only bright band-edge （3. 33eV） emissions with little or no deep-level e- mission related to defects.

Effects of high-dose Ge ion implantation and post-implantation annealing on ZnO thin films

This paper reports that ion implantation to a dose of 1 ×10^17 ions/cm^2 was performed on c-axis-orientated ZnO thin films deposited on （0001） sapphire substrates by the sol-gel technique. After ion implantation, the as-implanted ZnO films were annealed in argon ambient at different temperatures from 600 - 900 ℃. The effects of ion implantation and post-implantation annealing on the structural and optical properties of the ZnO films were investigated by x-ray diffraction （XRD）, photoluminescence （PL）. It was found that the intensities of （002） peak and near band edge （NBE） exitonic ultraviolet emission increased with increasing annealing temperature from 600- 900 ℃. The defect related deep level emission （DLE） firstly increased with increasing annealing temperature from 600 - 750 ℃, and then decreased quickly with increasing annealing temperature. The recovery of the intensities of NBE and DLE occurs at ～850℃ and ～750℃ respectively. The relative PL intensity ratio of NBE to DLE showed that the quality of ZnO films increased continuously with increasing annealing temperature from 600 - 900 ℃.

Surface engineering of ZnO electrocatalyst by N doping towards electrochemical CO_(2) reduction

The discovery of efficient,selective,and stable electrocatalysts can be a key point to produce the largescale chemical fuels via electrochemical CO_(2) reduction(ECR).In this study,an earth-abundant and nontoxic ZnO-based electrocatalyst was developed for use in gas-diffusion electrodes(GDE),and the effect of nitrogen(N)doping on the ECR activity of ZnO electrocatalysts was investigated.Initially,a ZnO nanosheet was prepared via the hydrothermal method,and nitridation was performed at different times to control the N-doping content.With an increase in the N-doping content,the morphological properties of the nanosheet changed significantly,namely,the 2D nanosheets transformed into irregularly shaped nanoparticles.Furthermore,the ECR performance of Zn O electrocatalysts with different N-doping content was assessed in 1.0 M KHCO_(3) electrolyte using a gas-diffusion electrode-based ECR cell.While the ECR activity increased after a small amount of N doping,it decreased for higher N doping content.Among them,the N:ZnO-1 h electrocatalysts showed the best CO selectivity,with a faradaic efficiency(FE_(CO))of 92.7%at-0.73 V vs.reversible hydrogen electrode(RHE),which was greater than that of an undoped Zn O electrocatalyst(FE_(CO)of 63.4%at-0.78 V_(RHE)).Also,the N:ZnO-1 h electrocatalyst exhibited outstanding durability for 16 h,with a partial current density of-92.1 mA cm^(-2).This improvement of N:ZnO-1 h electrocatalyst can be explained by density functional theory calculations,demonstrating that this improvement of N:ZnO-1 h electrocatalyst comes from(ⅰ)the optimized active sites lowering the free energy barrier for the rate-determining step(RDS),and(ⅱ)the modification of electronic structure enhancing the electron transfer rate by N doping.