DFT Study of the Effect of Temperature on ZnO Adsorbed on α-AI_2 O_3(0001)Surface

The adsorption and the growth of ZnO on α-Al2O3（0001） surface at various temperatures were theoretically calculated by using a plane wave pseudopotentials （USP） method based on density functional theory.The average adsorption energy of ZnO at 400, 600 and 800 ℃ is 4.16±0.08, 4.25±0.11 and 4.05±0.23 eV respectively. Temperature has a remarkable effect on the structure of the surface and the interface of ZnO/α-Al2O3（0001）. It is found that the Zn-hexagonal symmetry deflexion does not appear during the adsorption growth of ZnO at 400 ℃, and that the ZnO[10^-10] is parallel with the [10^-10] of the α-Al2O3（0001）, which is favorable for forming ZnO film with the Zn-terminated surface. It is observed from simulation that there are two kinds of surface structures in the adsorption of ZnO at 600 ℃： one is the ZnO surface that has the Zn-terminated structure, and whose [10^-10] parallels the [10^-10] of the substrate surface, and the other is the ZnO[10^-10] //sapphire [11-20] with the O-terminated surface. The energy barrier of the phase transition between these two different surface structures is about 1.6 eV, and the latter is more stable. Therefore,the suitable temperature for the thin film growth of ZnO on sapphire is about 600 ℃, and it facilitates the formation of wurtzite structure containing Zn-O-Zn-O-Zn-O double-layers as a growth unit-cell. At 600 ℃, the average bond length of Zn-O is 0.190±0.01 nm, and the ELF value indicates that the bond of （substrate）-O-Zn-O has a distinct covalent character, whereas the （Zn）O-Al （substrate） shows a clear character of ionic bond. However, at a temperature of 800 ℃, the dissociation of Al and O atoms on the surface of the α-Al2O3（0001） leads to a disordered surface and interface structure. Thus, the Zn-hexagonal symmetry structure of the ZnO film is not observed under this condition.

Enhanced surface-insulating performance of EP composites by doping plasmafluorinated ZnO nanofiller

The surface flashover of epoxy resin(EP) composites is a pivotal problem in the field of highvoltage insulation.The regulation of the interface between the filler and matrix is an effective means to suppress flashover.In this work,nano ZnO was fluorinated and grafted using lowtemperature plasma technology,and the fluorinated filler was doped into EP to study the DC surface flashover performance of the composite.The results show that plasma fluorination can effectively inhibit the agglomeration by grafting –CFxgroups onto the surface of nano-ZnO particles.The fluorine-containing groups at the interface provide higher charge binding traps and enhance the insulation strength at the interface.At the same time,the interface bond cooperation caused by plasma treatment also promoted the accelerating effect of nano ZnO on charge dissipation.The two effects synergistically improve the surface flashover performance of epoxy composites.When the concentration of fluorinated ZnO filler is 20%,the flashover voltage has the highest increase,which is 31.52% higher than that of pure EP.In addition,fluorinated ZnO can effectively reduce the dielectric constant and dielectric loss of epoxy composites.The interface interaction mechanism was further analyzed using molecular dynamics simulation and density functional theory simulation.

The First-principles Calculations of H_2S Adsorption and Decomposition on the ZnO(0001) Surface

The adsorption and decomposition of H2S on the ZnO（0001） surface have been investigated with first-principles calculations.The results reveal that H2S is dissociatively adsorbed on the clean ZnO（0001） surface to generate HS-and hydrogen species.To our interest,as indicated by Mulliken charge and density of states of the configuration calculation,the bonding mechanism of H2S on the ZnO（0001） surface can involve the donation of charge from the ＂s lone pairs＂ into the surface and the back donation of surface electrons to H2S.Therefore,the electrons should play an important role in decomposition.Furthermore,the reactivity of H2S adsorption and further thermal decomposition reactions on the ZnO（0001） surface have also been discussed by calculating the possible reaction pathways.As expected,H2 will be easily generated during the decomposition process.

Photocatalytic Dissociation of CH3OH on ZnO(0001) Surface

Photocatalysis of CH3OH on the ZnO(0001) surface has been investigated by using temperature-programmed desorption (TPD) method with a 266 nm laser light. TPD results show that part of the CH3OH adsorbed on ZnO(0001) surface are in molecular form, while others are dissociated. The thermal reaction products of H2, CH3·, H2O, CO, CH2O, CO2 and CH3OH have been detected. Experiments with the UV laser light indicate that the irradiation can promote the dissociation of CH3OH/CH3O· to form CH2O, which can be fu- ture converted to HCOO- during heating or illumination. The reaction between CH3OHZn and OHad can form the H2O molecule at the Zn site. Both temperature and illumination promote the desorption of CH3· from CH3O·. The research provides a new insight into the photocatalytic reaction mechanism of CH3OH on ZnO(0001).

Adsorption of fluorine and chlorine on Mg(0001) surface:A density functional theory investigation

The adsorption of low-coverage of F and Cl adatoms on the Mg（0001） surface was investigated using first-principles calculations based on the density functional theory（DFT）.The stability of the（2×2） structures formed by halogen atoms adsorbed at different sites was determined.The difference between the adsorption of F and Cl on Mg（0001） surface was also discussed.The calculation results show that hollow sites are the energetically most favorable at the low-coverage.It can be concluded from the Mulliken charges and density of states that electrons transfer from the substrate Mg atoms to the adatoms,which leads to the formation of adsorbate bond and further causes the stronger interaction between Mg atom and adatom.The interaction between Cl and Mg atoms is weaker than the interaction between F and Mg.

Probe the Effects of Surface Adsorbates on ZnO Nanowire Conductivity using Dielectric Force Microscopy

Characterization of electric properties of nanomaterials usually involves fabricating field effect transistors （FET） and deriving materials properties from device performances. However, the quality of electrode contacts in FET devices heavily influences the device performance, which makes it difficult to obtain the intrinsic electric properties of nanomaterials. Dielectric force microscopy （DFM）, a contactless method developed recently, can detect the low-frequency dielectric responses of nanomaterials without electric contact, which avoids the influence of electric contact and can be used to study the intrinsic conductivity of nanomaterials. Here we study the influences of surface adsorbates on the conductivity of ZnO nanowires （NWs） by using FET and DFM methods. The conductivity of ZnO NW is much larger in N2 atmosphere than that in ambient environment as measured by FET device, which is further proven by DFM measurement that the ZnO NW exhibits larger dielectric response in N2 environment, and the influence of electrode contacts on measurement can be ruled out. Based on these results, it can be concluded that the adsorbates on ZnO NW surface highly influence the conductivity of ZnO NW rather than the electrode contact. This work also verifies the capability of DFM in measuring electric properties of nanomaterials.

Effects of surface adsorbed oxygen, applied voltage, and temperature on UV photoresponse of ZnO nanorods

The ultraviolet（UV） photoresponses of ZnO nanorods directly grown on and between two micro Au-electrodes by using electric-field-assisted wet chemical method are measured comprehensively under different conditions, including ambient environment, applied bias voltage, gate voltage and temperature. Experimental results indicate that the photoresponses of the ZnO nanorods can be modulated by surface oxygen adsorptions, applied voltages, as well as temperatures. A model taking into account both surface adsorbed oxygen and electron-hole activities inside ZnO nanorods is proposed. The enhancement effect of the bias voltage on photoresponse is also analyzed. Experimental results shows that the UV response time（to 63%） of ZnO nanorods in air and at 59°C could be shortened from 34.8 s to 0.24 s with a bias of 4 V applied between anode and cathode.

First-principles Calculations of H_2O Adsorption Reaction on the GaN(0001) Surface

The adsorption and decomposition of H2O on GaN（0001） surface have been explored employing density functional theory （DFT）. Two distinct adsorption features of H2O on GaN（0001） corresponding to molecular adsorption and H-OH dissociative adsorption are revealed by our calculations. The activities of the surface reactions of H2O on GaN（0001） surface are investigated. For the stepwise processes of H2O decomposition into H2 in gas phase and adsorbed O atom （H2O（g）→H2O（chem）→OH（chem） ＋ H（chem）→2H（chem） ＋ O（chem）→H2（g） ＋ O（chem））, the first and second steps are facile and can even occur at room temperature; while the last two have high barriers and thus are difficult to proceed, especially the fourth step is endothermic. In short, H2O adsorption and decomposition into H2 in gas phase and adsorbed O atom on GaN（0001） surface are exothermic by -43.98 kcal/mol.

Water adsorption on the Be(0001) surface:from monomer to trimer adsorption

In this paper, the density functional theory has been used to perform a comparative theoretical study of water monomer, dimer, trimer, and bilayer adsorptions on the Be（0001） surface. In our calculations, the adsorbed water molecules are energetically favoured adsorbed on the atop sites, and the dimer adsorption is found to be the most stable with a peak adsorption energy of - 437 meV. Further analyses have revealed that the essential bonding interaction between the water monomer and the metal substrate is the hybridization of the water 3al-like molecular orbital with the （s, P2） orbitals of the surface beryllium atoms. While in the case of the water dimer adsorption, the lbz-like orbital of the H2O molecule plays a dominant role.

Surface Acoustic Wave Device with Reduced Insertion Loss by Electrospinning P(VDF–TrFE)/ZnO Nanocomposites

Surface acoustic wave(SAW) devices have been utilized for the sensing of chemical and biological phenomena in microscale for the past few decades. In this study, SAW device was fabricated by electrospinning poly(vinylidenefluoride-co-trifluoroethylene)(P(VDF-TrFE)) incorporated with zinc oxide(ZnO) nanoparticles over the delay line area of the SAW device. The morphology, composition, and crystallinity of P(VDF-TrFE)/ZnO nanocomposites were investigated. After measurement of SAW frequency response, it was found that the insertion loss of the SAW devices incorporated with ZnO nanoparticles was much less than that of the neat polymer-deposited device. The fabricated device was expected to be used in acoustic biosensors to detect and quantify the cell proliferation in cell culture systems.

Transparent ZnO/glass surface acoustic wave based high performance ultraviolet light sensors

Surface acoustic wave （SAW） resonators are a type of ultraviolet （UV） light sensors with high sensitivity, and they have been extensively studied. Transparent SAW devices are very useful and can be developed into various sensors and microfluidics for sensing/monitoring and lab-on-chip applications. We report the fabrication of high sensitivity SAW UV sensors based on piezoelectric （PE） ZnO thin films deposited on glass substrates. The sensors were fabricated and their performances against the post-deposition annealing condition were investigated. It was found that the UV-light sensitivity is improved by more than one order of magnitude after annealing. The frequency response increases significantly and the response becomes much faster. The optimized devices also show a small temperature coefficient of frequency and excellent repeatability and stability, demonstrating its potential for UV-light sensing application.

Density Functional Theory Study for Adsorption of Oxygen and Water Molecules on 6H-SiC(0001) Surface

6H-SiC is an important semiconductor material. The 6H-SiC wafer is always exposed to a high-humidity environment and the effect from the absorbed water molecule and some relative adsorbates is not negligible. Here, the oxygen and water molecules absorbed on the 6H-SiC(0001) surface and the dissociation process were studied with density functional theory. On the 6H-SiC(0001) surface, absorbed O2 is spontaneously dissociated into O*, which is absorbed on a hollow site, and further transforms the 6H-SiC(0001) surface into SiO2. The absorbed H2O is spontaneously broken into OH*and H*, which are both absorbed on the top of the Si atom, and OH* is further reversibly transformed into O* and H*. The H* could saturate the dangling Si bond and change the absorption type of O*, which could stabilize the 6H-SiC(0001) surface and prevent it from transforming into SiO2.

Surface Acoustic Wave Humidity Sensors Based on(1120) ZnO Piezoelectric Films Sputtered on R-Sapphire Substrates

ZnO films on R-sapphire substrates are prepared and characterized by x-ray diffraction and scanning electron microscopy, which indicate that the thin films are well crystallized with （1120） texture. Love wave and Rayleigh wave are used for fabrications of humidity sensors, which are excited in [1100] and [0001] directions of the （1120） ZnO piezoelectric films, respectively. The experimental results show that both kinds of sensors have good humidity response and repeatability, and the performances of the Love wave sensors are better than those of the Rayleigh wave sensors at room temperature. Moreover, the theoretical calculations of the mass sensitivity of the sensors are a/so carried out and the calculated results are in good agreement with the experimental measurements.

ZnO:Na纳米晶室温表面光电压气敏机理的研究

采用简单溶胶凝胶法在溅射有Au/Ti叉指电极的PET柔性基底上制备出不同Na掺杂浓度的ZnO纳米晶。通过对样品的微结构和光学性质表征,探究光辅助室温NO_(2)气敏机理与表面光电压之间的联系。X射线衍射(XRD)结果显示所有样品均为六方纤锌矿结构,Na的掺杂并没有出现Na及其氧化物的衍射峰。室温气敏测试结果显示Na掺杂ZnO纳米晶具有优良的室温气敏性能,能够检测到0.94 mg/m^(3)浓度的NO_(2),相对于纯ZnO纳米晶体气敏响应明显提高。表面光电压谱(SPV)和紫外可见分光光度计(UV-Vis)实验结果表明掺杂ZnO样品的室温气敏性可能与其表面缺陷含量和缺陷能级有关。Na掺杂能够显著增强光生电荷的分离,同时也引入了更多的氧空位(Vo)和活性位点,促进了NO_(2)气体与表面吸附电离氧缺陷的反应。另外光学带隙的蓝移和新产生的缺陷能级也进一步提高了对NO_(2)气体的灵敏度。

纳米ZnO/SBR复合改性乳化沥青及其微表处混合料性能

为了研究纳米ZnO与SBR对乳化沥青的复合改性效果和路用性能,开展了纳米ZnO/SBR复合改性乳化沥青的性能表征与评价工作,研究纳米ZnO掺量对乳化沥青以及微表处混合料路用性能的影响。研究表明,纳米ZnO对乳化沥青的流体特征(粒度、模量等)产生了明显影响,纳米ZnO掺量为2%、3%时提高了残留物的软化点、不可回复柔量和SPG等级等高温性能;纳米ZnO掺量为0~3%时,乳化沥青的高温等级均能达到SPG70。纳米ZnO改性乳化沥青应用于微表处混合料时,表现出破乳速度快、混合料早期强度高的特点;当纳米ZnO掺量大于2%后,乳化沥青稀浆料的工作性下降,破乳无法控制。

A DFT Study of Alkenes and Alkynes Reacting with H-GaN (0001) Surface

The addition reactions of alkenes and alkynes to the H-terminated GaN （0001） surface with a Ga dangling-bond have been studied employing periodic density functional theory （PDFT） calculations. Detailed information on the reaction pathways of these alkenes and alkynes with H-GaN （0001） surface is provided, which indicates that the reactions contain two steps separated by the metastable intermediates： elementary addition reaction and H-abstraction process. From the energy curves, the reactions are clearly viable in the cases of ethene, styrene and phenylacetylene; while for ethyne, the H-abstraction barrier is higher than the desorption barrier of the intermediate, so the adsorbed C2H2 in intermediate is more likely to be desorbed back into the gas phase than to form a stable adsorbed species. Furthermore, it is obvious that for either alkenes or alkynes, the systems substituted by phenyl have more stable intermediates because π conjugation could improve their stabilities.

Growth and characterization of ZnO multipods on functional surfaces with different sizes and shapes of Ag particles

Three-dimensional ZnO multipods are successfully synthesized on functional substrates using the vapor transport method in a quartz tube. The functional surfaces, which include two different distributions of Ag nanoparticles and a layer of commercial Ag nanowires, are coated onto silicon substrates before the growth of ZnO nanostructures. The structures and morphologies of the ZnO/Ag heterostructures are investigated using X-ray diffraction and field emission scanning electron microscopy. The sizes and shapes of the Ag particles affect the growth rates and initial nucleations of the ZnO structures, resulting in different numbers and shapes of multipods. They also influence the orientation and growth quality of the rods. The optical properties are studied by photoluminescence, UV-vis, and Raman spectroscopy. The results indicate that the surface plasmon resonance strongly depends on the sizes and shapes of the Ag particles.

Experimental Research of ZnO Surface Flashover Trigger Device of Pseudo-Spark Switch

Pseudo-spark switch（PSS） is one of the most widely used discharge switches for pulse power technology.It has many special characteristics such as reliability in a wide voltage range,small delay time,as well as small delay jitter.In this paper,the measuring method for the initial plasma of ZnO surface flashover triggering device of PSS is studied and the results of the measurement show that the electron emission charge is mainly influenced by trigger voltage,gas pressure and DC bias voltage.When the bias voltage increases from 2 kV to 6 kV with the gap distancc fixed at 3 mm,the electron emission charge changes from 2 μC to about 6μC.When the gap distance changes from 3 mm to 5 mm with the bias voltage fixed at 2 kV,the electron emission charge increases from 1.5 μC to 2.5μC.When the gap distance is 4 mm,the hold-off voltage of PSS is 45 kV at gas pressure of 2 Pa,the minimum operating voltage is less than 1 kV.So,the operating scope is from 2.22%to 99%of its self-breakdown voltage.The discharging delay time decreases from 450 ns to 150 ns when the trigger pulse voltage is 1 kV and the discharging voltage is changed from 1 kV to 12 kV.When the trigger pulse voltage is 6 kV,the discharging delay time is less than 100 ns and changes from 100 ns to 50 ns,and the delay jitters are less than30 ns.

First-principles study on properties and electron structure of CrB_2(0001) surface

Based on a first-principles density functional plane-wave ultrasoft pseudopotential method,the surface properties of two different types of terminated CrB2(0001)are calculated and compared,such as surface relaxation,surface energy and electricity structure.The results of surface relaxation show surface interlayer distance converges rapidly for both terminated CrB2(0001)when the number of the atoms layers reaches 9.Through analysis of charge density difference and partial density of states(PDOS),it can be concluded that CrB2(0001)models with B termination have smaller interface energy,stronger electronic interaction than another models and the form of termination is more stable.

Surface properties of Al-doped ZnO thin film before and after CF_4/Ar plasma etching

Al-doped ZnO(AZO) is considered as an alternative to transparent conductive oxide materials.Patterning and achieving a stable surface are important challenges in the development and optimization of dry etching processes, which must be overcome for the application of AZO in various devices. Therefore, in this study, the etch rate and surface properties of an AZO thin film after plasma etching using the adaptive coupled plasma system were investigated. The fastest etch rate was achieved with a CF_(4)/Ar ratio of 50:50 sccm. Regardless of the ratio of CF_(4) to Ar,the transmittance of the film in the visible region exceeded 80%. X-ray photoelectron spectroscopy analysis of the AZO thin film confirmed that metal-F bonding persists on the surface after plasma etching. It was also shown that F eliminates O vacancies. Consequently, the work function and bandgap energy increased as the ratio of CF-4 increased. This study not only provides information on the effect of plasma on AZO thin film, but identifies the cause of changes in the device characteristics during device fabrication.