Olefin metathesis reaction on GaN (0 0 0 1) surfaces

Proof-of-concept reactions were performed on GaN (0 0 0 1) surfaces to demonstrate surface termination with desired chemical groups using an olefin cross-metathesis reaction. To prepare the GaN surfaces for olefin metathesis, the surfaces were hydrogen terminated with hydrogen plasma, chlorine terminated with phosphorous pentachloride, and then terminated with an alkene group via a Grignard reaction. The olefin metathesis reaction then bound 7-bromo-1-heptene. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements following each step in the reaction scheme. The XPS data was used to qualitatively identify surface chemical species and to quantitatively determine molecular surface coverage. The bromine atom in 7-bromo-1-heptene served as a heteroatom for identification with XPS. The reaction scheme resulted in GaN substrates with a surface coverage of 0.10 monolayers and excellent stability towards oxidation when exposed to oxygen plasma.     

Atomic Design of Polarity of GaN Films Grown on SiC(0001)

Ab initio total energy calculations are used to determine the interface structure of GaN films grown on 6H-SiC(0001) with different substrate reconstructions. The results indicate that GaN films grown on bare SiC(0001) are of the Ga-polarity, while GaN films grown on SiC(0001) with Si adlayer are of the N-polarity if there is no N-Si interchange at the interface. With the interchange, the GaN films are of the Ga-polarity.     

Al2O3衬底无催化剂生长GaN纳米线及其光学性能

采用一种绿色的等离子增强化学气相沉积法,以Al2O3为衬底, Ga金属为镓源, N2为氮源,在不采用催化剂的情况下,成功制备获得了结晶质量良好的GaN纳米线.研究表明,生长温度可显著调控GaN纳米线的形貌,当反应温度为950℃时,生长出的GaN微米片为六边形;当反应温度为1000℃时,生长出了长度为10-20μm的超长GaN纳米线.随着反应时间增加, GaN纳米线的长度增加. GaN纳米线内部存在着压应力,应力大小为0.84 GPa.同时,也进一步讨论了GaN纳米线无催化剂生长机制. GaN纳米线光致发光结果显示, GaN纳米线缺陷较少,结晶质量良好,在360 nm处有一个较为尖锐的本征发光峰,可应用于紫外激光器等光电子器件.本研究结果将为新型光电器件低成本绿色制备提供一个可行的技术方案.     

Interface engineering of transition metal dichalcogenide/GaN heterostructures: Modified broadband for photoelectronic performance

The GaN-based heterostructures are widely used in optoelectronic devices, but the complex surface reconstructions and lattice mismatch greatly limit the applications. The stacking of two-dimensional transition metal dichalcogenide (TMD = MoS₂, MoSSe and MoSe₂) monolayers on reconstructed GaN surface not only effectively overcomes the larger mismatch, but also brings about novel electronic and optical properties. By adopting the reconstructed GaN (0001) surface with adatoms (N-ter GaN and Ga-ter GaN), the influences of complicated surface conditions on the electronic properties of heterostructures have been investigated. The passivated N-ter and Ga-ter GaN surfaces push the mid-gap states to the valence bands, giving rise to small bandgaps in heterostructures. The charge transfer between Ga-ter GaN surface and TMD monolayers occurs much easier than that across the TMD/N-ter GaN interfaces, which induces stronger interfacial interaction and larger valence band offset (VBO). The band alignment can be switched between type-I and type-II by assembling different TMD monolayers, that is, MoS₂/N-ter GaN and MoS₂/Ga-ter GaN are type-II, and the others are type-I. The absorption of visible light is enhanced in all considered TMD/reconstructed GaN heterostructures. Additionally, MoSe₂/Ga-ter GaN and MoSSe/N-ter GaN have larger conductor band offset (CBO) of 1.32 eV and 1.29 eV, respectively, extending the range from deep ultraviolet to infrared regime. Our results revel that the TMD/reconstructed GaN heterostructures may be used for high-performance broadband photoelectronic devices.     

Theoretical and experimental studies of Ag-Pt interactions for supported Ag-Pt bimetallic catalysts

The electronic structure and chemical properties of catalysts prepared by the electroless deposition (ED) of Ag onto Pt/SiO₂ were studied using a combination of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. XPS studies revealed a negative shift (up to −0.75 eV) in the Ag 3d binding energy (BE) relative to bulk Ag. Both the magnitude and direction of the shift are consistent with DFT calculations of model Ag/Pt(1 1 1) surfaces. DFT calculations have also been employed to study the adsorption of two probe molecules, carbon monoxide and 1-epoxy-3-butene (EpB), on the model surfaces. Combined with previously published reports, the results presented here suggest that (1) the AgPt/SiO₂ catalysts that are most active for hydrogenation of the EpB olefin function consist of an adlayer of Ag on Pt rather than a surface or bulk alloy and that (2) the higher activity and selectivity of ED-prepared Ag-Pt/SiO₂ catalysts for CC hydrogenation of EpB to 1-epoxybutane are consistent with computed electronic (ligand) and bifunctional effects.     

Electronic structure of the PLD grown mixed phase MoS2/GaN interface and its thermal annealing effect

We report the electronic structure of Molybdenum disulfide (MoS₂) ultrathin 2D films grown by pulsed laser deposition (PLD) on top of GaN/c-Al₂O₃ (0001) substrates annealed up to 550 °C in an ultrahigh vacuum. Our X-ray photoemission spectroscopy (XPS) study shows that the grown films are mixed phase character with semiconducting 2H and metallic 1T phases. After ultrahigh vacuum (UHV) annealing, the 1T/2H phase ratio is significantly modified and film-substrate bonding becomes the leading factor influencing variation of mixed phase compositions. The semiconducting phase is partially transformed to metallic phase by thermal annealing; suggesting that the metallic phase observed here may indeed have more stability compared to the semiconducting phase. The notable enhancement of the 1T/2H ratio induces significant changes in Ga 3d core level spectra taken from bare GaN and MoS₂/GaN sample. The impact of S and/or Mo atoms on the Ga core level spectra is further pronounced with the thermal annealing of grown films. The analysis shows that an enhancement of 1T metallic phase with thermal annealing in MoS₂ layers is manifested by the occurrence of new spectral component in the Ga 3d core level spectra with the formation of Ga-S adlayer interaction through the Ga bonding in defect assisted GaN structure.     

Self-assembled monolayer and multilayer formation using redox-active Ru complex with phosphonic acids on silicon oxide surface

The formation of self-assembled monolayer and multilayer using redox-active Ru complex molecules with phosphonic acids on SiO₂ surface has been examined using X-ray photoelectron spectroscopy (XPS), ellipsometry, and time of flight secondary mass-ion spectroscopy (TOF-SIMS). We found that an introduction of a Zr adlayer leads to higher surface molecular density of Ru complex SAMs on the SiO₂ surface, compared to that of obtained from the direct adsorption of Ru complex monolayer on the SiO₂ surface. We further tried to fabricate a multilayer film using this molecule with Zr(IV) ion acting as a chemical glue by a successive immersion process. The XPS data revealed that the molecular densities of the multilayers were also higher for the immobilization with Zr adlayer between Ru complex and SiO₂ surface than those without the Zr adlayer, suggesting that Zr adlayer is effective in forming highly packed molecular layer of phosphonic acids on SiO₂ surface. We found the film growth reached a saturation point after 6 layers on the SiO₂ surface. The film growth saturation can be explained by a molecular domain boundary effect encountered due to the large tilt angle of the molecular layer.     

Electronic energy transfer in benzophenone adlayer

The extent to which energy transfer occurs in electronically excited organic adlayer films on dielectric surfaces is investigated. Migration and subsequent trapping of the energy in the film are observed by pumping the singlet state of an organic adlayer of benzophenone and by monitoring the phosphorescence and fluorescence lifetimes. To observe the effects of adsorption, benzophenone was chosen as the adlayer because the energies of its well characterizedn, carbonyl states are remarkably sensitive to solvent interactions. Upon excitation with a nitrogen laser, the perturbation on the electronic states of benzophenone by the substrate caused the emergence of the normally absent fluorescence from the adlayer traps at the interface between the surface of the dielectric substrate and the adlayer. Energy transfer to this interface was observed as a function of film thickness. On the surface of a single crystal of an organic crystal, naphthalene, energy transfer from the adlayer to the substrate was observed, whereas such transfer was not energetically possible with the other dielectric surfaces.     

Half-metallicity and efficient spin injection in AlN/GaN:Cr (0001) heterostructure

First-principles investigations of the structural, electronic, and magnetic properties of Cr-doped AlN/GaN (0001) heterostructures reveal the possibility of efficient spin injection from a ferromagnetic GaN:Cr electrode through an AlN tunnel barrier. We demonstrate that Cr atoms segregate into the GaN region and that these interfaces retain their half-metallic behavior leading to a complete, i.e., 100%, spin polarization of the conduction electrons. This property makes the wide band-gap nitrides doped with Cr to be excellent candidates for high-efficiency magnetoelectronic devices.     

Surface properties of clean and Au or Pd covered hematite (α-Fe(2)O(3)) (0001)

The structure and electronic properties of different terminations of the α-Fe(2)O(3)(0001) surface were studied with spin-polarized density functional theory (DFT) and the DFT + U method accounting for the effect of strong on-site Coulomb correlations. The results for lattice relaxation, electronic and magnetic properties are presented and discussed. Though the DFT and DFT + U methods provide qualitatively very similar surface geometries they differ very much in the prediction of the electronic and magnetic properties, and the surface energetics of the clean α-Fe(2)O(3)(0001). The most stable single iron terminated (0001) surface and the oxygen-rich termination were chosen to study Au and Pd atom adsorption. The results show that both Au and Pd bind strongly to hematite surfaces and induce large changes in their geometry. The DFT + U bonding is weaker by 0.3-0.6 eV than DFT on the iron terminated surface and about 2 eV stronger on the oxygen terminated one. The binding is stronger for Pd than Au and for both adsorbates is distinctly stronger at the oxygen than at the iron terminated surface. On the iron terminated surface the adsorption binding energy per adatom increases both with Au and Pd coverage, whereas for the oxygen terminated one the opposite trend is observed.     

Controllable restructuring of a metal substrate: Tuning the surface morphology of gold

Organic thin films composed of naphtho[2,3-a]pyrene, a very promising multifunctional polyaromatic hydrocarbon for use in optoelectronic devices, are demonstrated to restructure the pristine Au(111) 22 × √3 surface. The perturbation of the herringbone reconstruction was used to gauge the interaction strength of the organic molecule with the substrate through a series of controlled adsorption and annealing treatments. The overall behavior of the system is interpreted as an interplay between thermodynamic and kinetic factors, dictated by the temperature of the sample and the surface coverage of the molecules. The restructuring mechanism involves the exchange of Au atoms from the herringbone reconstruction to the step edges. Our results reveal that the molecular and substrate equilibrium structure is only achieved after annealing the system to > 470 K. This infers that caution should be taken when organic–metal interfaces are constructed by low or room temperature deposition, as they may not correspond to the equilibrium structures, and therefore, may misrepresent the adlayer structure which exists at the realistic working conditions of devices.     

Cs/GaN(0001)吸附体系电子结构和光学性质研究

采用基于第一性原理的密度泛函理论平面波超软赝势方法计算了 1/4ML Cs原子吸附 (2 × 2) GaN(0001) 表面的吸附能、能带结构、电子态密度、电荷布居数、功函数和光学性质. 计算发现, 1/4ML Cs 原子在 GaN(0001) 表面最稳定吸附位为 N 桥位, 吸附后表面仍呈现为金属导电特性, Cs原子吸附GaN(0001)表面后主要与表面 Ga 原子发生作用, Cs6s 态电子向最表面 Ga 原子转移, 引起表面功函数下降. 研究光学性质发现, Cs 原子吸附 GaN(0001) 表面后, 介电函数虚部、吸收谱、反射谱向低能方向移动.     

Electronic structure of GaN(0001)‐2 × 2 thin films grown by PAMBE

Gallium nitride thin films were grown on silicon carbide (0001) by plasma‐assisted molecular beam epitaxy (PAMBE). The samples were cooled down in nitrogen plasma and characterized in situ by reflection high energy electron diffraction (RHEED), photoelectron spectroscopy (XPS/UPS), and atomic force microscopy (AFM) revealing stoichiometric and smooth GaN films virtually free of contaminations. We present valence band data obtained by UPS with strong emission from surface states inside the fundamental band gap. These states and the observed 2 × 2 surface reconstruction are highly sensitive towards residual molecules. Once these surface states have disappeared the original state could not be recovered by surface preparation methods underlining the necessity of in situ investigations on as‐grown surfaces. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Removal of GaN film over AlGaN with inductively coupled BCl3/Ar atomic layer etch

Atomic layer etching(ALE)of thin film GaN(0001)is reported in detail using sequential surface modification by BCl₃ adsorption and removal of the modified surface layer by low energy Ar plasma exposure in a reactive ion etching system.The estimated etching rate of GaN is~0.74 nm/cycle.The GaN is removed from the surface of AlGaN after 135 cycles.To study the mechanism of the etching,the detailed characterization and analyses are carried out,including scanning electron microscope(SEM),x-ray photoelectron spectroscopy(XPS),and atomic force microscope(AFM).It is found that in the presence of GaCl_x after surface modification by BCl₃,the GaCl_x disappears after having exposed to low energy Ar plasma,which effectively exhibits the mechanism of atomic layer etch.This technique enables a uniform and reproducible fabrication process for enhancement-mode high electron mobility transistors with a p-GaN gate.     

Scanning tunneling microscopy of the GaN(0001) surface

The wurtzite GaN(0001) surface is imaged by scanning tunneling microscopy. Terraces are observed with line-defect structures on them: primarily regularly spaced striations perpendicular to step edges. A model of these striations as ordered N-vacancies is presented.     

Characterization of peptide immobilization on an acetylene terminated surface via click chemistry

Peptide (A-A-A-A-G-G-G-E-R-G-D)¹ conjugated surfaces were prepared on silicon surfaces through click chemistry. The amino acid sequence RGD is the cellular attachment site of a large number of extracellular matrices such as blood and cell surface proteins. Recent research has focused on developing RGD peptides which mimic cell adhesion proteins and integrins [1], [2].The steps involved the formation of an alkyne-terminated monolayer on Si(111), followed by linking the peptide to 4-azidophenyl isothiocyanate via a specific and gentle reaction. This was followed by the attachment of the azido peptide to the surface-bound alkynes using the Cu (I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction. The surface structures of the alkyne terminated monolayer and the attached peptide were characterized using high resolution impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared (ATR-FTIR) Spectroscopy. EIS characterization revealed the alkyne layer and the hydrophobic and polar regions of the attached peptide. XPS analysis showed a high surface coverage of the peptide on the silicon substrates and this was confirmed by FTIR.Our results confirmed a specific covalent attachment of the peptide on the silicon surfaces. This approach offers a versatile, experimentally simple, method for the specific attachment of peptide ligands. This approach would have applications for cell attachment and biosensors.     

An XPS study of the interaction between tin(II) phthalocyanine and polycrystalline iron

The interaction between tin phthalocyanine (SnPc) and polycrystalline iron has been studied with XPS and synchrotron radiation excited XPS. After incremental annealing of a thin film of SnPc on a polycrystalline iron substrate, a low binding energy component of the Sn 3d core level became increasingly abundant. This component is attributed to metallic tin, and thus, it is suggested that a substitution reaction has occurred. Quantitative analysis of the carbon and nitrogen core level intensities is consistent with such a substitution. The reaction is observable at room temperature, but is enhanced at elevated temperatures.It is also shown that after thermal desorbtion of the SnPc adlayer, the residual carbon component is significantly reduced relative to a thermally cleaned polycrystalline surface.     

AlGaN/GaN高电子迁移率晶体管肖特基高温退火机理研究

在不同应力条件下,研究了AlGaN/GaN高电子迁移率晶体管高温退火前后的电流崩塌、栅泄漏电流以及击穿电压的变化.结果表明,AlGaN/GaN高电子迁移率晶体管通过肖特基高温退火以后,器件的特性得到很大的改善.利用电镜扫描(SEM)和X射线光电子能谱(XPS)对高温退火前、后的肖特基接触界面进行深入分析,发现器件经过高温退火后,Ni和AlGaN层之间介质的去除,并且AlGaN材料表面附近的陷阱减少,使得肖特基有效势垒提高,从而提高器件的电学特性. 关键词： AlGaN/GaN高电子迁移率晶体管 肖特基接触 界面陷阱     

Functionalization of carbon nanofibers with elastomeric block copolymer using carbodiimide chemistry

Surface functionalization of carbon nanofibers (CNFs) with aminopropyl terminated polydimethylsiloxane [(PDMS-NH₂)] and other organic diamines was achieved using carbodiimide chemistry. The carbodiimide chemistry provides faster reaction rate so that the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. CNF functionalized with PDMS-NH₂ fibers were further functionalized with oligomer of polyimide (6FDA-BisP) using imidization reaction. The formation of block copolymer on the surface of CNF is proposed as an effective method to engineer the interphase between the fiber and the polymer, which is essential to modulate and enhance the properties of the nanocomposite. The efficiency of the carbodiimide chemistry to functionalize amine terminated groups on CNF and the functionalization of block copolymer was characterized using thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and UV-vis spectroscopy.     

Formation and growth mechanism of ripple-like AlN nanowires

Single-crystal ripple-like AlN nanowire with tuned diameter was fabricated through direct reaction aluminum with nitrogen by arc discharge method. The nanowires grow along the [0001] direction and have a radial expansion along the [10[`1]0][10\bar{1}0] direction. The periodic variation of the radial expansion toward [10[`1]0][10\bar{1}0] direction produces the ripple-like AlN nanowires. The growth mechanism of the AlN nanowires is discussed by considering the Al adlayer diffusion on the polar (0001) surface.