Effect of substrate bias voltages on the diffusion barrier properties of Zr-N films in Cu metallization

Zr-N diffusion barriers were deposited on the Si substrates by rf reactive magnetron sputtering under various substrate bias voltages. Cu films were subsequently sputtered onto the Zr-N films by dc pulse magnetron sputtering without breaking vacuum. The Cu/Zr-N/Si specimens were then annealed up to 650 °C in N₂ ambient for an hour. The effects of deposition bias on growth rate, film resistivity, microstructure, and diffusion barrier properties of Zr-N films were investigated. An increase in negative substrate bias resulted in a decrease in deposition rate together with a decrease in resistivity. It was found that the sheet resistances of Cu/Zr-N(−200 V)/Si contact system were lower than those of Cu/Zr-N(−50 V)/Si specimens after annealing at 650 °C. Cu/Zr-N(−200 V)/Si contact systems showed better thermal stability so that the Cu₃Si phase could not be detected.     

The effects of annealing on Au/pyronine-B/MD n-InP Schottky structure

Thin film of non-polymeric organic compound pyronine-B has been fabricated on moderately doped (MD) n-InP substrate as an interfacial layer using spin coating technique for the electronic modification of Au/MD n-InP Schottky contact. The electrical characteristics have been determined at room temperature. The barrier height and the ideality factor values for Au/pyronine-B/MD n-InP Schottky diode have been obtained from the forward bias I-V characteristics at room temperature as 0.60 eV and 1.041; 0.571 and 1.253 eV after annealing at 100 and 250 °C, respectively. An increase in annealing temperature at the Au/n-InP Schottky junction is shown to increase the reverse bias leakage current by about one order of magnitude and decrease the Schottky barrier height by 0.027 eV. Furthermore, the barrier height values for the Au/pyronine-B/MD n-InP Schottky diode have also been obtained from the C-V characteristics at room temperature as 1.001 and 0.709 eV after annealing at 100 and 250 °C, respectively. Finally, it was seen that the diode parameters changed with increase in the annealing temperature.     

Ti-Cu-N hard nanocomposite films prepared by pulse biased arc ion plating

In this work, Ti-Cu-N hard nanocomposite films were deposited on high-speed-steel (HSS) substrates using a TiCu (88:12 at.%) single multi-component target by pulse biased arc ion plating. The influence of pulse bias voltages was examined with regard to elemental composition, structure, morphology and mechanical properties of the films. The Cu atomic content of Ti-Cu-N films was determined by Electron Probe Micro-Analyzer (EPMA). The structure and morphology were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Hardness and film/substrate adhesion were determined by nanoindenter and scratch test, respectively. The results showed that the content of Cu appeared to be in the range of 1.75-4.5 at.%, depending on pulse bias voltages. The films exhibit a preferred orientation TiN (1 1 1) texture when the substrate bias voltages were −100 V and −300 V, while the preferred orientation change to be a preferred orientation TiN (2 2 0) one when the substrate bias voltages increase to −600 V and −900 V. And no obvious sign of metal copper phase was observed. The SEM morphologies showed some macroparticles (MPs) on the surface of the films and the relative content of the MPs decreased significantly when the substrate bias voltages increased from −100 to −900 V. The maximum value (74 N) of the film/substrate adhesion of the films was obtained when the substrate bias voltage was −600 V with Cu content of 1.75 at.%. Hardness enhancement was observed, the value of the hardness increased firstly and reached a maximum value of 31.5 GPa, corresponding to Cu content of 1.75 at.%, and then it decreased when the substrate bias voltage changed from −100 to −900 V. The hardness enhancement was discussed related to the concept for the design of hard materials.     

In situ observation on Au(1 0 0) surface in molten EMImBF4 by electrochemical atomic force microscopy (EC-AFM)

The Au(1 0 0) surface structure in contact with 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF₄) has been observed using electrochemical atomic force microscopy (EC-AFM) under an electrochemically controlled potential. The AFM images, taken in EMImBF₄ in the potential range from −0.6 to 0.2 V vs. Ag/Ag(I), shows a fourfold symmetry with the distance between protrusions of ≈0.30-0.32 nm. This structure agrees well with the ideal surface structure of Au(1 0 0)-(1 × 1) and it is very similar to that previously obtained in a sulfuric acid aqueous solution.     

Electrical, structural and surface morphological properties of thermally stable low-resistance W/Ti/Au multilayer ohmic contacts to n-type GaN

A W/Ti/Au multilayer scheme has been fabricated for achieving thermally stable low-resistance ohmic contact to n-type GaN (4.0 × 10¹⁸ cm⁻³). It is shown that the as-deposited W/Ti/Au contact exhibits near linear I-V behaviour. However, annealing at temperature below 800 °C the contacts exhibit non-linear behaviour. After annealing at a temperature in excess of 850 °C, the W/Ti/Au contact showed ohmic behaviour. The W/Ti/Au contact produced specific contact resistance as low as 6.7 × 10⁻⁶ Ω cm² after annealing at 900 °C for 1 min in a N₂ ambient. It is noted that the specific contact resistance decreases with increase in annealing temperature. It is also noted that annealing the contacts at 900 °C for 30 min causes insignificant degradation of the electrical and thermal properties. It is further shown that the overall surface morphology of the W/Ti/Au stayed fairly smooth even after annealing at 900 °C. The W/Ti/Au ohmic contact showed good edge sharpness after annealing at 900 °C for 30 min. Based on the Auger electron spectroscopy and glancing angle X-ray diffraction results, possible explanation for the annealing dependence of the specific contact resistance of the W/Ti/Au contacts are described and discussed.     

Electrical and magnetic properties of Ni-Cu-Si heterojunction prepared by the liquid phase epitaxy technique

Ni-Cu-Si heterojunction was prepared by the liquid phase epitaxy (LPE) technique. Two growth solutions containing Indium (In) with Cu pieces and In with Ni pieces were employed during the fabrication process. The as-formed junction was directly characterized by different techniques including scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and thin film X-ray diffraction (XRD) measurements. The current-voltage (I-V) characteristics of the Au/Ni/Cu/Si diode were found to be nonlinear, asymmetric, having a good rectification behavior with a very small leakage current of 0.003 μA at a reverse bias voltage of 2.0 V. The value of turn on voltage was located at 0.2 V. The magnetic properties were also evaluated at room temperature with a vibrating sample magnetometer. Systematic study of junction fabrication and characterization of such a heterosystem, comparison of the behavior of flat silicon and nanoporous silicon as substrates are presented and thoroughly discussed.     

Electrical properties and dielectric relaxation of thermally evaporated zinc phthalocyanine thin films

The electrical transport properties and dielectric relaxation of Au/zinc phthalocyanine, ZnPC/Au devices have been investigated. The DC thermal activation energy at temperature region 400-500 K is 0.78 eV. The dominant conduction mechanisms in the device are ohmic conduction below 1 V and space charge limited conduction dominated by exponential trap distribution in potentials >1 V. Some parameters, such as concentration of thermally generated holes in valence band, the trap concentration per unit energy range at the valence band edge, the total concentration of traps and the temperature parameter characterizing the exponential trap distribution and their relation with temperatures have been determined. The AC electrical conductivity, σ_ac, as a function of temperature and frequency has been investigated. It showed a frequency and temperature dependence of AC conductivity for films in the temperature range 300-400 K. The films conductivity in the temperature range 400-435 K increased with increasing temperature and it shows no response for frequency change. The dominant conduction mechanism is the correlated barrier hopping. The temperature and frequency dependence of real and imaginary dielectric constants and loss tangent were investigated.     

Native oxidation of ultra high purity Cu bulk and thin films

The effect of microstructure and purity on the native oxidation of Cu was studied by using angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and spectroscopic ellipsometry (SE). A high quality copper film prepared by ion beam deposition under a substrate bias voltage of −50 V (IBD Cu film at V_s = −50 V) showed an oxidation resistance as high as an ultra high purity copper (UHP Cu) bulk, whereas a Cu film deposited without substrate bias voltage (IBD Cu film at V_s = 0 V) showed lower oxidation resistance. The growth of Cu₂O layer on the UHP Cu bulk and both types of the films obeyed in principle a logarithmic rate law. However, the growth of oxide layer on the IBD Cu films at V_s = 0 and −50 V deviated upward from the logarithmic rate law after the exposure time of 320 and 800 h, respectively. The deviation from the logarithmic law is due to the formation of CuO on the Cu₂O layer after a critical time.     

Optoelectronic characterization of Au/Ni/n-AlGaN photodiodes after annealing at different temperatures

The optoelectronic characteristics of Ni/Au Schottky photodiodes based on Al_0.35Ga_0.65N were investigated. The transmission of the Ni (50 Å)/Au (50 Å) layer was determined by evaporating it on a quartz substrate. As evaporated, the transmission coefficient in the 200–350 nm wavelength range was found to be 43 to 48%. Annealing at temperatures of up to 400 °C did not influence the transmission coefficient. After annealing at 500 °C, the transmission coefficient increased from 50 to 68% over the 200–350 nm range. The reverse bias current was optimised in terms of annealing temperature and was found to be as low as 1.94×10⁻¹³ A after annealing at 400 °C for a 0.6 mm diameter contact. The Schottky barrier heights increased with annealing temperature reaching as high as 1.46 and 1.89 eV for I–V and C–V measurements, respectively. The quantum efficiency was measured to be 20.5% and the responsivity reached its peak of 0.046 A/W at 275 nm. The cut-off wavelength was 292 nm.     

Interfacial differences in enhanced schottky barrier height Au/n-GaAs diodes deposited at 77 K

The use of cryogenic temperatures (∼77 K) during Au Schottky contact deposition onto n-GaAs produces an increase in barrier height from 0.73 eV for room temperature diodes to 0.82 eV. Not all Schottky metals show this enhancement—for example Pt and Ti do not show any significant change in barrier height whereas Au, Pd and Ni show increases between 7 and 18%. We used X-ray reflectivity to show that the main difference between Au deposited at 77 K and room temperature is a decreased metal roughness while the interfacial roughness between the Au and GaAs is basically the same. As the diodes are annealed to 300 °C both the difference in barrier height and interfacial roughness is lost. This is a simple method with potential for improving the performance of GaAs metal-semiconductor-field-effect-transistors (MESFETs).     

Annealing effects on the plasmonic excitations of metal/metal interfaces

The effects of the annealing procedure at 400-450 K on the electronic properties of nanoscale thin films of Ca, Au and Ag grown on Cu(1 1 1) at room temperature were probed by high-resolution electron energy loss spectroscopy measurements. Ca surface plasmon underwent to a significant red-shift upon annealing, due to the oxidation of the topmost Ca layer. Water strongly interacted with the CaO interface at room temperature. Au surface plasmon disappeared upon annealing the gold film, as a consequence of the formation of an Au-Cu alloy. Ag surface plasmon red-shifted both in the annealed adlayer and with increasing temperature compared with the frequency recorded for the as-deposited silver film.     

Bias-dependence of the conductance of Au nanocontacts at 4 K

The bias-dependence of the quantized conductance in Au nanocontacts has been measured at liquid He temperature. A well-defined 1G₀ peak (G₀=2e²/h is the conductance quantum unit) appears in the conductance histogram. With increasing the bias, the 1G₀ peak decreases in height, while its position remains unshifted. This behavior of the 1G₀ peak is just the same as that observed at room temperature [H. Yasuda, A. Sakai, Phys. Rev. B 56 (1997) 1069]. The critical bias V_bc at which the 1G₀ peak disappears is ∼2.2 V, which is not much different from V_bc at 300 and 77 K. This weak temperature dependence of V_bc is compatible with high-current contact instability due to electromigration of contact atoms.     

ZrB2-based Ohmic contacts to p-GaN

The annealing temperature dependence of contact resistance and layer stability of ZrB₂/Ti/Au and Ni/Au/ZrB₂/Ti/Au Ohmic contacts on p-GaN is reported. The as-deposited contacts are rectifying and transition to Ohmic behavior for annealing at ≥750 °C, a significant improvement in thermal stability compared to the conventional Ni/Au Ohmic contact on p-GaN, which is stable only to <600 °C. A minimum specific contact resistance of ∼2 × 10⁻³ Ω cm⁻² was obtained for the ZrB₂/Ti/Au after annealing at 800 °C while for Ni/Au/ZrB₂/Ti/Au the minimum value was 10⁻⁴ Ω cm⁻² at 900 °C. Auger Electron Spectroscopy profiling showed significant Ti, Ni and Zr out diffusion at 750 °C in the Ni/Au/ZrB₂/Ti/Au while the Ti and Zr intermix at 900 °C in the ZrB₂/Ti/Au. These boride-based contacts show promise for contacts to p-GaN in high temperature applications.     

Ir-based diffusion barriers for Ohmic contacts to p-GaN

Ir-based electrical contacts to p-type GaN have been fabricated and characterized. Both GaN//Ni/Au/Ir/Au and GaN//Ni/Ir/Au contact structures were deposited, however, only the former produced Ohmic current-voltage characteristics. At an anneal temperature of 500 °C, the Ni/Au/Ir/Au contact had a specific contact resistance of ∼2 × 10⁻⁴ Ω cm², comparable or superior to conventional Ni/Au contacts that are less thermally stable. Anneal temperatures above 500 °C caused the Ir-based contact to fail. Auger electron spectroscopy was used to obtain depth profiles of both types of contacts at a variety of temperatures in order to provide insight into the mechanism of Ohmic formation as well as potential reasons for failure. A comparison to other metallization schemes on p-GaN is also given.     

Photoemission study of glycine adsorption on Cu/Au(1 1 1) interfaces

The adsorption of glycine on Au(1 1 1) pre-deposited with different amounts of Cu was investigated with both conventional X-ray photoelectron spectroscopy (XPS) and synchrotron-based photoemission. In the Cu submonolayer range, glycine physically adsorbs on the Cu/Au(1 1 1) surfaces in its zwitterionic form and completely desorbs at 350 K. The C 1s, O 1s and N 1s core level binding energies monotonically increase with Cu coverage. This indicates that, in the Cu submonolayer range, the admetal is alloyed with Au rather than forming overlayers on the Au(1 1 1) substrate, consistent with our recent experimental and theoretical results [X. Zhao, P. Liu, J. Hrbek, J.A. Rodriguez, M. Pérez, Surf. Sci. 592 (2005) 25]. Upon increasing the amount of deposited Cu over 1 ML, part of the glycine overlayer transforms from the zwitterionic form to the anionic form (NH₂CH₂COO⁻) and adsorbs chemically on the Cu/Au(1 1 1) surface with the N 1s binding energy shifted by −2.3 eV. When the amount of deposited Cu is at 3.0 or 6.0 ML, the intensity of the N 1s chemisorption peak increases with aging time at 300 K. It indicates that glycine adsorption induces Cu segregation from the subsurface region onto the top layer of the substrate. Judging from the initial N 1s peak intensities, it is concluded that 64% and 36% of the top layer are still occupied by Au atoms before glycine adsorption even when the amounts of deposited Cu are 3.0 and 6.0 ML, respectively. On the Au(1 1 1) surface pre-dosed with 6.0 ML of Cu, part of the chemisorbed glycine will desorb and part will decompose upon heating to 450-500 K. In addition, about 20% of the glycine exists in the neutral form when the glycine overlayer was dosed on Cu/Au(1 1 1) held at 100 K.     

Ultraviolet photoconductive detector based on Al doped ZnO films prepared by sol-gel method

We report a study on the fabrication and characterization of ultraviolet photodetectors based on ZnO:Al films. Using sol-gel technique, highly c-axis oriented ZnO films with 5 mol% Al doping were deposited on Si(1 1 1) substrates. The photoconductive UV detectors based on ZnO:Al thin films, having a metal-semiconductor-metal (MSM) structure with interdigital (IDT) configuration, were fabricated by using Au as a contact metal. The characteristics of dark and photocurrent of the UV detector and the UV photoresponse of the detector were investigated. The linear current-voltage (I-V) characteristics under both forward and reverse bias exhibit ohmic metal-semiconductor contacts. Under illumination using monochromatic light with a wavelength of 350 nm, photo-generated current was measured at 58.05 μA at a bias of 6 V. The detector exhibits an evident wide-range spectral responsivity and shows a trend similar to that in transmittance and photoluminescence spectrum.     

Decay of nano-islands located on Au(1 0 0) electrode in room temperature molten salt (EMImBF4)

The behaviour of nano-islands located on an Au(1 0 0) single crystal surface in contact with a room temperature molten salt, that is, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF₄), has been investigated using electrochemical atomic force microscopy (EC-AFM) under potential control. It was found from the in situ EC-AFM observations that a nano-island located on an Au(1 0 0) electrode collapses in EMImBF₄ in the potential range between −1.05 and 0.2 V (vs. Ag/Ag⁺ in EMImBF₄). It was also found that the nano-islands decay faster when the Au(1 0 0) electrode potential is more positive. These in situ EC-AFM observations reveal that the behaviour of the nano-island in the EMImBF₄ shown above is quite similar to that observed in a sulfuric acid aqueous solution.     

Effect of substrate bias and temperature on magnetron sputtered CrSiN films

The combine influence of substrate temperature and bias on microstructure and mechanical properties of CrSiN film was examined. The silicon content and phase constitutions of the films are independent on substrate temperature and bias. The crystal preferred orientation is controlled by substrate bias but unrelated to substrate temperature. The influence of bias (0 V to −300 V) on hardness is more obvious than that of the substrate temperature (100-500 °C).     

Phase transition of thiophene molecules on Au(1 1 1) in solution

The orientation and packing arrangement of thiophene molecules on a well-defined Au(1 1 1) surface in 0.1 M HClO₄ solution have been investigated as a function of applied potentials by in situ scanning tunneling microscopy (STM) and electrochemical method. Thiophene molecules are found to form highly ordered adlayers in the double layer region. High-resolution STM images reveal different adlayer structures. Thiophene molecules take flat-lying and vertical orientation at 0.3 and 0.6 V, respectively. Compared with the results of electrochemical measurement, we concluded that the phase transition of thiophene on Au(1 1 1) occurs as the potential is changed between 0.1 and 0.65 V.     

Active oxidation of Cu3Au(1 1 0) using hyperthermal O2 molecular beam

Oxidation of Cu₃Au(1 1 0) using a hyperthermal O₂ molecular beam (HOMB) was investigated by X-ray photoemission spectroscopy in conjunction with a synchrotron light source. From the incident energy dependence of the O-uptake curve, the precursor-mediated dissociative adsorption occurs, where the trapped O₂ molecule can migrate and dissociate at the lower activation-barrier sites, dominantly at thermal O₂ exposures. Dissociative adsorption of O₂ on Cu₃Au(1 1 0) is as effective at the thermal O₂ exposure as on Cu(1 1 0). On the other hand, at the incident energies of HOMB where the direct dissociative adsorption is dominant, it was determined that the dissociative adsorption of O₂ implies a higher activation barrier and therefore less reactivity due to the Au alloying in comparison with the HOMB oxidation of Cu(1 1 0). The dissociative adsorption progresses with the Cu segregation on Cu₃Au(1 1 0) similarly as on Cu₃Au(1 0 0). The growth of Cu₂O for 2 eV HOMB suggests that the diffusion of Cu atoms also contribute to the oxidation process through the open face, which makes the difference from Cu₃Au(1 0 0).