Schottky metal library for ZNO-based UV photodiode fabricated by the combinatorial ion beam-assisted deposition

A binary alloy Schottky barrier diode on zinc oxide (ZnO) was developed using the combinatorial ion beam-assisted deposition system. The compositional fraction of the binary alloy was continuously varied using the composition-spread technique, to control the Schottky barrier height. After metal deposition, patterned Schottky diodes were fabricated on a ZnO single-crystal substrate. Pt-Ru alloy was selected from the work function viewpoint. Our experiments showed that the compositional fraction of the Schottky binary alloys changed continuously as designed and the Schottky barrier heights measured by current-voltage (I-V) measurements increased with increasing Pt content. Maximum barrier height difference for ZnO was 137 meV. Using ion beam deposition in parallel with the combinatorial system showed that the Schottky barrier heights for ZnO can be controlled by binary metal alloying.     

ZrB2/Pt/Au Ohmic contacts on bulk, single-crystal ZnO

There is a strong interest in developing thermally stable metallization schemes for ZnO and boride-based contact stacks are expected to have potential because of their thermodynamic stability. The contact characteristics on bulk single-crystal n-ZnO of a ZrB₂/Pt/Au metallization scheme deposited by sputtering are reported as a function of annealing temperature in the range 300-800°C. The contacts were rectifying for anneal temperatures <500 °C but exhibited Ohmic behavior at higher temperatures and exhibit a minimum specific contact resistivity of 9 × 10⁻³ Ω cm after 700 °C anneals. The contact stack reverts to rectifying behavior after annealing above 800 °C, coincident with a degraded surface morphology and intermixing of the Au, Pt and ZrB₂. The boride-based contacts exhibit higher thermal stability but poorer specific contact resistivity than conventional Ti/Au metal stacks on ZnO.     

Temperature dependence of the optical band gap and electrical conductivity of sol-gel derived undoped and Li-doped ZnO films

Undoped and lithium (Li)-doped ZnO films were prepared by sol-gel method using spin coating technique. The effects of Li content on the crystallinity and morphological properties of ZnO films were assessed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). XRD patterns of the films showed the hexagonal wurtzite type polycrystalline structure and that the incorporation of lithium leads to substantial changes in the structural characteristics of ZnO films. The SEM and AFM measurements showed that the surface morphology of the films was affected from the lithium incorporation. The wrinkle network was observed on the surface from both SEM and AFM results for undoped ZnO. The wrinkle structure disappeared with increasing Li content. The absorption spectra of the ZnO and 5% Li-doped ZnO (LZO5) films were carried out between 140 and 400 K temperatures. The optical band gap of ZnO and LZO5 films (calculated at various temperatures) showed a linear dependence on the temperature. The absolute zero value optical band gap and the rate of change of the band gap with temperature of the ZnO and LZO5 films were found to be 3.339 and 3.322 eV, and 2.95 × 10⁻⁴ and 1.60 × 10⁻⁴ eV/K, respectively. The transport mechanisms in the ZnO and LZO5 films have been investigated by analyzing of the temperature (80-300 K) dependence of the conductivity. The activation energies of the ZnO film increased with Li content.     

Influence of the interface structure on the barrier height of homogeneous Schottky contacts

Unreconstructed interfaces may be prepared by evaporation of thick Pb films onto surfaces at room temperature. Current-voltage and capacitance-voltage characteristics of such Schottky contacts were measured in the temperature range between 140 and 300 K. The experimental data are analyzed by applying the thermionic-emission theory of inhomogeneous metal-semiconductor contacts as well as the “standard” thermionic-emission theory. From both methods the Schottky barrier height of laterally homogeneous contacts results as 0.724 eV. This value is by 74 meV larger than the previously observed barrier heights of laterally homogeneous interfaces. Similar differences were reported for unreconstructed and reconstructed Al- and contacts. The reduced barrier heights of all these interfaces are explained by the electric dipole associated with the stacking faults of reconstructions at surfaces and interfaces. Received: 14 May 1998 /Revised and Accepted: 7 September 1998     

Electrical characteristics of the hydrogen pre-annealed Au/n-GaAs Schottky barrier diodes as a function of temperature

We investigated the passivation effects of hydrogen gas on the Au/n-GaAs Schottky barrier diodes in a wide temperature range. Reference diodes were prepared by evaporating barrier metal on semiconductor wafers un-annealed in N₂ gas atmosphere. The other diodes were made by evaporating barrier metal on n-GaAs semiconductor substrates annealed in H₂ atmosphere. Then, electrical measurements of all diodes were carried out by using closed-cycle Helium cryostat by steps of 20 K in the temperature range of 80-300 K in dark. The basic diode parameters such as ideality factor and barrier height were consequently extracted from electrical measurements. It was seen that ideality factors increased and barrier heights decreased with the decreasing temperature. The case was attributed to barrier inhomogeneity at the metal/semiconductor interface. Barrier heights of the diodes made from samples annealed in H₂ gas atmosphere were smaller than those of reference diodes at low temperatures. Here, it was ascribed to the fact that hydrogen atoms passivated dangling bonds on semiconductor surface in accordance with former studies.     

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).     

Examination of magnetite nanoparticles utilising the temperature dependent magnetorelaxometry

We investigated the magnetic properties of two kinds of magnetosomes (25-42 nm) produced by the magneto-tactic bacterium Magnetospirillum gryphiswaldense. At temperatures between 4.2 K and room temperature the temperature dependent magnetorelaxation (TMRX) method was used. We found three areas with magnetic signals and discuss them in this paper using the results of additional hysteresis loop measurements. The signals detected above 300 K show the lower end of a beginning energy barrier distribution. The signals between 70 and 120 K lie in the area of the Verwey transition and disappear over time due to aging processes. In addition to these signals, other signals at temperatures between 4.2 and 70 K were found and possible causes are discussed.     

Current–voltage temperature characteristics of Au/n-Ge (1 0 0) Schottky diodes

The variation in electrical characteristics of Au/n-Ge (1 0 0) Schottky contacts have been systematically investigated as a function of temperature using current–voltage (I−V) measurements in the temperature range 140–300 K. The I–V characteristics of the diodes indicate very strong temperature dependence. While the ideality factor n decreases, the zero-bias Schottky barrier height (SBH) (Φ_B) increases with the increasing temperature. The I–V characteristics are analyzed using the thermionic emission (TE) model and the assumption of a Gaussian distribution of the barrier heights due to barrier inhomogeneities at the metal–semiconductor interface. The zero-bias barrier height Φ_B vs. 1/2 kT plot has been used to show the evidence of a Gaussian distribution of barrier heights and values of Φ_B=0.615 eV and standard deviation σ_s0=0.0858 eV for the mean barrier height and zero-bias standard deviation have been obtained from this plot, respectively. The Richardson constant and the mean barrier height from the modified Richardson plot were obtained as 1.37 A cm⁻² K⁻² and 0.639 eV, respectively. This Richardson constant is much smaller than the reported of 50 A cm⁻² K⁻². This may be due to greater inhomogeneities at the interface.     

Spray pyrolysis deposition of ZnO thin films on FTO coated substrates from zinc acetate and zinc chloride precursor solution at different growth temperatures

ZnO thin films were fabricated using zinc chloride and zinc acetate precursors by the spray pyrolysis technique on FTO coated glass substrates. The ZnO films were grown in different deposition temperature ranges varying from 400 to 550 °C. Influences of substrate temperature and zinc precursors on crystal structure, morphology and optical property of the ZnO thin films were investigated. XRD patterns of the films deposited using chloride precursor indicate that (1 0 1) is dominant at low temperatures, while those deposited using acetate precursor show that (1 0 1) is dominant at high temperatures. SEM images show that deposition temperature and type of precursor have a strong effect on the surface morphology. Optical measurements show that ZnO films are obviously influenced by the substrate temperatures and different types of precursor solutions. It is observed that as temperature increases, transmittance decreases for ZnO films obtained using zinc chloride precursor, but the optical transmittance of ZnO films obtained using zinc acetate precursor increases as temperature increases.     

Self-limiting growth of ZnO films on (0 0 0 1) sapphire substrates by atomic layer deposition at low temperatures using diethyl-zinc and nitrous oxide

Atomic layer deposition (ALD) of zinc oxide (ZnO) films on (0 0 0 1) sapphire substrates was conducted at low temperatures by using diethyl-zinc (DEZn) and nitrous oxide (N₂O) as precursors. It was found that a monolayer-by-monolayer growth regime occurred at 300 °C in a range of DEZn flow rates from 5.7 to 8.7 μmol/min. Furthermore, the temperature self-limiting process window for the ALD-grown ZnO films was also observed ranging from 290 to 310 °C. A deposition mechanism is proposed to explain how saturated growth of ZnO is achieved by using DEZn and N₂O. Transmission spectroscopic studies of the ZnO films prepared in the self-limiting regime show that the transmittances of ZnO films are as high as 80% in visible and near infrared spectra. Experimental results indicate that ZnO films with high optical quality can be achieved by ALD at low temperatures using DEZn and N₂O precursors.     

Effects of ZnO film thickness on electrical and magnetoresistance characteristics of La0.8Sr0.2MnO3/ZnO heterostructures

The La_0.8Sr_0.2MnO₃/ZnO heterostructures with different thicknesses of ZnO films are fabricated by using RF magnetron sputtering technique. The heterojunctions exhibit excellent rectifying properties at 300 K. At low temperatures the temperature dependent junction resistance exhibits a metal-insulator transition like behavior. A magnetic field strongly impacts on electrical characteristics of La_0.8Sr_0.2MnO₃/ZnO p-n junctions, i.e., depressing the junction resistance greatly and driving the metal-insulator transition temperature (T_MI) towards higher temperatures. Large magnetoresistance is observed below T_MI, and it increases with increasing magnetic field and almost saturates at 5 T, i.e., above −90% at 100 K and 5 T.     

Investigation of electrical and ammonia sensing characteristics of Schottky barrier diode based on a single ultra-long ZnO nanorod

Novel ultra-long ZnO nanorods, with lengths about 0.5-1.5 mm and diameters ranging from 100 to 1000 nm, in mass production have been synthesized via the vapor-phase transport method with CuO catalyst at 900 °C. Rectifying Schottky barrier diodes have been fabricated by aligning a single ultra-long ZnO nanorod across paired Ag electrodes. The resulting current-voltage (I-V) characteristics of the SBD exhibit a clear rectifying behavior. The ideality factor of the diode is about 4.6, and the threshold voltage is about 0.54 V at room temperature (300 K). At the same time the detailed I-V characteristics have been investigated in the temperature range 423-523 K. In addition, after exposure of the Schottky diodes to NH₃, the forward and reverse currents increase rapidly, indicating a high sensitivity to NH₃ gas.     

Photoelectron spectroscopy study of the K-covered ZnO(1 0 1&#x0304; 0) surface; annealing-induced changes in the electronic structure and the chemical composition

The electronic structure and the chemical composition of the K-covered ZnO(1 0 1&#x0304; 0) surface at temperatures between 300 and 1200 K are investigated by X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. Adsorption of K on ZnO(1 0 1&#x0304; 0) at room temperature results in the formation of a two-dimensional disordered K overlayer and induces 0.2 eV downward bending of the substrate’s bands going from the bulk to the surface. Upon annealing the K-covered surface, initial downward bending turns to upward bending with maximum bending of 0.5 eV at 700-800 K. The thermally induced migration of the bulk O atoms and the resultant increase in the number of the O atoms on the surface is responsible for upward bending on the annealed surface. The accumulated O atoms interact with the predeposited K atoms on the surface to form non-stoichiometric K-O complexes with the O/K atomic ratio being 1.6-1.8 in the temperature range between 600 and 1000 K.     

Decay kinetics of the defect-based visible luminescence in ZnO

Photoluminescence spectra and decays under pulsed N₂ (337 nm) laser excitation were measured for hydrothermally grown bulk and liquid-phase epitaxy (LPE)-grown film ZnO samples within 9-300 K. Temperature dependence of integrated spectra over the exciton and visible spectral regions was evaluated using a model involving standard energy barrier processes. Decay curves measured within a broad time window (10 ns-1 ms) and with extreme signal/background ratio (five orders of magnitude) point to complex decay mechanism in which the exponential and inverse power-law processes can coexist. There is no straightforward interconnection between the observed temperature dependence of integrated visible photoluminescence intensity and its decay shape over the 9-300 K temperature interval.     

Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

Substrate temperature dependence of the properties of scandium-doped ZnO films deposited by sputtering

Structural and optical properties of Sc-doped ZnO films grown by RF magnetron sputtering at different substrate temperatures were investigated. All the ZnO:Sc films are polycrystalline with the hexagonal wurtzite structure. X-ray diffraction patterns of the films showed that the doped-films have (0 0 2) as preferred orientation when the deposition temperature was increased from 250 °C to 300 °C. All the films are in a state of compressive stress, whereas the stress decreases gradually with increasing substrate temperature. The average transmittance of these films was above 90% in the wavelength range from 400 nm to 800 nm. The optical band gap of these films was determined. The optical constants of these films were determined using transmittance and reflectance spectra.     

The influence of substrate temperature on electrical properties of Cu/CdS/SnO2 Schottky diode

Polycrystalline CdS samples on the SnO₂ coated glass substrate were obtained by vacuum evaporation method at low substrate temperatures (T_S=200 and 300 K) instead of the commonly used vacuum evaporation at high substrate temperatures (T_S>300 K). X-ray diffraction studies showed that the textures of the films are hexagonal with a strong (0 0 2) preferred direction. Circular Cu contacts were deposited on the upper surface of the CdS thin films at 200 K by vacuum evaporation. The effects of low substrate temperature on the current-voltage (I-V) characteristics of the Cu/CdS/SnO₂ structure were investigated in the temperature range 100-300 K. The Cu/CdS (at 300 K)/SnO₂ structure shows exponential current-voltage variations. However, I-V characteristics of the Cu/CdS (at 200 K)/SnO₂ structure deviate from exponential behavior due to high series resistance. The diodes show non-ideal I-V behavior with an ideality factor greater than unity. The results indicate that the current transport mechanism in the Cu/CdS (at 300 K)/SnO₂ structure in the whole temperature range is performed by tunneling with E₀₀=143 meV. However, the current transport mechanism in the Cu/CdS (at 200 K)/SnO₂ structure is tunneling in the range 200-300 K with E₀₀=82 meV.     

Rapid thermal annealing induced changes on the contact of Ni/Au to N-doped ZnO

N-doped p-type ZnO (p ∼ 10¹⁸cm^-3) was grown on sapphire(0 0 0 1) substrate by metal-organic chemical vapor deposition method. Ni/Au metal was evaporated on the ZnO film to form contacts. As-deposited contacts were rectifying while ohmic behavior was achieved after thermally annealing the contacts in nitrogen environment. Specific contact resistance was determined by circular transmission line method and a minimum specific contact resistance of 8 × 10⁻⁴ Ω cm² was obtained for the sample annealed at 650 °C for 30 s. However, Hall effect measurements indicate that, as the rapid thermal annealing temperature increased up to 550 °C or higher the samples’ conductive type have changed from p-type to n-type, which may be due to the instability nature of the present-day p-type N-doped ZnO or the dissociation of ZnO caused by annealing process in N₂ ambient. Evolution of the sample's electric characteristics and the increment of metal/semiconductor interface states induced by rapid thermal annealing process are supposed to be responsible for the improvement of electrical properties of Au/Ni/ZnO.     

On the high-resistivity contacts to YBa2Cu3O7 thin films, electrical behavior in the regime of high temperatures and high-bias voltages

We prepared in-situ Au contacts on high-quality epitaxial YBa₂Cu₃O₇ (YBCO) films. Very high specific contact resistivity values up to ∼10⁻² Ω cm² at 4.2 K were obtained on 12×5 μm² contact areas. This resistivity value decreased by two orders of magnitude as the temperature was raised to room temperature. In the temperature range T<200 K, the contacts showed non-ohmic behavior suggesting the presence of a well-defined insulating native Y-Ba-Cu-O barrier between the two electrodes. The electrical transport in this barrier layer was analyzed in the limit of high temperatures and high voltages to follow Mott's variable-range hopping conduction mechanism with physically reasonable parameters describing the localized states in the barrier. The high-resistivity contacts were tested successfully in quasiparticles injection experiments where the critical current I_c of the YBCO microbridge could be strongly suppressed on injection of an additional current through the contact into the superconducting channel.     

Influence of surface cleaning effects on properties of Schottky diodes on 4H-SiC

Ir/4H-SiC and IrO₂/4H-SiC Schottky diodes are reported in terms of different methods of surface pretreatment before contact deposition. In order to find the effect of surface preparation processes on Schottky characteristics the SiC wafers were respectively cleaned using the following processes: (1) RCA method followed by buffered HF dip. Next, the surface was oxidized (5.5 nm oxide) using a rapid thermal processing reactor chamber and circular geometry windows were opened in the oxide layer before metallization deposition; (2) the same as sequence (1) but with an additional in situ sputter etching step before metallization deposition; (3) cleaning in organic solvents followed by buffered HF dip. The I-V characteristics of Schottky diodes were analyzed to find a correlation between extracted parameters and surface treatment. The best results were obtained for the sequence (1) taking into account theoretical value of Schottky barrier height. The contacts showed excellent Schottky behavior with ideality factors below 1.08 and barrier heights of 1.46 eV and 1.64 eV for Ir and IrO₂, respectively. Very promising results were obtained for samples prepared using the sequence (2) taking into account the total static power losses because the modified surface preparation results in a decrease in the forward voltage drop and reverse leakage current simultaneously. The contacts with ideality factor below 1.09 and barrier height of 1.02 eV were fabricated for Ir/4H-SiC diodes in sequence (2).