Effect of ion damage on the electrical and optical behavior of p-type GaAs and InGap

The effect of ion damage generated by exposure to argon or hydrogen electron cyclotron resonance plasmas at various conditions was investigated for p-InGaP and p-GaAs. Room temperature photoluminescence (PL) and either capacitance-voltage or Hall measurements were performed to determine the effect of these various treatments on the efficiency of band edge recombination and the electrical compensation. The feasibility of damage removal was investigated by examining the electrical and optical behavior after annealing at various temperatures. For argon plasma exposed InGaP, restoration of the PL intensity to ∼30% of as-grown sample could be achieved at modest annealing temperatures of ∼600°C. For hydrogen plasma exposed carbon doped GaAs, on the other hand, almost 80 ∼ 90% of the PL intensity of the as-grown sample could be recovered at 600°C. For heavily C-doped GaAs (p ∼ 10²¹cm⁻³), there was significant degradation of the optical properties at annealing temperatures ≥600°C.     

Effect of annealing on the morphology and optoelectrical characteristics of ZnO thin films grown by plasma-assisted molecular beam epitaxy

The dependence of characteristics of plasma-assisted molecular beam epitaxy-grown ZnO thin films on different postgrowth annealing conditions was investigated. It was found that, under oxygen atmosphere, annealing temperature can profoundly affect the morphological, electrical, and optical properties of ZnO thin films. In particular, the surface morphology changed from a relatively smooth surface before annealing to various island morphologies after annealing above 800°C for samples grown directly on sapphire without a buffer layer. It is speculated that intrinsic stress due to lattice mismatch drives the island formation and the high temperature provides the energy needed for this surface rearrangement. Single-field Hall-effect measurement showed that the carrier concentration improved by an order of magnitude and the mobility increased from about 30 cm²/Vs to ∼70 cm²/Vs by annealing at 750°C. Variable-field Hall effect shows that a model with two carriers, one a degenerate low-mobility electron and the other a higher mobility non-degenerate electron, is needed to explain the transport properties of the thin film. Analysis indicates that annealing at 750°C decreased the carrier concentration and increased the mobility for the high-mobility carrier. Annealing also led to a significant improvement in photoluminescence, with temperatures of ∼750–850°C yielding the best results.     

Thermal annealing effects on p-type conductivity of nitrogendoped ZnSe grown by metalorganic vapor phase epitaxy

Post-growth thermal annealing (e.g., 500°C, 30 min), is proposed as one of the promising techniques to realize and to improve the quality of p-type ZnSe layers grown by metalorganic vapor phase epitaxy (MOVPE). The layers were grown at low temperature (350°C) by photo-assisted MOVPE with doping nitrogen from tertiarybutylamine (t-BuNH₂). The flow rate of t-BuNH₂ was limited to be relatively low, in order to avoid heavy doping, with which as-grown layers exhibited electrically high-resistivity; but the thermal annealing converted the layers to p-type. As the as-grown layers exhibited the stronger donor-to-acceptor pair recombination lines or the weaker donor-bound excitonic emission (I_x) lines in photoluminescence, the annealed layers resulted in higher net acceptor concentration, which was 1 x 10¹⁷ cm⁻⁴ at the optimum conditions at present.     

Characteristics of PECVD grown tungsten nitride films as diffusion barrier layers for ULSI DRAM applications

We have developed tungsten nitride (W-Nitride) films grown by plasma enhanced chemical vapor deposition (PECVD) for barrier material applications in ultra large scale integration DRAM devices. As-deposited W-Nitride films show an amorphous structure, which transforms into crystalline, β-W₂N and α-W phases upon annealing at 800°C. The resistivity of the as-deposited films grown at the NH₃/WF₆ gas flow ratio of 1 is about 160 μω-cm, which decreases to 50 μω-cm after an rapid thermal annealing treatment at 800°C. In the contact holes with the size of 0.35 μm and aspect ratio of 3.5, the bottom step coverage of the tungsten nitride films is about 60%, which is about three times higher than that of collimated-TiN films. We obtained contact resistance and leakage current with the tungsten nitride barrier layer comparable to those with conventional collimated TiN films. The contact resistance and leakage current are stable upon thermal stressing at 450°C up to 48 h.     

MBE growth and characterization of in situ arsenic doped HgCdTe

We report the results of in situ arsenic doping by molecular beam epitaxy using an elemental arsenic source. Single Hg_1−xCd_xTe layers of x ∼0.3 were grown at a lower growth temperature of 175°C to increase the arsenic incorporation into the layers. Layers grown at 175°C have shown typical etch pit densities of 2E6 with achievable densities as low as 7E4cm⁻². Void defect densities can routinely be achieved at levels below 1000 cm⁻². Double crystal x-ray diffraction rocking curves exhibit typical full width at half-maximum values of 23 arcsec indicating high structural quality. Arsenic incorporation into the HgCdTe layers was confirmed using secondary ion mass spectrometry. Isothermal annealing of HgCdTe:As layers at temperatures of either 436 or 300°C results in activation of the arsenic at concentrations ranging from 2E16 to 2E18 cm⁻³. Theoretical fits to variable temperature Hall measurements indicate that layers are not compensated, with near 100% activation after isothermal anneals at 436 or 300°C. Arsenic activation energies and 77K minority carrier lifetime measurements are consistent with published literature values. SIMS analyses of annealed arsenic doping profiles confirm a low arsenic diffusion coefficient.     

Structural and Passivative Behaviors of Cu(In) Thin Film

This investigation prepares a low-resistivity and self-passivated Cu(In) thin film. The dissociation behaviors of dilute Cu-alloy thin films, containing 1.5–5at.%In, were prepared on glass substrates by a cosputter deposition, and were subsequently annealed in the temperature range of 200–600 °C for 10–30 min. Thus, self-passivated Cu thin films in the form In₂O₃/Cu/SiO₂ were obtained by annealing Cu(In) alloy films at an elevated temperature. Structural analysis indicated that only strong copper diffraction peaks were detected from the as-deposited film, and an In₂O₃ phase was formed on the surface of the film by annealing the film at an elevated temperature under oxygen ambient. The formation of In₂O₃/Cu/SiO₂ improved the resistivity, adhesion to SiO₂, and passivative capability of the studied film. A dramatic reduction in the resistivity of the film occurred at 500 °C, and was considered to be associated with preferential indium segregation during annealing, yielding a low resistivity below 2.92 μΩcm. The results of this study can be potentially exploited in the application of thin-film transistor–liquid crystal display gate electrodes and copper metallization in integrated circuits.     

Effect of rapid thermal annealing on properties of thermally evaporated nanostructured CdTe thin film treated with CdCl2

The effects of rapid thermal annealing on properties of crystalline nanostructured CdTe films treated with CdCl₂ and prepared by vacuum evaporation are described. X-ray diffraction confirmed the crystalline nature of post-treated films with high preferential orientation around 23.7°, corresponding to a (1 1 1) diffracted plane of cubic phase. Optical band gap of CdTe films increased from 1.4 eV to 1.48 eV after annealing at 500 °C for 90 s. Atomic force microscopy of annealed films revealed an increase in root mean square roughness and grain size with increased annealing time. Electrical measurements of as-grown and annealed films are consistent with p-type; film resistivity has decreased significantly with increased annealing time.     

Effect of Annealing Ambient on the Self-Formation Mechanism of Diffusion Barrier Layers Used in Cu(Ti) Interconnects

Copper (titanium) [Cu(Ti)] films with low titanium (Ti) concentration were found to form thin Ti-rich barrier layers at the film/substrate interfaces after annealing, which is referred to as self-formation of the barrier layers. This Cu(Ti) alloy was one of the best candidates for interconnect materials used in next-generation ultra-large-scale integrated (ULSI) devices that require both very thin barrier layers and low-resistance interconnects. In the present paper, in order to investigate the influences of annealing ambient on resistivity and microstructure of the Cu alloys, the Cu(7.3at.%Ti) films were prepared on the SiO₂ substrates and annealed at 500°C in ultra-high vacuum (UHV) or argon (Ar) with a small amount of impurity oxygen. After annealing the film at 500°C in UHV, the resistivity was not reduced below 16 μΩ-cm. Intermetallic compounds of Cu₄Ti were observed to form in the films and believed to cause the high resistivity. However, after subsequently annealing in Ar, these compounds were found to decompose to form surface TiO _x and interfacial barrier layers, and the resistivity was reduced to 3.0 μΩ-cm. The present experiment suggested that oxygen reactive to titanium during annealing played an important role for both self-formation of the interfacial barrier layers and reduction of the interconnect resistivity.     

Electrical properties of silicon dioxide films fabricated at 700°C. II: Low pressure hydride deposition

We have investigated the effects of different annealing treatments on silicon dioxide films produced from the reaction of dichlorosilane and nitrous oxide at 700° C. The electrical quality of these LPCVD films was evaluated by measuring oxide charge and interface trap densities on metal oxide semiconductor (MOS) capacitors. These densities were measured before and after avalanche injection of electron currents into the oxide films. The results of these studies were as follows. (1) The LPCVD oxide films required a post deposition anneal at 1000° C to produce as-grown charge densities similar to those of a standarddry thermal oxide grown and annealed at 1000° C. (2) Post-injection charge densities of LPCVD films given a post deposition anneal at 1000°C were an order of magnitude greater than those of the standard dry thermal oxide. (3) Different annealing treatments produced a series of dominant electron trapping centers in the oxide bulk₁₇ with capture cross sections ranging from 10⁻¹⁴ cm² to 10⁻¹⁷ cm². (4) The electron traps in the LPCVD oxides films were similar to those previously observed in standardwet thermal oxides grown and annealed above 1000° C.     

InxGa1−xAs (x=0.25–0.35) grown at low temperature

In_xGa_1−xAs (x=0.25–0.35) grown at low temperature on GaAs by molecular beam epitaxy is characterized by Hall effect, transmission electron microscopy, and ultrafast optical testing. As with low temperature (LT) GaAs, the resistivity is generally higher after a brief anneal at 600°C. High-resolution transmission electron microscopy shows all the as-grown epilayers to be heavily dislocated due to the large lattice mismatch (2–3%). When the layers are annealed, in addition to the dislocations, precipitates are also generally observed. As with LT-GaAs, the lifetime shortens as growth temperature is reduced through the range 300–120°C; also, the lifetime in LT-In_xGa_1−xAs is generally shorter in as-grown samples relative to annealed samples. Metal-semiconductor-metal photodetectors fabricated on the material exhibit response times of 1–2 picoseconds, comparable to results reported on GaAs grown at low temperature, and the fastest ever reported in the wavelength range of 1.0–1.3 μm.     

Enhancement in optical characteristics of c-axis-oriented radio frequency–sputtered ZnO thin films through growth ambient and annealing temperature optimization

High-quality radio frequency–sputtered ZnO were grown on Si substrates at 400 °C at various partial gas pressures (Ar/Ar+O2). Subsequently, to remove as-grown defects, high temperature annealing from 700 to 900 °C on as-grown samples in constant oxygen flow for 10 s was performed. X-ray diffraction study confirmed the formation of highly crystalline films with a dominant peak at (002). The sample grown in 50% Ar and 50% O₂ ambient exhibited the lowest linewidth (2θ=~0.2728°) and highest stoichiometry. Grain size of the as grown samples decreased with increase in the partial pressure of oxygen till a certain ratio (1:1), and photoluminescence (PL) improved with increase in annealing temperature. Low-temperature (18 K) PL measurements showed a near-band-edge emission peak at 3.37 eV, and the highest peak intensity (more than six orders compared to others with narrow linewidth of ~0.01272 eV) was exhibited by the sample annealed at 900 °C and was six orders higher than that of the as-grown sample. All as-grown samples exhibited dominant visible-range peaks due to emission from defect states.     

Investigation of Ga oxide films directly grown on n-type GaN by photoelectrochemical oxidation using He-Cd laser

By using a He-Cd laser in a chemical solution of H₃PO₄ with a pH value of 3.5, Ga oxide films were directly grown on n-type GaN. From the energy-dispersive spectrometer (EDS) measurement and x-ray diffraction (XRD) measurement, the grown Ga oxide film was identified as (104) α-Ga₂O₃ structure. A small amount of phosphors existed and bonded with oxygen on the grown films. The as-grown films were amorphous. From the XRD analysis, it is evident that annealing of the α-Ga₂O₃ films led to a change in the microstructure from an amorphous to a polycrystalline phase. In addition, the as-grown low-density films gradually became dense films during the annealing process. Furthermore, the surface roughness of the annealed films also gradually decreased. Hexagonal pinholes on the grown films were observed. The density of the hexagonal pinholes was similar to the defect density of the n-type GaN. From the cross-sectional transmission electron microscopy (TEM) micrographs, it is evident that the hexagonal pinholes originated from defects in the n-type GaN.     

Effect of annealing temperature on structural,electrical and optical properties of spray pyrolytic nanocrystalline CdO thin films

Nanocrystalline CdO thin films were prepared onto a glass substrate at substrate temperature of 300 °C by a spray pyrolysis technique. Grown films were annealed at 250, 350, 450 and 550 °C for 2.5 h and studied by the X-ray diffraction, Hall voltage measurement, UV-spectroscopy, and scanning electron microscope. The X-ray diffraction study confirms the cubic structure of as-deposited and annealed films. The grain size increases whereas the dislocation density decreases with increasing annealing temperature. The Hall measurement confirms that CdO is an n-type semiconductor. The carrier density and mobility increase with increasing annealing temperature up to 450 °C. The temperature dependent dc resistivity of as-deposited film shows metallic behavior from room temperature to 370 K after which it is semiconducting in nature. The metallic behavior completely washed out by annealing the samples at different temperatures. Optical transmittance and band gap energy of the films are found to decrease with increasing annealing temperature and the highest transmittance is found in near infrared region. The refractive index and optical conductivity of the CdO thin films enhanced by annealing. Scanning electron microscopy confirms formation of nano-structured CdO thin films with clear grain boundary.     

Reduction of Inclusions in (CdZn)Te and CdTe:In Single Crystals by Post-Growth Annealing

(CdZn)Te with the composition of 3% Zn and In-doped CdTe single crystals were annealed at various annealing temperatures and under various Cd or Te pressures with the aim of eliminating Te or Cd inclusions. Te inclusions were reduced by Cd-saturated annealing at temperatures above 660°C. Only small (<1 μm) residual dark spots, located at the original position of as-grown inclusions, were observed after annealing. The size of Cd inclusions was reduced by Te-rich annealing at temperatures higher than 700°C. A specific cooling regime was used to eliminate new small Te precipitates (∼1 μm) concurrently formed on dislocations during Te-rich annealing. Poor infrared transmittance of samples with Cd inclusions was detected after Te-rich annealing; therefore, Cd-saturated re-annealing of annealed samples was used for increasing infrared transmittance to a value above 60%. Alternative models explaining the formation of star-shaped corona-surrounding inclusions are discussed.     

Effects of annealing in O2 and N2 on the electrical properties of tantalum oxide thin films prepared by electron cyclotron resonance plasma enhanced chemical vapor deposition

The tantalum oxide thin films with a thickness of 14 nm were deposited at 95°C by electron cyclotron resonance plasma enhanced chemical vapor deposition (ECRPECVD), and annealed at various temperatures (700∼850°C) in O₂ and N₂ ambients. The microstructure and composition of the tantalum oxide thin films and the growth of interfacial silicon oxide layer were investigated and were related to the electrical characteristics of the film. Annealing in an O₂ ambient led to a high dielectric constant (ε_r(Ta₂O₅) = 24) as well as a small leakage current (E_bd = 2.3 MV/cm), which were due to the improved stoichiometry and the decreased impurity carbon content. Annealing in an N₂ ambient resulted in poor and nonuniform leakage current characteristics. The as-deposited tantalum oxide films were crystallized into δ-Ta₂O₅ after annealing at above 750°C regardless of the ambient. The leakage current of the film abruptly increased after annealing at 850°C probably because of the stress caused by thermal expansion or contraction.     

Analysis of the stress and interfacial reactions in Pt/Ti/SiO2/Si for use with ferroelectric thin films

The microstructure of the Pt/Ti/SiO₂/Si structure has been investigated by scanning and transmission electron microscopy. Pt films of 100 nm thickness deposited by sputtering or evaporation onto unheated substrates gave complete coverage of the underlying Ti layer and showed a granular and faceted structure with grains ∼20 nm in diameter. They did not exhibit hillocks or surface TiO_x formation. X-ray diffraction was used to examine the film stress through use of the sin²ψ method with bulk values for the elastic constants (v=0.39, E=162 GPa). The as-deposited sputtered film had a compressive stress of ∼540 MPa, while the evaporated films had tensile stresses of ∼630 MPa. The films then received a 400°C rapid thermal anneal (RTA) for 90 s and a subsequent RTA of 650°C for 30s. Further investigation of the film stresses and microstructure were made after each annealing step. After the low temperature anneal, the film stress for the sputtered film became tensile. Plan-view sections examined by transmission electron microscopy (TEM) showed that the as-deposited sputtered films were dense but became porous after annealing. Initially, the evaporated films had a less dense microstructure, but were more stable with annealing. Little change in the stress for the evaporated film was observed after this initial low temperature annealing step. Additional annealing of the evaporated and sputtered samples caused complete consumption of the Ti layer including some TiO_x formation from the underlying SiO₂ layer and marked interaction with the Pt; however, little change in the stress was found. The surface of the Pt film revealed larger grains, but otherwise remained unaffected. The underlying phase changes were minimized once the Ti layer had reacted with the Pt. Due to the ratio of the layers, Pt:Ti of 2:1, the surface of the Pt was unaffected.     

The properties of annealed AlN films deposited by pulsed laser deposition

AlN films deposited on SiC or sapphire substrates by pulsed laser deposition were annealed at 1200°C, 1400°C, and 1600°C for 30 min in an inert atmosphere to examine how their structure, surface morphology, and substrate-film interface are altered during high temperature thermal processing. Shifts in the x-ray rocking curve peaks suggest that annealing increases the film density or relaxes the films and reduces the c-axis Poisson compression. Scanning electron micrographs show that the AlN begins to noticeably evaporate at 1600°C, and the evaporation rate is higher for the films grown on sapphire because the as-deposited film contained more pinholes. Rutherford backscattering spectroscopy shows that the interface between the film and substrate improves with annealing temperature for SiC substrates, but the interface quality for the 1600°C anneal is poorer than it is for the 1400°C anneal when the substrate is sapphire. Transmission electron micrographs show that the as-deposited films on SiC contain many stacking faults, while those annealed at 1600°C have a columnar structure with slightly misoriented grains. The as-deposited films on sapphire have an incoherent interface, and voids are formed at the interface when the samples are annealed at 1600°C. Auger electron spectroscopy shows that virtually no intermixing occurs across the interface, and that the annealed films contain less oxygen than the as-grown films.     

The effects of oxygen,nitrogen, and hydrogen annealing on Mg acceptors in GaN as monitored by electron paramagnetic resonance spectroscopy

Electron paramagnetic resonance (EPR) spectroscopy is used to study the unpassivated Mg-related acceptor in GaN films. As expected, the trends observed before and after O₂, N₂, or forming-gas anneals at temperatures <800°C are similar to those typically reported for electrical measurements. However, annealing at temperatures >850°C in O₂ or N₂ permanently removes the signal, contrary to the results of conductivity measurements. Approximately 10¹⁹ cm⁻³ Mg acceptors were detected in some GaN films grown by chemical vapor deposition (CVD) before acceptor activation, suggesting that it is possible to have electrically active Mg in as-grown CVD material.     

Effect of Annealing Ambient on the Electrical and Optical Properties of Aluminum-Doped ZnO Films Produced via a Sol–Gel Process

In this study, aluminum-doped ZnO (AZO) thin films were prepared by a sol–gel with spin coating process. The AZO films were annealed by a two-step process. The films were first annealed in air or nitrogen at 500°C for 3 h, followed by annealing in three types of ambient, i.e., vacuum (10^?3 Torr or 10^?6 Torr) or forming gas (10% H₂/90% N₂), at 500°C for 4 h. The effect of the annealing ambient on the microstructure, electrical and optical properties of the AZO films was explored by x-ray diffraction, field-emission scanning electron microscopy, four-point probe sheet resistivity measurements, Hall voltage measurements, and ultraviolet–visible spectroscopy. The results showed that the size of AZO particulates in the films was determined mainly by the first annealing step. The films annealed in air in the first step were composed of larger AZO particulates than those annealed in nitrogen. The conductivities of the AZO films were significantly increased by the second annealing step. Second annealing in a high-vacuum system (10^?6 Torr) led to the highest AZO film conductivity among the three ambients. Regardless of the various annealing processes, the films remained transparent under visible light and exhibited a sharp absorption edge in the ultraviolet region. The highest conductivity, i.e., 168 S cm^?1, was obtained from films annealed first in air and then in vacuum of 10^?6 Torr.     

Room-temperature ferromagnetic ordering in Mn-doped ZnO thin films grown by pulsed laser deposition

The ferromagnetic ordering in Mn-doped ZnO thin films grown by pulsed laser deposition (PLD) as a function of oxygen pressure and substrate temperature has been investigated. Room-temperature ferromagnetic behaviors in the Mn-doped ZnO films grown at 700°C and 800°C under 10⁻¹ torr in oxygen pressure were found, whereas ferromagnetic ordering in the films grown under 10⁻³ torr disappeared at 300 K. The large positive magnetoresistance (MR), ∼10%, was observed at 5 K at low fields and small negative MR was observed at high fields, irrespective of oxygen pressure. In particular, anomalous Hall effect (AHE) in the Mn-doped ZnO film grown at 700°C under 10⁻¹ Torr has been observed up to 210 K. In this work, the observed AHE is believed to be further direct evidence demonstrating that the Mn-doped ZnO thin films are ferromagnetic.