D.c. properties of ZnO thin films prepared by r.f. magnetron sputtering

In the development of ZnO-based varistors the electrical properties of ZnO/Bi₂O₃ junctions and of the two individual oxides are being investigated. Following our recent work on a.c. conductivity in Al---ZnO---Al sandwich structures we currently report d.c. measurements. The structures were prepared by r.f. magnetron sputtering in an argon/oxygen mixture in the ratio 4:1. Capacitance-voltage data confirm that the Al/ZnO interface does not form a Schottky barrier and measurements of the dependence of capacitance on film thickness indicate that the relative permittivity of the films is approximately 9.7. With increasing voltage the current density changed from an ohmic to a power-law dependence with exponent n≈3. Furthermore measurements of current density as a function of reciprocal temperature showed a linear dependence above about 240 K, with a very low activation energy below this temperature consistent with a hopping process. The higher temperature results may be explained assuming a room-temperature electron concentration n₀ and space-charge-limited conductivity, dominated by traps exponentially distributed with energy E below the conduction band edge according to N = N₀exp(−E/kT_t), where k is Boltzmann's constant. Typical derived values of these parameters are: n₀ = 7.2 × 10¹⁶ m⁻³, N₀ = 1.31 × 10⁴⁵ J⁻¹ m⁻³ and T_t = 623 K. The total trap concentration and the electron mobility were estimated to be 1.13 × 10²⁵ m⁻³ and (5.7−13.1) ×10⁻³m²V⁻¹s⁻¹ respectively.     

Crystallinity properties of parylene-n affecting its use as an ILD in submicron integrated circuit technology

Parylene-n (Poly-p-xylylene) (PA-n) [1–3] has a long history of use as a moisture barrier for printed circuit boards and hybrids. This paper evaluates this compound as a candidate vapor-depositable polymer interlayer dielectric for submicron integrated circuit technology due to its low dielectric constant, good step coverage, and high etch selectivity. To apply PA-n on high-density very large scale integrated circuits, its properties, such as deposition rate, deposition yield, and Crystallinity, are investigated as a function of deposition pressure and annealing temperature. The deposition rate was found in the range of 2.66 Pa to 13.3 Pa to be a linearly increasing function of pressure. Good-quality films were obtained when pressure was controlled below 10.64 Pa. Cloudy films, however, were found at 13.3 Pa. The deposition rate could be as high as 3.33 × 10⁻¹⁰ m s⁻¹ when deposited at 10.64 Pa. The plot of PA-n yield vs. pressure showed a constant plateau of 1 × 10⁻⁴ m kg⁻¹ from 2.66 Pa to 10.64 Pa. The optimum deposition rate was hence obtained at 10.64 Pa without compromising the deposition yield. The crystallinity-associated properties examined were hardness, dielectric constant, and water permeability. A lower deposition pressure was observed to produce higher Crystallinity that could be further enhanced by thermal annealing. A 5 × 10⁻⁸ m hard surface layer was detected with hardness 3.5 GPa, that was 3˜7 times larger than that of bulk hardness which was 0.4˜0.7 GPa. The bulk hardness was found to increase as Crystallinity increased. The dielectric constant tended to increase when the deposition pressure decreased. Furthermore, the dielectric constant was nearly constant when the polymer was heated up to temperatures as high as 698 K. This behavior, together with the formation of the hard layer and a higher Crystallinity, was believed to result from the improved film organization of the deposited films. The competition between the film build-up in the surface region and the monomer diffusion into the bulk region (penetration) was theorized to be responsible for the film organization. The water permeability, which was measured to be as low as 1.2 × 10⁻¹⁵ kg m⁻¹ s⁻¹ Pa⁻¹ and was found to increase as the deposition pressure was increased, further strengthened the film organization claim.     

Chemical vapor deposition of novel electronic materials from carbon disulfide

An organic amorphous semiconductor with unusual electrical switching capability has been synthesized by the direct decomposition of carbon disulfide. Metallic black highly conducting (above 10² Ω⁻¹ cm⁻¹) thin films of approximate composition C₃S have been prepared by the simple passage of dilute carbon disulfide vapors over an incandescent tungsten filament. Film growth rates greater than 10 μm h⁻¹ are observed. The coatings are hard, adherent on a wide variety of substrates, thermally stable, and remarkably inert to all but the most severe mineral acid digestion. The carbon sulfide solids behave like varistors, following Ohm's law over many decades of current up to a threshold voltage, typically 1–10 V, beyond which the current surges, independent of applied voltage. The threshold voltage is uniquely temperature dependent, reaching a maximum as the temperature is reduced from room temperature, then decreasing once again at cyrogenic temperatures.     

Highly conducting indium tin oxide (ITO) thin films deposited by pulsed laser ablation

Highly conducting and transparent indium tin oxide (ITO) thin films were prepared on SiO₂ glass and silicon substrates by pulsed laser ablation (PLA) from a 90 wt.% In₂O₃-10 wt.% SnO₂ sintered ceramic target. The growths of ITO films under different oxygen pressures (P_O2) ranging from 1×10⁻⁴–5×10⁻² Torr at low substrate temperatures (T_s) between room temperature (RT) and 200°C were investigated. The opto-electrical properties of the films were found to be strongly dependent on the P_O2 during the film deposition. Under a P_O2 of 1×10⁻² Torr, ITO films with low resistivity of 5.35×10⁻⁴ and 1.75×10⁻⁴ Ω cm were obtained at RT (25°C) and 200°C, respectively. The films exhibited high carrier density and reasonably high Hall mobility at the optimal P_O2 region of 1×10⁻² to 1.5×10⁻² Torr. Optical transmittance in excess of 87% in the visible region of the solar spectrum was displayed by the films deposited at Po₂≥1×10⁻² Torr and it was significantly reduced as the P_O2 decreases.     

Field-lowering carrier excitation in cadmium arsenide thin films

Cadmium arsenide is a II–V semiconductor which exhibits n-type intrinsic conductivity with high mobility up to μ_n=1.0–1.5 m²/V s. Potential applications include magnetoresistors and both thermal and photodetectors, which require electrical characterization over a wide range of deposition and measurement conditions. The films were prepared by vacuum evaporation with deposition rates in the range 0.5–6.0 nm/s and substrate temperatures maintained at constant values of 20–120°C. Sandwich-type samples were deposited with film thicknesses of 0.1–1.1 μm using evaporated electrodes of Ag and occasionally Au or Al. Above a typical electric field F_b of up to 5×10⁷ V/m all samples showed instabilities characteristic of dielectric breakdown or electroforming. Below this field they showed a high-field conduction process with logJ∝V^1/2, where J is the current density and V the applied voltage. This type of dependence is indicative of carrier excitation over a potential barrier whose effective barrier height has been lowered by the high electric field. The field-lowering coefficient β had a value of (1.2–5.3)×10⁻⁵ eV m^1/2/V^1/2 which is reasonably consistent with the theoretical value of β_PF=2.19×10⁻⁵ eV m^1/2/V^1/2 expected when the field-lowering occurs at donor-like centres in the semiconductor (Poole–Frenkel effect). For thinner films Schottky emission was more probable. The effects of the film thickness, electrode materials, deposition rate, and substrate temperature on the conductivity behaviour are discussed.     

Structure-composition-property dependence in reactive magnetron sputtered ZnO thin films

Thin films of zinc oxide (ZnO) were prepared by dc reactive magnetron sputtering on glass substrates at various oxygen partial pressures in the range 1×10⁻⁴–6×10⁻³ mbar and substrate temperatures in the range 548–723 K. The variation of cathode potential of zinc target on the oxygen partial pressure was explained in terms of target poisoning effects. The stoichiometry of the films has improved with the increase in the oxygen partial pressure. The films were polycrystalline with wurtzite structure. The films formed at higher substrate temperatures were (0 0 2) oriented. The temperature dependence of Hall mobility of the films formed at various substrate temperatures indicated that the grain boundary scattering of charge carriers was predominant electrical conduction mechanism in these films. The optical band gap of the films increased with the increase of substrate temperature. The ZnO films formed under optimized oxygen partial pressure of 1×10⁻³ mbar and substrate temperature of 663 K exhibited low electrical resistivity of 6.9×10⁻² Ω cm, high visible optical transmittance of 83%, optical band gap of 3.28 eV and a figure of merit of 78 Ω⁻¹ cm⁻¹.     

A novel technique for fabrication of metallic structures on polyimide by selective electroless copper plating using ion implantation

The successful use of palladium ion implantation into polyimide to seed an electroless plated film of copper on the polyimide surface is reported. Polyimide (Hitachi PIX 3400) was implanted with palladium ions to doses of 1.5 × 10¹⁵ − 1.2 × 10¹⁷ ions cm⁻² using a MEVVA ion implanter. The implanted ions acted as sites for nucleation of copper film. A copper film was then deposited on implanted polyimide using a commercial electroless plating solution. The ion energy was kept low enough to facilitate a low critical ‘seed’ threshold dose that was measured to be 3.6× 10¹⁶ Pd ions cm⁻². Test patterns were made using polyimide to study the adaptability of this technique to form thick structures. Plated films were studied with optical microscopy, Rutherford Backscattering Spectrometry (RBS) and Profilometry. The adhesion of films was qualitatively assessed by a ‘scotch tape test’. The film growth (thickness) was observed to be linear with plating time. A higher implantation dose led to greater plating rates. The adhesion was found to improve with increasing dose.     

Semiconducting and structural properties of CrSi2 A-type epitaxial films on Si(111)

Chromium disilicide (CrSi₂) films 1 000 Å thick have been prepared by molecular beam epitaxy on CrSi₂ templates grown on Si(111) substrate. The effect of the substrate temperature on the structural, electrical and optical properties of CrSi₂ films has been studied by transmission and scanning electron microscopies, optical microscopy, electrical resistivity and Hall effect measurements and infrared optical spectrometry. The optimal temperature for the formation of the epitaxial A-type CrSi₂ film have been found to be about 750°C. The electrical measurement have shown that the epitaxial A-type CrSi₂ film is p-type semiconductor having a hole concentration of 1 × 10¹⁷cm⁻³ and Hall mobility of 2 980 cm² V⁻¹ s⁻¹ at room temperature. Optical absorption coefficient data have indicated a minimum, direct energy gap of 0.34 eV. The temperature dependence of the Hall mobility (μ) in the temperature range of T = 180–500 K can be expressed as μ = 7.8 × 10¹⁰T⁻³cm²V⁻¹s⁻¹.     

Development of textures during the growth of silver films condensed in vacuum on glass

The crystal orientation of silver films evaporated onto glass in a vacuum of better than 1.33 × 10⁻³ Pa was studied as a function of the film thickness in the range 0.1–10 μm by means of the X-ray texture goniometer technique. When the substrate was at room temperature and the deposition rate was high (200 and 100 nm s⁻¹), the 111 orientation was prominent at small film thicknesses. Further film growth led to a rapid increase in the 100 orientation, which became predominant. Elevation of the substrate temperature at the same deposition rates resulted in a decrease in the number of crystallites oriented along the 100 axis, and at temperatures above 473 K the 111 orientation was dominant over the whole thickness range investigated. At a comparatively low deposition rate of 5 nm s⁻¹ at both room temperature and 573 K the crystallites were oriented with their (111) planes parallel to the substrate independent of the film thickness.     

New transparent conducting MgIn2O4---Zn2In2O5 thin films prepared by magnetron sputtering

New materials for a transparent conducting oxide film are demonstrated. Highly transparent Zn₂In₂O₅ films with a resistivity of 3.9 × 10⁻⁴ Ω cm were prepared on substrates at room temperature using a pseudobinary compound powder target composed of ZnO (50 mol.%) and In₂O₃ (50 mol.%) by r.f. magnetron sputtering. MgIn₂O₄---Zn₂In₂O₅ films were prepared using MgIn₂O₄ targets with a ZnO content of 0–100 wt.%. The resistivity of the deposited films gradually decreased from 2 × 10⁻³ to 3.9 × 10⁻⁴ Ω cm as the Zn/(Mg + Zn) atomic ratio introduced into the films was increased. The greatest transparency was obtained in a MgIn₂O₄ film. The optical absorption edge of the films decreased as the Zn/(Mg + Zn) atomic ratio was increased, corresponding to the bandgap energy of their materials. It was found that the resistance of the undoped Zn₂In₂O₅ films was more stable than either the undoped MgIn₂O₄, ZnO or In₂O₃ films in oxidizing environments at high temperatures.     

Reactions in Au/Nb bilayer thin films

The interdiffusion and intermetallic compound formation of Au/Nb bilayer thin films annealed at 200–400 °C have been investigated. The bilayer thin films were prepared by electron beam deposition. The Nb film was 50 nm thick and the Au film was 50–200 nm thick. The interdiffusion of annealed specimens was examined by measuring the electrical resistance and depth-composition profile and by transmission electron microscopy. Interdiffusion between the thin films was detected at temperatures above 325 °C in a vacuum of 10^-4 Pa. The intermetallic compound Au₂Nb₃ and other unknown phases form during annealing at over 400 °C. The apparent diffusion constants, determined from the penetration depth for annealing at 350 °C, are 3.5 × 10⁻¹⁵ m² s⁻¹ for Nb in Au and 8.6 × 110^7minus;15 m² s⁻¹ for Au in Nb. The Au surface of the bilayer films becomes uneven after annealing at over 400 °C due to the reaction.     

Underlying mechanisms for unique elastic properties of nanocrystalline Au

In order to get an insight into the grain boundaries (GBs) in nanocrystalline (n-) metal, we prepared the high-density n-Au with ρ/ρ₀>99% by the gas-deposition method and carried out the vibrating reed measurements, where ρ/ρ₀ is the relative density referring to the bulk density. The strain amplitude dependence (SAMD) of the resonant frequency (f) and the internal friction (Q⁻¹) was measured for the strain () amplitude between 10⁻⁶ and 2×10⁻³ and for temperature between 5 and 300 K. No plastic deformations are detected for the present strain range, where f decreases for up to 10⁻⁴ and then turns to increase, showing saturation for between 10⁻⁴ and 2×10⁻³. The low temperature irradiation by 2 MeV electrons or 20 MeV protons causes an increase in the Young’s modulus at 6 K, which is surmised to reflect a modification of the anelastic process in the GB regions. In contrast, the SAMD of f is hardly modified by irradiation, suggesting that it is indicative of a collective motion of atoms in n-Au.     

Highly conducting doped poly-Si deposited by hot wire CVD and its applicability as gate material for CMOS devices

Highly conducting p- and n-type poly-Si:H films were deposited by hot wire chemical vapor deposition (HWCVD) using SiH₄+H₂+B₂H₆ and SiH₄+H₂+PH₃ gas mixtures, respectively. Conductivity of 1.2×10² (Ω cm)⁻¹ for the p-type films and 2.25×10² (Ω cm)⁻¹ for the n-type films was obtained. These are the highest values obtained so far by this technique. The increase in conductivity with substrate temperature (T_s) is attributed to the increase in grain size as reflected in the atomic force microscopy results. Interestingly conductivity of n-type films is higher than the p-type films deposited at the same T_s. To test the applicability of these films as gate contact Al/poly-Si/SiO₂/Si capacitor structures with oxide thickness of 4 nm were fabricated on n-type c-Si wafers. Sputter etching of the poly-Si was optimized in order to fabricate the devices. The performance of the HWCVD poly-Si as gate material was monitored using C–V measurements on a MOS test device at different frequencies. The results reveal that as deposited poly-Si without annealing shows low series resistance.     

The optical and electrical properties of copper indium di-selenide thin films

Thin films of copper indium di-selenide (CIS) with a wide range of compositions near stoichiometry have been formed on glass substrates in vacuum by the stacked elemental layer (SEL) deposition technique. The compositional and optical properties of the films have been measured by proton-induced X-ray emission (PIXE) and spectrophotometry (photon wavelength range of 300–2500 nm), respectively. Electrical conductivity (σ), charge-carrier concentration (n), and Hall mobility (μ_H) were measured at temperatures ranging from 143 to 400 K. It was found that more indium-rich films have higher energy gaps than less indium-rich ones while more Cu-rich films have lower energy gaps than less Cu-rich films. The sub-bandgap absorption of photons is minimum in the samples having Cu/In ≈ 1 and it again decreases, as Cu/In ratio becomes less than 0.60. Indium-rich films show n-type conductivities while near-stoichiometric and copper-rich films have p-type conductivities. At 300 K σ, n and μ_H of the films vary from 2.15 × 10⁻³ to 1.60 × 10⁻¹ (Ω cm)⁻¹, 2.28 × 10¹⁵ to 5.74 × 10¹⁷ cm⁻³ and 1.74 to 5.88 cm² (V s)⁻¹, respectively, and are dependent on the composition of the films. All the films were found to be non-degenerate. The ionization energies for acceptors and donors vary between 12 and 24, and 3 and 8 meV, respectively, and they are correlated well with the Cu/In ratios. The crystallites of the films were found to be partially depleted in charge carriers.     

Excited-state absorption at 1.57 μm in U:CaF2 and Co:ZnSe saturable absorbers

Appreciable excited-state absorption (ESA) in U²⁺:CaF₂ and Co²⁺:ZnSe saturable absorbers was measured at λ=1.573 μm by optical transmission versus light fluence curves of 30–40 ns long pulses. The ground- and excited-state absorption cross-sections obtained were (9.15±0.3)×10⁻²⁰ and (3.6±0.2)×10⁻²⁰ cm², respectively, for U²⁺:CaF₂, and (57±4)×10⁻²⁰ and (12.5±1)×10⁻²⁰ cm² for Co²⁺:ZnSe. Thus, ESA is not negligible in U²⁺:CaF₂ and Co²⁺:ZnSe, as previously estimated.     

High polysilicon TFT field effect mobility reached thanks to slight phosphorus content in the active layer

The paper deals with the effect of slightly phosphorus atoms introduced during deposition of polysilicon films. Polysilicon films are used as an active layer in thin film transistors (TFTs) fabricated on glass substrates at a maximum temperature of 600 °C.Three phosphorus atoms contents, determined by the value of the phosphine to silane ratio: Γ (3.7 × 10^− 7, 8 × 10^− 7, 26 × 10^− 6), are used to optimize the active layer quality. The in-situ doped layers induce a better stability of the electrical characteristics, a higher mobility and lower value of the threshold voltage for the slightly doped active layers [M. Zaghdoudi, M.M. Abdelkrim, M. Fathallah, T. Mohammed-Brahim and F. Le-Bihan Control of the weak phosphorus doping in polysilicon, Materials Science and Forum, Vols. 480–481 (2005) pp.305.]. The present work shows that the effect of slightly phosphorus content improves the quality of oxide/polysilicon interface and decreases the defects density. Degradation of electrical properties is shown to originate from the creation of defect at the channel-interface oxide and in the grain boundaries. The effect of temperature change on the electrical properties was studied and the behaviour was also analyzed.     

A comparative study of Co thin film deposited on GaAs (1 0 0) and glass substrates

The structural, magnetic and transport properties of Co/GaAs (1 0 0) and Co/glass thin films have been investigated. The structural measurements reveal the crystalline nature of Co thin film grown on GaAs, while microcrystalline nature in case of glass substrate. The film grown on GaAs shows higher coercivity (49.0 G), lower saturation magnetization (3.65 × 10⁻⁴) and resistivity (8 μΩ cm) values as compared to that on glass substrate (22 G, 4.77 × 10⁻⁴ and 18 μΩ cm). The grazing incidence X-ray reflectivity and photoemission spectroscopy results show the interaction between Co and GaAs at the interface, while the Co layer grown on glass remains unaffected. These observed results are discussed and interpreted in terms of different growth morphologies and structures of as grown Co thin film on both substrates.     

Room temperature indium tin oxide by XeCl excimer laser annealing for flexible display

A XeCl excimer laser (λ=308 nm) has been used to anneal Indium Tin Oxide (ITO) films deposited at 25 °C using DC magnetron sputtering. With increasing laser fluence, the film crystallinity was improved while retaining the as-deposited 111 texture. As a result of laser irradiation, the sheet resistance of 100 nm ITO films decreased from 191 Ω/□ (1.91×10⁻³ Ω cm) to 25 Ω/□ (2.5×10⁻⁴ Ω cm), while the optical transmittance in the visible range increased from 70% to more than 85%. Surface roughness and etching properties were also significantly improved following laser annealing.     

Ordered Langmuir-Blodgett films of a substituted lutetium bisphthalocyanine

High-quality LB multilayers have been prepared from the Lu(III) sandwich complex of 2,3,9,10,16,17,23,24-octa (n-butoxy)phthalocyanine (LuPc₂(OBu)₁₆). Surface pressure-area isotherms were characterized and indicate that a stable monolayer is formed corresponding to an area per molecule of 2.4 nm² at 30 mN m⁻¹. The LB films were highly birefringent, and polarized spectra gave dichroic ratios of 3.3 for the 670 nm absorption band and between 0.5 and 2.8 for infrared absorptions. The results indicate that the phthalocyanine rings were highly oriented perpendicular to the dipping direction but somewhat tilted from the substrate normal. The order was shown to be absent when (i) unsubstituted LuPc₂ was used for LB films, or (ii) the horizontal lifting method of film deposition was used, or (iii) the surface pressure was increased to 50 mN m⁻¹, causing a molecular rearrangement. The ordering was improved at 100 °C and finally lost at 280 °C by annealing on a hot stage. The d.c. electrical conductivity of LB films of LuPc₂(OBu)₁₆ was low (σ ≈ 2 × 10⁻⁷ Ω⁻¹ m⁻¹), in contrast with unsubstituted LuPc₂ (σ ≈ 10⁻¹ Ω⁻¹ m⁻¹) and showed no evidence for anisotropy. The findings are in broad agreement with related studies and illustrate some of the many factors involved in improving the structure of phthalocyanine LB films for possible applications.     

Indium-doped ZnO thin films deposited by the sol–gel technique

Conducting and transparent indium-doped ZnO thin films were deposited on sodocalcic glass substrates by the sol–gel technique. Zinc acetate and indium chloride were used as precursor materials. The electrical resistivity, structure, morphology and optical transmittance of the films were analyzed as a function of the film thickness and the post-deposition annealing treatments in vacuum, oxygen or argon. The obtained films exhibited a (002) preferential growth in all the cases. Surface morphology studies showed that an increase in the films' thickness causes an increase in the grain size. Films with 0.18 μm thickness, prepared under optimal deposition conditions followed by an annealing treatment in vacuum showed electrical resistivity of 1.3 × 10^− 2 Ωcm and optical transmittance higher than 85%. These results make ZnO:In thin films an attractive material for transparent electrodes in thin film solar cells.