Effect of doping and substrate temperature on the structural and optical properties of reactive pulsed laser ablated tin oxide doped tantalum oxide thin films

5% SnO₂ doped tantalum oxide (Ta₂O₅) films are deposited on quartz substrates at different substrate temperatures of 300 K, 773 K, 873 K and 973 K using pulsed laser deposition in an oxygen ambient of 0.002 mbar. Undoped Ta₂O₅ films are also deposited on quartz substrates kept at substrate temperature 973 K under the same oxygen ambient using PLD. The films are characterized using GIXRD, AFM, FTIR, micro-Raman and UV-visible spectroscopy. Undoped films show an amorphous nature even at a substrate temperature of 973 K, whereas, SnO₂ doped films show crystalline nature even for deposition at 300 K. As far as our knowledge goes, this is the first report of crystalline Ta₂O₅ films deposited at room temperature. The average size of the crystallites calculated using the Debye-Scherrer formula, shows that the size of the crystallite decreases with increase in substrate temperature. FTIR and micro-Raman spectroscopic analysis reveals the presence of Ta-O-Ta, O-Ta and O-Ta-O vibrational bands in the films. Raman analysis indicates that the addition of SnO₂ suppresses the bond formation and changes the magnitude of bonds in Ta₂O₅. AFM patterns reveal the formation of Ta₂O₅ nanorods of diameter about 100 nm for the doped film deposited at 973 K. Optical transmittance of the films is found to be sensitive to substrate temperature as well as to the presence of SnO₂. A blue shift in the band-gap of the doped films is observed. The decrease of band-gap with decrease of particle size observed for SnO₂ doped films can be due to a band-bending effect. The transmittance of the films is found to depend on SnO₂ doping and substrate temperature.     

Enhanced dielectric properties of modified Ta2O5 thin films

 Tantalum oxide (Ta₂O₅) is a promising high dielectric constant material for the DRAM applications because of its ease of integration compared to other complex oxide dielectrics. The dielectric constant and thermal stability characteristics of bulk Ta₂O₅ samples were reported to enhance significantly through small substitutions of Al₂O₃. However, this improvement in the dielectric constant of (1-x)Ta₂O₅-xAl₂O₃ is not clearly understood. The present research attempts to explain the higher dielectric constant of (1-x)Ta₂O₅-xAl₂O₃ by fabricating thin films with enhanced dielectric properties. A higher dielectric constant of 42.8 was obtained for 0.9Ta₂O₅–0.1Al₂O₃ thin films compared to that reported for pure Ta₂O₅ (25–30). This increase was shown to be closely related to a-axis orientation. Pure Ta₂O₅ thin films with similar a-axis orientation also exhibited a high dielectric constant of 51.7, thus confirming the orientation effect. The leakage current properties and the reliability characteristics were also found to be improved with Al₂O₃ addition. Received: 24 November 1998 / Reviewed and accepted: 7 December 1998     

Conduction and dielectric polarization in thin anodic aluminium oxide films

The a.c. polarization of anodic Al₂O₃ films was studied in the thickness range 30–1500 Å and the frequency range 300 Hz to 15 kHz. The interfacial polarization mechanism involving distinct regions separated by flaws and/or voids in the bulk was thought to become dominant with decreasing thickness because of an increasing concentration of defects. The d.c. conductivity at the room temperature was also studied in the same thickness range. The observed linear log J versus E^1/2 characteristics for several thicknesses showed that d.c. conduction in these films obeys the Poole-Frenkel law over a certain range of applied electric fields. Anomalies observed in the electric field and the thickness dependences of the d.c. conductivity are considered to arise from the thickness dependence of the defect concentration. It was concluded that the same mechanism of carrier motion might be dominant in both a.c. polarization and d.c. conduction.     

Electrical characterization of Ta2O5 films deposited by laser reactive ablation of metallic Ta

Tantalum oxide films have been deposited by 355 nm pulsed laser ablation of metallic Ta target in O₃/O₂ ambient. The structure and the composition of as-deposited and annealed films were examined by X-ray diffraction and Fourier transform infrared spectroscopy. The measurements of the current–voltage and capacitance–voltage characteristics of the Al/Ta₂O₅/Si capacitors were performed to reveal the electrical properties of the Ta₂O₅ films. The effects of annealing temperature on the characteristics of thin films have been studied. The results suggest that the films annealed above 700°C have the structure of orthorhombic β-Ta₂O₅, thc annealing treatment at high temperature decreases the bulk trap charge, the border trap, and the interface trap densities of as-deposited films, and improves significantly the dielectric and electrical properties of Ta₂O₅ film.     

Optical properties of porous anodic aluminum oxide thin films on quartz substrates

Porous anodic aluminum oxide (AAO) thin films on quartz substrates were fabricated via evaporation of a 100-nm thick Al, followed by anodization with different durations and pore widening and Al removal by chemical etching. The transmittance and reflectance of AAO films on quartz substrates were measured by optical spectrophotometry. The microstructure and morphology were examined by scanning electron microscopy. The pore diameter of AAO films after pore widening and Al removal is 60 ± 4 nm and the interpore distance is 88 ± 5 nm. It is found that the reflectance decreases and the transmittance increases with the increase of the anodization time and pore widening. Compared to a bare substrate, the transmittance of AAO films after pore widening and Al removal is about 3.0% higher, while the reflectance is about 3.0% lower over a wide wavelength range. Additionally, after pore widening and Al removal, when AAO films are prepared on both sides of the quartz substrate, the highest transmittance is about 99.0% in the wavelength range 570-680 nm. The optical constants and thickness of AAO films after pore widening and Al removal were retrieved from normal incidence transmittance data. Results show that the refractive index is lower than 1.25 in the visible optical region and that the porosity is about 0.70.     

Properties of tantalum oxynitride thin films produced by magnetron sputtering: The influence of processing parameters

The main purpose of this work is to present and to interpret the change of structure and physical properties of tantalum oxynitride (TaN_xO_y) thin films, produced by dc reactive magnetron sputtering, by varying the processing parameters. A set of TaN_xO_y films was prepared by varying the reactive gases flow rate, using a N₂/O₂ gas mixture with a concentration ratio of 17:3. The different films, obtained by this process, exhibited significant differences. The obtained composition and the interpretation of X-ray diffraction results, shows that, depending on the partial pressure of the reactive gases, the films are: essentially dark grey metallic, when the atomic ratio (N + O)/Ta < 0.1, evidencing a tetragonal β-Ta structure; grey-brownish, when 0.1 < (N + O)/Ta < 1, exhibiting a face-centred cubic (fcc) TaN-like structure; and transparent oxide-type, when (N + O)/Ta > 1, evidencing the existence of Ta₂O₅, but with an amorphous structure. These transparent films exhibit refractive indexes, in the visible region, always higher than 2.0.The wear resistance of the films is relatively good. The best behaviour was obtained for the films with (N + O)/Ta ≈ 0.5 and (N + O)/Ta ≈ 1.3.     

Formation of amorphous anodic oxide films of controlled composition on aluminium alloys

Binary, non-equilibrium Al-29at%Nb, Al-44at%Ta, Al-19at%Ti, Al-25at%Ti and Al-32at%Zr alloys were prepared by magnetron sputtering and subsequently anodized at high Faradaic efficiency to grow barrier-type anodic films. Examination in the transmission electron microscope revealed amorphous anodic films of relatively uniform compositions across the film thicknesses, except for a layer of relatively pure alumina, of about 5% of the film thickness, present at the film/electrolyte interface of the Al-Ta alloy. The film compositions, from Rutherford backscattering spectroscopy, indicate that the alloy constituents are oxidized in their alloy proportions to form films comprising intimately mixed units of the various oxides, namely alumina, niobia, titania, tantala and zirconia. The films grow by co-operative transport of metal and oxygen ions under the electric field with formation of film material by both migration of metal ions outwards and of oxygen, and possibly hydroxyl, ions inwards. The average migration rates of Al³⁺, Nb⁵⁺, Ti⁴⁺ and Zr⁴⁺ ions are similar, to within 10%, but Ta⁵⁺ ions migrate more slowly than Al³⁺ ions. The results of the study show that a wide range of compositions of amorphous oxide films can be readily formed by anodic oxidation of appropriate alloys, including compositions containing units of normally crystalline anodic oxides, namely TiO₂ and ZrO₂.     

Properties of aluminum oxide thin films deposited by pulsed laser deposition and plasma enhanced chemical vapor deposition

The chemical, structural, mechanical and optical properties of thin aluminum oxide films deposited at room temperature (RT) and 800 °C on (100) Si and Si-SiO₂ substrates by pulsed laser deposition and plasma enhanced chemical vapor deposition are investigated and compared. All films are smooth and near stoichiometric aluminum oxide. RT films are amorphous, whereas γ type nano-crystallized structures are pointed out for films deposited at 800 °C. A dielectric constant of ∼ 9 is obtained for films deposited at room temperature and 11-13 for films deposited at 800 °C. Young modulus and hardness are in the range 116-254 GPa and 6.4-28.8 GPa respectively. In both cases, the results show that the deposited films have very interesting properties opening applications in mechanical, dielectric and optical fields.     

Photoluminescent properties of barrier anodic oxide films on aluminum

We have investigated the photoluminescence (PL) spectra of barrier anodic oxide films on aluminum, formed in citric acid and in boric acid + borax. Strong PL bands are present in spectra of both electrolytes, featuring two distinct peaks in the 300 nm to 600 nm range. The first one is centered at about 460 nm, while the other peak shifts with the excitation wavelength. The PL intensity increases upon annealing, reaching the maximum value at about 500 °C. Experimental results indicate that the PL originates from optical transitions in two kinds of centers which are related to oxygen vacancies, F⁺ and F. In addition, the PL of oxide coatings formed under anodic spark deposition was performed and a third peak at around 327 nm was observed.     

Thermal stability of indium tin oxide thin films co-sputtered with zinc oxide

The thermal stability of indium tin oxide (ITO) films and ITO co-sputtered with zinc oxide (ZnO) films at different zinc atomic ratios in various atmospheres are investigated. The resistivity of the annealed ITO films decreased with increased annealing temperatures. The improved electrical properties were attributed mainly to the increase in carrier concentration originating from the significant formation of oxygen vacancies in the ITO films. In contrast, due to the lower oxidation potential of zinc ions, the resistivity of the annealed co-sputtered films showed no significant reduction and an increase with annealing temperatures. The film decomposition due to the high degree outdiffusion of oxygen atoms and aggregation of In atoms observed from the metal-like In phase in the diffraction patterns was responsible for the drastic thermal degradation in the electrical and optical properties of the samples annealed at elevated temperatures in reducing gas atmosphere. In contrast, the superior thermal stability of the co-sputtered films, at an atomic ratio of 60% annealed in reducing gas atmospheres, was ascribed to the stable Zn₃In₂O₆ crystalline structure that appeared in the diffraction pattern. The absorption edge observed from the optical transmittance of these annealed films also showed evidence of carrier concentration evolution in various annealing atmospheres. The lower oxidation potential of the zinc atoms introduced into the ITO films was concluded to be efficient in compensating for the formation of oxygen vacancies resulting in the alleviated decomposition behavior during thermal annealing.     

Color emission and dielectric properties of Eu-doped Gd2O3 gate oxide thin films

High-k Gd₂O₃ used for thin film transistor (TFT) gate insulators has been synthesized via a simple solution process. Phase analysis and capacitive performance reveal that a high dielectric constant of ~ 20 and a low leakage current level of < 10⁻⁸ A/cm² at 1 MV/cm with a good transparency under the visible wavelength region are readily produced by the sol-gel method. Eu³⁺ doping leads to an increased dielectric constant induced by the additional electric dipole transition, which is evidently visualized by the photoluminescence behavior and/or by the defect-controlled thin film microstructures. Thus, the solution-processed (Gd,Eu)₂O₃ film is a viable gate insulator to be considered for the proposed “color emissive” switching devices as well as for the low power-driven TFT devices.     

Direct comparison of the electrical properties in metal/oxide/nitride/oxide/silicon and metal/aluminum oxide/nitride/oxide/silicon capacitors with equivalent oxide thicknesses

We examine the electrical properties of metal/oxide/nitride/oxide/silicon (MONOS) capacitors with two different blocking oxides, SiO₂ and Al₂O₃, under the influence of the same electric field. The thickness of the Al₂O₃ layer is set to 150 Å, which is electrically equivalent to a thickness of the SiO₂ layer of 65 Å, in the MONOS structure for this purpose. The capacitor with the Al₂O₃ blocking layer shows a larger capacitance-voltage memory window of 8.6 V, lower program voltage of 7 V, faster program/erase speeds of 10 ms/1 μs, lower leakage current of 100 pA and longer data retention than the one with the SiO₂ blocking layer does. These improvements are attributed to the suppression of the carrier transport to the gate electrode afforded by the use of an Al₂O₃ blocking layer physically thicker than the SiO₂ one, as well as the effective charge-trapping by Al₂O₃ at the deep energy levels in the nitride layer.     

Fabrication of polycrystalline aluminum oxide thin films via hydrolysis and hydrothermal reactions in solutions

Polycrystalline Al₂O₃ thin films were fabricated through a method combining urea hydrolysis and hydrothermal reactions. The overall growth temperature of these films was achieved as low as 150 °C. Although cracks occurred across the gel film after hydrolysis, a subsequent nucleation under elevated pressure and temperature resulted in a closely packed morphology. Moreover, the hydrothermal treatment led to high oxide content and an increase in crystallinity within the films.     

Properties of tantalum oxide thin films grown by atomic layer deposition

Thin tantalum oxide films were deposited using atomic layer deposition from TaCl₅ and H₂O at temperatures in the range 80–500 °C. The films deposited at temperatures below 300 °C were predominantly amorphous, whereas those grown at higher temperatures were polycrystalline containing the phases TaO₂ and Ta₂O₅. The oxygen to tantalum mass concentration ratio corresponded to that of TaO₂ at all growth temperatures. The optical band gap was close to 4.2 eV for amorphous films and ranged from 3.9 to 4.5 eV for polycrystalline films. The refractive index measured at λ = 550 nm increased from 1.97 to 2.20 with an increase in growth temperature from 80 to 300 °C. The films deposited at 80 °C showed low absorption with absorption coefficients of less than 100 cm⁻¹ in the visible region.     

Characterization of complex anodic alumina films by electrochemical impedance spectroscopy

Complex anodic alumina films are formed by pore-filling (reanodization) of porous anodic films (matrices). These films are characterized by electrochemical impedance spectroscopy. It is determined that the recorded impedance spectra are well described by an equivalent circuit, containing a Constant Phase Element. The fitted parameters of the complex films are calculated, and information about certain dielectric characteristics of these films in contact with an electrolyte is obtained. The paper also discusses changes in the surface non-homogeneity of the complex films in comparison with those of the porous matrix.     

Plasma-enhanced chemical vapor deposition of TiO2 thin films for dielectric applications

Amorphous TiO₂ thin films were formed by plasma-enhanced chemical vapor deposition (PECVD) from mixtures of titanium IV isopropoxide (Ti(O-i-C₃H₇)₄) and oxygen. The deposition rate was found to be weakly activated, with an apparent activation energy of 4.5 kJ/mol. The deposition rate increased with equivalence ratio and decreased with plasma power. This dependence on atomic oxygen density was consistent with behavior observed in other metal oxide PECVD systems. Metal-insulator-silicon devices were fabricated, and characterized using capacitance-voltage measurements. The apparent dielectric constant of the TiO₂ thin films increased from 15 to 82 with film thickness. The observed variations were consistent with the formation of an interfacial SiO₂ layer. Assuming that a TiO₂/SiO₂ bilayer behaves as two capacitors in series, an intrinsic TiO₂ dielectric constant of 82 ± 10 and an interfacial SiO₂ layer thickness of 3 ± 1 nm were extracted from electrical measurements.     

Effects of aluminum doping on lanthanum oxide gate dielectric films

This work reports a novel method for improving the electrical properties of lanthanum gate oxide (La₂O₃) by using aluminum doping and rapid thermal annealing (RTA) techniques. In the bulk of the Al-doped La₂O₃ film together with 600 °C RTA, we found that the aluminum atoms were incorporated into the oxide network and the film was transformed into lanthanum aluminate complex oxide. At the interface, a thin Al₂O₃ layer was formed. This interfacial Al₂O₃ layer suppressed the out-diffusion of substrate Si, the formation of interfacial silicate layer and silicide bonds. These effects resulted in a significant reduction on the bulk and interface trap densities and hence the gate leakage current.     

Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

Characterization of copper oxide thin films deposited by the thermal evaporation of cuprous oxide (Cu2O)

Thin films of copper oxide were deposited by thermal evaporation of cuprous oxide (Cu₂O) powder. The substrates were either unheated or heated to a temperature of 300 °C. The films were also annealed in air at a temperature of 500 °C for 3 h. The films were characterized by X-ray photoelectron spectroscopy, X-ray diffraction and UV-visible spectrophotometry. The effects of the substrate temperature and post-deposition annealing on the chemical, structural and optical properties of the films were investigated. As-deposited films on unheated substrates consisted of mixed cupric oxide (CuO) and Cu₂O phases, with a higher concentration of the Cu₂O phase. However, the films deposited on heated substrates and the annealed films were predominantly of the CuO phase.     

Dielectric properties of DC reactive magnetron sputtered Al2O3 thin films

Alumina (Al₂O₃) thin films were sputter deposited over well-cleaned glass and Si < 100 > substrates by DC reactive magnetron sputtering under various oxygen gas pressures and sputtering powers. The composition of the films was analyzed by X-ray photoelectron spectroscopy and an optimal O/Al atomic ratio of 1.59 was obtained at a reactive gas pressure of 0.03 Pa and sputtering power of 70 W. X-ray diffraction results revealed that the films were amorphous until 550 °C. The surface morphology of the films was studied using scanning electron microscopy and the as-deposited films were found to be smooth. The topography of the as-deposited and annealed films was analyzed by atomic force microscopy and a progressive increase in the rms roughness of the films from 3.2 nm to 4.53 nm was also observed with increase in the annealing temperature. Al-Al₂O₃-Al thin film capacitors were then fabricated on glass substrates to study the effect of temperature and frequency on the dielectric property of the films. Temperature coefficient of capacitance, AC conductivity and activation energy were determined and the results are discussed.