Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

Electrical and compositional properties of TaSi2 films

Tantalum silicide (TaSi₂) thin films were sputter deposited on p- and n-type silicon substrates using ultrapure TaSi₂ targets. The TaSi₂/Si samples were annealed in nitrogen or forming gas or oxygen containing steam at temperatures in the range of 400–900°C. The sheet resistances of TaSi₂/Si were measured by four-point probe before and after anneal. The structure of these films was investigated using x-ray diffraction (XRD) methods. It has been found that the sheet resistance decreases with the increase in annealing temperature and also with the increase in film thickness. X-ray diffraction patterns show changes in the morphological structure of the films. Oxidation characteristics of the film have been investigated in the temperature range of 400–900°C in oxygen containing steam ambient. The oxidation time ranged from 0.5 to 1.5 h. No oxide formation of the tantalum silicide films was observed in this investigation. This has been attributed to the high purity of TaSi₂ sputter targets used in the preparation of the films.     

Study of amorphous Ta2O5 thin films by DC magnetron reactive sputtering

The dc magnetron reactive sputtering deposition of tantalum pentoxide (Ta₂O₅) thin films was investigated. By combining Schiller's criterion and Reith’s “target preoxidation” procedure, high quality Ta₂O₅ thin films were prepared at a high deposition rate of about lOOÅ;/min. The deposited films were amorphous, with a refractive index around 2.07 and a dielectric constant of 20. An optical transmit-tance of 98.6% was obtained for a 4500Â thick film. The leakage current density is 5 × 10^?9 A/cm² at an electric field strength of 1 MV/cm and its breakdown field strength is above 2 MV/cm. The temperature coefficient of capacitance for capacitors fabricated using the deposited films is approximately +230 ppm/°C. X-ray photoelectron spectroscopy shows that the films are stoichiometric tantalum pentoxide, Ta₂O₅, and exhibit good stability.     

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.     

The effect of O<Subscript>2</Subscript> ambient annealing on the microstructure of Cu(Mg) in the form of a Cu(Mg)/SiO<Subscript>2</Subscript>/Si multilayer

The effect of annealing in an O₂ ambient on Cu(Mg)/SiO₂/Si multilayer films was investigated. As-deposited Cu(Mg)/SiO₂/Si multilayer samples with film thicknesses in the 1,000–3,000 ? range were annealed for 30 min in oxygen ambients at pressures ranging from vacuum to 100 mtorr. The results showed that annealing in an 8-mtorr O₂ ambient significantly decreased the electrical resistivity of a 1,000 ? sample from 10.5 μΩ-cm to 3.7 μΩ-cm. Annealing in the O₂ ambient enhanced Mg diffusion to the surface in comparison to vacuum annealing. Furthermore, O₂ ambient annealing leads to excessive grain growth. However, the effect of O₂ ambient annealing on resistivity is less when the thickness of the film increases.     

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.     

Influence of the annealing temperature on the ferroelectric properties of niobium-doped strontium–bismuth tantalate

Characteristics of ferroelectric thin films of niobium-doped strontium–bismuth tantalate (SBTN), which were deposited by magnetron sputtering on Pt/TiO₂/SiO₂/Si substrates, are investigated. To form the ferroelectric structure, deposited films were subjected to subsequent annealing at 700–800°C in an O₂ atmosphere. The results of X-ray diffraction showed that the films immediately after the deposition have an amorphous structure. Annealing at 700–800°C results in the formation of the Aurivillius structure. The dependences of permittivity, residual polarization, and the coercitivity of SBTN films on the modes of subsequent annealing are established. Films with residual polarization 2P_r = 9.2 µC/cm², coercitivity 2E_c = 157 kV/cm, and leakage current 10^–6 A/cm² are obtained at the annealing temperature of 800°C. The dielectric constant and loss tangent at frequency of 1.0 MHz were ε = 152 and tan δ = 0.06. The ferroelectric characteristics allow us to use the SBTN films in the capacitor cell of high density ferroelectric random-access non-volatile memory (FeRAM).     

Effects of Growth Temperature and Annealing on Properties of Zn3Sn2O7 Thin Films and Application in TFTs

The effects of growth temperature and annealing on the physical properties of Zn₃Sn₂O₇ thin films were investigated in this work. The Zn₃Sn₂O₇ thin films were deposited on glass substrates by radio frequency (rf) magnetron sputtering. It is found that the films are amorphous regardless of the growth temperature. The film grown at room temperature shows the highest mobility of 8.1 cm² V^?1 s^?1 and the lowest carrier concentration of 2.0 × 10¹⁵ cm^?3. The highest carrier concentration of 1.6 × 10¹⁹ cm^?3 is obtained at the growth temperature of 250°C. Annealing treatment of the Zn₃Sn₂O₇ thin films resulted in increases of carrier concentration and mobility. The average transmittance of the as-deposited and annealed films reaches 80%. By using a Zn₃Sn₂O₇ thin film as the channel and a Ta₂O₅ thin film as the insulating layer, we fabricated transparent Zn₃Sn₂O₇ thin-film transistors with field-effect mobility of 21.2 cm² V^?1 s^?1, on/off current ratio of 10⁵, threshold voltage of 0.8 V, and subthreshold swing of 0.8 V/decade.     

Deposition of tantalum oxide films by dual spectral source assisted metalorganic chemical vapor deposition (MOCVD)

Dual spectral source assisted metalorganic chemical vapor deposition (MOCVD) is an ideal technique for the deposition of high dielectric constant materials. Tungsten halogen lamps and a deuterium lamp are used as the sources of optical and thermal energy. In this paper, we have reported the deposition and characterization of tantalum penta oxide films. Ta₂O₅ films were deposited at 660°C for 15 min and annealed at 400°C for 1 h. The leakage current densities of 10.6 nm thick films are as low as 10₋₁₀ A/cm² for gate voltage under 4V. To the best of our knowledge, these are the best results reported to date by any researcher. The high energy photons used in the in-situ cleaning and deposition process play an important role in obtaining high quality films of Ta₂O₅.     

Influence of N2 and O2 annealing treatment on the optical bandgap of polycrystalline Ga2O3:Cu films

Cu-doped Ga₂O₃ thin films were deposited by electron beam evaporation with subsequent annealing at 1000 °C in N₂ and O₂ for 1 h. The influence of the annealing atmosphere on the crystal structure, surface morphology and optical properties of Ga₂O₃:Cu films was investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and transmittance and photoluminescence (PL) spectroscopy. The optical bandgap deduced from the absorption spectrum was greater for the O₂ annealed than for N₂ annealed samples. In both cases the bandgap was wider than for bulk β-Ga₂O₃. The grain size and surface roughness were sensitive to the annealing atmosphere. Results confirmed that the annealed samples were polycrystalline β-Ga₂O₃ with some amorphous phase. We hypothesize that annealing in oxygen led to recrystallization of the Ga₂O₃:Cu film. Annealing treatment improved the crystal quality of Ga₂O₃:Cu films and the PL intensity of the samples increased.     

Preparation and Characterization of Ultralow-Dielectric-Constant Porous SiCOH Thin Films Using 1,2-Bis(triethoxysilyl)ethane,Triethoxymethylsilane, and a Copolymer Template

Ultralow-dielectric-constant (k) porous SiCOH films have been prepared using 1,2-bis(triethoxysilyl)ethane, triethoxymethylsilane, and a poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymer template by means of spin-coating. The resulting films were characterized by cross-section scanning electron microscopy, small-angle x-ray diffraction, atomic force microscopy, Fourier-transform infrared spectroscopy, nanomechanical testing, and electrical measurements. Thermal treatment at 350°C for 2 h resulted in the formation of ultralow-k films with k of ∼2.0, leakage current density of 3 × 10⁻⁸ A/cm² at 1 MV/cm, reduced modulus (E _r) of ∼4.05 GPa, and hardness (H) of ∼0.32 GPa. After annealing between 400°C and 500°C for 30 min, the resulting films showed fluctuant k values of 1.85 to 2.22 and leakage current densities of 3.7 × 10⁻⁷ A/cm² to 3 × 10⁻⁸ A/cm² at 0.8 MV/cm, likely due to the change of the film microstructure. Compared with 350°C annealing, higher-temperature annealing can improve the mechanical strength of the ultralow-k film, i.e., E _r ≈ 5 GPa and H ≈ 0.56 GPa after 500°C annealing.     

Formation of thin-film HfO<Subscript>2</Subscript>/Si(100) structures by high-frequency magnetron sputtering

The results of X-ray structural investigations and current-voltage measurements of the HfO₂/Si(100) structures are presented. The HfO₂ films of 50 nm thickness were deposited in a Si substrate by high-frequency magnetron sputtering in argon plasma and subjected to rapid thermal annealing at 500, 700, and/or 800°C in the Ar or O₂ ambient. It is shown that the HfO₂ films become polycrystalline after annealing. The presence of various crystalline phases in them and the form of the I–V characteristics of the Al/HfO₂/Si(100) test structures strongly depend on the growth conditions and the gas ambient during the rapid thermal annealing. It is established that the HfO₂ films deposited at a high-frequency bias at a substrate of −7 V during the growth and then passed through rapid thermal treatment in the O₂ ambient at 700°C have the highest breakdown voltages.     

The Transparent Conductive Properties of Manganese-Doped Zinc Oxide Films Deposited by Chemical Bath Deposition

Manganese-doped zinc oxide (Mn-doped ZnO) thin films were prepared using chemical bath deposition (CBD), and the impacts of the manganese dopant concentration on the structure, electrical resistivity, optical transmission, and magnetic properties were investigated using x-ray diffractometry, Hall-effect measurements, ultraviolet–visible–near-infrared (UV–Vis–IR) spectrophotometry, and vibrating sample magnetometry (VSM), respectively. The concentration of the manganese dopant in the ZnO thin film critically impacted the resulting properties, and the 4.0 at.% Mn-doped ZnO film had a resistivity of 5.8 × 10⁻² Ωcm, transmittance of 75.6% in the visible light range, and bandgap of 3.30 eV when the film was annealed at 600°C in an Ar + H₂ atmosphere. Annealing the film could enhance its magnetic properties such that the film had a saturation magnetization of 21.0 emu/cm³ and a coercivity of 45.7 Oe after annealing at 600°C. Because of these electrical, optical, and magnetic properties, Mn-doped thin films are promising for use in spintronic devices.     

Effect of oxygen plasma on the properties of tantalum oxide films

The effect of oxygen plasma on the leakage current, permittivity, and the dielectric loss tangent of Ta₂O₅ thin layers (300–400 nm) is studied. It is suggested to treat tantalum oxide films in oxygen plasma to control their electrical and dielectric characteristics.     

Structural and electrical properties of radio frequency magnetron sputtered tantalum oxide films: Influence of post-deposition annealing

The as-deposited and annealed radio frequency reactive magnetron sputtered tantalum oxide (Ta₂O₅) films were characterized by studying the chemical binding configuration, structural and electrical properties. X-ray photoelectron spectroscopy and X-ray diffraction analysis of the films elucidate that the film annealed at 673 K was stoichiometric with orthorhombic β-phase Ta₂O₅. The dielectric constant values of the tantalum oxide capacitors with the sandwich structure of Al/Ta₂O₅/Si were in the range from 14 to 26 depending on the post-deposition annealing temperature. The leakage current density was <20 nA cm^?2 at the gate bias voltage of 0.04 MV/cm for the annealed films. The electrical conduction mechanism observed in the films was Poole–Frenkel.     

Effect of post deposition heat treatment on microstructure parameters,optical constants and composition of thermally evaporated CdTe thin films

Thin film microstructure and its properties can be effectively altered with post deposition heat treatments. In this respect, CdTe thin films were deposited on glass substrates at a substrate temperature of 200 °C using thermal evaporation technique, followed by air annealing at different temperatures from 200 to 500 °C. Structural analysis reveals that CdTe thin films have a cubic zincblend structure with two oxide phases related to CdTe₂O₅ and CdTeO₃ at annealing temperature of 400 and 500 °C respectively. Regardless of the annealing temperature, the plane (111) was found to be the preferred orientation for all films. The crystallite size was observed to increase with annealing temperature. All films were found to display higher lattice parameters than the standard, and hence found to carry a compressive stress. Optical measurements suggest high uniformity of films both before and after post deposition heat treatment. Films annealed at 400 °C displayed superior optical properties due to its high refractive index, optical conductivity, relative density and low disorder. Furthermore, according to the compositional measurements, CdTe thin films were found to exhibit Te rich and Cd rich nature at regions near the substrate and center of the film respectively, for all annealing temperatures. However, composition of the regions near the substrate was found to become more Te rich with increasing annealing temperature. The study suggests that changing the annealing temperature as a post deposition treatment affects structural and optical properties of CdTe thin film as well as its composition. According to the observations, films annealed at 400 °C can be concluded to be the best films for photovoltaic applications due to its superior optical and structural properties.     

Thin RF sputtered and thermal Ta2O5 on Si for high density DRAM application

Tantalum pentoxide thin films on Si prepared by two conventional for modern microelectronics methods (RF sputtering of Ta in Ar + O₂ mixture and thermal oxidation of tantalum layer on Si) have been investigated with respect to their dielectric, structural and electric properties. It has been found that the formation of ultra thin SiO₂ film at the interface with Si, during fabrication implementing the methods used, is unavoidable as both, X-ray photoelectron spectroscopy and electrical measurements, have indicated. The initial films (as-deposited and as-grown) are not perfect and contain suboxides of tantalum and silicon which act as electrical active centers in the form of oxide charges and interface states. Conditions which guarantee obtaining high quality tantalum oxide with dielectric constant of 32–37 and leakage current density less than 10⁻⁷ A/cm² at 1.5 V applied voltage (Ta₂O₅ thickness equivalent to about 3.5 nm of SiO₂) have been established. These specifications make the layers obtained suitable alternative to SiO₂ for high density DRAM application.     

Formation of aluminum oxide films from aluminum hexafluoroacetylacetonate at 350–450° c

A study of the thermally activated decomposition of Al(hfa)₃ (aluminum hexafluoroacetylacetonate) from the gas phase to form Al₂O₃ on silicon substrates is reported. The decomposition process was carried out in an open tube atmospheric pressure reactor in either argon or oxygen/argon mixtures in the temperature range, 350–450° C. The chemical vapor deposition process resulted in the formation of aluminum oxide films in all instances. The dielectric strength of Al/Al₂O₃/Si capacitors which received a post-metal anneal, but did not receive a high temperature annealing treatment, with aluminum oxide films prepared from Al(hfa)₃ in argon, was found to be in the range 2–6 MV/cm. The difference between the flatband voltage of the MOS structures and the metal-silicon work function difference was positive, indicative of a net negative oxide charge with a density of approximately 3 × 10¹¹ – 3 × 10¹² cm^-2, assuming the charge is located at the oxide-silicon interface. Decomposition of Al(hfa)₃ was also carried out in oxygen/argon mixtures with the oxygen concentration in the range 10–60 vol %. This process led to the deposition of aluminum oxide films with breakdown fields in the range 8–9 MV/cm. However, the flatband voltages of the Al/Al₂O₃/Si capacitors were even more positive than those obtained with Al₂O₃ formed in pure argon. High temperature (800–1000° C) oxygen or nitrogen annealing treatments of alumina films deposited in either argon or oxygen/argon mixtures were evaluated from the point of view of their influence on the oxide film properties. In particular, an annealing process in oxygen at 1000° C for 15 min was found to result in a reduction of the net negative oxide charge, and an improvement of the dielectric strength of films deposited in argon. Films formed in oxygen/argon mixtures did not change appreciably following oxygen annealing, as far as breakdown fields are concerned, but the oxide net negative charge was reduced. As in an earlier study by the authors, of copper film deposition from Cu(hfa)₂, it was found that essentially carbon free films could be obtained under appropriate conditions.     

Structural,chemical, and electrical properties of Y2O3 thin films grown by atomic layer deposition with an (iPrCp)2Y(iPr-amd) precursor

Y₂O₃ thin films were grown by atomic layer deposition (ALD) through a heteroleptic liquid (iPrCp)₂Y(iPr-amd) precursor at 350 °C. The structural and chemical properties of both as-deposited and annealed Y₂O₃ films at 500 °C and 700 °C are analyzed by atomic force microscopy for variation in surface roughness, X-ray diffraction for crystalline structure, and X-ray photoelectron spectroscopy for chemical states. The as-deposited Y₂O₃ film shows the same crystalline orientation along the plane (222), a stoichiometric state, and minimal hydroxylate formation up to 700 °C. Being the dielectric layer in the metal-oxide-semiconductor capacitor, the as-deposited ALD-Y₂O₃ films with liquid (iPrCp)₂Y(iPr-amd) precursor without any post-deposition annealing show the much lower leakage density than ALD-Y₂O₃ with solid Y(MeCp)₃.     

Conductor Formation Through Phase Transformation in Ti-Oxide Thin Films

The resistance and transmittance of Ti-oxide thin films sputtered on quartz substrates were studied. The electrical and optical properties can be changed by varying the percentage of O₂ introduced during the sputtering. The lowest resistivity for the sputtered Ti-oxide thin film was 2.30 × 10⁻² Ω cm for 12.5% O₂, which was obtained after annealing at 400°C in ambient oxygen. The results of x-ray photoelectron spectroscopy (XPS) curve-fitting indicate that the Ti-oxide thin film contained both Ti₂O₃ and TiO₂ phases during deposition. The Ti₂O₃ phase was transformed into the stable TiO₂ phase during annealing. The Ti₂O₃-TiO₂ phase transformation initiated the substitution reaction. The substitution of Ti⁴⁺ ions in the TiO₂ phase for the Ti³⁺ ions in the Ti₂O₃ phase created the free electrons. This Ti₂O₃-TiO₂ phase transformation demonstrates the potential mechanism for conduction in the annealed Ti-oxide thin films. The transmittance of the annealed Ti-oxide thin films can be as high as approximately 90% at the 400 nm wavelength with the introduction of 16.5% O₂. This result indicates that the annealed Ti-oxide thin films are excellent candidates for use as transparent conducting layers for ultraviolet (UV) or near-UV light-emitting diode (LED) devices.