Cu(In,Ga)Se<Subscript>2</Subscript> Thin Film Preparation from a Cu(In,Ga) Metallic Alloy and Se Nanoparticles by an Intense Pulsed Light Technique

The main contribution of this paper is the development of a novel process for the formation of copper indium gallium diselenide (CIGS) films. CIGS films with a thickness of 4 μm and grain size from 0.3 μm to 1 μm were prepared from a Cu(In_0.7Ga_0.3) (CIG) metallic alloy and Se nanoparticles by the intense pulsed light (IPL) technique. The melting of the CIG and Se nanoparticles and nucleation of CIGS occurred in a very short reaction time of 2 ms. It is believed that the Se diffuses into the CIG lattice to form the CIGS chalcopyrite crystal structure. The tetragonal chalcopyrite crystal structure was confirmed by x-ray powder diffraction (XRD), while the microstructure and composition were determined by field-emission scanning electron microscopy (FESEM), energy-dispersive x-ray spectroscopy (EDAX), and x-ray fluorescence (XRF) spectroscopy.     

Nitrogen-doped Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> films for nonvolatile memory

Nitrogen-doped Ge₂Sb₂Te₅ (GST) films for nonvolatile memories were prepared by reactive sputtering with a GST alloy target. Doped nitrogen content was determined by using x-ray photoelectron spectroscopy (XPS). The crystallization behavior of the films was investigated by analyzing x-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results show that nitrogen doping increases crystallization temperature, crystallization-activation energy, and phase transformation temperature from fcc to hexagonal (hex) structure. Doped nitrogen probably exists in the grain vacancies or grain boundaries and suppresses grain growth. The electrical properties of the films were studied by analyzing the optical band gap and the dependence of the resistivity on the annealing temperature. The optical band gap of the nitrogen-doped GST film is slightly larger than that of the pure GST film. Energy band theory is used to analyze the effect of doped nitrogen on electrical properties of GST films. Studies reveal that nitrogen doping increases resistivity and produces three relatively stable resistivity states in the plot of resistivity versus annealing temperature, which makes GST-based multilevel storage possible. Current-voltage (I-V) characteristics of the devices show that nitrogen doping increases the memory’s dynamic resistance, which reduces writing current from milliampere to microampere.     

Low-Resistivity Ru-Ta-C Barriers for Cu Interconnects

Ru-Ta-C films deposited on silicon substrates were evaluated as barriers for copper metalization. The films were prepared by magnetron cosputtering using a Ru target and a Ta-C target. Compositions and structure of resultant films were optimally tuned by the respective deposition power of each target. The fabricated Ru-Ta-C films were characterized via four-point probe measurement, x-ray diffractometry, field-emission electron probe microanalysis, and transmission electron microscopy. Failure temperature was evaluated by the sudden rise in electrical resistivity after annealing the Cu/Ru-Ta-C/Si sandwich films, and a reference bilayer Cu/(5 nm Ru)/(5 nm Ta-C)/Si scheme. The optimal compositions were 10 nm Ru₇₇Ta₁₅C₇ and (5 nm Ru)/(5 nm Ta-C), both of which showed failure temperature of 650°C for 30 min and electrical resistivity less than 150 μΩ cm. Because of their high thermal stability and low electrical resistivity, both Ru-Ta-C and Ru/Ta-C films are promising barriers for Cu metalization.     

Electrical properties of carbon nitride thin films: Role of morphology and hydrogen content

The influence of hydrogen content and ambient humidity on the electrical properties of carbon nitride (CN_x) films deposited by reactive magnetron sputtering from a graphite target in Ar discharges mixed with N₂ and H₂ at a substrate temperature of 350°C have been investigated. Carbon films deposited in pure Ar exhibit a dark resistivity at room temperature of ∼4 × 10⁻² Ωcm, while the resistivity is one order of magnitude lower for CN_0.25 films deposited in pure N₂, due to their denser morphology. The increasing H₂ fraction in the discharge gas leads to an increased resistivity for all gas mixtures. This is most pronounced for the nitrogen-free films deposited in an Ar/H₂ mixture, where the resistivity increases by over four orders of magnitude. This can be related to a decreased electron mobility as H inhibits the formation of double bonds. After exposure to air, the resistivity increases with time through two different diffusion regimes. The measured electrical properties of the films are related to the apparent film microstructure, bonding nature, and ambient humidity.     

Effects of growth and postgrowth parameters on the microstructure and copper distribution in Al(Cu)/SiO2 thin films

Rutherford backscattering spectroscopy (RBS), x-ray diffraction (XRD), and transmission electron microscopy (TEM) have been employed to study sputter-deposited Al(Cu)/SiO₂ films with as low as 0.2 at.% concentration of copper at the wafer target. It is shown that (1) copper concentration is not uniform throughout the film and (2) copper is depleted near the Al/SiO₂ interface. The nonuniformity of copper at the interface has been discussed in terms of grain boundaries, their dynamics under film-growth conditions, and the nonuniformity’s consequences in microelectronic device fabrications.     

Laser processing of TiSi2 and CoSi2 thin films on silicon (100) substrates

We have investigated the formation of TiSi₂ and CoSi₂ thin films on Si(100) substrates using laser (wave length 248 nm, pulse duration 40 ns and repetition rate 5 Hz) physical vapor deposition (LPVD). The films were deposited from solid targets of TiSi₂ and CoSi₂ in vacuum with the substrate temperature optimized at 600° C. The films were characterized using x-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and four point probe ac resistivity. The films were found to be polycrystalline with a texture. The room temperature resistivity was found to be 16 μΩ-@#@ cm and 23 μΩ-cm for TiSi₂ and CoSi₂ films, respectively. We optimized the processing parameters so as to get particulate free surface. TEM results show that the silicide/silicon interface is quite smooth and there is no perceptible interdiffusion across the interface.     

The CVD growth of Cu films using H2 as carrier gas

Copper chemical vapor deposition from Cu(hexafluoroacetylacetonate)trimethylvinylsilane (Cu(hfac)TMVS) was studied using a low pressure chemical vapor deposition system of a cold wall vertical reactor. The Cu films deposited using H₂ as a carrier gas revealed no impurities in the films within the detection limits of Auger electron spectroscopy and x-ray photoelectron spectroscopy. Using hydrogen as a carrier gas, the hydrogen not only acts as a reducing agent, but also reacts with the residual fragment of precursor. As a result, using H₂ as a carrier gas for Cu(hfac)TMVS resulted in Cu films of lower resistivity, denser microstructure and faster deposition rate than using Ar or N₂ as the carrier gas. Moreover, we found that N₂ plasma treatment on the substrate surface prior to Cu deposition increased the deposition rate of Cu films.     

Synthesis of low resistivity complex oxides on MgO using Pt as buffer layer

Highly crystalline SrRuO₃ (SRO) and La_0.5Sr_0.5CoO₃ (LSCO) thin films were deposited on (100) Pt/ MgO by pulsed laser deposition. The films were mainly (001) textured normal to the substrate surface with a high degree of in-plane orientation with respect to the substrate’s major axes. These films were characterized using x-ray diffraction, Rutherford backscattering, four-point probe resistivity measurement, and transmission electron microscopy. The room temperature resistivity for LSCO and SRO films on Pt/MgO was found to be ∼35 and ∼40 μΩ-cm, respectively. An ion beam minimum channeling yield of ∼43% and ∼33% was obtained for LSCO and SRO films, respectively. The interface between Pt and oxide was found to be smooth and free from any interfacial diffusion. This result showed that high-quality low resistivity oxide thin films can be deposited on Pt.     

The reaction characteristics of ultra-thin Ni films on undoped and doped Si (100)

Reaction characteristics of ultra-thin Ni films (5 nm and 10 nm) on undoped and highly doped (As-doped and B-doped) Si (100) substrates are investigated in this work. The sheet resistance (Rs) measurements confirm the existence of a NiSi salicidation process window with low Rs values within a certain annealing temperature range for all the samples except the one of Ni(5 nm) on P⁺-Si(100) substrate (abnormal sample). The experimental results also show that the transition reaction to low resistivity phase NiSi is retarded on highly doped Si substrates regardless of the initial Ni film thickness. Micro-Raman and x-ray diffraction (XRD) measurement show that NiSi forms in the process window and NiSi₂ forms in a higher temperature annealing process for all normal substrates. Auger electron spectroscopy (AES) results for the abnormal sample show that the high resistivity of the formation film is due to the formation of NiSi₂.     

ZnO films deposited on GaAs substrates with a SiO2 thin buffer layer

Sputter deposition of ZnO films on GaAs substrates has been investigated. ZnO films were radio frequency (rf)-magnetron sputter deposited on GaAs substrates with or without SiO₂ thin buffer layers. Deposition parameters such as rf power, substrate-target distance, and gas composition/pressure were optimized to obtain highly c-axis oriented and highly resistive films. Deposited films were characterized by x-ray diffraction, scanning electron microscopy (SEM), capacitance, and resistivity measurements. Thermal stability of sputter-deposited ZnO films (0.5–2.0 μm thick) was tested with a post-deposition heat treatment at 430°C for 10 min, which is similar to a standard ohmic contact alloying condition for GaAs. The ZnO/SiO₂/GaAs films tolerated the heat treatment well while the ZnO/GaAs films disintegrated. The resistivity (10¹¹ Ω-cm) of the ZnO films on SiO₂-buffered GaAs substrates remained high during the heat treatment. The post-deposition anneal treatment also enhances c-axis orientation of the ZnO films dramatically and relieves intrinsic stress almost completely. These improvements are attributed to a reduction of grain boundaries and voids with the anneal treatment as supported by SEM and x-ray diffraction measurement results.     

Mg2Si buffer layers on Si(100) prepared by a simple evaporation method

The formation of Mg₂Si(100), a_o= 6.39Å, on Si(100) substrates has been investigated. Mg was first evaporated onto Si(100) surfaces and Mg₂Si (100) films were formed in a subsequent annealing process. The Mg₂Si layers were characterized by x-ray diffraction and transmission electron microscopy analysis. Optical and scanning electron microscopy analysis show the surface morphology to be smooth. The films are stable under thermal cycling and exhibit low resistivity. Epitaxial films of Mg₂Si on Si(100) could be an ideal substrate for mercury cadmium telluride and antimonide based III-V semiconductor for mid-infrared devices because of its close lattice matching (the lattice misfit factor is less than 1.5%).     

Preparation of high Tc (Yb,Y)Ba2Cu3O7-δ thin films by co-evaporation from effusion cells

We have prepared superconducting thin films of (Yb,Y)Ba₂Cu₃O_7-δ by evaporation of copper, ytterbium or yttrium, and barium fluoride from Knudsen effusion cells. A simple two chamber vacuum system produced stable evaporation rates of 5–10 nm/min using various Knudsen cells without realtime feedback control. Excellent stoichiometry was obtained in the films by optimizing the deposition of Cu from a dual filament cell, Yb from a single filament cell and Y and BaF₂ from high temperature cells. Films were deposited mainly on SrTiO₃ substrates at temperatures ranging from 120 to 600° C and O₂ partial pressure up to 1.5 ⋻ 10⁻⁵ Torr. Post deposition anneals in O₂ and O₂ + H₂O produced films with room temperature resistivities as low as 227μΩ-cm andT _c (R = 0) at 91 K. Films were characterized using x-ray diffractometry, Rutherford backscattering spectrometry, energy dispersive x-ray analysis, scanning electron microscopy as well as electronic transport measurements.     

Synthesis and Characterization of In<Subscript>2</Subscript>S<Subscript>3</Subscript> Thin Films Deposited by Chemical Bath Deposition on Polyethylene Naphthalate Substrates

Indium sulfide (In₂S₃) thin films were deposited on polyethylene naphthalate (PEN) by chemical bath deposition (CBD). The materials were characterized by ultraviolet (UV)–visible spectroscopy, x-ray photoelectron spectroscopy (XPS), energy-dispersive x-ray spectroscopy (EDX), scanning electron microscopy (SEM), and x-ray diffraction (XRD) to investigate the influence of the polymeric substrate on the resulting thin In₂S₃. The films showed polycrystalline (cubic and tetragonal) structure. A reduction of the ordering of the polymeric chains at the surface of the PEN was also observed, demonstrated by the appearance of two infrared bands at 1094 cm⁻¹ and 1266 cm⁻¹. Presence of oxygen during the early stages of In₂S₃ growth was also identified. We propose a reaction mechanism for both the equilibrium and nucleation stages. These results demonstrate that In₂S₃ can be deposited at room temperature on a flexible substrate.     

Crystallization and failure behavior of Ta-TM (TM=Fe, Co) nanostructured/amorphous diffusion barriers for copper metallization

This work examined the thin-film properties and diffusion barrier behavior of sputtered Ta-TM (TM=Fe, Co) films, aiming at depositing a highly crystallization-resistant and conductive diffusion barrier film for Cu metallization. Four-point probe measurement, x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and a secondary ion mass spectrometer (SIMS) were used to examine the barrier properties. Structural examination indicated that intermetallic-compound-free amorphous Ta-TM films were obtained by magnetron sputtering, thus giving a resistivity of 146.82 μΩ-cm and 247.01 μΩ-cm for Ta_0.5Fe_0.5 and Ta_0.5Co_0.5 films, respectively. The Si/Ta_0.5Fe_0.5/Cu and Si/Ta_0.5Co_0.5/Cu stacked samples were observed to fail completely at temperature above 650°C and 700°C because of the formation of Cu₃Si protrusions between silicon and the Ta-TM interface. Ta_0.5Co_0.5 is thus superior to Ta_0.5Fe_0.5 in preventing copper from diffusion. Highly thermally stabilized amorphous Ta-TM thin film can thus be potentially adopted as a diffusion barrier for Cu metallization.     

Structural and chemical characterization of as-deposited microcrystalline indium oxide films prepared by dc reactive magnetron sputtering

Microcrystalline indium oxide (InO_x) films with thickness of 120–1600 nm were prepared by dc reactive magnetron sputtering in various mixtures of oxygen in argon at room temperature. The depositions were carried out onto Corning 7059 glass and silicon substrates. The conductivity of the as-deposited films can change in a controllable and fully reversible manner by about six orders of magnitude by alternately exposing the films to ultraviolet (UV) light (hv≥3.5eV) in vacuum and reoxidizing them in ozone. The microstructure of the films was investigated using transmission electron microscopy (TEM) and electron diffraction. For this purpose, films with a thickness of about 100 nm were deposited onto NaCl substrates. The surface and depth composition of the films were examined using Auger electron spectroscopy (AES) combined with depth profiling analysis. The depth profiles showed that all the films exhibit an extremely good in-depth uniformity, all the way to the interface with the glass substrate, regardless of their thickness. Quantitative Auger and energy dispersive x-ray (EDX) analyses were employed to determine the stoichiometry of the films. An oxygen deficiency of 2–5% has been observed with respect to the stoichiometric composition. The effects of film thickness and oxygen content in the sputtering gas on the stoichiometry were examined. Both AES and EDX analyses confirmed that the stoichiometry is invariant for these parameters.     

Effect of Substrate on the Structure and Thermoelectric Properties of n-Type Bi2Te3?ySey Thin Films Prepared by Electrodeposition

n-Type Bi₂Te_3−y Se _y thin films were prepared by potentiodynamic electrodeposition onto Au, Bi, and Bi₂Te_3−y Se _y substrates at room temperature. The electrochemical behaviors of Bi³⁺, HTeO₂ ⁺, and H₂SeO₃ on different substrates were investigated by cyclic voltammetry. The morphology, composition, and structure of the films were studied by using environmental scanning electron microscopy (ESEM), energy-dispersive spectroscopy (EDS), and x-ray diffraction (XRD), respectively. The thermoelectric properties of n-type Bi₂Te_3−y Se _y films were determined by measuring the Seebeck coefficient (α) and electrical resistivity (ρ). The results showed that the composition and morphology of the films were sensitive to the substrate material. X-ray diffraction (XRD) analysis indicated that the preferred orientation of annealed films was affected by the substrate and that the film prepared on the Bi₂Te_3−y Se _y substrate exhibited the strongest (015) orientation, with rhombohedral structure. It was proved that the properties of the annealed films could be affected by the substrate and that the film with the highest power factor (P = α ²/ρ) was obtained on the Bi₂Te_3−y Se _y substrate.     

Enhancement in Conductivity and Transmittance of Zinc Oxide Prepared by Chemical Bath Deposition

Highly conductive and transparent zinc oxide thin films were prepared on cleaned Corning Eagle²⁰⁰⁰ glass substrates by chemical bath deposition (CBD) using Zn(NO₃)₂ and (CH₃)₂NHBH₃; the effects of annealing on the structural, electrical and optical properties were investigated. The electrical properties of the film were greatly affected by annealing. Structural characterization was performed by x-ray diffraction and field emission scanning electron micro- scopy. The thin film had a low resistivity of 2.9 × 10⁻² Ω cm, an average transmittance of 81.2%, and a bandgap of 3.23 eV (which is in the visible range) when the film was annealed at 600°C in Ar + H₂. The results demonstrated that a low-resistivity and high-transmittance zinc oxide film can be prepared by CBD, which makes the process readily applicable for a roll-to-roll process.     

Heteroepitaxial silicon-carbide nitride films with different carbon sources on silicon substrates prepared by rapid-thermal chemical-vapor deposition

Cubic crystalline silicon-carbon nitride (Si_1−x−yC_xN_y) films have been grown successfully using various carbon sources by rapid-thermal chemical-vapor deposition (RTCVD). The characteristics of the Si_1−x−yC_xN_y films grown with SiH₃CH₃, C₂H₄, and C₃H₈ are examined and compared by x-ray photoelectron spectroscopy (XPS) spectra, scanning electron microscopy (SEM) images, and transmission electron microscopy (TEM) patterns. The XPS spectra show that the differences of chemical composition and chemical-bonding state are co-related to the C bonding type of the different carbon source. The SEM images and TEM analysis indicate that the better Si_1−x−yC_xN_y film can be obtained using C₃H₈ gas as the carbon source. In addition, correlations between the growing stages to the microstructure of the cubic-crystalline Si_1−x−yC_xN_y films have been illustrated in detail.     

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.     

Barrier Properties of Amorphous Binary Ta-Ni Thin Films for Cu Interconnection

Highly thermally stable amorphous Ta _x Ni_1–x (x = 0.25 and 0.75) thin films were deposited on Si and Si/SiO₂ substrate by magnetron dc sputtering, and the performance of films (20-nm thick) as barriers for copper (Cu) interconnection was evaluated. The failure behaviors of the films were elucidated using a four-point probe, x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Auger emission spectrometry (AES). A highly (111) textured Cu film could be obtained when Cu was deposited on Si/Ta_0.25Ni_0.75 and Si/SiO₂/Ta_0.25Ni_0.75 substrates. The failure temperatures of Si/Ta_0.25Ni_0.75/Cu- and Si/Ta_0.75Ni_0.25/Cu-stacked films were 550°C and 600°C, respectively. Failure of the studied films initiated the penetration of Cu into the Si/Ta _x Ni_1–x interface and triggered the partial dissociation of the Ta _x Ni_1–x barrier layer, forming Cu₃Si precipitates, Ni-silicide and Ta-silicide. Increasing the Ta content enhanced the microstructural and thermal stability of the stacked films, markedly improving barrier properties. The experimental findings demonstrated that the barrier characteristic of Ta_0.75Ni_0.25 was substantially superior to that of Ta_0.25Ni_0.75.