Reliability of multistacked tantalum-based structure as the barrier film in ultralarge-scale integrated metallization

Diffusion barrier properties of Ta films with and without plasma treatments have been investigated in the study. The nitrogen-incorporated Ta films were prepared by NH₃ plasma treatment or reactive sputtering. Barrier properties were evaluated by sheet resistance, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and reverse-biased junction leakage current. An amorphous-like TaN_x layer was formed on Ta barrier film after plasma treatments. The thickness of the amorphous TaN_x layer is about 3 nm and NH₃ plasma-treated Ta films (TaN_x/Ta) possess lower resistivity and smaller grain sizes. The Cu/TaN_x/Ta(10 nm)/Si remained stable after annealing at 750 °C for 1 h. NH₃ plasma-treated Ta films (TaN_x/Ta) possess better thermal stability than Ta and TaN films. It is attributed to the formation of a new amorphous layer on the surface of Ta film after the plasma treatments. For thermal stability of Cu/Ta(-N)/n⁺-p diodes, Cu/Ta/n⁺-p and Cu/TaN/n⁺-p junction diodes resulted in large reverse-bias junction leakage current after annealing at 500 and 525 °C, respectively. On the other hand, TaN_x/Ta diffusion barriers will improve the integrity of Cu/Ta(-N)/n⁺-p junction diodes to 650 °C.     

On the crystal structure and thermoelectric properties of thin Si<Subscript>1–<Emphasis Type="Italic">x</Emphasis> </Subscript>Mn<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript> films

Thin (25 nm) Si_1–xMn_x/Si(100) films are fabricated by pulsed laser deposition. According to high-resolution transmission electron microscopy data, the films have a nanotextured crystalline structure and are chemically homogeneous. The temperature dependences of the resistivity and thermopower are measured in the range of 300–500 K, and the temperature dependences of the Seebeck coefficient and power factor are calculated.     

Surface and Interface Properties of Metal-Organic Chemical Vapor Deposition Grown a -Plane Mg x Zn1– x O (0?≤ x ≤?0.3) Films

The a-plane Mg _x Zn_1−x O (0 ≤ x ≤ 0.3) films were grown on r-plane () sapphire substrates using metal-organic chemical vapor deposition (MOCVD). Growth was done at temperatures from 450°C to 500°C, with a typical growth rate of ∼500 nm/h. Field emission scanning electron microscopy (FESEM) images show that the films are smooth and dense. X-ray diffraction (XRD) scans confirm good crystallinity of the films. The interface of Mg _x Zn_1−x O films with r-sapphire was found to be semicoherent as characterized by high-resolution transmission electron microscopy (HRTEM). The Mg _x Zn_1−x O surfaces were characterized using scanning tunneling microscopy (STM) in ultrahigh vacuum (UHV). Low-energy electron diffraction (LEED) shows well-ordered and single-crystalline surfaces. The films have a characteristic wavelike surface morphology with needle-shaped domains running predominantly along the crystallographic c-direction. Photoluminescence (PL) measurements show a strong near-band-edge emission without observable deep level emission, indicating a low defect concentration. In-plane optical anisotropic transmission was observed by polarized transmission measurements.     

Backside copper metallization of GaAs MESFETs using TaN as thediffusion barrier

Backside copper metallization of GaAs MESFETs using TaN as the diffusion barrier was studied. A thin TaN layer of 40 nm was sputtered on the GaAs substrate before copper film metallization, as judged from the data of X-ray diffraction (XRD), Auger electron spectroscopy (AES), and cross-sectional transmission electron microscopy (TEM), the Cu/TaN films with GaAs were very stable without interfacial interaction up to 550°C annealing; the copper metallized MESFETs were thermally stressed at 300°C. The devices showed very little change in the device characteristics (<3%) after thermal stress, and the changes of the electrical parameters and RF characteristics of the devices after thermal stress were of the same order as those devices without Cu metallization, these results show that TaN is a good diffusion barrier for Cu in GaAs devices and the Cu/TaN films can be used for the backside copper metallization of GaAs MESFETs     

Atomic layer deposition of titanium nitride from TDMAT precursor

TiN was grown by atomic layer deposition (ALD) from tetrakis(dimethylamino)titanium (TDMAT). Both thermal and plasma enhanced processes were studied, with N₂ and NH₃ as reactive gases. Using an optimized thermal ammonia based process, a growth rate of 0.06 nm/cycle and a resistivity of 53 × 10³ μΩ cm were achieved. With an optimized plasma enhanced NH₃ process, a growth rate of 0.08 nm/cycle and a resistivity of 180 μΩ cm could be obtained. X-ray photo electron spectroscopy (XPS) showed that the difference in resistivity correlates with the purity of the deposited films. The high resistivity of thermal ALD films is caused by oxygen (37%) and carbon (9%) contamination. For the film deposited with optimized plasma conditions, impurity levels below 6% could be achieved. The copper diffusion barrier properties of the TiN films were determined by in-situ X-ray diffraction (XRD) and were found to be as good as or better than those of films deposited with physical vapor deposition (PVD).     

Epitaxial TiN based contacts for silicon devices

We have grown high quality epitaxial TiN/Si(100) and Cu/TiN/Si(100) heterostructures by pulsed laser deposition. The epitaxial TiN films have the same low (15 μΩ-cm) resistivity as TiSi₂ (C-54) phase with excellent diffusion barrier properties. In addition, Schottky barrier height of TiN was close to that of TiSi₂ (0.6-0.7 eV). Auger and Raman spectroscopy revealed that the films were stoichiometric TiN and free from oxygen impurities. The x-ray diffraction and transmission electron microscope (TEM) results showed that the TiN films deposited at 600°C were single crystal in nature with epitaxial relationship TiN|| Si. The Rutherford baskscattering channeling yield for TiN films was found to be in the range of 10–13%. The epitaxy of Cu on TiN was found to be cube-on-cube, i.e., Cull<100>TiN||Si. The Cu/TiN and TiN/Si interfaces were found to be quite sharp without any indication of interfacial reaction. The growth mechanism of copper on TiN was found to be three-dimensional. We discuss domain matching epitaxy as a mechanism of growth in these large lattice mismatch systems, where three lattice constants of Si(5.43?) match with four of TiN(4.24?) and seven units of Cu(3.62?) match with six of the TiN. Thus, for next generation of device complementary metal oxide semiconductor structures, Cu/TiN/Si(100) contacts hold considerable promise, particularly since Cu is a low resistivity metal (1.6 μΩ-cm) and is considerably more resistant to electromigration than Al. The implications of these results in the fabrication of advanced microelectronic devices are discussed.     

Texture of atomic layer deposited ruthenium

Ruthenium films were grown by plasma enhanced atomic layer deposition (ALD) on Si(1 0 0) and ALD TiN. X-ray diffraction (XRD) showed that the as-deposited films on Si(1 0 0) were polycrystalline, on TiN they were (0 0 2) oriented. After annealing at 800 °C for 60 s, all Ru films were strongly (0 0 2) textured and very smooth. Electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) demonstrated that the lateral grain size of the annealed films was several 100 nm, which was large compared to the 10 nm thickness of the films. No ruthenium silicide was formed by annealing the ALD Ru films on Si(1 0 0). Comparison with sputter deposited films learned that this occurred because the ammonia plasma created a SiO_xN_y reaction barrier layer prior to film growth.     

Study of diffusion barrier properties of ionized metal plasma (IMP) deposited TaN between Cu and SiO2

The diffusion barrier properties of IMP deposited TaN between Cu and SiO₂ have been investigated in the Cu (200 nm)/TaN (30 nm)/SiO₂ (250 nm)/Si multi-layer structure. The IMP-TaN thin film shows better Cu diffusion barrier properties than chemical vapor deposition (CVD) and conventional physical vapor deposition (PVD) deposited TaN films. The thermal stability was evaluated by electrical measurement and X-ray diffraction (XRD) analysis. As a main part of thermal stability studies, the atomic intermixing, new compound formation and phase transitions in the test structure were also studied. Furthermore, a failure mechanism was also examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), secondary ion mass spectroscopy (SIMS) and Rutherford backscattering spectroscopy (RBS) in conjunction with electrical measurements. The 30 nm thick IMP-TaN was found to be stable up to 800°C for 35 min.     

Pulsed laser deposition of titanium nitride and diamond-like carbon films on polymers

We have investigated the deposition of titanium nitride (TiN) and diamond-like carbon (DLC ) films on polymethylmethacrylate (PMMA) substrates using pulsed laser deposition (PLD) technique. The TiN and diamond-like films were deposited by laser ablation (KrF excimer laser λ = 248 nm, pulse duration τ～25 × 10^?9 s, energy density ～2?15J/cm²) of TiN and graphite targets, respectively, at room temperature. These films were characterized by transmission electron microscopy, scanning electron microscopy, x-ray diffraction, Auger electron spectroscopy, UV-visible absorption spectroscopy, and Raman spectroscopy. The TiN films were smooth and found to be polycrystalline with average grain size of 120Å. The diamond-like carbon films were amorphous with a characteristic Raman peak at 1550 cm^?1. The TiN films are highly adherent to the polymer substrates as compare to DLC films. The adhesion strength of DLC films on polymers was increased by interposing thin TiN layer (200Å) on polymers byin-situ pulsed laser deposition. The DLC films were found to be amorphous with good adhesion to TiN/PMMA substrates.     

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.     

Material Characterization of Ge1−x Sn x Alloys Grown by a Commercial CVD System for Optoelectronic Device Applications

High-quality compressive-strained Ge_1?x Sn _x /Ge films have been deposited on Si(001) substrate using a mainstream commercial chemical vapor deposition reactor. The growth temperature was kept below 450°C to be compatible with Si complementary metal–oxide–semiconductor processes. Germanium tin (Ge_1?x Sn _x ) layers were grown with different Sn composition ranging from 0.9% to 7%. Material characterizations, such as secondary-ion mass spectrometry, Rutherford backscattering spectrometry, and x-ray diffraction analysis, show stable Sn incorporation in the Ge lattice. Comparison of the Sn mole fractions obtained using these methods shows that the bowing factor of 0.166 nm (in Vegard’s law) is in close agreement with other experimental data. High-resolution transmission electron microscopy and atomic force microscopy results show that the films have started to relax through the formation of misfit and threading dislocations. Raman spectroscopy, ellipsometry, and photoluminescence (PL) techniques are used to study the structural and optical properties of the films. Room-temperature PL of the films shows that 7% Sn incorporation in the Ge lattice results in a decrease in the direct bandgap of Ge from 0.8 eV to 0.56 eV.     

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.     

Structural and optical investigation of InGaN/GaN multiple quantum well structures with various indium compositions

We have studied the influence of indium (In) composition on the structural and optical properties of In_x Ga_1−xN/GaN multiple quantum wells (MQWs) with In compositions of more than 25% by means of high-resolution x-ray diffraction (HRXRD), photoluminescence (PL), and transmission electron microscopy (TEM). With increasing the In composition, structural quality deterioration is observed from the broadening of the full width athalf maximum of the HRXRD superlattice peak, the broad multiple emission peaks oflow temperature PL, and the increase of defect density in GaN capping layers and InGaN/GaN MQWs. V-defects, dislocations, and two types of tetragonal shape defects are observed within the MQW with 33% In composition by high resolution TEM. In addition, we found that V-defects result in different growth rates of the GaN barriers according to the degree of the bending of InGaN well layers, which changes the period thickness of the superlattice and might be the source of the multiple emission peaks observed in the In_xGa_1−xN/GaN MQWs with high in compositions.     

Low temperature passivation of Si1−xGex alloys by dry high pressure oxidation

Thermal passivation of Si_1−xGe_x using high pressure (70 MPa) oxidation was studied for potential use in MOS-device applications. Alloys of CVD-grown Si_1−xGe_x (x = 10 and 15 at.%, 200 and 150 nm thick, respectively), were oxidized at 500 and 550°C using high purity dry oxygen at a pressure of 70 MPa. For comparative purposes, a second set of alloys were oxidized using conventional wet atmospheric pressure oxidation at 800°C. X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, transmission electron microscopy (TEM), and metal-oxide semiconductor capacitance-voltage (C-V) measurements were used to characterize the as-grown oxides. Chemical analysis by XPS confirmed that under high pressure conditions compositionally congruent oxides are grown from these alloys. High resolution TEM and Raman spectroscopy show that the as-grown oxide/semiconductor interface is planar and free of Ge enrichment on a scale of 1-2 monolayers. A midgap interface state density for both the 10 and 15 at.% samples of 1 × 10¹² cm⁻² eV⁻¹ was estimated based on 1 MHz C-V measurement.     

Synthesis of GaN nanowires by ammoniation of Ga2O3 films on Nb layer deposited on Si(1 1 1) substrates

Single-crystalline GaN nanowires have been successfully synthesized on Si(1 1 1) substrates by magnetron sputtering through ammoniation of Ga₂O₃/Nb films at 900 °C in a quartz tube. The as-synthesized GaN nanowires are confirmed to be single-crystalline GaN with wurtzite structure by X-ray diffraction (XRD), selected-area electron diffraction (SAED) and field-emission transmission electron microscopy (FETEM); scanning electron microscopy (SEM) shows that the GaN nanowires are smooth, with diameters of about 50 nm and lengths typically up to several microns, which could provide an attractive potential for incorporation in future GaN electronic devices into Si-based large-scale integrated circuits. Finally, the growth mechanism of GaN nanowires is also briefly discussed.     

Growth of AlxGa1−x as by metalorganic chemical vapor deposition using trimethylgallium and trimethylamine alane

High-quality Al_xGa_1−xAs layers with aluminum arsenide contentx up to 0.34 have been grown in a low pressure metalorganic chemical vapor deposition (MOCVD) system using trimethylgallium (TMG), trimethylamine alane (TMAA) and arsine. The carbon content in these films depended on growth conditions but was in general lower than in those obtained with trimethylaluminum (TMA) instead of TMAA in the same reactor under similar conditions. Unlike TMA grown layers, the TMAA grown Al_xGa_1−xAs layers, (grown at much lower temperature—down to 650° C), exhibited room temperature photolu-minescence (PL). Low temperature (25 K) PL from these films showed sharp bound exciton peaks with a line width of 5.1 meV for Al_0.25Ga_0.75As. A 39 period Al_0.28Ga_0.72As (5.5 nm)/GaAs (8.0 nm) superlattice grown at 650° C showed a strong PL peak at 25 K with a line width of 5.5 meV attesting to the high quality of these layers.     

Vanadium Oxide Thin Films Alloyed with Ti, Zr, Nb, and Mo for Uncooled Infrared Imaging Applications

Microbolometer-grade vanadium oxide (VO _x ) thin films with 1.3 < x < 2.0 were prepared by pulsed direct-current (DC) sputtering using substrate bias in a controlled oxygen and argon environment. These films were systematically alloyed with Ti, Nb, Mo, and Zr using a second gun and radiofrequency (RF) reactive co-sputtering to probe the effects of the transition metals on the film charge transport characteristics. The results reveal that the temperature coefficient of resistance (TCR) and resistivity are unexpectedly similar for alloyed and unalloyed films up to alloy compositions in the ～20 at.% range. Analysis of the film structures for the case of the 17% Nb-alloyed film by glancing-angle x-ray diffraction and transmission electron microscopy shows that the microstructure remains even with the addition of high concentrations of alloy metal, demonstrating the robust character of the VO _x films to maintain favorable electrical transport properties for bolometer applications. Postdeposition thermal annealing of the alloyed VO _x films further reveals improvement of electrical properties compared with unalloyed films, indicating a direction for further improvements in the materials.     

Effects of ammonia concentration on property of Cd1−xZnxS films by chemical bath deposition

Cd_1−xZn_xS thin films were grown on soda–lime glass substrates by chemical-bath deposition (CBD) at 80 °C with stirring. All the samples were annealed at 200 °C for 60 min in the air. The crystal structure, surface morphology, thickness and optical properties of the films were studied with transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), step height measurement instrument and spectrophotometer respectively. The results revealed that Cd_1−xZn_xS thin films had cubic crystal structure and the intensity of the diffraction peak increased gradually as ammonia concentration rose and the grain size varied from 5.1 to 8.3 nm. All of Cd_1−xZn_xS thin films had a granular surface with some smaller pores and the average granule sizes increased from 92 to 163 nm with an increase in ammonia concentration. The Cd_1−xZn_xS thin films had the highest transmittance with ammonia concentration of 0.5 M L⁻¹, whose thickness was 50 nm and band gap was 2.62 eV.     

Influence of magnesium doping on the structural and optical properties of tin (II) oxide thin films deposited by electron beam evaporation

Single-phase polycrystalline magnesium-doped tin oxide (Mg_xSn_1?xO; x=0, 0.04, and 0.08) thin films were deposited by electron beam evaporation on the glass substrate. X-ray diffraction analysis showed that the peaks intensity of the polycrystalline α-SnO thin films increased along with the increasing Mg content. The crystallite size calculated from X-ray diffraction data decreased by increasing the Mg doping concentration, which was also confirmed by atomic force microscopy. The stoichiometry and thickness of the thin films were determined by Rutherford backscattering spectroscopy. An increase in both the optical transmission (57–95%) and band gap (2.5–2.82 eV) of the Mg_xSn_1?xO thin films were observed which were investigated by UV–vis spectroscopy. Photoluminescence of Mg_xSn_1?xO thin films revealed that there were two extra peaks at 482 nm and 550 nm due to the crystal defects introduced by the Mg doping and these peaks become weaker and shifted to longer wavelength by increasing the Mg doping concentration.     

Band gap engineering by substitution of S by Se in nanostructured CdS1−xSex thin films grown by soft chemical route for photosensor application

Ternary alloys of CdS_1−xSe_x (x=0, x=0.2, x=0.4, x=0.6, x=0.8, x=1) thin films were prepared on to glass substrates by a simple and economical soft chemical route (chemical bath deposition) at 50° to 80 °C in air. The as-grown films were characterized by optical and electrical measurement systems, X-ray diffraction (XRD), Energy dispersive X-ray analysis (EDAX) and SEM (scanning electron microscopy). The optical study reveals shift in the absorption edge towards the higher wavelengths, i.e. the band gap decreases as a function of ‘x’ (quantity of selenium in the bath). I–V measurement of CdS (resulted when x=0), CdS_1−xSe_x (x=0.2, x=0.4, x=0.6, x=0.8) and CdSe (resulted when x=1) thin films under dark and illumination conditions (60 W) were measured. Increase in photoconductivity is observed, suggesting its applicability in photosensor devices. Electrical resistivity shows semiconducting behavior and activation energy decreases. The XRD patterns reveals that deposited thin films have hexagonal mixed structure. EDAX confirmed the compositional parameters. SEM images showed uniform deposition of the material over the entire glass substrate.