Copper diffusion in TaN-based thin layers

The diffusion of Cu through TaN-based thin layers into a Si substrate has been studied. The barrier efficiency of TaN/Ta/TaN multilayers of 150 nm in thickness has been investigated and is compared with that of TaN single layers. Thermal stabilities of these TaN-based thin layers against Cu diffusion were determined from in situ X-ray diffraction experiments, conducted in the temperature range of 773-973 K. The TaN/Ta/TaN barrier appeared to be more efficient in preventing Cu diffusion than the TaN single layer.     

Complete filling of 41 nm trench pattern using Cu seed layer deposited by SAM-modified electroless plating and electron-beam evaporation

To overcome the limitation of the sputtered Cu seed layer in electroplating of Cu interconnects imposed by the shadow effect, a new method for depositing a Cu seed layer on a 41 nm trench pattern based on combination of electroless plating (ELP) and electron-beam (E-Beam) evaporation was developed. A Cu seed layer formed by ELP alone was too thin to be used for electroplating due to its high resistivity. To solve this problem, an additional Cu layer was deposited on top of the trench by E-Beam evaporator to enhance the electrical conductivity of the Cu seed layer. The electrical resistivity of the resulting Cu layer was reduced to 4.8 μΩ cm, which was sufficient for the conductive seed layer for electroplating the 41 nm trench pattern. The gap-filling capability also improved and there were no voids or seams in the 41 nm trench pattern. The proposed method can be an effective solution for fabrication of a conductive seed layer to fill a 41 nm trench pattern by electroplating.     

Effect of tin-doped indium oxide film as capping layer on the agglomeration of copper film and the appearance of copper silicide

In this work, the effect of tin-doped indium oxide (ITO) film as capping layer on the agglomeration of copper film and the appearance of copper silicide was studied. Both samples of Cu 100 nm/ITO 10 nm/Si and ITO 20 nm/Cu 100 nm/ITO 10 nm/Si were prepared by sputtering deposition. After annealing in a rapid thermal annealing (RTA) furnace at various temperatures for 5 min in vacuum, the samples were characterized by four probe measurement for sheet resistance, X-ray diffraction (XRD) analysis for phase identification, scanning electron microscopy (SEM) for surface morphology and transmission electron microscopy (TEM) for microstructure.The results show that the sample with ITO capping layer is a good diffusion barrier between copper and silicon at least up to 750 °C, which is 100 °C higher than that of the sample without ITO capping layer. The failure temperature of the sample with ITO capping layer is about 800 °C, which is 100 °C higher than that of the sample without ITO capping layer. The ITO capping layer on Cu/ITO/Si can obstacle the agglomeration of copper film and the appearance of Cu₃Si phase.     

Interfacial reactions during sputter deposition of Ta and TaN films on organosilicate glass: XPS and TEM results

The evolution of the interface between organosilicate glass (OSG) and sputter deposited Ta or TaN films has been characterized by X-ray phototelectron spectroscopy (XPS). Cross-sectional TEM (XTEM) was also used to analyze Ta/OSG and TaN/OSG/interfaces for samples formed under different deposition conditions. XPS data show that Ta deposition onto OSG results in formation of an interphase between 1 and 2 nm thick composed of oxidized Ta and C. Metallic Ta is then formed on top of the interfacial region. In contrast, Ta-rich TaN formation occurs with some nitridation of the substrate, but with no significant interphase formation. The XPS data are consistent with the XTEM data. The XTEM results for Ta/OSG indicate a spatially irregular interface over a length scale of ∼2 nm, while results for TaN/OSG indicate a spatially abrupt region.     

Effect of interface layer on growth behavior of atomic-layer-deposited Ir thin film as novel Cu diffusion barrier

Growth and nucleation behavior of Ir films grown by atomic layer deposition (ALD) on different interfacial layers such as SiO₂, surface-treated TaN, and 3-nm-thick TaN were investigated. To grow Ir thin film by ALD, (1,5-cyclooctadiene) (ethylcyclopentadienyl) iridium (Ir(EtCp)(COD)) and oxygen were employed as the metalorganic precursor and reactant, respectively. To obtain optimal deposition conditions, the deposition temperature was varied from 240 to 420 °C and the number of deposition cycles was changed from 150 to 300. The Ir film grown on the 3-nm-thick TaN surface showed the smoothest and most uniform layer for all the deposition cycles, whereas poor nucleation and three-dimensional island-type growth of the Ir layer were observed on Si, SiO₂, and surface-treated TaN after fewer number of deposition cycles. The uniformity of the Ir film layer was maintained for all the different substrates up to 300 deposition cycles. Therefore we suggest that the growth behavior of the Ir layer on different interface layer is related to the chemical bonding pattern of the substrate film or interface layer, resulting in better understand the growth mechanism of Ir layer as a copper diffusion barrier. The ALD-grown Ir films show the preferential direction of (1 1 1) for all the reflections, which indicates the absence of IrO₂ in metallic Ir.     

Inter-diffusion study in MgO tunneling magneto-resistive (TMR) system by XPS

In this paper, we investigated the elemental inter-diffusion in MgO TMR system, namely, between MgO barrier and free layer (CoFeB, NiFe or their combination) interface and the oxygen diffusion into the capping layers (Ta, Ru, TaN) at elevated temperatures using simple sheet film stack to simplify the results interpretation. Boron, cobalt, iron, and nickel show various diffusion tendencies into the MgO barrier after annealing the sheet film stack. Oxygen has different penetration depth into single CoFeB free layer upon annealing under N₂ + Ar protective atmosphere for different capping layers. Ru and TaN capping layer provide much better O₂ diffusion barrier, compared with Ta capping layer. This could potentially change the boron segregation tendency at free layer and capping layer interface and thus affect the interface crystallization process and lattice matching between the crystallized CoFeB free layer and the MgO(0 0 1) barrier layer. All these effects will impact the overall TMR performance.     

X-ray metrology for advanced silicon processes

X-ray reflectivity (XRR), X-ray fluorescence (XRF) and small angle X-ray scattering (SAXS) techniques are used to the monitoring of Cu/porous low κ processes, which are developed for the next generation (≤65 nm) integrated circuits. Sensitivity of XRR and XRF is sufficient to detect drifts of the copper barrier layer, copper seed layer and Cu CMP (chemical-mechanical polishing) processes. Their metrology key parameters comply with production requirements. SAXS allows determining the pore structure of low κ films: average pore size and pore size distribution.     

Electron microscopic study on interfacial characterization of electroless Ni-W-P plating on aluminium alloy

The interface between electroless plating Ni-W-P deposit and aluminium alloy (Al) matrix at different temperature heated for 1 h was studied using transmission electron microscope. The results show that the interface between as-deposited Ni-W-P deposit and Al matrix is clear. There are no crack and cavity. The bonding of Ni-W-P deposit and Al matrix is in good condition. The Ni-W-P plating is nanocrystalline phase (5-6 nm) in diameter. After being heated at 200 °C for 1 h, the interface of Ni-W-P deposit and Al matrix is clear, without the appearance of the diffusion layer. There exist a diffusion layer and educts of intermetallic compounds of nickle and aluminium such as Al₃Ni, Al₃Ni₂, NiAl, Ni₅Al₃ and so on between Ni-W-P deposit and Al matrix after being heated at 400 °C for 1 h.     

Failure behavior of ITO diffusion barrier between electroplating Cu and Si substrate annealed in a low vacuum

A structure of Cu/ITO(10 nm)/Si was first formed and then annealed at various temperatures for 5 min in a rapid thermal annealing furnace under 10⁻² Torr pressure. In Cu/ITO(10 nm)/Si structure, the ITO(10 nm) film was coated on Si substrate by sputtering process and the Cu film was deposited on ITO film by electroplating technique. The various Cu/ITO(10 nm)/Si samples were characterized by a four-point probe, a scanning electron microscope, an X-ray diffractometer, and a transmission electron microscope. The results showed that when the annealing temperature increases near 600 °C the interface between Cu and ITO becomes unstable, and the Cu₃Si particles begin to form; and when the annealing temperature increases to 650 °C, a good many of Cu₃Si particles about 1 μm in size form and the sheet resistance of Cu/ITO(10 nm)/Si structure largely increases.     

Chemical characterization by XPS of Cu/Ge ohmic contacts to n-GaAs

Chemical composition of Cu/Ge layers deposited on a 1 μm thick n-type GaAs epitaxial layer (doped with Te to a concentration of 5 × 10¹⁸ cm⁻³) and its interface were examined ex situ by XPS combined with Ar⁺ sputtering. These measurements indicate a diffusion of Cu and Ge from the Cu/Ge layer towards GaAs and, also, an out-diffusion of Ga and As from the GaAs layer to the metallic films. The Auger parameter corrected Auger spectra and XPS spectra show only Cu and Ge metals in the in the Cu/Ge layer and in the interface.     

TaN underlayers for spin valves deposited directly on top of Si substrates

TaN underlayers for spin valves were studied, which were deposited directly on top of Si substrates. The experimental results obtained with the TaN underlayer were compared with those obtained with other (Ta, Mo, and MoN) underlayers. The spin valve structure was Si/Underlayer(tÅ)/NiFe(21 Å)/CoFe(28 Å)/Cu(22 Å)/CoFe(18 Å)/IrMn(65 Å)/Ta(25 Å). The TaN underlayer for a spin valve element exhibited good adhesion to the Si substrate. The XRD patterns of the annealed TaN on bare Si substrate at 900 °C showed no Ta silicide phases, which suggests that the TaN layer may also be used as a diffusion barrier between Si substrate and the ensuing spin valve active layers, as well as an underlayer. A spin valve element having TaN underlayer deposited directly on top of a Si substrate showed a high MR ratio of about 8.3% after annealing at 200 °C. It is concluded that it is advantageous to use a TaN underlayer if one wants to fabricate spin valve elements directly on top of Si substrates.     

Structural and morphological characterisation of hybrid Cu/Si(0 0 1) structures

The structural and morphological properties of epitaxial Cu/Si(0 0 1) type of structures have been investigated by a combination of electron, X-ray and scanning probe imaging techniques. Auger electron spectroscopy measurements indicate the presence of Si in the Cu layer for Cu thicknesses up to 10 nm. In addition, X-ray scattering results show that there is a mosaic spread in the Cu(0 0 1) crystal which decreases as the Cu thickness increases, from 8° at 15 nm to 4.5° at 100 nm. This behaviour is corroborated by reflection high energy electron diffraction patterns of the Cu surface measured during growth, which exhibit a twinning in the diffraction spots for the 15 and 30 nm Cu films. Atomic force and scanning electron microscopy imaging of Cu(4 nm)/Co(7,17 nm)/Cu(100 nm)/Si(0 0 1) structures allow one to visualise and characterise the sample surface in real space; from these measurements, an average roughness amplitude of ∼0.5 nm and a correlation length of ∼50 nm are obtained. Our results provide a better understanding of an important system which has been widely used as a template for the growth of epitaxial ultrathin magnetic films.     

Highly stable carbon-doped Cu films on barrierless Si

Electrical resistivities and thermal stabilities of carbon-doped Cu films on silicon have been investigated. The films were prepared by magnetron sputtering using a Cu-C alloy target. After annealing at 400 °C for 1 h, the resistivity maintains a low level at 2.7 μΩ-cm and no Cu-Si reaction is detected in the film by X-ray diffraction (XRD) and transmission electron microscopy (TEM) observations. According to the secondary ion mass spectroscopy (SIMS) results, carbon is enriched near the interfacial region of Cu(C)/Si, and is considered responsible for the growth of an amorphous Cu(C)/Si interlayer that inhibits the Cu-Si inter-diffusion. Fine Cu grains, less than 100 nm, were present in the Cu(C) films after long-term and high-temperature annealings. The effect of C shows a combination of forming a self-passivated interface barrier layer and maintaining a fine-grained structure of Cu. A low current leakage measured on this Cu(C) film also provides further evidence for the carbon-induced diffusion barrier interlayer performance.     

Initial stages of oxidation of Cu(1 1 1)

Several surface analysis techniques were combined to study the initial stages of oxidation of Cu(1 1 1) surfaces exposed to O₂ at low pressure (<5 × 10⁻⁶ mbar) and room temperature. Scanning tunneling microscopy (STM) results show that the reactivity is governed by the restructuring of the Cu(1 1 1) surface. On the terraces, oxygen dissociative adsorption leads to the formation of isolated O adatoms and clusters weakly bound to the surface. The O adatoms are located in the fcc threefold hollow sites of the unrestructured terraces. Friedel oscillations with an amplitude lower than 5 pm have been measured around the adatoms. At step edges, surface restructuring is initiated and leads to the nucleation and growth of a two-dimensional disordered layer of oxide precursor. The electronic structure of this oxide layer is characterised by a band gap measured by scanning tunneling spectroscopy to be ∼1.5 eV wide. The growth of the oxide islands progresses by consumption of the upper metal terraces to form triangular indents. The extraction of the Cu atoms at this interface generates a preferential orientation of the interface along the close-packed directions of the metal. A second growth front corresponds to the step edges of the oxide islands and progresses above the lower metal terraces. This is where the excess Cu atoms extracted at the first growth front are incorporated. STM shows that the growing disordered oxide layer consists of units of hexagonal structure with a first nearest neighbour distance characteristic of a relaxed Cu-Cu distance (∼0.3 nm), consistent with local Cu₂O(1 1 1)-like elements. Exposure at 300 °C is necessary to form an ordered two-dimensional layer of oxide precursor. It forms the so-called “29” superstructure assigned to a periodic distorted Cu₂O(1 1 1)-like structure.     

Magnetic layer thickness dependence of magnetization reversal in electrodeposited CoNi/Cu multilayer nanowires

The magnetization reversal of electrodeposited CoNi/Cu multilayer nanowires patterned in an array using a hole template has been investigated. The reversal mode is found to depend on the CoNi layer thickness t(CoNi); with increasing t(CoNi) a transition occurs from coherent rotation to a combination of coherent and incoherent rotation at around t(CoNi)=51 nm. The reversal mode has been identified using the magnetic hysteresis loops measured at room temperature for CoNi/Cu nanowires placed at various angles between the directions of the nanowire axis and external fields using a vibrating sample magnetometer. The nanowire samples have a diameter of ∼250 nm and constant Cu layer thickness of 4.2 nm with various t(CoNi) ranging from 6.8 nm to 7.5 μm. With increasing t(CoNi), the magnetic easy axis moves from the direction perpendicular to nanowires to that parallel to the nanowires at around t(CoNi)=51 nm, indicating a change in the magnetization reversal mode. The reversal mode for the nanowires with thin disk-shaped CoNi layers (t(CoNi)=6.8, 12 and 17 nm) is of a coherent rotation type, while that for long rod-shaped CoNi layers (t(CoNi)=150 nm, 1.0, 2.5 and 7.5 μm) can be consistently explained by a combination of coherent rotation and a curling mode. The effects of dipole–dipole interactions between nanowires and between adjacent magnetic layers in each nanowire on the reversal process have been discussed.     

Interface study of ion irradiated Cu/Ni/Cu(0 0 2)/Si magnetic thin film by X-ray reflectivity

The irradiation effect of 1 MeV C⁺ on the interface and magnetic anisotropy of epitaxial Cu/Ni system with a perpendicular magnetic anisotropy was investigated by using magneto-optical Kerr effects, grazing incident diffraction and X-ray reflectivity. The magnetic easy-axis was altered from the direction along the surface normal to in-plane and the strain in the Ni layer was relaxed after ion irradiation. Though the interface between the top Cu layer and the Ni layer becomes rough, the contrast of electron densities of Cu and Ni layer increases and the grain-growth occurs during ion irradiation. These phenomena arise from thermo-chemical driving force, i.e. heat of formation, which may be a crucial factor in determining the interface shape in the case of indirect energy transfer mechanism. Therefore, the change of the magnetic anisotropy of the Ni/Cu system after ion irradiation is not due to the formation of the intermixed layer at the interface. The ion irradiation effects on the grain-growth and enhancement of the electronic contrast between Ni and Cu are explained by the interfacial atomic movement caused by thermo-chemical driving force.     

Bi surfactant effects of Co/Cu multilayered films prepared by sputter deposition

The influence of a Bi surfactant layer on the structural and magnetic properties of Co/Cu multilayers grown onto Cu(1 1 0) buffer layer by RF magnetron sputtering has been studied. The results of X-ray diffraction revealed the initial deposition of a 2.0 Å-thick Bi layer onto the Cu buffer layer prior to the deposition of the Co/Cu multilayer yielded high-quality fcc-(1 1 0) oriented epitaxial films. The X-ray photoelectron spectra revealed that Bi was segregated at around the top of the surface. Therefore, Bi was concluded to be an effective surfactant to enhance the epitaxial growth of Co/Cu(1 1 0) multilayer. The maximum giant magnetoresistance and antiferromagnetic interlayer coupling ratios of the Co/Cu multilayers were increased by using the Bi surfactant layer.     

Effect of Ru crystal orientation on the adhesion characteristics of Cu for ultra-large scale integration interconnects

The adhesion of Cu on Ru substrates with different crystal orientations was evaluated. The crystal orientation of sputter deposited Ru could be changed from (1 0 0) to (0 0 1) by annealing at 650 °C for 20 min. The adhesion of Cu was evaluated by the degree of Cu agglomeration on Ru. Cu films on annealed Ru films with the (0 0 1) crystal orientation showed 28% lower RMS values and 50% lower Ru surface coverage than Cu as-deposited on Ru having the (1 0 0) crystal orientation after annealing at 550 °C for 30 min, which suggest that Cu wettability on the Ru(0 0 1) was better than that on the Ru(1 0 0) plane. The low lattice misfit of 4% between Cu(1 1 1) and Ru(0 0 1) may be the reason for this good adhesion property.     

Epitaxial growth of Al on Si(1 1 1) with Cu buffer layers

The structure of thin Al films grown on Si(1 1 1) with thin Cu buffer layers has been investigated using synchrotron radiation photoemission spectroscopy. A thin Cu(1 1 1) layer between the Si(1 1 1) substrate and an Al film may enhance quantum well effects in the Al film significantly. The strength of quantum well effects has been investigated qualitatively with respect to the thickness of the Cu buffer layer and to the Al film thickness. Deposition of Cu on Si(1 1 1)7 × 7 leads to formation of a disordered silicide layer in an initial regime before a well-ordered Cu(1 1 1) film is formed after deposition of the equivalent of 6 layers of Cu. In the regime below 6 layers of Cu the disorder is transferred to Al layers subsequently grown on top. The initial growth of up to 8 layers of Al on a well-ordered Si/Cu(1 1 1) layer leads to a disordered film due to the lattice mismatch between the two metals. When the Cu buffer layer and the Al over-layer are above 6 and 8 layers, respectively the Al film shows sharp low energy electron diffraction patterns and very sharp quantum well peaks in the valence band spectra signalling good epitaxial growth.     

The γ-Fe formation in epitaxial Cu(0 0 1)/Fe(0 0 1) thin films by the solid-state synthesis: Structural and magnetic features

The γ-Fe formation in epitaxial Cu(0 0 1)/Fe(0 0 1) bilayers with the annealing temperature increasing has been studied. Using Mössbauer spectroscopy, X-ray diffraction, and magnetic analysis, structural and chemical characterization of the interface between cooper and iron layers has been performed. After annealing at 850 °C and subsequent cooling to room temperature, paramagnetic γ-Fe(0 0 1) precipitates with an average size of 30 nm coherent to a Cu(0 0 1) matrix form. Conditions of intermixing and the γ-Fe formation at the Cu/Fe interface are explained in terms of the solid-state synthesis in thin films. Specific features of the martensitic transition γ↔α are discussed.