Titanium nitride diffusion barrier for copper metallization on gallium arsenide

The diffusion properties of Cu, Cu/titanium nitride (TiN) and Cu/TiN/Ti metallization on GaAs, including as-deposited film and others annealed at 350-550 °C, were investigated and compared. Data obtained from X-ray diffractometry, resistivity measurements, scanning electron microscopy, energy dispersive spectrometer and Auger electron spectroscopy indicated that in the as-deposited Cu/GaAs structure, copper diffused into GaAs substrate, and a diffusion barrier was required to block the fast diffusion. For the Cu/TiN/GaAs structure, the columnar grain structure of TiN films provided paths for diffusion at higher temperatures above 450 °C. The Cu/TiN/Ti films on GaAs substrate were very stable up to 550 °C without any interfacial interaction. These results show that a TiN/Ti composite film forms a good diffusion barrier for copper metallization with GaAs.     

Diffusion barrier performance of nano-structured and amorphous Ru-Ge diffusion barriers for copper metallization

In the experiment, nano-structured and amorphous ultrathin Ru-Ge interlayers (∼15 nm in thickness) were deposited between Cu(Ru) alloy film and Si substrate via co-sputtering functioning as preventive diffusion barrier layers. After annealing at different temperatures, X-ray diffraction and four-point probe method revealed that the amorphous Ru-Ge layer effectively suppressed the Cu diffusion into Si substrate up to a temperature of at least 873 K; however, it is less than 773 K for the nano-structured Ru-Ge layer. A self-formed amorphous multilayer of Ru(RuO_x)/RuGe_xCu_y could be attained by annealing Cu/Cu(Ru)/Ru-Ge(amorphous)/Si system at a very low temperature (even 473 K). The results proved that the amorphous Ru-Ge system could self-form the multilayer diffusion barrier before the diffusion reaction between Cu and Si and improved the thermal stability of the Cu interconnection significantly.     

Diffusion barrier capability of Zr-Si films for copper metallization with different substrate bias voltage

Efficiency of Zr-Si diffusion barriers in Cu metallization has been investigated. Amorphous Zr-Si diffusion barriers were deposited on the Si substrates by reactive magnetron sputtering with different negative substrate bias. The mass density of Zr-Si films increases with substrate bias voltage up to − 150 V. The deposition rate decreased with the negative substrate bias from 5.4 nm/min to 1.8 nm/min. XRD measurements show that the Zr-Si barriers have amorphous structure in the as-deposited state. The FE-SEM images show that the sizes of spherical granules on the Zr-Si film surface increase with increasing the substrate bias. The Cu/Zr-Si/Si structures were prepared and annealed in Ar ambient at temperatures varying from 500 to 650 °C for an hour. It is shown from the comparison study that the Zr-Si film deposited with − 150 V is better at maintaining good performance in Cu/Zr-Si/Si contact system than that of Zr-Si film deposited with − 50 V.     

Evaluation of diffusion barrier and electrical properties of tantalum oxynitride thin films for silver metallization

The thermal stability and the diffusion barrier properties of DC reactively sputtered tantalum oxynitride (Ta-O-N) thin films, between silver (Ag) and silicon (Si) p⁺n diodes were investigated. Both materials characterization (X-ray diffraction analysis, Rutherford backscattering spectrometry (RBS), Auger depth profiling) and electrical measurements (reverse-biased junction leakage current-density) were used to evaluate diffusion barrier properties of the thin films. The leakage current density of p⁺n diodes with the barrier (Ta-O-N) was approximately four orders of magnitude lower than those without barriers after a 30 min, 400 °C back contact anneal. The Ta-O-N barriers were stable up to 500 °C, 30 min anneals. However, this was not the case for the 600 °C anneal. RBS spectra and cross-sectional transmission electron microscopy of as-deposited and vacuum annealed samples of Ag/barrier (Ta-O-N)/Si indicate the absence of any interfacial interaction between the barrier and substrate (silicon). The failure of the Ta-O-N barriers has been attributed to thermally induced stresses, which cause the thin film to crack at elevated temperatures.     

用于Cu互连阻挡层的非晶Ni-Al薄膜研究

以非晶Ni-Al薄膜作为Cu互连的阻挡层材料,采用射频磁控溅射法构架了Cu/Ni-Al/Si的异质结.利用原子力显微镜、X射线衍射仪和四探针测试仪研究了不同温度下高真空退火样品的表面形貌、微观结构与输运性质.实验发现非晶Ni-Al薄膜在高达750℃的退火温度仍能保持非晶结构,各膜层之间没有明显的反应和互扩散存在,表明了非晶Ni-Al薄膜具有良好的阻挡效果,可以用作Cu互连的阻挡层材料.     

Self-forming AlOx layer as Cu diffusion barrier on porous low-k film

The copper diffusion barrier properties of an ultrathin self-forming AlO_x layer on a porous low-k film have been investigated. Cu-3 at.% Al alloy films were directly deposited onto porous low-k films by co-sputtering, followed by annealing at various temperatures. Transmission electron microscopy micrographs showed that a ∼ 5 nm layer self-formed at the interface after annealing. X-ray photoelectron spectroscopy analysis showed that this self-formed layer was Al₂O₃. Sharp declines of the Cu and Si concentrations at the interface indicated a lack of interdiffusion between Cu and the porous low-k film for annealing up to 600 °C for 30 min. The leakage currents from Cu(Al)/porous low-k/Si structures were similar to as-deposited films even after a 700 °C, 5 min anneal while a Cu sample without Al doping failed at lower temperatures. Adding small amounts of Al to bulk Cu is an effective way to self-form copper diffusion layer for advanced copper interconnects.     

用于Cu互连的Ta/Ti-Al集成薄膜的结构和阻挡性能

应用射频磁控溅射法在(001)Si衬底上制备了Cu(120nm)/Ta(5nm)/Ti-Al(5nm)/Si异质结,借助原子力显微镜(AFM)、X射线衍射(XRD)和四探针测试仪(FPP)等方法研究了Ta(5nm)/Ti-Al(5nm)集成薄膜用作Cu和Si之间阻挡层的结构和性能。研究发现,Cu/Ta/Ti-Al/Si异质结即使经受850℃高温退火后,样品的XRD图中也没有出现杂峰,表明样品各层之间没有发生明显的化学反应。相对于800℃退火的样品,850℃退火样品的表面均方根粗糙度急剧增大,同时方块电阻也增加了一个数量级,表明Ta(5nm)/Ti-Al(5nm)集成薄膜在850℃时,阻挡性能完全失效。由于Ta和Cu之间存在良好粘附性以及Ti-Al强的化学稳定性,Ta(5nm)/Ti-Al(5nm)集成薄膜在800℃以下具有良好的阻挡性能。     

Diffusion barrier performance of amorphous W-Ti-N films in Cu metallization

W-Ti-N films were prepared on a Si wafer by reactive sputter-deposition, followed by a deposition of a Cu thin film by DC magnetron sputtering. The Cu/W-Ti-N/Si samples prepared were annealed at different temperatures under vacuum and then characterized using X-ray diffraction, scanning electron microscopy and auger electron microscopy. The sheet resistivity was determined by four point probe analysis. The results show that the amorphous W-Ti-N film is mainly composed of TiN and W and the crystallization temperature is above 800 °C. W-Ti-N thin films prepared have good thermal stability at 700 °C, but the Cu film tends to agglomerate when the temperature is above 700 °C. A failure mechanism of the diffusion barrier is proposed based on the thermal stress and interface reaction.     

Diffusion barrier properties of AlMoNbSiTaTiVZr high-entropy alloy layer between copper and silicon

The application of an AlMoNbSiTaTiVZr high-entropy alloy film as diffusion barrier for copper metallization has been investigated. The AlMoNbSiTaTiVZr and copper layers are deposited sequentially, without breaking vacuum, onto silicon substrates by DC magnetron sputtering. The AlMoNbSiTaTiVZr films are found to possess a stable amorphous structure due to their high-entropy and limited diffusion kinetics. The AlMoNbSiTaTiVZr high entropy alloy film is determined to prevent copper-silicide formation up to 700 °C for 30 min. Thus, HEAs appear to have potential use as effective diffusion barriers for copper metallization.     

Measurements of the thermal gradient over EB-PVD thermal barrier coatings

Conventional two-layered structure thermal barrier coatings (TBCs), graded thermal barrier coatings (GTBCs) and graded thermal barrier coatings with micropores were prepared onto superalloy DZ22 tube by electron beam physical vapor deposition (EB-PVD). Thermal gradient of the TBCs was evaluated by embedding two thermal couples in the surfaces of the tube and the top coat at different surrounding temperatures with and without cooling gas flowing through the tube. The results showed that higher thermal gradient could be achieved for the GTBCs with micropores compared to the two-layered structure TBCs and GTBCs. However, after the samples were heated at 1050°C, the thermal gradient for the GTBCs with or without micropores decreased with the increase of heating time. On the other hand, the thermal gradient for the TBCs increased with the increase of heating time. Cross-section observations by scanning electron microscopy showed that the change in microstructure was the main reason for the change of the thermal gradient.     

Effect of the molecular weight of polyethylene glycol as single additive in copper deposition for interconnect metallization

Void-free deposition for integrated circuit interconnect with polyethylene glycol (PEG) as the single additive has been developed based on the characteristics of the current-potential responses at an acid copper sulfate bath containing PEG and chloride ions (Cl⁻). Several electrochemical methods were employed, including chronopotentiometry, linear sweep voltammetry and cyclic voltammetry to study the effect of PEG molecular weight on adsorption behaviors and suppression ability of PEG. Field emission scanning electron microscopy was utilized for the characterization of microstructural evolution, related with the suppression ability. The filling capabilities were carried out using acid copper baths containing PEG at various molecular weights, ranging from 3200 to 20,000g mol^− 1. Better filling capacity can be obtained as the molecular weight of PEG increases.     

Composite ceramics thermal barrier coatings of yttria stabilized zirconia for aero-engines

Composite ceramics thermal barrier coatings(TBCs) are widely used in the aero-engines field due to their excellent thermal insulation, which improves the service life and durability of the inherent hot components. The most typical, successful and widely used TBCs material is yttria stabilized zirconia(YSZ). In this paper, fabrication methods, coating structures, materials, failure mechanism and major challenges of YSZ TBCs are introduced and reviewed. The research tendency is put forward as well. This review provides a good understanding of the YSZ TBCs and inspires researchers to discover versatile ideas to improve the TBCs systems.     

Modeling of residual stresses variation with thermal cycling in thermal barrier coatings

Thermal barrier coatings (TBCs) are commonly used as protective coatings for engine metal components to improve performance. Many investigations have shown that residual stresses in TBCs applications play an important role, but the residual stresses are mainly obtained by simulation method. As we know, there are a few analytical solutions of residual stress in TBCs system. In this paper, a new two-dimensional analytical solution has been obtained under the condition of non-linear coupled effects of temperature gradient, thermal fatigue, deposited residual stress, thermally grown oxide (TGO) thickening, elasto-plasticity deformation and creep deformation of TBC. Moreover, the influences of bending moment and curvature on stress variation in TBCs are considered during thermal cycling. The calculated results are in agreement with the prior experimental results.     

Lattice distortion and thermal stability of nano-crystalline copper

Molecular dynamics simulations of high temperature annealing of copper bicrystals with varying grain sizes in nano-meter range have been carried out. Planar 1 1 1-tilt CSL grain boundaries are set. An EAM potential of FS type is used for calculating inter-atomic forces in copper. For comparison, similar simulations for aluminum and tungsten have been conducted. The results show that in the copper bicrystals of present grain boundary geometry, mismatch between the {1 1 1} planes of the neighboring grains occurs at the grain boundary, resulting in a general shear lattice distortion within the grains. The shear strain is inversely proportional to the grain size. The energy of such mismatched grain boundary is found lower than that of the mismatch-free grain boundary. For aluminum such kind of mismatch is much smaller, and for tungsten no such mismatch appears. The nano-sized copper bicrystals with grains smaller than a critical size are found instable at high temperature, where grain boundary motion and atomistic reconstruction lead to annihilation of the grain boundaries after an incubation time.     

Effect of phosphorus on the copper diffusion barrier properties of electroless CoWP films

The properties of electroless CoWP barrier films with different phosphorus contents in Cu/CoWP/Si stacked samples were explored. The Cu/CoWP/Si stacked samples with 30 nm CoWP films, contained about 5.7, 8.2 and 10.8 at.% P, were prepared by electroless deposition, and then annealed in a rapid thermal annealer at a temperature between 300 and 700 °C. The effect of phosphorus content in CoWP film on the barrier properties in preventing copper diffusion and the failure of the Cu/CoWP/Si stacked samples after thermal annealing were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES), and sheet resistance measurement. Increasing the phosphorus content in the electroless CoWP film markedly improves the barrier properties. The failure temperature of Cu/CoWP/Si increased from 500 to 600 °C with the phosphorus content in CoWP film increasing from 5.7 to 10.8 at.%, and the failure of the Cu/CoWP/Si has mainly arisen from the interdiffusion of copper and cobalt during thermal annealing.     

Stored energy, vacancies and thermal stability of ultra-fine grained copper

The stored energy and thermal stability of oxygen-free high conductivity copper processed by equal channel angular pressing up to 16 passes at room temperature was studied by differential scanning calorimetry. Stored energy increased with strain up to four passes, after which it saturated at 0.95 ± 0.05 J/g. This saturation value is 20% higher than from conventional cold rolling. The microstructure of the copper after eight passes was characterized by an average subgrain size of about 0.21 μm and high-angle boundary fraction of about 35%. The contributions to the stored energy from defects were calculated and compared, suggesting that the stored energy mainly originates from boundaries and vacancies. The restoration activation energy after eight passes was between 77 and 80 kJ/mol. The higher stored energy and lower activation energy compared to cold-rolled copper is attributed to excess vacancies.     

Advances on strategies for searching for next generation thermal barrier coating materials

Thermal barrier coating(TBC) materials play important roles in gas turbine engines to protect the Nibased super-alloys from the high temperature airflow damage. High melting point, ultra-low thermal conductivity, large thermal expansion coefficient, excellent damage tolerance and moderate mechanical properties are the main requirements of promising TBC materials. In order to improve the efficiency of jet and/or gas turbine engines, which is the key of improved thrust-to-weight ratios and the energysaving, significant efforts have been made on searching for enhanced TBC materials. Theoretically, density functional theory has been successfully used in scanning the structure and properties of materials, and at the same time predicting the mechanical and thermal properties of promising TBC materials for high and ultrahigh temperature applications, which are validated by subsequent experiments. Experimentally,doping and/or alloying are also widely applied to further decrease their thermal conductivities. Now, the strategy through combining theoretical calculations and experiments on searching for next generation thermal insulator materials is widely adopted. In this review, the common used techniques and the recent advantages on searching for promising TBC materials in both theory and experiments are summarized.     

Formation of diffusion barrier on the Ni-based superalloy by low-pressure pre-oxidation

The formation of diffusion barrier on the Ni-based superalloy substrate by low-pressure pre-oxidation is studied in this paper. The pre-oxidation was carried out by heating the substrate under a low-oxygen partial pressure with electron beam of the electron beam physical vapor deposition (EB-PVD) facility. The effect of diffusion barrier was investigated by both isothermal and cyclic oxidations at 1373 K, and the oxidation-kinetic curves were then obtained. The diffusion barrier mainly contains NiO, α,θ-Al₂O₃ and Cr₂O₃, and has a thickness of 185-225 nm. The investigation indicates that the barrier could partially inhibit the interdiffusion of elements of the superalloy substrate and then improve the oxidation-resistance performance of thermal barrier coatings (TBCs) to some extent. However, the difference of thermal cycling lifetime between TBCs samples with and without diffusion barrier is not extremely visible.     

Development of a thermal barrier material using combustion synthesis

The present investigation employs combustion synthesis as a method to produce a functionally graded Ni₃Al/Al₂O₃+TiB₂ composite material for use as a thermal barrier system for nickel-based alloys at elevated temperatures. Starting materials were Ni, Al, TiO₂ and B₂O₃ in powder form. Adiabatic thermodynamic calculations used to determine the maximum theoretical temperature reached during combustion suggest that up to 1600 K may be reached in the Ni+Al metallic layer, easily sufficient to initiate the ceramic-based reaction. The latter reaction is predicted to reach 3000 K. Experiments were first conducted in an induction furnace to establish conditions necessary for combustion to occur. Subsequent experimentation, with applied pressure during combustion, was conducted in a Gleeble 1500 thermomechanical test unit modified to accept the samples of interest. Characterisation of the combustion products by means of hardness measurements, X-ray diffraction, scanning electron microscopy and electron probe microanalysis confirmed that the products were Ni₃Al and Al₂O₃+TiB₂. Also, the mechanical integrity was unchanged after 10 thermal cycles in the modified Gleeble unit. Finally, the coating thickness required to keep a Ni-based substrate below 850°C in a 1100°C environment is estimated to be 1.8 mm, based on thermal conductivity calculations using a finite element method.     

High thermal stability,electrical and optical properties of amorphous IGZO film by coating ultrathin amorphous ITO film as barrier layer

As one kind of well known amorphous transparent conductive oxide films, In–Ga–Zn–O (IGZO) based films were broadly used as electric functional layer in optoelectronic devices. As IGZO film is sensitive to temperature and oxygen, and its electrical and optical properties may probably be deteriorated after subsequent high temperature and air atmosphere. In this work, amorphous indium tin oxide (ITO) layer with two adjustable type of thickness were employed to improve the thermal stability of IGZO films. The doubled ITO/IGZO films were deposited on glass by magnetron sputtering and annealed at high temperatures subsequently to investigate its thermal stability. Accordingly, the crystal structure, optical and electrical properties of ITO/IGZO films were further studied. The XRD results demonstrated that the annealed IGZO films could keep amorphous structure, and the ITO/IGZO films were consisted of uniform small particles which showed comparable dense structure and closely integration with the glass substrate. Furthermore, the sheet resistance results indicated that the increased thickness of top ITO film could suppress oxygen and improve thermal stability of electrical property. Moreover, the transmittance in the visible range was about 85%, and showed a little increase after annealing. The protective ITO layer was found to keep improved thermal stability, good electrical and optical properties at temperatures up to 550 °C.