Dopant effects on the thermal stability of FUSI NiSi

The thermal stability of fully silicided (FUSI) NiSi with arsenic or boron doping on silicon on insulator (SOI) was investigated. After the stacks were subjected to a typical back-end of line (BEOL) thermal annealing in a N₂ ambient, abnormal oxidation of As doped FUSI NiSi stacks is observed by X-ray photoelectron spectroscopy (XPS), and confirmed by high-resolution transmission electron microscopy (HRTEM). X-ray diffraction (XRD) results show Ni-rich phases like Ni₃Si are formed due to abnormal oxidation of FUSI NiSi. In contrast to As doped stacks, no phase transformation nor abnormal oxidation are observed for B doped stacks under similar annealing. However, backside secondary ion mass spectrometry (SIMS) results indicate B penetration through a 3 nm SiON layer into the Si channel after N₂ annealing for 4 h at 400 °C. There is no evidence for Ni diffusion into the Si channel for B doped stacks. However, Ni penetration into the Si channel is observed for As doped stacks due to the enhancement of abnormal oxidation of FUSI NiSi.     

The improvement of thermal stability of nickel silicide by adding a thin Zr interlayer

This is the first report of a technique for inserting a thin Zr interlayer into a nickel film to improve the thermal stability of the silicide formed from this film. The sheet resistance of resulting Ni(Zr)Si film was lower than 2 Ω/□. X-ray diffraction and Raman spectral analysis showed that only the silicides low resistance phase (NiSi), rather than high resistance phase (NiSi₂), was present in the sandwich structure. This proves that the incorporation of a thin Zr interlayer into NiSi delayed the occurrence of NiSi₂ phase and widened the upper boundary of silicide formation window by about 100 °C. These experimental results could be explained by Gibbs free energy theory. Furthermore, Ni(Zr)Si/Si Schottky diodes were fabricated by rapid thermal annealing at 650, 700, 750 and 800 °C in order to study the I–V characteristics of the SBD diodes. The barrier height generally fixed at 0.63 eV, and the ideality factor was close to 1. These results show that Ni(Zr)Si film is a favorable local interconnection and contact silicide material.     

A Hafnium interlayer method to improve the thermal stability of NiSi film

The effect of a thin Hafnium interlayer on the thermal stability of NiSi film has been investigated. Both X-ray diffraction and Raman spectra show that no high resistivity NiSi₂ appears in the Hf-additioned films which were post-annealed at temperatures ranging from 600 °C to 800 °C. Auger electron spectroscopy and Rutherford back scattering show that the Hf interlayer has moved to the top of the film after rapid thermal annealing, working as the diffusion barrier for upper Ni atoms. The three-dimensional surface morphology by atom force microscopy shows that the agglomeration of NiSi is effectively suppressed, which is attributed to the barrier effect of the Hf interlayer. The fabricated Ni(Hf)Si/Si Schottky diodes still displays good current-voltage characteristics even after annealed at temperatures varied from 650 °C to 800 °C, which further show that the Hf interlayer can improve the thermal stability of NiSi.     

Thermal stability of Ni silicide films on heavily doped n and p Si substrates

Electrical and structural properties of Ni silicide films formed at various temperatures ranged from 200 °C to 950 °C on both heavily doped n⁺ and p⁺ Si substrates were studied. It was found that surface morphology as well as the sheet resistance properties of the Ni silicide films formed on n⁺ and p⁺ Si substrates at the temperatures higher than 600 °C were very different. Agglomerations of Ni silicide films on n⁺ Si substrates begin to occur at around 600 °C while there is no agglomeration observed in Ni silicide films on p⁺ Si substrates up to a forming temperature of 700 °C. It was also found that the phase transition temperature from NiSi phase to NiSi₂ phase depend on substrate types; 900 °C for NiSi film on n⁺ Si substrate and 750 °C for NiSi film on p⁺ Si substrate, respectively. Our results show that the agglomeration is, especially, important factor in the process temperature dependency of the sheet resistance of Ni silicides formed on n⁺ Si substrates.     

Electrical characteristics of thin Ni2Si,NiSi, and NiSi2 layers grown on silicon

We have determined the resistivity, carrier concentration, and Hall mobility as a function of thickness (700–3000 Å) of Ni₂Si, NiSi, and NiSi₂ layers formed by vacuum annealing at 270÷v300°C, ≈ 400°C, and ≈ 800°C, respectively, of nickel films vacuum-deposited on a silicon substrate (111 n-type and 100 p-type Si ρ ≈ 1KΩ). The layer thicknesses were measured by 2 MeV⁴He⁺ backscattering spectrometry. The silicide phase was confirmed by x-ray measurements. The electrical measurements were carried out using van der Pauw configuration. We found the electrical transport parameters to be independent of the film thickness within the experimental uncertainty. The Hall factors were assumed to be unity. The majority carriers are electrons in NiSi and holes in Ni₂Si and NiSi₂. The resistivity values are 24±2, 14±1, and 34±2 μΩcm, the electron concentrations are 9±3, 10 and 7±1, and ≈ 2 × 10²² cm^?3, and the Hall mobilities are 3±1, ≈ 4.5 and 6, and ≈ 9 cm²/Vs for Ni₂Si, NiSi (〈100〉 and 〈111〉), and NiSi₂, respectively. The systematic error in the measured values caused by currents in the high resistivity substrate is estimated to be less than 6% for the Hall coefficient. The results show that Ni₂Si, NiSi, and NiSi₂ layers formed by a thin film reaction are electrically metallic conductors, a result which concurs with those reported previously (1) for refractory metal silicides. The Hall mobility increases with the Si content in the silicide. The electron concentration is lowest for NiSi₂ leading to the highest resistivity for the epitaxial phase of NiSi₂.     

The effects of doping impurities and substrate crystallin on the formation of nickel suicides on silicon at 200–280° C

Transmission electron microscopy and Auger electron spectroscopy have been applied to investigate the effects of doping impurities and substrate crystallinity on the formation of nickel suicides at 200–280° C in nickel thin films on silicon. The systems investigated included samples with as-implanted BF₂, B, F, As, and P and recrystallized (001) Si as well as P-doped low pressure chemical vapor deposited (LP-P) and B-doped plasma enhanced chemical vapor deposited (PE-B) amorphous silicon substrates. In samples annealed at 220–280° C, substantial amounts of epitaxial NiSi₂ were found to form on crystalline structure of BF₂, B and F implanted samples to various extents at different temperatures. High resolution lattice imagings of cross-sectional samples showed that the epitaxial NiSi₂/Si interfaces are coherent. No NiSi₂ was detected in all nickel thin films deposited on implantation-amorphous specimens. NiSi₂ epitaxy was found to be a sensitive function of annealing temperature. Good correlation was found between the atomic size factor and resulting stress and NiSi₂ epitaxy at low temperature. The formation of Ni₂Si and NiSi was observed to be influenced by the dopant species and crystallinity of the substrates. The vast difference in inducing the formation of nickel suicides in implantation-amorphous and recrystallized samples is likely due to variations in initial structure and/or dopant distribution. The finding that bothn-type andp-type dopants influenced the formation of Ni₂Si and NiSi suggested that they may be related to the electrical activity of the doping species in recrystallized samples. NiSi, possessing one of the lowest resistivity among all metal silicides, was found to be the only phase formed in all implantation-amorphous as well as LP-P and PE-B amorphous silicon samples annealed at 280° C. Nickel thin film appears to be an attractive candidate for the metallization of amorphous silicon devices.     

Improvement of thermal stability of Ni silicide on N-Si by direct deposition of group III element (Al, B) thin film at Ni/Si interface

The direct deposition of a thin Al or B layer at Ni/Si interface was proposed as a new method to solve a problem of degraded thermal stability of Ni silicide on heavily doped N⁺-Si substrates. Significant improvement of thermal stability evaluated by the sheet resistance vs. silicidation temperature properties was observed. The improvement is attributed to suppression of agglomeration of the silicide layers. The Al layer was effective only when it was located at the Ni/Si interface before the silicidation process. The deposited Al and B layers under Ni layer segregated at the surface after the silicidation process. The use of B layer was preferable to control the phase transition from NiSi to NiSi₂.     

Study of NiSi/Si Interface by Cross-Section Transmission Electron Microscopy

采用不同硅化工艺制备了NiSi薄膜并用剖面透射电镜(XTEM)对样品的NiSi/Si界面进行了研究.在未掺杂和掺杂(包括As和B)的硅衬底上通过物理溅射淀积Ni薄膜,经快速热处理过程(RTP)完成硅化反应.X射线衍射和喇曼散射谱分析表明在各种样品中都形成了NiSi.还研究了硅衬底掺杂和退火过程对NiSi/Si界面的影响.研究表明:使用一步RTP形成NiSi的硅化工艺,在未掺杂和掺As的硅衬底上,NiSi/Si界面较粗糙;而使用两步RTP形成NiSi所对应的NiSi/Si界面要比一步RTP的平坦得多.高分辨率XTEM分析表明,在所有样品中都形成了沿衬底硅〈111〉方向的轴延-NiSi薄膜中的一些特定晶面与衬底硅中的(111)面对准生长.同时讨论了轴延中的晶面失配问题.     

Ti中间层对超薄Ni膜硅化反应特性的影响

在多种Si衬底上利用离子束溅射淀积超薄Ni膜以及Ni/Ti双层膜，经过快速热退火处理完成薄膜的固相硅化反应，通过四探针法、微区喇曼散射法和俄歇深度分布测试法研究了Ti中间层对Ni硅化反应的影响. 实验结果证明Ti中间层抑制了集成电路生产最需要的NiSi相的形成.     

Improved thermal stability of Ni-silicides on Si:C epitaxial layers

The thermal stability of Ni-silicides on tensily strained in situ P doped Si:C epitaxial layers was evaluated. The baseline Ni silicidation process was shown to be compatible with Si:C Recessed Source-Drain (RSD) stressors for NMOS strain engineering while the thermal stability of NiSi:C contacts was significantly improved compared to NiSi ones. Dominant degradation mechanism was shown to be the transition to the NiSi₂:C phase. It was demonstrated that the Si:C strain level affects the silicide formation but has no significant effect on the NiSi:C thermal stability. A mechanism responsible for the improved thermal stability of NiSi:C silicides is discussed.     

Effects of prolonged annealing on NiSi at low temperature (500°C)

The effects of prolonged annealing (10 h) at low temperature (500°C) have been studied in 20-nm Ni/Si (100) thin films using Rutherford backscattering spectroscopy (RBS), x-ray diffraction (XRD), scanning electron microscopy (SEM) in conjunction with energy-dispersive spectrometry (EDS), and four-point probe techniques. We observe that nickel monosilicide (NiSi) is stable up to 4 h annealing at 500°C. It is also found that, after 6 h and 10 h annealing, severe agglomeration sets in and NiSi thin films tear off and separate into different clusters of regions of NiSi and Si on the surface. Due to this severe agglomeration and tearing off of the NiSi films, sheet resistance is increased by a factor of 2 despite the fact that no NiSi to NiSi₂ transition occurs. It is also observed that, with increasing annealing time, the interface between NiSi and Si becomes rougher.     

NiSi/Si界面的剖面透射电镜研究

采用不同硅化工艺制备了NiSi薄膜并用剖面透射电镜(XTEM)对样品的NiSi/Si界面进行了研究.在未掺杂和掺杂(包括As和B)的硅衬底上通过物理溅射淀积Ni薄膜,经快速热处理过程(RTP)完成硅化反应.X射线衍射和喇曼散射谱分析表明在各种样品中都形成了NiSi.还研究了硅衬底掺杂和退火过程对NiSi/Si界面的影响.研究表明:使用一步RTP形成NiSi的硅化工艺,在未掺杂和掺As的硅衬底上,NiSi/Si界面较粗糙;而使用两步RTP形成NiSi所对应的NiSi/Si界面要比一步RTP的平坦得多.高分辨率XTEM分析表明,在所有样品中都形成了沿衬底硅〈111〉方向的轴延-NiSi薄膜中的一些特定晶面与衬底硅中的(111)面对准生长.同时讨论了轴延中的晶面失配问题.     

一种利用夹层Ta难熔金属提高NiSi薄膜热稳定性的新方法

本文首次给出了一种具有规律性的能用来提高镍硅化物热稳定性的方法.依据此方法,首次摸索出在Ni中掺入夹层金属Ta来提高NiSi硅化物的热稳定性.Ni/Ta/Ni/Si样品经600 ～ 800℃快速热退火后,薄层电阻率保持较小值,约2Ω□.XRD衍射分析结果表明,在600～800℃快速热退火温度下形成的Ni(Ta)S薄膜中...     

In situ X-ray diffraction study of thin film Ir/Si solid state reactions

The solid state reaction between a thin (30 nm) Ir film and different Si substrates (p-type Si(1 0 0), n- and p-type Si(1 1 1), silicon on insulator (SOI) and polycrystalline Si) was studied using a combination of in situ X-ray diffraction (XRD), in situ sheet resistance and laser light scattering measurements. No significant influence of either the dopants or the substrate orientation was detected as a phase formation sequence of IrSi, Ir₃Si₄,Ir₃Si₅ and IrSi₃ was found for all samples. The presence of a thin (<4 nm) amorphous IrSi film at room temperature and its subsequent crystallization could be deduced from the appearance of a broad semi-amorphous diffraction peak in the XRD spectrum around 400 °C. The results were verified using ex situ Rutherford Backscattering Spectroscopy, Scanning Electron Microscopy and 4-point probe measurements on quenched samples. The activation energy of the crystallization process and the silicide growth was determined using a Kissinger analysis on ramp anneals with different ramp rates. In addition, the influence of up to 25 volumetric % (20.5 atomic %) of Ir to the silicide formation in the Ni/Si system was studied on SOI and polycrystalline Si substrates. In the presence of Ir, the temperature range over which the low resistivity NiSi exists, is reduced both through an increase in formation temperature and an earlier consumption by the formation of NiSi₂. After the heat treatment, a continuous distribution of Ir throughout the NiSi₂ phase was detected using X-ray photoelectron spectroscopy depth profiling. A low sheet resistance of was maintained on both substrates up to 900 °C.     

Boron redistribution during reactive diffusion in Ni-Si contacts

The NiSi silicide that forms by reactive diffusion between Ni and Si-rich active regions of nanotransistors is currently used for contacts in nanoelectronics because of its low resistivity. The redistribution of boron during reactive diffusion between Ni (30 nm) and B doped-Si has been investigated by laser assisted wide-angle tomographic atom probe (LAWATAP). Two states were characterized (room temperature and rapid thermal annealing at 450 °C for 1 min).LAWATAP shows that after deposition of Ni (30 nm) at room temperature a very thin film (7 nm) of Ni silicide was formed. The initial boron distribution in silicon is almost unchanged. After a heat treatment in vacuum at 450 °C (1 min) the nickel monosilicide NiSi was formed. Boron distribution at this stage is very different from that at room temperature. Boron is shown to accumulate at NiSi/Si interface due to snowplow effect. Very small amounts of boron were also found in NiSi phase close to the surface.     

Pt层对Ni/Si(100)固相反应NiSi薄膜高温稳定性的增强效应

研究了顺次淀积在Si(100)衬底上的Ni/Pt和Pt/Ni的固相硅化反应．研究发现,当1nm Pt作为中间层或覆盖层加入Ni/Si体系中时,延缓了NiSi向NiSi2的转变,相变温度提高．对于这种双层薄膜体系,800℃退火后,XRD测试未检测到NiSi2相存在;850℃退火后的薄膜仍有一些NiSi衍射峰存在．800℃退火后的薄膜呈现较低的电阻率,在23—25μΩ*cm范围．上述薄膜较Ni/Si直接反应生成膜的热稳定性提高了100℃以上．这有利于NiSi薄膜材料在Si基器件制造中的应用．     

Effect of a thin W, Pt, Mo, and Zr interlayer on the thermal stability and electrical characteristics of NiSi

It is reported that the thermal stability of NiSi is improved by employing respectively the addition of a thin interlayer metal (W, Pt, Mo, Zr) within the nickel film. The results show that after rapid thermal annealing (RTA) at temperatures ranging from 650 °C to 800 °C, the sheet resistance of formed ternary silicide Ni(M)Si was less than 3 Ω/□, and its value is also lower than that of pure nickel monosilicide. X-ray diffraction (XRD) and raman spectra results both reveal that only the Ni(M)Si phase exists in these samples, but the high resistance NiSi₂ phase does not. Fabricated Ni(M)Si/Si Schottky barrier devices displayed good I-V electrical characteristics, with the barrier height being located generally between 0.65 eV and 0.71 eV, and the reverse breakdown voltage exceeding to 40 V. It shows that four kinds of Ni(M)Si film can be considered as the satisfactory local connection and contact material.     

Thickness scaling issues of Ni silicide

Ni silicidation processes without a capping layer and with a TiN capping layer are studied from the point of view of process window, morphology of the resulting silicide, and mechanisms of degradation at higher temperatures. The thermal stability of NiSi films on As- and on B-doped (100) Si substrates was investigated for Ni film thicknesses ranging from 5 to 30 nm. While agglomeration was the mechanism of degradation for the thin films, both morphological changes and transformation to NiSi₂ were possible for thicker films depending on anneal temperature and time. Activation energy of 2.5 eV for NiSi on n+ (100) Si and p+ (100) Si was determined for the process of morphological degradation. The measured temperature and time dependences for the thermal degradation of NiSi films suggest that the activation energy for transformation to NiSi₂ is higher than for morphological degradation.     

High-resolution transmission electron microscopy of silicide formation and morphology development of Ni/Si and Ni/Si<Subscript>1−x</Subscript>Ge<Subscript>x</Subscript>

Nickel-silicide phase formation in the Ni/Si and Ni/Si_1−xGe_x (x=0.20) systems and its correlation with variations in sheet resistance have been studied using high-resolution transmission electron microscopy (HRTEM) and related techniques. Following a 500°C anneal, uniform and low-resistivity NiSi and NiSi_1−xGe_x (x<0.20) crystalline films were formed in the respective systems. Annealed at 900°C, NiSi₂, in the form of pyramidal or trapezoidal islands, is found to replace the NiSi in the Ni/Si system. After a 700°C anneal, threading dislocations were observed for the first time in the Ni/Si_1−xGe_x system to serve as heterogeneous nucleation sites for rapid lateral NiSi_1−xGe_x growth.     

Nickel silicide encroachment formation and characterization

The stability of nickel-based silicides integrated in CMOS circuits has been studied. The evolution of transistor electrical failures is then reported, linked to Ni abnormal migration through different process steps. We have found in our studies that Ni encroachment is not only due to NiSi₂ clusters formation but also to NiSi precipitates formation. Silicon substrate doping, surface preparation, nickel film thickness and the thermal treatments were identified to modify occurrences of this randomly localized phenomenon. Ni-rich phase initial formation is preferable to prevent Ni encroachment even though other upstream process steps for CMOS integration are also key for Ni migration control.