High energy xenon ion beam assisted deposition of TiN film and its industrial application

TiN films have been synthesized by ion beam assisted deposition employing xenon ions with an energy of 40 keV. The formed TiN films were investigated systematically in respect of surface morphology, composition, structure and mechanical properties. Then, they were applied to surface protection of scoring dies. Atomic force microscopy and interferometric observation showed that the TiN film is relatively smooth. Rutherford backscattering spectroscopy analysis indicated that few xenon atoms are retained in the film. It was found by transmission electron microscopy and X-ray diffraction experiments that the formed TiN is a nanocrystal (< 10 nm) film and exhibits slightly (200) preferred orientation. An ultra low load microhardness indentor system was used to examine the plastic property of the film and a hardness of 2300 kgf mm^–2 was calculated from the measured data. Scratch tests showed that the adhesion of TiN film deposited by ion beam assisted deposition at ambient temperature is superior to that of high temperature physical vapour deposited (PVD) TiN film. Both a pin-on-dick tribotest and SRV wear test revealed that the wear resistance of the specimen can be greatly improved by TiN coating. A five times increase of service life of different scoring dies could be obtained by protection of TiN coating.     

新型铁电薄膜底电极TiN的结构与电性能研究

自制了导电的TiN薄膜底电极,并在其上制备了铁电钽酸锂薄膜,测试了TiN薄膜电阻随热处理温度变化的关系,以及TiN底电极上钽酸锂薄膜的介电和漏电特性.实验结果表明,当热处理温度低于700℃时,TiN薄膜的电阻率小于0.004QΩ·cm,具有良好的导电性,可用作钽酸锂薄膜底电极;TiN底电极上钽酸锂薄膜的漏电电流大于Pt衬底上钽酸锂薄膜的漏电电流;N2气氛下在TiN底电极上结晶的钽酸锂薄膜的介电损耗远大于O2气氛下结晶的钽酸锂薄膜的介电损耗;氧缺位是TiN底电极上钽酸锂薄膜介电损耗大和漏电大的主要原因.     

Auto-organizing ZrAlN/ZrAlTiN/TiN multilayers

The possibility to form secondary phases during annealing of a two-phase ternary nitride material is studied. By the use of an initial multilayer structure the new phase forms at the sublayer interfaces, resulting in an enhanced layering of the film. This is illustrated by a ZrAlN/TiN thin film where formation of a cubic structure ZrTi(Al)N phase at the sublayer interfaces improves the mechanical properties after annealing above 900 °C.     

Effects of metal stacks and patterned metal profiles on the electromigration characteristics in super-thin AlCu interconnects for sub-0.13 μm technology

The electromigration (EM) characteristics of super-thin aluminum-copper alloy (AlCu) interconnects for sub-0.13 μm complementary metal-oxide-semiconductor logic technology were investigated by varying the AlCu underlayers and etched sidewall profile of AlCu wire. Super-thin AlCu wire with a Ti/TiN underlayer and a smooth etched sidewall profile was confirmed to have the best EM resistance in terms of the mean-time-to-failure (MTTF) and the failure distribution. The Ti/TiN underlayer is believed to lead to a longer MTTF by dramatically reducing the effective current density at the super-thin AlCu film in the entire of EM test line with a smaller formation of TiAl₃ at the TiN/AlCu interface. The smooth etched sidewall profile is considered to induce a steeper EM failure distribution by removing the early EM failure at the rough sidewall of aluminum. In terms of the location of EM-induced voids, the super-thin AlCu film inhibits the formation of EM-induced voids directly under the tungsten via by insignificant current crowding at the via-metal line corner.     

Microstructural characteristics and mechanical properties of magnetron sputtered nanocrystalline TiN films on glass substrate

Nanocrystalline TiN thin films were deposited on glass substrate by d.c. magnetron sputtering. The microstructural characteristics of the thin films were characterized by XRD, FE-SEM and AFM. XRD analysis of the thin films, with increasing thickness, showed the (200) preferred orientation up to 1·26 μm thickness and then it transformed into (220) and (200) peaks with further increase in thickness up to 2·83 μm. The variation in preferred orientation was due to the competition between surface energy and strain energy during film growth. The deposited films were found to be very dense nanocrystalline film with less porosity as evident from their FE-SEM and AFM images. The surface roughness of the TiN films has increased slightly with the film thickness as observed from its AFM images. The mechanical properties of TiN films such as hardness and modulus of elasticity (E) were investigated by nanoindentation technique. The hardness of TiN thin film was found to be thickness dependent. The highest hardness value (24 GPa) was observed for the TiN thin films with less positive micro strain.     

用DC-PCVD装置在绝缘体蓝宝石上沉积TiN

用直流等离子体化学气相沉积装置(简称 DC-PCVD)在绝缘体蓝宝石上沉积了与基体结合力强的 TiN,探讨了机制及影响成膜的因素。     

磁控溅射制备TiN薄膜影响因素的研究

采用磁控溅射法在硅基片表面沉积TiN薄膜,研究了溅射气压、氮气流量、氩气流量、溅射电流等溅射参数对TiN薄膜导电性能的影响.实验参数采用正交设计法选取,经模糊分析得出,所考察的因素对薄膜光催化性能的影响次序由大到小依次为溅射电流、气体流量、溅射气压.进一步研究影响最大的溅射电流对薄膜结构与电学性能的影响,结果发现:溅射电流的增大使溅射粒子的动能随之增大,薄膜生长加快;薄膜的电阻率存在最小值.     

Diffusion barrier property of TiN and TiN/Al/TiN films deposited with FMCVD for Cu interconnection in ULSI

Flow modulation chemical vapor deposition (FMCVD) with titanium tetrachloride (TiCl₄) and ammonia (NH₃) is effective for depositing titanium nitride (TiN) films with conformal morphology, good step coverage, low electrical resistivity, and low chlorine residual contamination. It means that FMCVD TiN film is a good candidate of diffusion barriers for copper interconnection technology in ULSI. But the diffusion barrier property of FMCVD TiN film against Cu diffusion has not been confirmed. So, firstly, we deposited Cu (100 nm)/FMCVD TiN (25 nm)/Si multilayer films and investigated the thermal stability of Cu/TiN/Si structure. Vacuum annealing was done at 400, 500, 550 and 600 °C. For films annealed for 30 min at 400 °C, Cu diffused through the TiN layer and formed copper silicides on the surface of Si substrates. Therefore, FMCVD films formed under such conditions are unsatisfactory diffusion barriers. To enhance the diffusion barrier property of FMCVD TiN films, we used sequential deposition to introduce a monolayer of Al atoms between two TiN films. Etch-pit tests showed that for TiN films with Al interlayer, Cu diffusion through the barrier occurred at 500 °C and that is 100 °C higher than TiN film without Al interlayer. Al atoms formed AlO_x with oxygen atoms present in the TiN films as impurities, and fill up the grain boundaries of TiN film, thereby blocking the diffusion of Cu atoms.     

Si(100)衬底上激光分子束外延制备高质量TiN薄膜

采用激光分子束外延(LMBE)技术在Si(100)上制备了高质量的TiN薄膜.对N2分压和激光脉冲能量对TiN薄膜晶体结构、生长模式和表面形貌影响的研究表明,TiN单晶薄膜呈(200)择优取向,在N2分压为10-1 Pa时,薄膜的结晶度高且表面平整致密.随着N2分压的增加,TiN(200)衍射峰向低角度移动.激光脉冲能...     

Room-temperature growth of AlN/TiN epitaxial multi-layer by laser molecular beam epitaxy

We have fabricated epitaxial AlN thin films at room temperature on sapphire (0001) substrates with a TiN (111) epitaxial buffer layer by pulsed laser deposition in ultra-high vacuum (laser molecular beam epitaxy method). The TiN buffer layers were also fabricated at room temperature. Four-circle X-ray diffraction analysis and reflection high-energy electron diffraction results indicate the heteroepitaxial structure of AlN (0001)/TiN (111)/sapphire (0001) with the epitaxial relationship of AlN [10-10]||TiN [11-2]||sapphire [11-20]. The surface of the room-temperature grown AlN film was found to be atomically flat, reflecting the nano-stepped surface of ultrasmooth sapphire substrates. Then, we could achieve the room-temperature epitaxial growth of [AlN/TiN] multi-layer. The temperature dependence of resistivity of the AlN/TiN multi-layer film was also measured.     

Morphology of TiN coating produced by laser ablation

The morphology of TiN thin films on a steel surface produced by the process of laser ablation has been investigated. The process involves material removal from a titanium target by means of an ultraviolet excimer pulse laser. Both the target and the steel substrate are in an ammonia atmosphere and therefore the titanium atoms react with the nitrogen under the influence of a laser-induced plasma, and the product, which is TiN, is deposited on the surface of the steel. The investigation revealed that at the beginning of the process the TiN film is uniform; however, with increasing number of pulses, small micrometre-sized particles begin to appear on the surface and after a large number of pulses all the surface is covered with these particles.     

Microstructure and optical properties of cubic AlN/TiN bilayers deposited by laser molecular beam epitaxy

AlN/TiN bilayers were deposited on Si(100) substrates with varying laser pulse energy by laser molecular beam epitaxy (LMBE) technique, and their growth mode, crystal structure and optical properties were investigated. The results indicated that atomically flat TiN single films and AlN/TiN bilayers with layer-by-layer growth mode were successfully grown on Si(100) substrates at optimal laser pulse energy. Both TiN and AlN in the grown bilayers exhibited the NaCl-type cubic structure with the same (200) preferred orientation, showing an excellent epitaxial relationship. TiN single film was more reflective in the infrared range and presented a small transparent window centered at wavelength of 404 nm. Reflectance spectrum of AlN film on top of TiN indicated the sharp absorption at about 246 nm, yielding a bandgap energy of 5.04 eV comparable to the theoretical calculation of bulk cubic AlN, but scarcely reported by the experimental data.     

Alteration of internal stresses in SiO2/Cu/TiN thin films by X-ray and synchrotron radiation due to heat treatment

A break of wiring by stress-migration becomes a problem with an integrated circuit such as LSI. The present study investigates residual stress in SiO₂/Cu/TiN film deposited on glass substrates. A TiN layer, as an undercoat, was first deposited on the substrate by arc ion plating and then Cu and SiO₂ layers were deposited by plasma coating. The crystal structure and the residual stress in the deposited multi-layer film were investigated using in-lab. X-ray equipment and a synchrotron radiation device that emits ultra-high-intensity X-rays. It was found that the SiO₂ film was amorphous and both the Cu and TiN films had a strong {1 1 1} orientation. The Cu and TiN layers in the multi thick (Cu and TiN:1.0 μm)-layer film and multi thin (0.1 μm)-layer film exhibited tensile residual stresses. Both tensile residual stresses in the multi thin-layer film are larger than the multi thick-layer film. After annealing at 400 °C, these tensile residual stresses in both the films increased with increasing the annealing temperature. Surface swelling formations, such as bubbles were observed in the multi thick-layer film. However, in the case of the multi thin-layer films, there was no change in the surface morphology following heat-treatment.     

在室温条件下制备高质量纳米结构TiN薄膜研究

在室温条件下,利用磁过滤等离子体在单晶硅和不锈钢表面上制备了性能优异的纳米结构TiN薄膜.运用原子力显微镜和掠角入射X射线衍射仪对其结构与形貌进行了表征,利用纳米压痕仪测量了TiN薄膜的硬度和弹性模量.结果表明:TiN薄膜表面光滑,致密,无柱状晶;TiN晶粒的平均尺寸为50nm,薄膜硬度达50 GPa,是传统CVD和PVD技术沉积氮化钛的两倍多;XRD衍射试验表明,纳米TiN的衍射角都普遍向小角度移动,TiN晶粒沿(111)择优生长.     

直流反应磁控溅射法制备氮化钛薄膜

研究了采用直流反应磁控溅射法制备TiN薄膜的工艺条件。研究发现：在保持其它工艺参数不变的条件下,溅射的TiN薄膜在不同温度区域存在的物相不同,薄膜的主要成分是多晶立方相TiN,240℃附近是薄膜择优取向由（111）向（200）转变的临界点。随着基底温度升高,薄膜表面粗糙度先变小后变大,沉积最佳基底温度值是330℃,该温度下薄膜的粗糙度最小,膜层致密均匀,没有大尺寸缺陷且光洁度好。     

反应溅射TiN纳米晶薄膜的结构特征和耐蚀性

利用直流反应溅射技术在不锈钢和硅基体上沉积了TiN纳米晶薄膜,采用场发射扫描电镜(FESEM)、X射线衍射(XRD)和电化学阻抗谱(EIS)技术研究了薄膜的表面形貌、相结构和耐蚀性与偏压的关系。结果表明,TiN薄膜的表面结构明显取决于所施加的偏压,适当提高偏压有利于获得细小、均匀、致密和光滑的膜层。XRD分析发现,TiN薄膜为面心立方结构,其择优取向为(111)面。实验显示,对应0V和-35V偏压的薄膜为欠化学计量比的,而偏压增加至-70V和-105V时的薄膜为化学计量比的TiN。EIS结果表明,较高偏压下的TiN薄膜几乎在整个频率范围内均表现为容抗特征,其阻抗模值明显高于低偏压下的膜层,这主要与较高偏压下的薄膜具有相对致密的微结构有关。较低偏压的TiN薄膜因结构缺陷较多其耐蚀性低于基体不锈钢。EIS所揭示的薄膜结构特征与FESEM观测结果一致。可见,减少穿膜针孔等结构缺陷有利于改善反应溅射TiN纳米晶薄膜耐蚀性。     

Microstructure, chemistry and coating properties of ion-plated TiN on type 304 stainless steel

Characterization of TiN coatings on type 304 stainless steel was carried out using a Zeiss EM 902A energy filtering transmission electron microscope equipped with an electron energy loss spectroscopy (EELS) detector. TiN thin films were produced by a hollow cathode discharge ion plating coater. It was found by plan-view transmission electron microscopy that the microstructure of the TiN coatings is thickness dependent. The grain size of TiN ranges from 88 nm at the coating surface down to 9 nm near the TiN/steel interface. In addition, the TiN surface layer shows some degree of texture, but the subsurface and internal TiN layers are mainly equiaxial and randomly oriented. Chemical analysis by EELS shows that the relative oxygen content increases linearly from the TiN surface to the TiN/steel interface, whereas the relative nitrogen content first decreases slowly and then drops rapidly near the interface. The presence of a Ti₂N phase and the deficiency of nitrogen near the TiN/steel interface suggest that the early-deposited TiN is nonstoichiometric. By the periodic cracking method, the ultimate shear stress at the TiN/steel interface and the residual stress in the TiN thin film were estimated to be 2.2 GPa and 12.8 GPa, respectively.     

Microstructure and Tribological Behavior of Stripe Patterned TiN Film Prepared with Filtered Cathodic Vacuum Arc Deposition (FCVAD)

This paper describes an experimental investigation into the influence of the stripe interspace and applied load on the tribological behavior of stripe patterned TiN films. The stripe patterned TiN films are deposited on an H13 steel surface by masked deposition with the filtered cathodic vacuum arc discharge (FCVAD) technique. The surface micro morphology, chemical composition, crystal structure, and mechanical properties of the films is characterized using 3D white light interferometry, scanning electron microscopy (SEM), X‐ray diffractometry (XRD), and a nano‐indentation tester, respectively. The tribological performance of patterned TiN is measured using a UMT‐5 tribometer, and the friction and wear mechanisms are analyzed, compared with that of the full TiN film and H13 steel substrate. The results show that the stripe patterned TiN films has better tribological properties than the full TiN film. These results are attributed to the synergistic effect between the surface pattern and the TiN film. The stripe interspace and the applied load has a more significant effect on the wear rate of the stripe patterned TiN films than the coefficient of friction of their friction pairs. A further study, however, is needed to analyze the relationship between the applied load and the wear rates of the stripe patterned TiN films.

     

结构调制超硬Ti/TiN纳米多层膜的制备及其尺寸效应

使用多弧离子镀技术在高速钢基体上制备了调制周期为5~40 nm的Ti/TiN纳米多层膜,用扫描电子显微镜(SEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)、纳米压痕仪和划痕仪等手段表征薄膜的微观结构和性能,研究了调制周期对Ti/TiN纳米多层膜性能的影响,并讨论了在小调制周期条件下Ti/TiN纳米多层膜的超硬效应和多弧离子镀技术对纳米多层膜硬度的强化作用。结果表明,与单层TiN相比,本文制备的Ti/TiN纳米多层膜分层情况良好,薄膜均匀致密,没有明显的柱状晶结构,TiN以面心立方结构沿(111)方向择优生长。随着调制周期的减小薄膜的硬度呈现先增大后减小的趋势,并在调制周期为7.5 nm时具有最大的硬度42.9 GPa和H/E值。这表明,Ti/TiN在具有最大硬度的同时仍然具有良好的耐磨性和韧性。Ti/TiN纳米多层膜的附着力均比单层TiN薄膜的附着力高,调制周期为7.5 nm时多层膜的附着力为(58±0.9) N。     

Texture and sheet resistance of Al alloy thin films on Ti and TiN thin films

Ti films prepared by ionized physical vapor deposition (I-PVD) and TiN films prepared by metalorganic chemical vapor deposition (MOCVD) were examined as the underlayers of the Al interconnect films. The crystallographic texture of the Al films and the sheet resistance of the thin-film stacks were investigated at various thicknesses of the Ti or TiN thin film. The sheet resistance of the thin-film stacks was also measured after annealing at 400 °C in an N₂ ambient. For the I-PVD Ti underlayer, the excellent texture of the Al (1 1 1) was obtained even on a 5-nm thick Ti film. However, the sheet resistance of the multilayer structure increased after the annealing due to the reaction between Al and Ti. MOCVD TiN layers between the Ti film and the Al film could suppress the Al–Ti reaction without severe degradation of the Al (1 1 1) texture. Excellent texture of the Al film was obtained with thin MOCVD TiN films below 5 nm.