Cu互连中Ta/Ta-N和Ti/Ta-N双层膜的扩散阻挡性能比较

采用磁控溅射法在SiO2/Si基底上沉积Cu/Ta/Ta-N及Cu/Ti/Ta-N薄膜,在高纯的Ar/H2气氛保护下对样品进行快速热退火处理,用XRD、SEM、EDS及四探针电阻测试仪(FPP)等分析测试方法对Ta/Ta-N和Ti/Ta-N双层薄膜的热稳定性及互扩散阻挡性能进行了比较分析。结果表明,当退火温度低于700℃时,Cu/Ta/Ta-N/SiO2/Si和Cu/Ti/Ta-N/SiO2/Si多层膜结构表面平整,方阻值均比较小(Cu/Ta/Ta-N/SiO2/Si约为0.175Ω/□,Cu/Ti/Ta-N/SiO2/Si约为0.154Ω/□);当退火温度到达700℃时,Cu/Ta/Ta-N/SiO2/Si试样开始出现Ta2O5和Cu3Si,由于Cu向基底扩散打破Si-Si和Si-O键,Si、O经扩散通道分别与Cu、Ta反应生成了Cu3Si和Ta2O5,表明Ta/Ta-N阻挡层开始失效;而Cu/Ti/Ta-N/SiO2/Si试样的Cu/Ti相界面形成了很薄的扩散溶解层——Cu4Ti、Cu4Ti3与Cu3Ti2,有力地阻断Cu向基底扩散的通道,从而提高了Ti/Ta-N双层膜的阻挡性能,使Ti/Ta-N双层膜对Cu的有效阻挡温度高达700℃。因此,Ti/Ta-N双层膜是一种良好的扩散阻挡层。     

缓冲层Ta对退火Co/Cu/Co薄膜微观结构和界面互扩散的影响

用直流磁控溅射法在Si/SiO₂基底上制备了Co/Cu/Co薄膜和加入缓冲层的Ta/Co/Cu/Co薄膜,用扫描电子显微镜、原子力显微镜、X射线衍射和俄歇电子能谱研究了薄膜的微观结构、表面形貌、织构和界面互扩散现象。结果表明:退火后薄膜中均存在{111}和{002}衍射峰,加入缓冲层Ta后,Co/Cu/Co薄膜的衍射峰强度明显增强,并存在较强的{111}纤维织构,薄膜表面孔洞及粗糙度大幅减小。退火后薄膜界面处产生互扩散现象,层状结构被破坏。缓冲层Ta提高了薄膜与基底材料间的润湿性,可有效缓解界面互扩散现象。     

Cu／SiO2/Si（100）体系中Cu和Si的扩散和界面反应

室温下,利用磁控溅射方法在P型Si(100)衬底上沉积了铜(Cu)膜.采用X射线衍射(XRD)和卢瑟福背散射(RBS)分析了未退火以及在不同温度点退火后的样品,研究了Cu/SiO3/Si(100)体系的扩散和界面反应.RBS分析得出对于Cu/SiO2/Si(100)体系,当退火温度高于350℃时,才产生明显的扩散,并且随着温度的升高,体系扩散越明显;当退火温度在450℃以下时,XRD没有测得铜硅化合物生成;当温度到500℃时才有铜硅化合物生成.这比已有文献报道的温度低.     

(Pb0.90La0.10)Ti0.975O3/LaNiO3薄膜的射频磁控溅射制备和性能研究

采用射频磁控溅射技术,以LaNiO3(LNO)作为过渡层,在SiO2/Si(100)、Pt(111)/Ti/SiO2/Si(100)衬底上分别获得了(100)、(110)取向的(Pb0.90La0.10)Ti0.975O3(PLT)铁电薄膜.研究了LNO/Pt(111)/Ti/SiO2/Si(100)和LNO/SiO2/Si(100)基底对PLT薄膜微结构和铁电性能的影响.实验结果表明,与在LNO/Pt(111)/Ti/SiO2/Si(100)基底上沉积的(110)取向的PLT薄膜相比较,在LNO/SiO2/Si(100)基底上沉积的高度(100)取向的PLT薄膜具有更好的微结构和更高的剩余极化强度,其2Pr为40.4μC/cm2.     

掺杂Ti的纳米CrSi_2薄膜的制备

利用多靶磁控溅射设备交替沉积Cr、Ti和Si层,并通过随后的真空退火处理,制备了掺杂Ti的CrSi2薄膜。交替沉积薄膜500℃退火2h,薄膜中除含有(Cr,Ti)Si2相外,还有部分残留的沉积Si相和少量反应生成的CrSi相;退火时间增加,沉积Si相和CrSi相减少而(Cr,Ti)Si2相增多;500℃退火6h及以上时,薄膜中仅有(Cr,Ti)Si2相。测量薄膜X射线衍射峰半高宽,利用谢乐公式估算薄膜平均晶粒尺寸表明,退火时间从2h增加到8h,薄膜中(Cr,Ti)Si2相晶粒尺寸由68nm近似线性增加到81nm。退火获得的(Cr,Ti)Si2薄膜具有纳米结构和(111)面单一取向。随着掺杂Ti原子分数的增加,薄膜X射线衍射谱中(Cr,Ti)Si2(111)晶面衍射角逐渐向低角度方向移动,这反映(Cr,Ti)Si2相的晶格常数a和c逐渐增大。晶格常数的变化与掺杂Ti的原子分数近似呈线性关系,这是结构中半径较大的Ti原子替换半径较小的Cr原子所造成的。计算分析显示,单晶Si(100)上(Cr,Ti)Si2(111)晶面外延生长是它们的界面晶格畸变能较低的结果;Ti原子分数增加,(Cr,Ti)Si2薄膜的(111)晶面择优取向程度下降。     

Ti/Si(100)样品在快速退火(RTA)时的界面反应的研究

运用俄歇电子能谱(AES)、X射线光电子能谱(XPS)以及卢瑟福背散射谱(RBS)研究了Ti/Si(100)样品在快速热退火(RTA)过程中的界面反应机理及物种分布。研究结果表明,Ti/Si(100)样品在600℃快速热退火10s后,界面上的钛和硅就发生了明显的界面反应,形成了TiSi_2金属硅化物相。在750℃RTA后,TiSi_2相已基本形成完善,再提高RTA温度,TiSi_2相增加甚少。快速热退火过程不同于一般的慢退火过程,主要通过TiSi_2晶格传递Si,从而促使界面处的钛和硅的继续反应。界面扩散的速度很快,TiSi_2物相的形成速度由Ti和Si的反应速度限制,不受Si扩散效应的影响。此外,俄歇线形分析还揭示了,在硅化物的形成过程中,钛硅物相在各界面层中的存在形式。     

透明导电AZO/Cu双层薄膜制备及其性能

采用直流磁控溅射方法在玻璃衬底上室温生长了AZO/Cu双层薄膜,Cu层厚度控制在9nm,研究了AZO层厚度对薄膜电学和光学性能的影响。当AZO层厚度为20～80nm时,AZO/Cu双层薄膜具有良好的综合光电性能,方块电阻为12～14Ω/sq,可见光平均透过率为70～75%,品质因子为2×10-3～5×10-3Ω-1。AZO/Cu双层薄膜可以观察到Cu（111）和ZnO（002）的XRD衍射峰。通过退火研究表明,AZO/Cu双层薄膜的光电性能可在400℃下保持稳定,具有良好的热稳定性。本研究制备的透明导电AZO/Cu双层薄膜具有室温制程、综合光电性能良好、结晶性能较好、稳定性高的优点,可以广泛应用于光电器件透明电极及镀膜玻璃等领域。     

Ti种子层对Cu薄膜的微观织构和表面形貌的影响

用磁控溅射法制备无种子层的Cu薄膜和加入Ti作为种子层的Ti/Cu薄膜,用电子背散射衍射技术(EBSD)研究了无种子层的Cu薄膜及有Ti种子层的Ti/Cu薄膜的微观织构,并用原子力显微镜(AFM)观察了两种薄膜的表面形貌。结果表明,加入Ti作为种子层增强了Cu薄膜的{111}纤维织构,对薄膜生长有很好的外延作用。同时,加入Ti种子层可降低退火处理后薄膜内退火孪晶的产生几率,但是在退火过程中使孔洞出现。     

微波热处理在钛的硅化工艺中的应用

采用微波等离子体退火方法使溅射的金属Ti膜与Si(111)衬底发生固相反应,直接生成低阻态的金属硅化物薄膜,XRD检测显示最终生成的C54相TiSi2在Si(111)衬底上有明显的织构,证明了微波等离子体退火应用于钛的硅化工艺中的可行性.     

几种无限供应的金属/硅体系离子束混合相变

研究了五种无限供应的 Bilayer 膜金属/硅体系中(Ni/Si,Cu/Si,Nb/Si,Mo/Si,Ti/Si),因离子束注入引起的界面原子交混及相变过程。界面温度和注入离子剂量显著影响薄膜相变,在生成各种金属 Si 化物及固溶体时,反应温度和生长激活能大大降低,相变动力学过程与热退火反应不尽相同,诱导离子和基体取向对成相生长也有影响。讨论了相应微观机理。     

铜与硅之间W/Mo-N薄膜的扩散阻挡层性能

研究了铜与硅之间W／Mo-N薄膜的扩散阻挡性能。在Si(100)基片上利用反应溅射沉积一层Mo-N薄膜,然后再利用直流溅射在Mo-N上面沉积Cu／W薄膜。样品在真空下退火,并利用四点探针、X射线衍射分析、扫描电镜分析、俄歇电子能谱原子深度剖析等测试方法研究了Cu／W／Mo-N／Si的热稳定性及W／Mo-N薄膜对铜与硅的扩散阻挡性能。实验分析表明,Cu／W／Mo-N／Si结构具有非常好的热稳定性,在600℃退火30min仍未发生相变,并能有效的阻挡铜与硅之间的扩散。     

Barrier capability of Zr–N films with titanium addition against copper diffusion

Zr–Ti–N film prepared by sputtering deposition has been employed as a potential diffusion barrier for Cu metallization. It is thought that the existing states of Ti and Zr in the films are Ti–N and Zr–N phase in Zr–Ti–N films. Material analysis by XRD, XPS and sheet resistance measurement reveal that the failure of Zr–N film is mainly due to the formation of Cu₃Si precipitates at the Zr–N/Si interface by Cu diffusion through the grain boundaries or local defects of the Zr–N barrier layer into Si substrate. In conjunction with sheet resistance measurement, XRD and XPS analyses, the Cu/Zr–Ti–N/Si contact system has high thermal stability at least up to 700 °C. The incorporation of Ti atoms into Zr–N barrier layer was shown to be beneficial in improving the thermal stability of the Cu/barrier/Si contact system.     

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.     

Characteristics of post-annealed SrTiO3 thin films prepared by mirror-confinement-type ECR plasma sputtering

SrTiO₃ films were synthesized on Pt/Ti/SiO₂/Si multilayer substrates by mirror-confinement-type ECR plasma sputtering without substrate heating. All films were found to be well crystallized at a substrate temperature below 450 K. A low temperature post-annealing of the films by electromagnetic-wave radiation drastically improved the crystallographic and electric properties of Pt/SrTiO₃/Pt/Ti/SiO₂/Si capacitors. The crystallinity of the films indicated little variation by post-annealing, but irradiation of electromagnetic wave was confirmed to be effective for decreasing the post-annealing time and temperature. The electric properties of films annealed without Pt upper electrodes were better than those with them, and the film dielectric constant reached a value of 260, which is nearly equal to the bulk one, at an annealing temperature of 573 K.     

Characteristics of post-annealed SrTiO3 thin films prepared by mirror-confinement-type ECR plasma sputtering

SrTiO₃ films were synthesized on Pt/Ti/SiO₂/Si multilayer substrates by mirror-confinement-type ECR plasma sputtering without substrate heating. All films were found to be well crystallized at a substrate temperature below 450 K. A low temperature post-annealing of the films by electromagnetic-wave radiation drastically improved the crystallographic and electric properties of Pt/SrTiO₃/Pt/Ti/SiO₂/Si capacitors. The crystallinity of the films indicated little variation by post-annealing, but irradiation of electromagnetic wave was confirmed to be effective for decreasing the post-annealing time and temperature. The electric properties of films annealed without Pt upper electrodes were better than those with them, and the film dielectric constant reached a value of 260, which is nearly equal to thebulk one, at an annealing temperature of 573 K.     

热处理温度对铁电薄膜底电极Pt和Pt／Ti物相与形貌的影响

随着热处理温度上升，在ＳｉＯ２／Ｓｉ衬底上溅射的Ｐｔ、Ｐｔ／Ｔｉ电极中，构成Ｐｔ薄膜的晶粒由小变大，由分布均匀到晶粒局部聚集，最后分离成小岛。Ｔｉ层可提高Ｐｔ薄膜与基片间的粘附性和高温下的稳定性。快速热处理可提高Ｐｔ薄膜在高温下的连续性。并研究了Ｐｔ薄膜对ＰＬＴ铁电薄膜的成品率和分散性的影响。     

Investigations of failure mechanisms at Ta and TaO diffusion barriers by secondary neutral mass spectrometry

One of the most important processes in Cu metallization for highly integrated circuits is to fabricate reliable diffusion barriers. Recently, thin films made of refractory metals and their compounds have been widely used in solid-state electronics as barriers because of their good electric properties, favourable thermal properties and chemical stability. Thermal stability of Tantalum (Ta) and Tantalum-oxide (TaO_x) layers as a diffusion barrier in Si/Ta/Cu, Si/TaO_x/Cu and Si/Ta-TaO_x/Cu systems have been investigated. Si/Ta (10 nm)/Cu (25 nm)/W (10 nm), Si/TaO_x (10 nm)/Cu (25 nm)/W (10 nm) and Si/Ta (5 nm)TaO_x (5 nm)/Cu (25 nm)/W (10 nm) thin layers were prepared by DC magnetron sputtering. A tungsten cap layer was applied to prevent the oxidation of the samples during the annealing process. The samples were annealed at various temperatures (473 K-973 K) in vacuum. Transmission Electron Microscopy, X-ray diffraction, X-Ray Photoelectron Spectroscopy and Secondary Neutral Mass Spectrometry were used to characterize the microstructure and diffusion properties of the thin films. Our results show that at the beginning phase of the degradation of the Si/Ta/Cu system Ta atoms migrate through the copper film to the W/Cu interface. In the Si/TaO_x/Cu system the crystallization of TaO and the diffusion of Si through the barrier determine the thermal stability. The Ta-TaO bilayer proved to be an excellent barrier layer between the Si and Cu films up to 1023 K. The observed outstanding performance of the combined film is explained by the continuous oxidation of Ta film in the TaO_x-Ta bilayer.     

Effects of molybdenum, silver dopants and a titanium substrate layer on copper film metallization

Annealing of 100 nm-thick Cu, Cu(Mo) and Cu(Ag) films was carried out to investigate the effect of dopant atoms on the films. Molybdenum (Mo) and silver (Ag) were selected as immiscible dopants for out-diffusion studies. A thermally grown SiO₂ layer and a sputtered Ti layer were used as substrates. The dopant and substrate effects were characterized in terms of surface morphology, resistivity, preferred orientation, and diffusional characteristics. The lowest observed resistivity was 2.32 · cm in the Cu(Ag) film, which was lower than that in a pure Cu film of the same thickness. Ag addition enhanced the surface morphology and thermal stability of the Cu(Ag) films. The highest thermal stability was obtained in the case of a Cu(Mo)/Ti film which maintained film integrity to 800°C. A Ti substrate enhanced Cu(111) texture growth. A highly oriented Cu(111)-texture was obtained in the Cu(Mo)/Ti films. Cu diffusion through the Ti layer was limited in the (111)-textured Cu(Mo)/Ti films, which showed good potential as a diffusion barrier.     

Investigation of thermal stability of Mo thin-films as the buffer layer and various Cu metallization as interconnection materials for thin film transistor-liquid crystal display applications

Cu/Mo/Si multi-layer structures were fabricated to investigate diffusion behaviors and thermal stability between Cu and Mo. Physical vapor deposition (PVD), chemical vapor deposition, electroplating and electrolessplating were used to grow 100 nm thick Cu films as interconnection materials, and radio-frequency sputtering system was introduced to grow 37.5 nm thick Mo films as a buffer layer. All Cu/Mo/Si multi-layer specimens were annealed at 350 to 700 °C for 30 min. When the annealing temperature was over 600 °C, the Cu diffused through Mo into Si, and the Cu₃Si phase and Mo-Si intermetallic compounds formed at the Mo/Si interface. The diffusion mechanism is the grain boundary diffusion. The results indicate that Cu film deposited by PVD had best crystallinity, lower roughness, large adhesive energy and resistivity. The values of the resistivity, diffusion activity energy and large adhesive energy are 5.47 μΩ-cm, 0.948 eV and 2.46 N/m, respectively.     

Comparative study of Cu-Zr and Cu-Ru alloy films for barrier-free Cu metallization

The properties of Cu-Zr and Cu-Ru alloy films were comparatively studied to evaluate their potential use as alloying elements. Cu alloy films were deposited on SiO₂/Si substrates by magnetron sputtering. Samples were subsequently annealed and analyzed by four-point probe measurement, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and Auger electron spectroscopy. X-ray diffraction data suggest that Cu film has preferential (111) crystal orientation and no extra peak corresponding to any compound of Cu, Zr, Ru, and Si. According to transmission electron microscopy results, Cu grains grow in size for both systems but the grain sizes of the Cu alloy films are smaller than that of pure Cu films. These results indicate that Cu-Zr film is suitable for advanced barrier-free metallization in terms of interfacial stability and lower resistivity.