Reaction between amorphous Si and crystalline Al in Al/Si and Si/Al bilayers: microstructural and thermodynamic analysis of layer exchange

Aluminium-induced crystallization of amorphous silicon (a-Si) in Al/Si and Si/Al bilayers was studied upon annealing at 250 °C by X-ray diffraction and Auger electron spectroscopy. The Al/a-Si bilayers and a-Si/Al bilayers were prepared by sputter deposition on single-crystal silicon wafers with a silicon-oxide film on top. During the isothermal annealing a layer-exchange process occurred in both types of bilayers. A continuous polycrystalline silicon (poly-Si) film was formed within, and thereby gradually replacing, the initial Al metal layer. The sublayer sequence in the original bilayer influenced the speed of the poly-Si formation and the layer-exchange process. After annealing, the Al fiber texture in the as-deposited bilayers had become stronger, the Al crystallites had grown laterally, and the macrostress in the Al layer had been released. The amorphous Si layer had crystallized into an aggregate of nanocrystals with {111} planes parallel to the surface, with a crystallite size of about 15–25 nm. An extensive analysis of the Gibbs energy change due to annealing showed that the layer exchange may be promoted by the release of elastic energy and grain growth for the Al phase. PACS 05.70.Jk; 61.43.Dq; 68.35.Rh; 61.72.Cc; 68.55.Jk     

On the Discontinuity of Polycrystalline Silicon Thin Films Realized by Aluminum-Induced Crystallization of PECVD-Deposited Amorphous Si

Crystallization of glass/Aluminum (50, 100, 200 nm) /hydrogenated amorphous silicon (a-Si:H) (50, 100, 200 nm) samples by Aluminum-induced crystallization (AIC) is investigated in this article. After annealing and wet etching, we found that the continuity of the polycrystalline silicon (poly-Si) thin films was strongly dependent on the double layer thicknesses. Increasing the a-Si:H/Al layer thickness ratio would improve the film microcosmic continuity. However, too thick Si layer might cause convex or peeling off during annealing. Scanning electron microscopy (SEM) and Energy Dispersive X-ray spectroscopy (EDX) are introduced to analyze the process of the peeling off. When the thickness ratio of a-Si:H/Al layer is around 1 to 1.5 and a-Si:H layer is less than 200 nm, the poly-Si film has a good continuity. Hall measurements are introduced to determine the electrical properties. Raman spectroscopy and X-ray diffraction (XRD) results show that the poly-Si film is completely crystallized and has a preferential (111) orientation.     

AlCl3-induced crystallization of amorphous silicon thin films

It is reported that the direct contact between Al and amorphous silicon (a-Si) enhances the crystallization of a-Si films. But the polycrystalline silicon (poly-Si) films crystallized by the direct contact of Al metal film suffer the problems of rough surface. In our study, we utilized the AlCl₃ vapor during the a-Si films deposition instead of Al metal film to enhance crystallization. X-ray diffraction (XRD) shows that the AlCl₃ vapor so successfully enhanced the crystallization of a-Si films that the crystallization was completed in 5 h at 540 °C. And the orientation of the poly-Si film deposited with AlCl₃ vapor is much more random than that of annealed with Al metal under layer. But the average grain size is much larger than that. Moreover, the surface of the AlCl₃-induced crystallized poly-Si film was much smoother than that of the Al-induced poly-Si film. The Al and Cl incorporation into the poly-Si film was confirmed using X-ray photoelectron spectroscopy (XPS) and found that the quantity of Al and Cl incorporated into the Si film was below the detection limit of XPS.     

Origins of interdiffusion, crystallization and layer exchange in crystalline Al/amorphous Si layer systems

Aluminium-induced crystallization of amorphous silicon (a-Si) in Al/a-Si and a-Si/Al bilayers was studied upon annealing at low temperatures between 165 and 250 °C, by X-ray diffraction (XRD) and Auger electron spectroscopy (AES). Upon annealing the inward diffusion of Si along grain boundaries in Al takes place, followed by crystallization of this diffused Si. Continuous annealing leads to (more or less) layer exchange in both types of bilayers. The change in bulk energy of the Al phase (release of macrostress and microstrain, increase of grain size) promotes the occurrence of layer exchange, whereas changes in surface and interface energies counteract the layer exchange.     

退火对Ge诱导晶化多晶Si薄膜结晶特性的影响

本文采用磁控溅射法, 衬底温度500 ℃下在硅衬底上分别制备具有Ge填埋层的a-Si/Ge 薄膜和a-Si薄膜, 并进行后续退火, 采用Raman光谱、X射线衍射、原子力显微镜及场发射扫描电镜等对所制薄膜样品进行结构表征. 结果表明, Ge有诱导非晶硅晶化的作用, 并得出以下重要结论: 衬底温度为500 ℃时生长的a-Si/Ge薄膜, 经600 ℃退火5 h Ge诱导非晶硅薄膜的晶化率为44%, 在相同的退火时间下退火温度提高到700 ℃, 晶化率达54%. 相同条件下, 无Ge填埋层的a-Si薄膜经800 ℃退火5 h薄膜实现晶化, 晶化率为46%. 通过Ge填埋层诱导晶化可使在相同的条件下生长的非晶硅晶薄膜的晶化温度降低约200 ℃. Ge诱导晶化多晶Si薄膜在Si(200)方向具有高度择优取向, 且在此方向对应的晶粒尺寸约为76 nm. 通过Ge诱导晶化制备多晶Si薄膜有望成为制备高质量多晶Si薄膜的一条有效途径.     

Microwave-induced low-temperature crystallization of amorphous Si thin films

Microwave heating was utilized for low-temperature crystallization of amorphous Si (a-Si) films. Microwave heating lowered the annealing temperature and reduced the annealing time. By microwave heating the hydrogen in the amorphous films was diffused out long before the nucleation of polycrystalline Si (poly-Si). The combination of NiCl₂ coating on a-Si and microwave heating greatly reduced crystallization temperature. The combination of metal-induced crystallization and microwave-induced crystallization might be a useful technique to develop high-quality poly-Si films at low temperature.     

Aluminium-induced crystallization of amorphous silicon films deposited by DC magnetron sputtering on glasses

Amorphous silicon (a-Si) and hydrogenated amorphous silicon (a-Si:H) films were deposited by DC magnetron sputtering technique with argon and hydrogen plasma mixture on Al deposited by thermal evaporation on glass substrates. The a-Si/Al and a-Si:H/Al thin films were annealed at different temperatures ranging from 250 to 550 °C during 4 h in vacuum-sealed bulb. The effects of annealing temperature on optical, structural and morphological properties of as-grown as well as the vacuum-annealed a-Si/Al and a-Si:H/Al thin films are presented in this contribution. The averaged transmittance of a-Si:H/Al film increases upon increasing the annealing temperature. XRD measurements clearly evidence that crystallization is initiated at 450 °C. The number and intensity of diffraction peaks appearing in the diffraction patterns are more important in a-Si:H/Al than that in a-Si/Al layers. Results show that a-Si:H films deposited on Al/glass crystallize above 450 °C and present better crystallization than the a-Si layers. The presence of hydrogen induces an improvement of structural properties of poly-Si prepared by aluminium-induced crystallization (AIC).     

Ultrathin amorphous Ti–Al film used as a diffusion barrier for copper metallization

The viability of ultrathin amorphous Ti–Al film (～4 nm) as a diffusion barrier layer between Cu and Si for the application in Si-based ultra-large scale integration (ULSI) has been investigated. The Cu/Ti–Al/Si heterostructures are annealed in a high vacuum at various temperatures. There is no impurity peaks in the X-ray diffraction patterns for the samples up to annealing temperature of 800 ^°C, although the island-like grains were observed on the surface of the 800 ^°C annealed sample due to dewetting and agglomeration of the Cu film. No inter-reactions can be found from the images of transmission electron microscopy and Ti–Al is still amorphous after high-temperature annealing. These results indicate that Ti–Al film can effectively separate Cu from Si at high temperatures, and that the amorphous ultrathin Ti–Al film can be a very good barrier layer for Cu metallization.     

Si-W/Si/SiO2/Si(100)的横截面电子显微镜研究

本文用横截面电子显微镜法分析了Si-W/Si/SiO₂/Si(100)在440—1000℃退火后的晶化过程,以及各个界面的变化情况.发现Si-W合金膜中,WSi₂并未优先在表面、界面处形成晶核.当退火温度不高于700℃时,反应在合金膜内发生,表面、界面起伏和缓.退火温度高达800—1000℃时,界面、表面出现原子扩散,造成剧烈的界面起伏;表面则出现小的热沟槽,Si/SiO₂界面也出现高分辨电子显微镜才能观察到的起伏.表面、界面的原子迁移的动力来源于晶界与表面、界面张力.由于SiO₂中Si—O键很稳定,不易发生Si和O在界面处的互扩散,所以Si/SiO₂界面起伏很小. 关键词：     

Microstructural changes in amorphous Si/crystalline Al thin bilayer films upon annealing

Microstructural changes occurring in a sputter deposited Si (150 nm, amorphous)/Al (50 nm, crystalline); {111} fibre textured bilayer, upon annealing at 523 K for 60 min in a vacuum of 2.0×10^-4 Pa, were analyzed employing X-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, atomic force microscopy and focused-ion beam imaging. After the annealing the Al and Si sublayers had largely exchanged their locations in the bilayer; i.e. the Si layer was adjacent to the substrate after annealing. Simultaneously, the amorphous Si layer had crystallized into an aggregate of {111} oriented nanocrystals, with a crystallite size of about 15 nm. The Al layer, now adjacent to the surface, had formed a uniformly net-shaped layer in association with an increase of the surface roughness. Upon this rearrangement, the already initially present Al {111} fibre texture had become stronger, the Al crystallites had grown laterally and the macrostress in the Al layer had relaxed. An extensive analysis of thermodynamic driving forces for the transformation indicated that the largest gain in energy upon transformation is due to the crystallization of the amorphous Si. The only identifiable driving force for the layer exchange appears to be the release of elastic energy upon the rearrangement of the Si and Al phases in the layer. PACS 61.43.D; 61.72.C; 62.40; 65.70; 68.55.J; 68.60.BThis revised version was published online in September 2004. Due to technical problems the PDF of the previous version was incomplete.     

The influence of boron concentrations on structural properties in disorder silicon films

In this work we present a detailed structural of a series of B-doped hydrogenated microcrystalline silicon (μc-Si:H) films deposited by plasma-enhanced chemical vapor deposition (PECVD) and B-doped polycrystalline silicon (poly-Si) films produced by step-by-step laser crystallization process from amorphous silicon. The influence of doping on the structural properties and structural changes during the sequential crystallization processes were monitored by Raman spectroscopy. Unlike μc-Si:H films, that consist of a two-phase mixture of amorphous and ordered Si, partially crystallized sample shows a stratified structure with polycrystalline silicon layer at the top of an amorphous layer. With increasing doping concentration the LO-TO phonon line in poly-Si shift to smaller wave numbers and broadens asymmetrically. The results are discussed in terms of resonant interaction between optical phonons and direct intraband transitions known as a Fano resonance. In μc-Si:H films, on the other hand, the Fano effect is not observed. The increase of doping in μc-Si:H films suppressed the crystalline volume fraction, which leads to an amorphization in the film structure. The structural variation in both μc-Si:H and poly-Si films leads to a change in hydrogen bonding configuration.     

Pd adsorption on Si(1 1 3) surface: STM and XPS study

Pd-induced surface structures on Si(1 1 3) have been studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). In the initial process of the Pd adsorption below 0.10 ML, Pd silicide (Pd₂Si) clusters are observed to form randomly on the surface. By increasing the Pd coverage to 0.10 ML, the clusters cover the entire surface, and an amorphous layer is formed. After annealing the Si(1 1 3)-Pd surface at 600 °C, various types of islands and chain protrusions appears. The agglomeration, coalescence and crystallization of these islands are observed by using high temperature (HT-) STM. It is also found by XPS that the islands correspond to Pd₂Si structure. On the basis of these results, evolution of Pd-induced structures at high temperatures is in detail discussed.     

Low-Temperature (<100°C) Poly-Si Thin Film Fabrication on Glass

Polycrystalline silicon (poly-Si) thin-film is fabricated on Al-coated planar glass substrates at the temperature below 100°C, using aluminium-induced crystallized (AIC) amorphous silicon (a-Si) deposited by dc-magnetron sputtering under an electric field. The properties of NA poly-Si films (AIC of dc-magnetron sputtered silicon non-annealing) are characterized by Raman spectroscopy and x-ray diffraction (XRD) spectroscopy. A narrow and symmetrical Raman peak at a wave number of about 521cm^-1 is observed for samples, showing that the films are fully crystallized. XRD spectra reveal that the films are preferentially (111) oriented. Furthermore, the XRD spectrum of the sample prepared without electric field does not show any XRD peaks for poly-Si, which only appears at about 38°for Al (111) orientation. It is indicated that the electric field plays an important role in crystallization of poly-Si during the dc-magnetron sputtering. Thus, high quality poly-Si film can be obtained at low temperature and separate post-deposition step of AIC of a-silicon can be avoided.     

铝诱导非晶硅薄膜的场致低温快速晶化及其结构表征

铝诱导非晶硅薄膜晶化可以降低退火温度、缩短退火时间，是制备多晶硅薄膜的一种重要方法.在此基础上，通过在退火过程中加入电场加速了界面处硅、铝原子间的互扩散，实现了非晶硅薄膜的快速低温晶化.实验结果表明，外加电场，退火温度为400℃，退火时间为60min时，薄膜的晶化率大于60％；退火温度为450℃退火时间为30min时，薄膜已经呈现明显的晶化现象；退火温度为500℃退火时间为15min时，薄膜的x射线多晶峰强度与非晶峰强度之比为未加电场的3—4倍. 关键词： 非晶硅薄膜 多晶硅薄膜 外加电场     

The influence of a poly-Si intermediate layer on the crystallization behaviour of Ni-Ti SMA magnetron sputtered thin films

Shape memory alloy Ni-Ti thin films as sputtered are amorphous if the substrate is not intentionally heated during deposition. Therefore, these films have to be heat treated to induce crystallization in order to exhibit the shape-memory effect. Several films have been prepared by dc magnetron sputtering and then studied concerning the influence of the type of substrate (single-crystal Si, polycrystalline Si) on the crystallization kinetics and the final structure. The structural development of the films during crystallization (at a constant temperature of 430 °C) has been studied by X-ray diffraction in grazing incidence geometry off-plane (GIXD) at a synchrotron-radiation beamline. These experiments allow us to establish a correlation between the deposition conditions and the kinetics of crystallization. For films deposited at an electrode distance of 70 mm on a Si(100) substrate, a longer crystallization time is needed compared with films obtained at 40 mm, for otherwise fixed deposition parameters. The analysis of the nucleation kinetics by using the Johnson–Mehl–Avrami equation leads to exponents between 2.6 and 3. The presence of an intermediate layer of poly-Si drastically enhances the crystallization process. Additionally, ex situ annealing of identical samples at 500 °C during 1 h and complementary characterization of the structure and morphology of the films by cross-sectional transmission electron microscopy and selected-area electron diffraction were performed. The temperature dependence of the electrical resistivity was measured, identifying the phase transformation temperature ranges. An increase of the overall resistivity with the precipitation of Ni₄Ti₃ has been detected. Results obtained by X-ray reflectometry and GIXD suggest that during crystallization excess nickel is driven into an amorphous region ahead of the crystal/amorphous interface, thus leading to a higher concentration of Ni at the surface and further precipitation of Ni₄Ti₃. PACS 81.15.Cd; 61.10.Nz; 68.55.Jk     

Enhanced metal-induced-crystallization of hydrogenated amorphous silicon by electric field

This article demonstrates that metal-induced crystallization of PECVD grown amorphous silicon can be enhanced by the application of an external electrical field. Results from the observation of the Si(111) XRD peak height of the thermally annealed Si/Al/glass structure show that at very high vertical electric field (up to 7000 V/cm) no enhancement on aluminum induced crystallization of a-Si is found, whereas a clear enhancement of crystallization can be observed for the horizontal electric field as low as 100 V/cm. Mechanisms are proposed to explain such an observation, and it is suggested that the vertical Al/Si interdifussion process is prolonged under horizontal electric fields because of the presence of electron-collision caused by Al or AlSi_x ions, which allows more nucleation to take place. PACS 61.10.Kw; 81.10.Jt; 81.40.-z     

In situ spectromicroscopic study of nickel induced lateral crystallization of amorphous silicon thin film using SPESM

Scanning photoelectron spectromicroscopy (SPESM) has been used to study nickel metal induced lateral crystallization (Ni-MILC) of amorphous silicon (a-Si) thin films, produced by in situ annealing of vacuum deposited Ni patterned films on a-Si. The spatial variations in the chemical composition of the Ni-MILC of a-Si were directly imaged. High-resolution photoemission spectra of both Si 2p and Ni 3p core levels and valence band were used to evaluate morphological changes and chemical interactions. Our direct spectromicroscopic characterization clearly shows that the Ni-MILC process in UHV leads to the lower crystallization temperature and a faster crystallization speed of a-Si, and a poly-Si film with high-crystallinity can be obtained. A unified mechanism for the enhanced growth rate of the high-crystallinity poly-Si film produced by Ni-MILC in UHV is proposed.     

Comparative investigation of unipolar resistance switching effect of Pt/Mg0.6Zn0.4O/Pt devices with different electrode patterns for nonvolatile memory application

In this report, we study crystallization and Raman spectral and transmission electron microscopy (TEM) changes in amorphous and nanocrystalline Si. Micro-Raman spectra combined with TEM show that considerable crystallization occurs in a-Si:H and a-Si(Al) (the structure of aluminum-diffused amorphous Si/Al/c-Si), but no additional crystallization was observed for nc-Si:H, after the exposure to a laser or accelerating electrons. Meanwhile, moving toward lower or higher energy for a-Si:H and nc-Si:H, by contrast, the Raman shift appeared for a-Si(Al) as if it were for single-crystalline Si, in which it remained constant at one energy, as the laser intensity increased or decreased.     

Interface Evolution of TiN/Poly Si as Gate Material on Si/HfO2 Stack

TiN as gate electrode in Si/HfO₂/TiN/poly-Si stack is evaluated after the postmetal annealing treatments. Interface reactions are investigated usingelectron-energy-loss spectroscopy and x-ray photoelectron spectroscopy. The work function of the TiN/poly-Si stack shows strong dependence on the postmetal deposition annealing conditions. The interfacial product in TiN/poly-Si interface is inferred as TiSiN, which is beneficial for the whole high-k stack since TiSiN possesses higher work function compared to TiN and poly-Si.     

Electrical and ellipsometry study of sputtered SiO2 structures with embedded Ge nanocrystals

SiO₂ layer structures with a middle layer containing Ge nanocrystals were prepared by sputtering on n- and p-type Si substrates, and by consecutive annealing. Ge content in the middle layer was varied in the range of 40-100%. Most of the structures exhibited low breakdown voltages. The current through the structures became Schottky-like after breakdown. However, some p-type samples showed a considerable memory effect. It was obtained by spectroscopic ellipsometry that the middle layer contains amorphous Ge phase as well. The results also suggest intermixing of the layers during the sputtering and/or the annealing process.