Investigation into layers formed by selective transfer CMP mechanisms with atomic force microscope

To understand mechanisms of chemical mechanical planarization (CMP), an atomic force microscope (AFM) was used to characterize polished layer surfaces formed by selective transfer after a set of polishing experiments. It is know that in the process of friction of two materials and in the presence of own lubricants, wear phenomenon itself manifests as a transfer of material from an element of a friction couple on the other, this phenomenon being characteristic to the selective transfer process. A selective transfer can be safely achieved in a friction couple, if there is a favorable energy, and in the presence of relative movement, if in the friction area is a material made by copper and the lubricant is adequate (glycerin or special lubricant). The forming selective layer on the contact surfaces makes that the friction force to be very low because of the structure formed by selective transfer. To optimize the CMP process, one needs to obtain information on the interaction between the slurry abrasive particles (with the size range of about 30–70 nm) and the polished surface. To study such interactions, we used AFM. Surface analysis of selective layer using the AFM revealed detailed surface characteristics obtained by CMP. Studying the selective layer CMP, of which the predominated one is copper (in proportion of over 85%), we found that the AFM scanning removes the surface oxide layer in different rates depending on the depth of removal and the pH of the solution. Oxide removal happens considerably faster than the copper CMP removal from the selective layer. This is in agreement with generally accepted models of copper CMP. It was found that removal mechanisms depend on the slurry chemistry, potential per cent of oxidizer, and the applied load. This presentation discusses these findings. Both load force and the friction forces acting between the AFM tip and surface during the polishing process were measured. One big advantage of using the AFM tip (of radius about 50 nm) as abrasive silica particle is that we can measure forces acting between the particle-tip and the surface being polished. Here, we report measurement of the friction force while scratching and polishing. The correlation between those forces and removal rate is discussed.     

Models of nanoparticles movement,collision, and friction in chemical mechanical polishing (CMP)

Nanoparticles have been widely used in polishing slurry such as chemical mechanical polishing (CMP) process. The movement of nanoparticles in polishing slurry and the interaction between nanoparticles and solid surface are very important to obtain an atomic smooth surface in CMP process. Polishing slurry contains abrasive nanoparticles (with the size range of about 10–100 nm) and chemical reagents. Abrasive nanoparticles and hydrodynamic pressure are considered to cause the polishing effect. Nanoparticles behavior in the slurry with power-law viscosity shows great effect on the wafer surface in polishing process. CMP is now a standard process of integrated circuit manufacturing at nanoscale. Various models can dynamically predict the evolution of surface topography for any time point during CMP. To research, using a combination of individual nanoscale friction measurements for CMP of SiO₂, in an analytical model, to sum these effects, and the results scale CMP experiments, can guide the research and validate the model. CMP endpoint measurements, such as those from motor current traces, enable verification of model predictions, relating to friction and wear in CMP and surface topography evolution for different types of CMP processes and patterned chips. In this article, we explore models of the microscopic frictional force based on the surface topography and present both experimental and theoretical studies on the movement of nanoparticles in polishing slurry and collision between nanoparticles, as well as between the particles and solid surfaces in time of process CMP. Experimental results have proved that the nanoparticle size and slurry properties have great effects on the polishing results. The effects of the nanoparticle size and the slurry film thickness are also discussed.     

绿色环保化学机械抛光液的研究进展

原子级加工制造是实现半导体晶圆原子尺度超光滑表面的有效途径.作为大尺寸高精密功能材料的原子级表面制造的重要加工手段之一,化学机械抛光(chemical mechanical polishing,CMP)凭借化学腐蚀和机械磨削的耦合协同作用,成为实现先进材料或器件超光滑无损伤表面平坦化加工的关键技术,在航空、航天、微电子等众多领域得到了广泛应用.然而,为了实现原子层级超滑表面的制备,CMP工艺中常采用的化学腐蚀和机械磨削方法需要使用具有强烈腐蚀性和高毒性的危险化学品,对生态系统产生了不可逆转的危害.因此,本文以绿色环保高性能抛光液作为对象,对加工原子量级表面所采用的化学添加剂进行分类总结,详尽分析在CMP过程中化学添加剂对材料表面性质调制的作用机理,为在原子级尺度下改善表面性质提供可参考的依据.最后,提出了CMP抛光液在原子级加工研究中面临的挑战,并对未来抛光液发展方向作出了展望,这对原子尺度表面精度的进一步提升具有深远的现实意义.     

Generation and removal of pits during chemical mechanical polishing process for MgO single crystal substrate

Magnesium oxide (MgO) single crystal is an important substrate for high temperature superconductor, ferroelectric and photoelectric applications. The function and reliability of these devices are directly affected by the quality of polished MgO surface because any defect on the substrate, such as pit or scratch, may be propagated onto device level. In this paper, chemical mechanical polishing (CMP) experiments were conducted on MgO (1 0 0) substrate using slurry mainly comprised of 1-hydroxy ethylidene-11-diphosphonic acid (HEDP) and silica or ceria particles. Through monitoring the variations of the pits topography on substrate surface, generation and removal mechanism of the pits were investigated. The experimental results indicate that the pits were first generated by an indentation or scratch caused by particles in the slurry. If the rate of chemical etching in the defect area is higher than the material removal rate, the pits will grow. If chemical reaction in the defect area is slower than the material removal rate, the pits will become smaller and eventually disappear. Consequently, these findings may provide insight into strategies for minimizing pits during CMP process.     

Electrochemical characterization of surface complexes formed on Cu and Ta in succinic acid based solutions used for chemical mechanical planarization

Open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H₂O₂, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. The data analysis steps are discussed in detail to demonstrate how the D.C. and A.C. electrochemical probes can be combined in the framework of the RDE technique to design and test CMP slurry solutions.     

Tests of surface segregation theory: I. The Ni-5Pt alloy

The surface composition of polycrystalline samples of the binary metallic alloy Ni-5Pt (at%) has been studied as a function of temperature. This alloy is of particular interest as it lies in a relatively unexplored quadrant of a plot of binary alloy surface tension ratios versus atomic size ratios. Such plots have been used to predict which component of a binary alloy will surface segregate and solute (Pt) segregation is anticipated in the present case. Mechanically polished specimens were purged of bulk impurities by prolonged heating and exposure to oxygen. Quantitative Auger data, collected from clean equilibrated surfaces after rapid cooling from elevated temperatures in the range 1050 to 1540 K, showed Pt surface enrichment compared to the bulk composition. The surface composition was temperature dependent with a heat of segregation in the range −10 to −30 kJ mol⁻¹. The expected heat of segregation for this alloy was calculated by assuming that segregation was driven solely by the lowering of surface free energy and the relief of bulk lattice strain. If the strain term is neglected, Ni surface enrichement is predicted but, when both terms are included, Pt enrichment with a heat of segregation of −14 kJ mol⁻¹ is predicted for the Ni-5Pt(100) surface. This value lies within the limits of the experimental data for polycrystalline Ni-5Pt surfaces and it is concluded that the simple theory adequately accounts for the main segregation mechanisms in this type of alloy.     

Ultrasonic flexural vibration assisted chemical mechanical polishing for sapphire substrate

The sapphire substrates are polished by traditional chemical mechanical polishing (CMP) and ultrasonic flexural vibration (UFV) assisted CMP (UFV-CMP) respectively with different pressures. UFV-CMP combines the functions of traditional CMP and ultrasonic machining (USM) and has special characteristics, which is that ultrasonic vibrations of the rotating polishing head are in both horizontal and vertical directions. The material removal rates (MRRs) and the polished surface morphology of CMP and UFV-CMP are compared. The MRR of UFV-CMP is two times larger than that of traditional CMP. The surface roughness (root mean square, RMS) of the polished sapphire substrate of UFV-CMP is 0.83 Å measured by the atomic force microscopy (AFM), which is much better than 2.12 Å obtained using the traditional CMP. And the surface flatness of UFV-CMP is 0.12 μm, which is also better than 0.23 μm of the traditional CMP. The results show that UFV-CMP is able to improve the MRR and finished surface quality of the sapphire substrates greatly. The material removal and surface polishing mechanisms of sapphire in UFV-CMP are discussed too.     

Chemical mechanical planarization of Ge_2Sb_2Te_5 using IC1010 and Politex reg pads in acidic slurry

In the paper, chemical mechanical planarization(CMP) of Ge2Sb2Te5(GST) is investigated using IC1010 and Politex reg pads in acidic slurry. For the CMP with blank wafer, it is found that the removal rate(RR) of GST increases with the increase of pressure for both pads, but the RR of GST polished using IC1010 is far more than that of Politex reg. To check the surface defects, GST film is observed with an optical microscope(OM) and scanning electron microscope(SEM). For the CMP with Politex reg, many spots are observed on the surface of the blank wafer with OM, but no obvious spots are observed with SEM. With regard to the patterned wafer, a few stains are observed on the GST cell, but many residues are found on other area with OM. However, from SEM results, a few residues are observed on the GST cell, more dielectric loss is revealed about the trench structure. For the CMP with IC1010, the surface of the polished blank wafer suffers serious scratches found with both OM and SEM, which may result from a low hardness of GST, compared with those of IC1010 and abrasives. With regard to the patterned wafer, it can achieve a clean surface and almost no scratches are observed with OM, which may result from the high-hardness SiO2 film on the surface, not from the soft GST film across the whole wafer. From the SEM results, a clean interface and no residues are observed on the GST surface, and less dielectric loss is revealed. Compared with Politex reg, the patterned wafer can achieve a good performance after CMP using IC1010.     

Low energy electron diffraction studies of the surfaces of molecular crystals (ice,ammonia, naphthalene,benzene)

Low Energy Electron Diffraction (LEED) has been used to study the surface structures of thin films of molecular crystals. The samples were grown epitaxially on metal single crystal substrates at low temperatures. Both Pt(111) and Ag(111) surfaces were used as substrates in order to identify the influence of the substrate on molecular film structure. Previous observations of ice (0001) and naphthalene (001) surfaces on films grown on Pt(111) substrates [Surface Sci. 55 (1976) 413], were confirmed using the Ag(111) substrate. The NH₃(111) and benzene (111) surfaces were also studied on films grown on either substrate. All observed molecular crystal surfaces showed no evidence of surface reconstruction. To minimize sample charging and electron beam induced damage, LEED experiments were performed on samples of thickness less than 10?10² nm, with low energy electron exposures less than 1 C cm^?2. The maximum thickness and exposure values were characteristic of the particular molecular crystal. The relationship between the structure of the initial adsorbed monolayer and the molecular crystal orientation is discussed.     

Nano-deformation of a Ni-P coating surface after nanoparticle impacts

Chemical mechanical polishing (CMP) has become a primary planarization technique required for the manufacture of a computer hard disk substrate. In CMP, erosive wear, which is regarded as one of the wear mechanisms underlying the interaction between the abrasive particles and polished surfaces, can occur when materials are removed by the surface collision of particles which are carried by a fluid medium. A fundamental understanding of the process in which nanoparticles impact on the surface of the nickel-phosphorous (Ni-P) coating plated on the computer hard disk substrate is important to the control and preventing of surface defects during CMP. In this study, a cylindrical liquid jet containing de-ionized water and SiO₂ nanoparticles impacts obliquely on the surface of Ni-P coating at a speed of 10 m/s. Microscopic examinations of the impacted surface are performed using a high resolution transmission electron microscope, an atomic force microscope, etc. Experimental results indicate that craters and scratches in the surface have taken place after nanoparticle impacts, and crystal grains in nano-scale and an element phosphorus concentration can be found in the sub-surface layer of the impacted surface.     

Ultra-smooth metal surfaces generated by pressure-induced surface deformation of thin metal films

We present a mechanical pressing technique for generating ultra-smooth surfaces on thin metal films by flattening the bumps, asperities, rough grains and spikes of a freshly vacuum deposited metal film. The method was implemented by varying the applied pressure from 100 MPa to 600 MPa on an e-beam evaporated silver film of thickness 1000 Å deposited on double-polished (100)-oriented silicon surfaces, resulting in a varying degree of film smoothness. The surface morphology of the thin film was studied using atomic force microscopy. Notably, at a pressure of ～600 MPa an initial silver surface with 13-nm RMS roughness was plastically deformed and transformed to an ultra-flat plane with better than 0.1 nm RMS. Our demonstration with the e-beam evaporated silver thin film exhibits the potential for applications in decreasing the scattering-induced losses in optical metamaterials, plasmonic nanodevices and electrical shorts in molecular-scale electronic devices.     

Novel mesoscale defect structure on NiO(1 0 0) surfaces by atomic force microscopy

Cleaved NiO(1 0 0) surfaces were imaged with atomic force microscopy (AFM) to determine defect concentrations and morphology. Random 〈0 1 0〉 and 〈0 0 1〉 oriented steps, which have been previously characterized, were the most common defect observed on the cleaved surface and formed with step heights in multiples of 2.1 Å, the Ni-O nearest-neighbor distance, and terrace widths in the range of 25-100 nm. In addition, the surface showed novel mesoscale (∼0.5-2 μm) square pyramidal defects with the pyramid base oriented along 〈1 0 0〉 symmetry related directions. Upon etching, the pyramidal defects converted to more stable cubic pits, consistent with (1 0 0) symmetry related walls. The square pyramidal pits tended to cluster or to form along step edges, where the weakened structure is more susceptible to surface deformations. Also, a small concentration of square pyramidal pits, oriented with the base of the pyramid along 〈0 1 1〉, was observed on the cleaved NiO surfaces. For comparison purposes, chemical mechanical polished (CMP) NiO(1 0 0) substrates were imaged with AFM. Defect concentrations were of comparable levels to the cleaved surface, but showed a different distribution of defect types. Long-ranged stepped defects were much less common on CMP substrates, and the predominant defects observed were cubic pits with sidewalls steeper than could be accurately measured by the AFM tip. These defects were similar in size and structure to those observed on cleaved NiO(1 0 0) surfaces that had been acid etched, although pit clustering was more pronounced for the CMP surfaces.     

Surface cleaning of metals by pulsed-laser irradiation in air

The surface-cleaning effect of metals was investigated using KrF-excimer-laser irradiation of metal surfaces in air. The laser-induced cleaning of copper, stainless steel and aluminum surfaces was studied. It is found that laser cleaning is an effective cleaning process for metals even if the metal surfaces are heavily contaminated. It is also found that short wavelength and pulse duration are necessary for laser surface-cleaning. The energy density of the laser pulse is an important parameter in the cleaning process. Low energy density results in a cleaner surface but a larger pulse number is required, whereas high energy density can achieve higher cleaning efficiency but the temperature rise can cause surface oxidation and secondary contamination. In contrast to the KrF-excimer-laser, the pulsed CO₂ laser is not effective in surface-cleaning. The mechanisms of laser cleaning may include laser photodecomposition, laser ablation and surface vibration due to the impact of the laser pulse. Laser cleaning provides a new dry process to clean different substrate surfaces and can replace the conventional wet cleaning processes such as ultrasonic cleaning with CFC and other organic solvents.     

描述甲烷在Pt(110)-(21)表面的化学吸附解离的密度泛函评估

本文探讨了几种梯度近似(GGA)密度泛函及元梯度近似(meta-GGA)密度泛函在描述甲烷在重构的Pt(110)-(2×1)上的解离化学吸附作用的适用性. 金属的体相和表面结构、甲烷的吸附能量和解离能垒等被用来评估泛函的可靠性. 另外,在从头算分子动力学计算中,采用范德瓦尔斯矫正的GGA函数(optPBE-vdW)和范德瓦尔斯矫正的meta-GGA函数(MS-PBEl-rVV10）计算粘附概率. 计算结果表明,使用这两种泛函能更好地与现有的实验结果吻合,从而为发展甲烷在Pt(110)-(2×1)表面解离的可靠机器学习势能面打下重要基础.     

Automatic recognition and evaluation of micro-contaminant particles on ultra-smooth optical substrates using image analysis method

Micro-contaminant particles on surface of optical substrate have unfavorable influence on light characteristics and instability of optical devices. Proper recognition and evaluation of micro-contaminant particles on post-cleaning substrate are important in fabricating high-performance optical substrates. Based on image analysis and difference of gray scale threshold in image zones, this paper presents a technique for automatically recognizing micro-contamination, and the relevant software developed for on-line evaluation of the level of cleanliness on ultra-smooth optical substrate. Using the self-developed software incorporating high-resolution microscope, optical yttrium iron garnet (YIG) and K8 substrate surfaces of post-chemical mechanical polishing (CMP) were investigated. Results from analyzing the YIG and K8 optical substrates before-and-after laser cleaning illustrated the success of the developed automatic recognition and on-line evaluation system in identifying the micro-contaminant particles on the ultra-smooth substrate surface.     

Influence of acceptor and donor adsorbates (CO,K, NH3) on Pt surface core-level shifts

4f core-level shifts have been measured for clean surfaces of Pt(111), Pt(331), and Pt(557). Surface peaks due to terrace sites are shifted toward lower binding energy (0.32 ± 0.05 eV) from the bulk peak, whereas peaks from step atoms are shifted by 0.58 ± 0.05 eV also to lower binding energy. The intensity ratios for the two sites differ considerably between the stepped Pt surfaces. Chemisorption of carbon monoxide on the Pt(331) surface is preferential to step sites, with a Pt 4f binding energy shift of ～ 1.29 eV toward higher binding energy. Chemisorption of potassium and ammonia also produces Pt 4f surface shifts which are at higher binding energy than the bulk peak. These experiments do not support the concept of electron donation by these adsorbates into metal d orbitals. The results are discussed in view of, and supported by, tight-binding LCAOMO calculations of potassium and ammonia interacting with a Pt(111) thin film.     

Localized corrosion effects and modifications of acidic and alkaline slurries on copper chemical mechanical polishing

This study demonstrates the CMP performance can be enhanced by modifying the corrosion effects of acidic and alkaline slurries on copper. A corrosion test-cell with a polishing platform is connected with the potentiostat to investigate the corrosion behaviors of copper CMP in various alumina slurries. Experiments show that the slurry needs to be maintained in acidic pH<4.56 or alkaline pH>9.05 surroundings and thus better dispersion of alumina particles and less residual contaminant on copper surface can be obtained. The surface defects after copper CMP using acidic and alkaline slurries are described by pitting corrosion mechanisms, and these mechanisms can be regarded as a basis to modify their corrosion effects. Experimental results indicate that it is necessary to modify the dissolution of HNO₃ and oxidization of NH₄OH for copper CMP slurries. Consequently, the slurries of 5 wt.% HNO₃ by adding 0.1 wt.% BTA or 5 wt.% KNO₃ by adding 1 wt.% NH₄OH achieve good CMP performance for copper with higher CMP efficiency factor (CMPEF), 1460 and 486, and lower surface roughness (R_q), 4.019 and 3.971 nm, respectively. It is found that AFM micrographs can support the effectiveness of corrosion modifications for copper CMP in various slurry chemistries.     

Ceria concentration effect on chemical mechanical polishing of optical glass

It was found material removal rate (MRR) sharply increased from 250 to 675 nm/min as the concentration decreased from 1 to 0.25 wt% in optical glass chemical mechanical polishing (CMP) using ceria slurries. Scanning electron microscopy was employed to characterize the ceria abrasive used in the slurry. Atomic force microscopy results showed good surface had been got after CMP. Schematic diagrams of the CMP process were shown. Furthermore, the absorption spectra indicated a sudden change from Ce⁴⁺ to Ce³⁺ of the ceria surface when the concentration decreased, which revealed a quantum origin of the phenomenon.     

Thinning and polishing of cross-section of depth-graded WSi2 /Si multilayer for linear zone plate application

A linear zone plate named multilayer laue lens (MLL) is fabricated using a depth-graded multilayer structure. The lens shows considerable potential in focusing an X-ray beam into a nanometer scale with high efficiency. In this letter, a depth-graded multilayer consisting of 324 alternating WSi 2 and Si layers with a total thickness of 7.9 μm is deposited based on the thickness sequence according to the demands of the zone plate law. Subsequently, the multilayer sample is sliced and thinned to an ideal depth along the cross-section direction using raw abrasives and diamond lapping. Finally, the cross-section is polished by a chemical mechanical polishing (CMP) technique to remove the damages and improve the surface smoothness. The final depth of the MLL is approximately 7 μm with an achieved aspect ratio greater than 400. Results of scanning electron microscopy (SEM) and atomic force microscopy (AFM) indicate that interfaces are sharp, and the multilayer structure remains undamaged after the thinning and polishing processes. The surface roughness achieved is 0.33 nm.     

Chiral surfaces and metal/ceramic heteroepitaxy in the Pt/SrTiO3(621) system

Low-energy electron diffraction (LEED), atomic force microscopy (AFM), and X-ray diffraction (XRD) have been used to investigate the structural and morphological character of a naturally chiral ceramic SrTiO₃(621) substrate and of Pt and Cu thin films deposited on its surface. AFM experiments showed that as-received chirally-oriented SrTiO₃(621) substrates display atomically smooth surface morphologies, while LEED patterns revealed that the surface structure has a net chirality. Pt(621) and Cu(621) thin films were grown heteroepitaxially on SrTiO₃(621) substrates, as confirmed by XRD. AFM showed that the film surfaces were atomically smooth and LEED illustrated that the Pt films exhibit surface chirality, and by implication that the atomically-flat chirally-oriented Cu films also have chiral surfaces. The characteristics of the observed LEED patterns, where splitting of diffraction spots is considered to arise from the kinked step features of naturally chiral fcc metal surfaces, are discussed with respect to existing models. These results indicate that the chiral SrTiO₃(621) ceramic surface drives the growth of single-enantiomer, chiral, metal (621) thin films.