Effect of organic acids on copper chemical mechanical polishing

In chemical mechanical polishing (CMP) of Cu, organic acids are often used as additives of slurries. This paper studied the effects of citric acid, oxalic acid, glycolic acid and glycine on Cu CMP performance. Our experiments explored the difference of these organic acids in surface reactions with Cu. The results showed that organic acids could chelate the passive film of Cu, and oxalic acid would further form precipitates with copper ions to change the chemical and mechanical action during CMP. Potential-pH diagrams, electrochemical polarization and impedance analyses were used to examine the behaviors of Cu in various organic acid slurries. The results indicated that the proposed equivalent circuits from impedance analysis for Cu CMP system could provide a good index to surface roughness. Furthermore, we also discussed the effects of used organic acids on reducing particle contamination after Cu CMP by measuring the difference of isoelectric points between Cu and α-Al₂O₃. The result showed that the addition of organic acid could efficiently decrease particle contamination.     

Ultra-smooth BaTiO3 surface morphology using chemical mechanical polishing technique for high-k metal-insulator-metal capacitors

The surface roughness of barium titanate (BTO) following its implication by aerosol deposition method (ADM), is a very important characteristic affecting its potential for use in high-k metal-insulator-metal capacitors. The ADM is the best candidate to deposit ceramic films but has two major problems: macroscopic defects and rough interface effects on the BTO surface. In this work, a chemical mechanical polishing (CMP) technique is applied to obtain an ultra-smooth BTO surface morphology by the optimization of several factors including the slurry type, the head rotational speed, and the down pressure. Statistically, we were able to achieve a root mean square (RMS) value of the BTO surface of 1.746 nm by utilizing a two-step polishing process, applied at a head rotational speed of 70 rpm under 5 kg/cm² of down pressure; this RMS value is improved at least 8 times over previous studies. This analysis is based on representative pattern images, three-dimensional images, line profiles, histograms, and power spectra of selected BTO surface areas, further verified with data from both energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy.     

A new weakly alkaline slurry for copper planarization at a reduced down pressure

This study reports a new weakly alkaline slurry for copper chemical mechanical planarization （CMP）, it can achieve a high planarization efficiency at a reduced down pressure of 1.0 psi. The slurry is studied through the polish rate, planarization, copper surface roughness and stability. The copper polishing experiment result shows that the polish rate can reach 10032 A/rain. From the multi-layers copper CMP test, a good result is obtained, that is a big step height （10870 A） that can be eliminated in just 35 s, and the copper root mean square surface roughness （sq） is very low （〈 1 rim）. Apart from this, compared with the alkaline slurry researched before, it has a good progress on stability of copper polishing rate, stable for 12 h at least. All the results presented here are relevant for further developments in the area of copper CMP.     

Improvement of TEOS-chemical mechanical polishing performance by control of slurry temperature

Effects of slurry temperature on the chemical mechanical polishing (CMP) performance of tetra-ethyl ortho-silicate (TEOS) film with silica and ceria slurries were investigated. The change of slurry properties as a function of different slurry temperatures was also studied to obtain higher removal rates and smoother surface morphology. The changes observed with increasing temperature are as follows: the pH showed a slight tendency to decrease, the conductivity of the slurry showed a tendency to increase, the particle size in the slurry decreased, and the zeta potential of the slurry decreased with temperature. The removal rates linearly increased and maintained at the temperature of about 40 °C. The hydroxyl (OH⁻) groups increased in the slurry as the slurry temperature increased and then they diffused into the TEOS film. The surface of the TEOS film became hydro-carbonated by the diffused hydroxyl groups. The hydro-carbonated surface of TEOS film could be removed more easily. Better surface morphology of TEOS films could be obtained at 40 °C of silica slurry and at 90 °C of ceria slurry. It is found that the CMP performance of TEOS film could be significantly improved or controlled by change of slurry temperature with the same slurry.     

在铜CMP过程中降低抛光压力与磨料的机械作用

Chemical mechanical planarization(CMP) is a critical process in deep sub-micron integrated circuit manufacturing. This study aims to improve the planarization capability of slurry, while minimizing the mechanical action of the pressure and silica abrasive. Through conducting a series of single-factor experiments, the appropriate pressure and the optimum abrasive concentration for the alkaline slurry were confirmed. However, the reduced mechanical action may bring about a decline of the polishing rate, and further resulting in the decrease of throughput.Therefore, we take an approach to compensating for the loss of mechanical action by optimizing the composition of the slurry to enhance the chemical action in the CMP process. So 0.5 wt% abrasive concentration of alkaline slurry for copper polishing was developed, it can achieve planarization efficiently and obtain a wafer surface with no corrosion defect at a reduced pressure of 1.0 psi. The results presented here will contribute to the development of a “softer gentler polishing” technique in the future.     

Synergistic roles of mixed inhibitors and the application of mixed complexing ligands in copper chemical mechanical polishing

In the copper chemical mechanical polishing process, the mixed complexing ligands (glycine and disodium ethylene diamine tetraacetic acid (Na₂edta)) were utilized to enhance the polishing rate and to reduce the formation of Cu-BTA reabsorbed molecules, and the mixed dissolution inhibitors (benzotriazole and methylbenzotriazole) were applied to reduce the surface roughness. We propose that the enhanced polishing rate is due to the formation of easier removed water-soluble Cu-edta and Cu-glycine complexes, and the reduced surface roughness is mainly owing to the reduction of the Cu-BTA reabsorbed molecules and the formation of denser surface film based on complementary “space-filling” adsorption mechanism for Cu-BTA/TTA molecules.     

Endpoint detection method for CMP of copper

A novel method to detect the endpoint during Cu-CMP has been developed. It is based on the determination of the Cu concentration within the slurry on the pad that has just polished the wafer. The measurement of the ion concentration is performed using a capillary and an ion-selective electrode. The endpoint of the CMP process is detected by the decrease of Cu ion concentration, which is displayed by an decreased potential at the electrode. An experimental set-up has been established which can be applied to a commercial polishing tool. The method has been tested under various process conditions. The new endpoint detection system revealed to work independently of the polishing tool and the wafer size.     

Electrochemical corrosion effects and chemical mechanical polishing characteristics of tungsten film using mixed oxidizers

In this paper, the effects of mixed oxidizers on tungsten-chemical mechanical polishing (W-CMP) process were studied using three different kinds of oxidizers such as Fe(NO₃)₃, KIO₃ and H₂O₂. Moreover, the interaction between the tungsten film and the oxidizer was discussed by potentiodynamic polarization test, in order to compare the CMP performances and electrochemical behavior of the tungsten film as a function of mixed oxidizers. The potentiodynamic polarization results indicated that the corrosion current densities of the 5 wt% H₂O₂ and 5 wt% H₂O₂ + 5 wt% Fe(NO₃)₃ were higher than the other mixed oxidizers. Such an electrochemical corrosion effect implies that slurries with the highest removal rate have a high dissolution rate at lower pH. Therefore, we conclude that W-CMP performances are strongly dependent on the kind of oxidizers and the amounts of oxidizer additive.     

A study on the chemical mechanical polishing of oxide film using a zirconia (ZrO2)-mixed abrasive slurry (MAS)

We have studied the chemical mechanical polishing (CMP) characteristics of mixed abrasive slurry (MAS) retreated by adding of zirconium oxide (ZrO₂) abrasives within 1:10 diluted silica slurry. These mixed abrasives in the MAS are evaluated with respect to their particle size distribution, surface morphology, and CMP performance such as removal rate and non-uniformity. As an experimental result, the comparable slurry characteristics when compared to the original silica slurry were obtained from the viewpoint of high removal rate and low non-uniformity for excellent CMP performance. Therefore, our proposed ZrO₂-MAS can be useful to save on the high cost of slurry consumption since we used a 1:10 diluted silica slurry.     

大分子螯合剂在低压力低磨料条件下铜膜的化学机械抛光中的应用

The mechanism of the FA/O chelating agent in the process of chemical mechanical polishing （CMP） is introduced. CMP is carried on a φ300 mm copper film. The higher polishing rate and lower surface roughness are acquired due to the action of an FA/O chelating agent with an extremely strong chelating ability under the condition of low pressure and low abrasive concentration during the CMP process. According to the results of several kinds of additive interaction curves when the pressure is 13.78 kPa, flow rate is 150 mL/min, and the rotating speed is 55/60 rpm, it can be demonstrated that the FA/O chelating agent plays important role during the CMP process.     

Design of experiment (DOE) method considering interaction effect of process parameters for optimization of copper chemical mechanical polishing (CMP) process

Chemical mechanical polishing (CMP) has been widely accepted for the metallization of copper interconnection in ultra-large scale integrated circuits (ULSIs) manufacturing. It is important to understand the effect of the process variables such as turntable speed, head speed, down force and back pressure on copper CMP. They are very important parameters that must be carefully formulated to achieve desired the removal rates and non-uniformity. Using a design of experiment (DOE) approach, this study was performed investigating the interaction effect between the various parameters as well as the main effect of the each parameter during copper CMP. A better understanding of the interaction behavior between the various parameters and the effect on removal rate, non-uniformity and ETC (edge to center) is achieved by using the statistical analysis techniques. In the experimental tests, the optimized parameters combination for copper CMP which were derived from the statistical analysis could be found for higher removal rate and lower non-uniformity through the above DOE results.     

Evaluation of electrical and optical properties of indium tin oxide thin film using chemical mechanical polishing technique

In this study, the optimum process parameters and the influences of their process parameters were investigated for indium tin oxide-chemical mechanical polishing (ITO-CMP) with the sufficient removal rate and the good planarity. And then, the optical property such as transmittance and absorption efficiency, and the electrical characteristics such as sheet resistance, carrier density and Hall mobility were discussed in order to evaluate the possibility of CMP application for the organic light emitting display (OLED) device using an ITO film. Light transmission efficiency and current-voltage characteristics of ITO thin film were improved after CMP process using optimized process parameters compared to that of as-deposited thin film before CMP process.     

Investigation and modelling of hybrid laser-waterjet micromachining of single crystal SiC wafers using response surface methodology

A hybrid laser-waterjet micromachining technology was proposed to implement near damage-free and high-efficient micromachining of thermal-sensitive hard and brittle materials. A new material removal concept was used where a waterjet is applied off-axially to expel the “softened” elemental material by laser radiation and cool the material to eliminate thermal damages during the material removal process. The present study investigates the effect of process parameters and their interaction on the cutting depth, cutting width and the material removal rate in the hybrid laser-waterjet micromachining of single crystal SiC wafers. The analysis of variance (ANOVA) indicates that waterjet inclination angle, waterjet offset distance, nozzle stand-off distance, traverse speed of hybrid cutting head, average laser power and waterjet pressure are the significant terms on cutting depth, cutting width as well as material removal rate. The quadratic backward-eliminated regression models are developed using response surface methodology (RSM). The models show that the material removal ability and the material removal rate increase with the increased average laser power and decrease with the increased nozzle stand-off distance and waterjet pressure. Waterjet offset distance has a knee-point value on the machining results. Cutting depth and width decrease with the increased traverse speed of hybrid cutting head but material removal rate increases with the increased traverse speed when the traverse speed is smaller than a certain value. The turbulent water breaks down the laser optically and weakens its heating ability. The critical waterjet offset distance can also be changed since the interactive effect of the process parameters. The verification results show the models can perform predictions with acceptable errors. Moreover, as compared to laser dry ablation, the photographs of the machined surface and its 3D profile illustrate that hybrid laser-waterjet micromachining can obtain much deeper and wider groove with V-sharp cross-sectional profile. It can significantly reduce or even eliminate thermal damages such as heat-affected zone (HAZ) and re-solidified layer by using the hybrid laser-waterjet micromachining technology.     

A model for wafer scale variation of material removal rate in chemical mechanical polishing based on viscoelastic pad deformation

It is well known that within-wafer nonuniformity (WIWNU) due to the variation in material removal rate (MRR) in chemical mechanical polishing (CMP) significantly affects the yield of good dies. The process control for a batch CMP operation is further complicated by wafer-to-wafer nonuniformity (WTWNU) caused by MRR decay when a number of wafers are polished with the same unconditioned pad. Accordingly, the present work focuses on modeling the WIWNU and WTWNU in CMP processes. Various material removal models suggest that the MRR is strongly influenced by the interface pressure. It is also well known that the viscoelastic properties of the pad play an important role in CMP. In the present work, an analytical expression for pressure distribution (and its associated MRR) at the wafer-pad interface for a viscoelastic pad is developed. It is observed that under constant load, which is typical during main polishing in CMP, the spatial distribution of the interface pressure profile may change with time from edge-slow to edge-fast, depending on the combination of wafer curvature, down pressure, and pad properties. For constant displacement operations, the pressure profile retains its edge-slow or edge-fast characteristics over time. The analytical model predictions of MRR based on viscoelastic pad properties also correlate very well to existing experimental observations of MRR decay when an unconditioned pad is used to polish a number of wafers. Based on these observations, it may be conjectured that the viscoelastic material properties of the pad play a primary role in causing the observed MRR decay. The analytical results obtained in the present work can also provide an estimation of evolution of thickness removal distribution over the entire wafer. This may be used for determining the optimum thickness of the overburden material and its polishing time, and for effective control of CMP processes.