Chemical Mechanical Planarization Performance Research Articles

Particle size dependence of nanoclustered ceria abrasives on surface activity and chemical mechanical planarization performance

The particle size of cerium oxide (ceria) abrasives plays a crucial role in the design and development of advanced self-stopping slurries for the chemical mechanical planarization (CMP) process in semiconductor device manufacturing. However, a lack of ceria nanoparticles (NPs) with a narrow size distribution and uniform shape poses challenges in investigating the fundamental principles of the relationship between abrasive size and CMP performance. In this study, we thoroughly investigated the effect of ceria NP size on the removal rate (RR) of silicon oxide using uniform-sized nanoclustered (NC) ceria NPs with three diameters: 51.4 nm (NC51), 68.6 nm (NC69), and 108.0 nm (NC108). While all three types of ceria NPs shared a crystallinity of ∼ 70.6 %, they exhibited distinct physicochemical characteristics. As the particle size decreased, the specific surface area and chemical activity (i.e., Ce3+/Ce4+) increased by 155 % and 69 %, respectively. In the CMP process, where direct contact between the abrasives and wafer occurs, the abrasive size influences CMP performance. Experimentally, NC51 achieved the highest RR among the three slurries, along with complex size-dependent contact properties and chemical activities. These experimental results offer significant insights into precise semiconductor manufacturing in a practical manner.

Understanding and mitigating temperature-induced agglomeration in silica-based chemical mechanical planarization (CMP) slurry storage

This study explores the impact of temperature on silica particle agglomeration in Chemical Mechanical Planarization (CMP) slurries during storage. Slurries were stored at 15 °C, room temperature, and 45 °C, and analyzed. ATR-FTIR, RAMAN, SEM, zeta potential, and LPC were employed providing qualitative and quantitative data on slurry stability and agglomeration tendencies. Elevated temperature storage significantly increased agglomeration and large particle counts with particle counts value of ∼1.2×107 Part./ml, likely due to water molecule dehydration leading to destabilization. Low-temperature storage also induced agglomeration but to a lesser extent with particle counts the value of ∼4.0×106 Part./ml compared with the RT (∼2.0×106 Part./ml). Short-term storage yielded soft agglomerates with LPC of ∼(2.0–4.0)×106 Part./ml, while long-term high-temperature storage led to hard agglomerates with LPC of ∼3.0×107 Part./ml. The ATR-FTIR and Raman analysis indicate that the spectroscopic features of the original slurry exhibited changes upon variation of storage temperature from RT to 15 and 45 °C. The study also explored the reversibility of agglomeration post-treatment, indicating a potential mitigation pathway. The results demonstrated an inverse relationship between temperature and dissolved oxygen (DO) in silica slurries. For example. the curves depict a decrease in oxygen content from ∼10 ppm at RT to 7 ppm at 45 °C with increasing aging time. A mechanism outlining the temperature and aging-induced agglomeration was proposed, linking temperature fluctuations and thermodynamic aspects to colloidal stability. These findings offer a robust understanding of temperature-induced agglomeration in silica-based CMP slurry storage, paving the way for developing strategies to alleviate these issues and ensuring consistent CMP performance in semiconductor manufacturing.

Development of Novel Conditioning Method Using Thermal Shape Memory Characteristics of Polyurethane CMP Pad

Traditionally, the pad roughness has been maintained by wearing down the polyurethane pad with diamond disk. However, that method generates debris and reduces pad lifetime. This study propose a new approach to pad surface recovery by synthesizing a polyurethane-based raw material that exhibits shape memory behavior and can recover its shape upon heating. The findings suggest that the pad’s surface can be maintained by utilizing its shape memory trait and designing a system to heat the pad. The pad recovery tests were conducted using universal test machine (UTM) samples and found that, in terms of heat recovery, increasing the temperature had a greater effect than increasing the exposure time. CMP test was performed by using three conditioning potions: diamond disk conditioning, heat conditioning, and no conditioning. The results showed that pad asperity was recovered more efficiently with heat conditioning than with no conditioning (demonstrated by a 19% higher removal rate). The experimental results can be expected that combines diamond disk conditioning with heat conditioning could be a superior alternative for pad surface refreshment. Shape memory pads can return to their original form, leading to better chemical mechanical planarization (CMP) performance and an extended pad lifetime.

Effects of aging time in hydrogen peroxide-glycine-based Cu CMP slurry

Hydrogen peroxide is widely used as an oxidizer in metal chemical mechanical planarization (CMP) slurry due to its strong oxidizing ability and being a non-metal product. However, hydrogen peroxide is unstable and easily decomposes into water and oxygen molecules. In this experiment, the aging of a hydrogen peroxide-glycine-based Cu CMP slurry was investigated in terms of the chemical concentration and CMP performance. Ultraviolet–visible–near-infrared spectroscopy was used to measure the change of hydrogen peroxide concentration with slurry aging. As the slurry aging time was increased, the removal rate decreased for several reasons. With slurry aging, not only decreases of hydrogen peroxide concentration but also decreases of pH and glycine decomposition were observed. Therefore, the removal rate was suppressed due to complex factors, including the decreased oxidizing ability with decreased hydrogen peroxide concentration, decomposition of the glycine chelating agent, and decrease in pH. This study suggests the necessity of monitoring slurry aging and management for optimizing CMP process performance.

Preparation of Ceria-Coated Silica Nanoparticles and Their Chemical Mechanical Planarization Performance on Si-Face 6H-SiC Substrates

Ceria-coated silica (SiO2/CeO2) composite abrasives were prepared through a novel homogeneous precipitation method using commercial silica (SiO2) sol as the silicon resource and cerium nitrate (Ce(NO3)3) and hexamethylenetetramine (HMT) aqueous mixtures as coating precursors. The phase composition, nano-topography, size distribution, and chemical structure of as-prepared particles were characterized by X-ray diffraction, transmission electron microscopy, Zetasizer Nano ZS90 and Fourier infrared spectra. In addition, the possible coating mechanism was discussed. Then, chemical mechanical planarization behaviors of SiO2 sol, ceria (CeO2) sol, and the novel abrasives and on Si-face (0001) 6H-SiC were investigated by atomic force microscopy. The results indicated that the composite particles were mono-dispersed nano-spheres composed of amorphous SiO2 core and cubic fluorite CeO2 shell, possessing complete core–shell structure and particle size of about 110 nm. CeO2 shell (10 nm) grew on the surface of SiO2 core by formation of Ce–O–Si chemical bonds, forming stable core–shell structure. SiO2/CeO2 composite abrasives provided an exponentially high material remove rate (MRR) of 1207 nm h−1 and an impressive surface finish with roughness average (Ra) 0.216 nm due to its active chemical property and unique structure.

Size distribution monitoring for chemical mechanical polishing slurries: An intercomparison of electron microscopy, dynamic light scattering, and differential mobility analysis

In chemical mechanical planarization (CMP), a particle slurry is used in polishing semiconductor wafers. Key to CMP performance is the size distribution of the particles. We evaluate the potential of an aerosol technique, namely differential mobility analysis (in a liquid nanoparticle sizer, LNS, system) to characterize size distributions of CMP slurries. LNS measurements are compared to size distributions inferred from electron microscopy (SEM), and dynamic light scattering (DLS). LNS measurements are more repeatable than DLS measurements, and for 4 silica slurries, LNS distributions are in better agreement with SEM measurements than DLS. We find also that the LNS can quantify multimodal size distributions. For non-silica slurries, LNS, DLS, and SEM measurements have geometric mean diameters which can vary from another by 10 nm or more. However, because each measurement type is internally consistent, the combination of LNS and DLS, which are automated, yields augmented information on slurry properties.

Evaluation of a Photosensitizer Redox Couple for Oxide Removal Rate Tunability in Shallow Trench Isolation Chemical Mechanical Planarization

As technology continues to expand beyond that predicted by Moore’s Law the need to alter chemical mechanical planarization (CMP) processes to meet consumer demands is critical. To achieve higher oxide material removal rates (MRR), slurry formulations have become more complex by implementing rate enhancing additives to increase the slurry’s chemical activity. However, the modulation of MRR in situ requires changes in mechanical parameters, such as downforce, platen speed, and flow rate. These parameters effectively increase the chemical activity of the slurry; however, they can result in greater defectivity due to increased shear force. Therefore, this work employs the use of a photosensitizer redox couple to tune MRR using an external stimulus (i.e., light). Specifically, Rose Bengal (RB) is used to disrupt the adsorbed O2 equilibrium at the CeO2 surface via 1O2 generation. A secondary redox additive is employed to trap the 1O2 thereby preventing readsorption and increasing the number of active surface sites necessary for enhanced MRR. This photosensitized mechanism is supported through the correlation of CMP performance (i.e., MRR) to analytical measurements (i.e., 1O2 generation, contact angle, and quartz crystal microbalance (QCM)) with and without the presence of irradiation.

Investigation of CMP Performance According to Pad Surface Condition and Abrasive Types

Chemical mechanical planarization (CMP) is a planarization technique that combines mechanical and chemical factor for enhanced polishing and finishing. CMP process reduces the surface roughness to meet the requirements of semiconductors. The characteristics of CMP, such as material removal rate (RR), thickness uniformity and surface quality, are determined by various mechanical and chemical factors. CMP has many consumables. Slurry, conditioner, and pad are typically used in CMP process. These consumables’ interaction is very important in CMP process. The reason why, the other can affect each other. These factors are known to significantly affect the results of CMP. During the process time, the lack of conditioner will block the pore and glazing on the pad surface. The longer process time, the lower pad cut rate is occurred because of poor conditioner performance [1]. And then pad glazing is occurred. When the pad glazing occurred, RR is changed [2]. At this point, the RR has different value according to abrasive. The number of particles that can act on the wafer depends on the pad surface changed. This affects the local pressure acting on the wafer. As the amount of abrasive acting on the wafer increases, the local pressure on the wafer is decreased. As briefly think about the situation, reduction of local pressure should result in decreasing removal rate. However, when the pad glazing situation, the RR has difference phenomenon according to abrasive types. Normally, Fig.1 (a) shows RR using ceria abrasive. It has higher RR after pad glazing. Fig.1 (b) shows RR using silica abrasive. It has lower RR after pad glazing. In this research, the difference in RR according to abrasive types generated during pad glazing was investigated. Based on these phenomena, I present the optimum pad land area each abrasive. Reference [1] C. Shin, H. Qin, S. Hong, S. Jeon, A. Kulkarni, and T. Kim, Journal of Mechanical Science and Technology, pp. 5659-5665, (2016).[2] H. Kim et al., Wear, pp. 93-98, (2017). Figure 1

Understanding the Role of Slurry Additive Molecular Structure on Modulating the Interfacial Dynamics for Oxide CMP Applications

As feature sizes continue to shrink well beyond the 7-nm node, understanding the delicate balance present in the chemical mechanical planarization (CMP) process is of utmost importance. In order to achieve high through-put and defect-free CMP processes it is critical to develop predictive analytical techniques that directly correlate to macroscopic STI CMP performance metrics (i.e. oxide/nitride removal, defectivity, and dishing/erosion). This work employed a suite of techniques to monitor the CeO2 nanoparticle interfacial redox processes in the presence of structurally diverse rate modulating additives. Specifically, utilizing a UV-Vis spectroscopic technique, the Ce3+/Ce4+ ratio in the presence of different slurry additives was monitored and proved to directly correlate to removal rate performance (i.e. an increase in Ce3+/Ce4+ ratio shows an increase in rate). This finding coupled with the rate of dissolved O2 evacuation and a modified QCM technique determined the mode of interaction/adsorption which validates that the mechanism of oxide removal does not strictly depend on redox capacity, but also depends on the dynamic O2 equilibrium at the CeO2 nanoparticle surface. In this work, the additives selected provide multiple modes of interaction spanning from noncovalent surface adsorbers to redox active functional groups. It was determined that the modulation of oxide removal was directly related to the distribution of interactions (i.e. steric vs redox) and was highly dependent on the slurry additive functionality.

Comparative Analysis of Chemical Mechanical Planarization Performance on Low-K Films

Mirroring the pursuit for ever-shrinking feature size in memory architectures, the need for materials capable of preventing crosstalk between increasingly closer conducting lines has led to the replacement of silicon dioxide with alternative low-k materials. Within this subset of materials exist films with notably low dielectric constants; however, these materials present unique challenges for chemical mechanical planarization (CMP) in comparison to more traditional dielectrics, the least of which include undesirable scratching and erosion (e.g. dishing) of low-lying areas. Fortunately, some degree of tuning of film properties (e.g. modulus and hardness) is possible through various deposition methods and post treatment conditions, among others. In this study, two slurries containing common Ceria abrasives were utilized to examine a selection of films of varying properties and preparations across several CMP process conditions. A structural test vehicle having a series of feature sizes designed to feed CMP modeling was used for analysis. Static etch rate and material removal rate were measured using optical metrology. Dishing was quantified via atomic force microscopy (AFM), and scratching performance was analyzed via optical methods. Using the collected data, a mechanism for removal was proposed for each slurry. Figure 1

Role of Molecular Structure on Modulating the Interfacial Dynamics for Shallow Trench Isolation (STI) Chemical Mechanical Planarization (CMP) Applications

As feature sizes continue to shrink well beyond the 7 nm node, understanding the delicate balance present in the chemical mechanical planarization (CMP) process is of utmost importance. In order to achieve high through-put and defect-free CMP processes it is critical to develop predictive analytical techniques that directly correlate to macroscopic STI CMP performance metrics (i.e. oxide/nitride removal, defectivity, and dishing/erosion). This work employed a suite of techniques to monitor the CeO2 nanoparticle interfacial redox processes in the presence of structurally diverse rate modulating additives. Specifically, utilizing a UV–vis spectroscopic technique, the Ce3+/Ce4+ ratio in the presence of different slurry additives was monitored and proved to directly correlate to removal rate performance (i.e. an increase in Ce3+/Ce4+ ratio shows an increase in rate). This finding coupled with the rate of dissolved O2 evacuation and a modified QCM technique determined the mode of interaction/adsorption which validates that the mechanism of oxide removal does not strictly depend on redox capacity, but also depends on the dynamic O2 equilibrium at the CeO2 nanoparticle surface. It was determined that the modulation of oxide removal was directly related to the distribution of interactions (i.e. steric vs redox) and was highly dependent on the slurry additive functionality.

Direct and quantitative study of ceria–SiO2 interaction depending on Ce3+ concentration for chemical mechanical planarization (CMP) cleaning

The importance of chemical mechanical planarization (CMP) and post-CMP cleaning is highly critical because both directly affect the yields and performance of semiconductor devices. Ceria nanoparticles are widely used as abrasives for SiO2 CMP because strong ceria–SiO2 interaction enhances CMP performance. However, the interaction is a major drawback in post-CMP cleaning processes where residual ceria nanoparticles must be completely removed from the SiO2 surface. The interaction depends on the cerium oxidation state of the ceria nanoparticles surface. In this study, the ceria–SiO2 interaction was investigated systemically using an atomic force microscope and a quartz crystal microbalance. The analysis revealed that the adhesion energy between ceria and SiO2 and the adsorption rate of ceria nanoparticles on a SiO2 surface increased with the surface concentration of Ce3+. This is direct evidence showing that the ceria–SiO2 interaction becomes stronger as the surface Ce3+ concentration of ceria nanoparticles increases, suggesting that the surface Ce3+ concentration should be reduced for effective post-CMP cleaning.

Engineering Surface Texture of Pads for Improving CMP Performance of Sub-10 nm Nodes

Shallow trench isolation (STI) chemical mechanical planarization (CMP) will continue to be a critical step in the device fabrication of future technology nodes. A CMP process needs the right combination of pad, slurry, and pad conditioner to be able to deliver the best performance. Engineered pad surface along with usage of non-Prestonian ceria slurries can be used to solve key STI CMP challenges. Herein, it is demonstrated that relative to a reference pad, reducing and optimizing pad surface roughness, can help improve material removal rate by 26%–95% at different wafer pressures, lower the dishing by 34%–51% for feature size of 50–200 μm, thereby leading to an improved planarization performance. This work illustrates that the surface texture of a pad can be used to achieve a stable dishing range over different feature scales for various over polish times. Also, optimizing the pad surface roughness minimizes slurry consumption by 33% and enables polishing at a lower downforce. Further, it is demonstrated that relative to a reference pad, defectivity can be improved up to 85% for the pad without impacting the planarization performance by reducing the pad material hardness and polishing at an optimized pad surface roughness.

Influence of abrasive morphology and size dispersity of Cu barrier metal slurry on removal rates and wafer surface quality in chemical mechanical planarization

Chemical mechanical planarization (CMP) is widely used in the fabrication of semiconductor devices to achieve global planarization. The overall CMP performance is affected by material removal rates. Defects and dishing generated on wafers during CMP increase device failure rate. In the present study, we examined the effect of silica abrasive morphology and size dispersity on removal rates and surface morphologies of wafers. The slurry composed of polydispersed irregular silica (PI) showed the highest overall removal rates (for interconnection, barrier, and dielectric materials), although the removal rate of the slurry consisting of polydispersed spheric silica for the interconnection material (Cu) was higher than that of PI. The overall removal rate increased with increasing silica concentration. The lowest surface roughness was achieved by polydispersed irregular abrasives. The surface roughness increased by increasing the concentration of abrasives. The polydispersed irregular abrasives also allowed for the lowest defects. Small dishing values were observed for the slurry systems manufactured in this study, indicating that the abrasive morphology seldom influenced the dishing behaviors. The understanding of morphology and size dispersity can be beneficial to CMP global planarization with high removal rates and low defects.

The Effect of Surface Polarity on the CMP Behavior of 6H-SiC Substrates

The chemical mechanical planarization (CMP) performance of the Si-face and C-face 6H-SiC substrates were compared using potassium permanganate (KMnO4) as an oxidizer and the alumina (Al2O3) nanoparticles as the abrasive particles over a pH range from 2 to 10. The results indicate that there was a significant difference in the CMP performance between Si-face and C-face 6H-SiC substrates, indicating that the CMP process was sensitive to the surface polarity of the 6H-SiC substrates. A higher material removal rate (MRR) was obtained during the CMP of C-face 6H-SiC substrates, as compared to that of Si-face 6H-SiC substrates. The maximum MRR of the C-face 6H-SiC substrates was reached to 6412 nm/h with an average surface roughness Ra of 0.54 nm when using the slurries containing 2 wt% alumina nanoparticles, 0.05 M KMnO4 at pH 2. While the Si-face 6H-SiC substrates was 1554 nm/h with an average surface roughness Ra of 0.53 nm. Furthermore, the polishing mechanism was also discussed based on the MRR, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) analysis of the dipped and polished 6H-SiC surfaces.

Interfacial Chemical and Mechanical Reactions between Tungsten-Film and Nano-Scale Colloidal Zirconia Abrasives for Chemical-Mechanical-Planarization

In tungsten (W) film chemical-mechanical-planarization (CMP), the chemical and mechanical reaction behaviors of the W film surface play a critical role in the CMP performance, as determined by oxidation (i.e.,WO3), corrosion (i.e., WO42−), and the electrostatic force at the interface between abrasives and the surface. Unlike a conventional catalyst (i.e., Fe(NO3)3) for a Fenton reaction in a CMP slurry, a new catalyst ((i.e., potassium ferric oxalate: K3Fe(C2O4)3)) and a new nano-scale (i.e., 23 nm in diameter) abrasives (i.e., Zirconia:ZrO2) provides specific CMP performance behavior: the maximum W-film polishing rate and a corrosion-free surface are achieved at a specific catalyst concentration (0.03 wt%), and the number of remaining abrasives adsorbed on the W film surface after CMP decreases with increasing concentration of the K3Fe(C2O4)3. These CMP performance characteristics are associated with the following results: (i) The degrees of two different CMP mechanisms (oxidation-dominant or corrosion-dominant) determine the corrosion-free surface of W film. (ii) The dependency of the electrostatic force at the interface between abrasives and the film on the K3Fe(C2O4)3 concentration determines the polishing rate. Finally, (iii) the zeta potential distribution at the interface between the abrasives and the film directly affects the number of remaining abrasives on the surface after CMP.

Role of Molecular Structure on Controlling the Dynamic Equilibrium of the Ecosystem Present in Shallow Trench Isolation (STI) Chemical Mechanical Planarization (CMP) Slurry Formulations

Chemical Mechanical Planarization (CMP) has emerged as a critical process step for achieving angstrom-level uniformity in advanced integrated circuit manufacturing and has ultimately lead to the extension of Moore’s Law. This work specifically looks at Shallow Trench Isolation (STI) CMP, which is used in the electrical isolation of the active components in an integrated circuit by actively removing oxide overburden and stopping on Si3N4 to achieve global planarity and limit defectivity. This planarity is achieved through the synergistic balance of an applied mechanical force and the incorporation of a colloidal dispersion (slurry) containing ceria (CeO2) nanoparticles, rheology modifiers, and stability additives. In addition to the aforementioned additives, a main initiative of STI slurry formulation development has been centered around oxide rate control and selectivity enhancement. Current research has emphasized the addition of compounds that contain carboxylic acid, amine, and amino acid functionality. While the mechanism behind these additives is still of great debate, results have shown the importance of additive surface adsorption and nanoparticle surface redox properties. More specifically, in order to achieve optimal performance, the slurry additive must not impede the presence of surface oxygen vacancies on the nanoparticle, which are known to facilitate high oxide material removal rate (MRR). Slurry additives with redox activity as well as antioxidant properties show the highest MRR due to an increase in the surface oxygen vacancies and a decrease in the non-productive surface interactions. A suite of dynamic, analytical techniques such as atomic force microscopy (AFM), contact angle measurements, pre/post characterization of particle properties (size and zeta potential), coefficient of friction (COF), and UV-Vis spectroscopy, were employed. Results indicate a strong correlation between additive structure, slurry macro-environment, and overall CMP performance.

Development of “Soft” Cleaning Chemistries for Enhanced STI Post-CMP Cleaning

Due to the emergence of sub-10 nm technologies, limiting device defects has become of utmost importance in maintaining high performing integrated circuits. Shallow trench isolation (STI) chemical mechanical planarization (CMP) uses a synergistic balance of ceria (CeO2) nanoparticles and functional chemistry to modulate critical surface adsorption interactions necessary to remove excess topography. Literature has identified that the surface redox state of the CeO2 nanoparticle (Ce3+/4+) is a critical factor in controlling CMP performance. More specifically, controlling the oxygen vacancies has been shown to directly impact removal rate (Ce3+ state), as well as post-CMP cleaning efficiency (Ce4+ state). Current post-CMP cleaning processes utilize oxidation/reduction reactions, etching, encapsulation, and ultrasonic methods as a means of undercutting the particle from the substrate surface. These methods have proven to be highly effective at particle removal but have shown to potentially induce further defectivity due to the aggressive cleaning conditions. This work aims to develop a post-CMP cleaning chemistry that enhances particle removal via soft encapsulation of undesirable nanoparticle/slurry chemistry non-covalent complexes on the wafer surface. By employing a polyelectrolyte/surfactant (PES) matrix, a surface adsorbing/charge-flipping encapsulation process is proposed as a vehicle to remove slurry contamination at low friction. Investigation into the synergy between slurry chemistry and PES cleaning chemistry, with respect to defect aggregate formation, was correlated to the cleaning efficiency as well as friction. Techniques were developed to study real-time properties such as the defect aggregate formation mechanism via in-line dynamic light scattering (DLS), coefficient of friction (COF), particle removal, and scratch defectivity to draw a correlation between cleaning chemistry structure and post-CMP performance.

Investigation of step structure in CMP retainer ring to improve within-wafer non-uniformity

A retainer ring structure was investigated to improve non-uniformity in a chemical mechanical planarization (CMP) process. During the CMP process, the stress distribution on the wafer affects the CMP performance in terms of material removal rate (MRR) and within-wafer non-uniformity (WIWNU). The non-uniformity is related to edge exclusion and affects the process yield. For this purpose, the stress distribution between pad and wafer was calculated via the finite-element method (FEM) and compared with the experimental results of a 300 mm wafer polishing test. The retainer ring with a step structure exhibited an improved stress distribution along the wafer surface. Consequently, the non-uniformity was improved by 16.6 %. These results can be used to optimize CMP processes (in particular, CMP retainer ring structures) and determine adequate process conditions.

Role of Additive Structure on Controlling Ceria/Substrate Interactions Relevant to Shallow Trench Isolation (STI) Chemical Mechanical Planarization (CMP)

Chemical Mechanical Polishing (CMP) has emerged as a critical process step for achieving global planarization in advanced integrated circuit manufacturing and has lead to the extension of Moore’s Law. Specifically, Shallow Trench Isolation (STI) CMP is used in the electrical isolation of the active components in an integrated circuit by actively removing TEOS and stopping on Si3N4 to achieve angstrom level uniformity and limit defectivity. Planarization of the overburden material is achieved through a balance of an applied mechanical force and the delivery of a colloidal dispersion (slurry) containing ceria (CeO2) nanoparticles, complexing additives, and rheology modifiers to the substrate surface. Currently, STI slurries contain chemical additives that selectively boost material removal rate (MRR) as well as enhance selectivity via non-covalent passivation films formed at the polishing substrate surface. A crucial factor in maintaining a high MRR is the presence of CeO2 surface oxygen vacancies, commonly associated with Ce3+surface oxidation state, which can be achieved either from pre-dispersion particle processing or though additive/nanoparticle surface reactions present in the slurry formulation. This study probed the impact of the slurry additive functionality, such as carboxylic acids, amines, and phenols, on the removal rate and post-CMP defectivity. Results suggest that the Ce3+ oxidation state is critical to performance but the Ce4+ oxidation state is also a viable reaction site as long as it remains uncomplexed and free of any site-blocking additives. The additive adsorption to the CeO2 surface will result in altering the dynamic interplay of the abrasive particle/chemistry at the substrate surface shifting CMP performance. Employing and correlating a suite of modified analytical methods, such as atomic force microscopy (AFM), electrochemical quartz crystal nanobalance (EQCN), dynamic contact angle measurements, fluorescence microscopy, pre/post characterization of particle properties (size and zeta potential), and dynamic contact angle, a strong correlation between surface energy and CMP performance metrics has been uncovered.