Additive-abrasive interactions in chemical-mechanical planarization (CMP) slurries are investigated using fluorescence correlation spectroscopy (FCS). The FCS technique provides quantitative determinations of the interaction between additives and abrasive particles by characterizing the competitive adsorption of the additive and a fluorescent probe molecule by an abrasive particle. Adsorption of the CMP additives glycine and benzotriazole (BTA) on precipitated and sol-gel colloidal silica abrasives are characterized. Significant differences in the fluorescent probe’s adsorption to the different silica abrasives in the presence of the additives suggest surface chemistry differences between the different types of silica. Extensions of the analysis of FCS data are proposed for improving the quantitative determination of the competitive adsorption of fluorescent probe dyes and CMP additives on abrasive particles.

Micromachined structures with diameters ranging from 50 — 100 μm have been applied to the measurement of the microscale shearing forces present at the wafer-pad interface during chemical mechanical polishing (CMP). The structures are 80 μm high poly-dimethyl-siloxane posts with bending stiffnesses ranging from 1.6 to 14 μN/μm. The structures were polished using a stiff, ungrooved pad and 3 wt% fumed silica slurry at relative velocities of approximately 0.5 m/s and downforces of approximately 1 psi. Observed lateral forces on the structures were on the order of 5–500 μN, and highly variable in time.

Methyl depletion and subsequent moisture uptake have been found to be the primary plasma damages leading to dielectric loss in porous organosilicate (OSG) low-k dielectrics. A vacuum vapor silylation process was developed for dielectric recovery of plasma damaged OSG low-k dielectrics. The methyl or phenyl containing silylation agents were used to convert the hydrophilic -OH groups to hydrophobic groups. Compared with Trimethylchlorosilane (TMCS) and Phenyltrimethoxysilane (PTMOS), Dimethyldichlorosilane (DMDCS) was found to be more effective in recovering surface carbon concentration and surface hydrophobicity. But the carbon recovery effect was limited to the surface region.

Alternatively, UV radiation with thermal activation was applied for dielectric recovery of plasma damaged OSG low-k dielectrics. The combined UV/thermal process was found to be efficient in reducing −OH, physisorbed water, and C=O bonds. The dielectric constant was recovered within 5% of the pristine sample and the leakage current was also much reduced. Aging test in air showed that no moisture retake was observed, indicating the repaired film was stable.

The results of copper Chemical Mechanical Planarization (CMP) experiments with a model slurry chemistry based on the combination of Glycine-water-Benzotriazole (Gly-H2O2-BTA), and different types of composite A (silane coupling agents between the polymer core and the silica shell) and B (electrostatic attraction between the polymer core and the silica shell) abrasives, are presented. While the presence of BTA allows a ten-fold reduction in the static etch rate from 95 nm/min. to 10 nm/min., combining oxidizer and complexing agent leads to removal rates higher than 400 nm/min. Different surface morphology and RMS roughness are observed after polishing with composite abrasives and different peroxide concentrations. Oxidizer concentrations as low as 0.1 vol.% lead to high non-uniformity and defectivity values. In particular, composite B performs better than pure colloidal/fumed silica during copper CMP using the IC-1000 pad, giving comparable Material Removal Rate (MRR), but a better surface finish due to the contribution of the elasticity of the polymer in gently transferring the applied load to the wafer surface. Cu CMP with pure polymer particles is a promising alternative to the hard inorganic material especially if combined with suitable surfactants that act from both particle stabilization and friction reduction / lubrication improvement perspectives.

The use of the medium/high-hardness pad IC-1000 is compared to the use of a soft Politex pad. In the former case, differences in terms of MRR, MRS roughness, and total defects are observed between the composite abrasives A and B; in the latter case, the behaviour of the two composites is similar. In the case of a soft pad in combination with composite abrasives, there is a remarkable improvement in the defectivity without any loss in MRR.

As revealed by SEM inspection of the composite particles collected in the slurry drain after CMP, for all the composites, the silica shell coverage is not disrupted by the shear forces and chemistry during the 1 min. polishing. Consequently, the stability and agglomeration properties of the particles in the complex Cu CMP chemistry can be helpful in explaining the experimental results in terms of MRR and surface finishing.

During an O2 plasma ashing process, carbon depletion and subsequent moisture uptake caused increase of keff and the leakage current in an organosilicate (OSG) low-k dielectric. For dielectric restoration, additional CH4 plasma treatment on the O2 plasma ashed OSG low-k dielectric was investigated using angle resolved x-ray photoelectron spectroscopy (ARXPS), XPS depth profiling, x-ray reflectivity (XRR), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and contact angle goniometer. After CH4 plasma treatment on the O2 plasma ashed OSG, the surface carbon concentration and surface hydrophobicity were partially recovered. A dense surface layer containing C=C bonds was found to have formed on the top of the damaged OSG. The C-V hysteresis and the leakage current were reduced as a result of the CH4 plasma treatment. XPS depth profiling revealed that the recovery effect was limited to the surface region.

This paper describes the fabrication and calibration of micromachined shear stress sensors intended for characterization of the local pad-wafer contact forces present during chemical-mechanical polishing. Sensors consist of arrays of microfabricated poly-dimethyl-siloxane (PDMS) posts and are able to measure forces ranging from 2 to 200 μN. The posts are 100 μm high and have diameters of 40-100 μm. Calibrated post deflection sensitivities are linear and lie between 0.2 μm/μN and 1.3μm/μN. Sensor design, fabrication, and calibration are detailed. Feasibility is established for sensor integration into a CMP scale model test setup, including an optical viewing method for observing post deflection during polishing. Initial micrographs of post deflection during polishing do not yet have sufficient resolution to determine the microscale forces during polishing.

It is becoming increasingly clear that understanding the small scale polishing mechanisms operating during CMP requires knowledge of the nature of the pad-wafer contact. Dual Emission Laser Induced Fluorescence (DELIF) can be used to study the fluid layer profile between the polishing pad and the wafer during CMP. Interactions between the polishing pad surface and the wafer can then be deduced from the fluid layer profile. Previous investigations of pad-wafer interactions using DELIF include in-situ measurements of average fluid layer thickness and asperity layer compressibility, surface roughness measurements and polishing pad rebound into etched wells. In this paper, DELIF is used to determine pad-wafer contact, the point at the fluid film thickness goes to zero. We present a technique and some preliminary data for instantaneous measurement of in-situ pad-wafer contact using DELIF. The imaging area is 1.30×1.74 mm with a resolution of 2.5 μm/pixel. At this magnification, some regions imaged contain contact, whereas others do not. For the contact regions discussed in this paper, contact percentage varies from 0.07% to 0.27% on a Cabot Microelectronics D100 polishing pad. The asperity contact area increases with applied load, which was varied from 0.28 to 3.1 psi.

Although dielectric polishing is primarily mechanical in nature, surface chemical effects can be tailored to enhance material removal, selectivity and planarity. The use of ceria abrasives in oxide polishing is particularly attractive because of favorable polishing characteristics that are generally not obtainable using conventional fumed or colloidal silica abrasives. Unfortunately, a characteristic of ceria abrasive is an enhanced tendency toward defectivity in comparison with conventional silica. Entirely novel composite structures comprising 300 nm polymer particles coated by ceria (specific surface area of the powder 61 m2/g), are achieved by either adding silane coupling agents (Composite A) or tuning the pH in order to form electrostatic attractive interactions between the core and the shell (Composite B). The polymer core shows mechanical properties that are highly tunable by variation of its synthesis parameters, while the major advantage of the ceria coating is an enhanced chemical action of the abrasive particles, commonly referred to as the chemical tooth model. In this study we report the evolution of RR, haze, and defects such as particles and scratches in CMP experiments on high-density plasma (HDP) silicon oxide using four abrasive types (14 nm primary size ceria particles, 300 nm polymer particles, composites A and B) at pH 3 and 10. Interestingly, the two types of composite exhibit different RR. This is attributed to differences in morphology and surface composition. Composite B presents more similarities with the ceria, as confirmed by particle / silica surface adhesion forces in different pH solutions, measured by a colloidal AFM technique.

The design of nanostructured materials like CMP slurries on an industrial scale requires the control of disperse systems of nanoparticles as well as of single isolated "bad" particles . It is well known that slurry abnormalities resulting from large abrasive particles and abrasive particles agglomeration can cause defects on wafer surfaces during CMP.

Particle-particle interactions generate secondary nanometer structures, clusters or agglomerates, which can dominate the relevant properties of the bulk material. Size and structure of these particle agglomerates/structures are the result of a dynamic equilibrium between agglomeration and desagglomeration. There is still a lack of understanding of these secondary soft nano- up to micro- particles because no adequate characterization methods are established.

Dilution and other preparation treatment to enable analysis by laboratory methods like TEM or AFM will distort the interparticle forces and will generate artifacts. Hence characterization methods are under investigation which can tolerate a high number of particles in the sensing zone. These high concentration methods often deliver ambiguous results. Consequently different physical principles have to be combined to get unambiguous information on the disperse state.

Performance characteristics of ultrasonic spectroscopy, photon correlation spectroscopy, analytical photo-centrifugation method combined with the high spatial resolution as well as special single particle optical counters are discussed on examples.

A new particle sizing and counting method based on the coupling of flow field-flow fractionation (FFF) with dual-sensor, single particle optical sensing (SPOS) detection is reported. The integration of FFF and SPOS systems was accomplished by means of a dilution interface that preserved the resolution of FFF-separated particles. Analysis of a model mixture of polystyrene latex standards of different diameters established that the FFF-SPOS system can resolve particles into discrete peaks for subsequent particle counting. Application of this method for the analysis of a colloidal silica standard demonstrated its use for materials commonly employed as CMP abrasives. Further development and refinement of the technique will enable compositional and structural analyses of heterogeneous large particle populations constituting commercial CMP slurries.

Colloidal probe technique has been widely employed to measure the adhesion between micro- and nanosize objects using atomic force microscopy (AFM). However, majority of studies concerns model systems, which do not incorporate real abrasive particles. The approach applied allows measuring adhesion between real CMP nanoparticles and different surfaces. Thin polymer film with high affinity to the particles was used to anchor the particles to a surface. Hollow glass bead (20-30 μm) representing flat surface was attached to soft AFM cantilever. Application of large hollow bead and the cantilever with small spring constant allows measuring the interactions with high sensitivity. Titanium, tungsten and tantalum metals were sputtered on the bead surface. The effect of different factors such as pH value, concentration and type of a surfactant on adhesion between surfaces of metals and silica slurry has been studied. Character and intensity of interactions at the moment of contact have been evaluated from experimental force-distance curves.

Adhesion between abrasive particles and surfaces being polished plays an important role in chemical mechanical planarization (CMP) processes. The changes in particle - surface and particle – particle interactions can significantly influence the effectiveness of material removal and cleaning methods. To determine the adhesion between actual abrasive particles and different surfaces treated by the CMP process a method employing atomic force microscopy (AFM) technique is being developed.

The monolayer of silica abrasive nanoparticles was deposited on silicon wafer covered with polymer anchoring layer. High affinity of the thin polymer film to the particles and wafer ensures the stability of particles monolayer on the surface during measurements. AFM cantilever was modified with attachment of 20-40 microns hollow glass bead (representing a flat surface), which then was covered with copper using physical vapor deposition technique. Force-distance curves were collected employing AFM force volume mode and used to calculate the adhesion value. The effect of different factors (such as pH, presence of surfactants) on adhesion between copper surface and silica slurry has been studied.

Slurries used for copper CMP have a rich chemistry, which may change during the course of polishing due to consumption and decomposition of molecular species. Various aspects, such as small layer thickness (<50 μm), continuous flow of the slurry, and dynamics of the film removal process pose great challenge to the monitoring of slurry components between the pad and the wafer. The slurry constituents such as oxidants and corrosion inhibitors have unique signatures that can be detected using spectroscopic techniques. In this paper, work carried out to explore the use of Raman spectroscopy to detect and quantitate chemical species such as hydroxylamine, benzotriazole and hydrogen peroxide in-situ will be presented. More detailed study pertaining to the protonation of hydroxylamine with respect to the pH will also be presented. An abrasion cell integrated with a Raman spectrometer was used to make the measurements.

The electrical and mechanical properties of low-k dielectric materials have received a great deal of attention in recent years; however, measurements of thermal properties such as the coefficient of thermal expansion remain minimal. This absence of data is due in part to the limited number of experimental techniques capable of measuring this parameter. Even when data does exist, it has generally not been collected on samples of a thickness relevant to current and future integrated processes. We present a procedure for using x-ray reflectivity to measure the coefficient of thermal expansion of sub-micron dielectric thin films. In particular, we elucidate the thin film mechanics required to extract this parameter for a supported film as opposed to a free-standing film. Results of measurements for a series of plasma-enhanced chemical vapor deposited and spin-on low-k dielectric thin films will be provided and compared.

The implementation of porous low-k and ultra-low k dielectrics to reduce RC delay in integrated circuit interconnect wiring has been fraught with numerous challenges. The obvious challenges of materials design and preservation of the desired electrical and mechanical properties upon subsequent processing have been significant. The vulnerability of these films to damage from fast ion and radiation damage will be discussed in the context of post-deposition processing (including low-k cure and plasma processing damage). This paper attempts to review the challenges associated with destructive and non-destructive measurement of low k dielectric films with respect to underlying physical principles of the metrology. Metrology techniques, assumed to be non-destructive based on experience with dense silicon dioxide, will be discussed with regards to newer and more fragile low-k dielectric films.

The interaction of the wafer, slurry and pad determines the material removal rate during Chemical Mechanical Planarization (CMP). Dual emission laser induced fluorescence (DELIF) provides a means to measure the slurry layer thickness between the wafer and a Fruedenbergy FX9 pad during CMP with high spatial (4.3 μm/pixel) and temporal resolution (2 Hz). In this paper we present some preliminary measurements of pad compression using DELIF to measure the standard deviation of asperity height. Static slurry layer images were captured at high (70 kPa) and low (0 kPa) down-force applied to the wafer. In-situ, dynamic images at 10 kPa downforce applied to etched wafers were imaged. Two wafers were etched such that they contain square wells, one wafer with 27 μm and the other will 14.5 μm deep wells. In the static case, asperity compression is directly related the amount of fluid displaced. In the dynamic case, asperity compression is 35% greater under the 27 μm wells than the 14.5 μm wells.

One of the critical parameters in chemical mechanical polishing (CMP) technology is adhesion between abrasive particles and surfaces being polished. Accumulated up to date theoretical and experimental facts insist that development of advanced material removal and cleaning methods requires understanding and evaluation of particle adhesion in these processes. To this end, our research focuses on AFM studies of interaction between the slurry particles and different substrates treated by CMP processes. To conduct adhesion measurements, the particles present in a CMP system and model latex particle were first attached to the surface of silicon wafer covered with monolayer of polymer(s) having high affinity to particles and the silicon wafer. Glass/quartz sphere (10-60 microns) was attached to AFM cantilever with appropriate spring constant. (The sphere represented the surface of material being polished and might be covered with various materials during future investigations.) Next, AFM force volume mode, which utilizes the collection of the force-distance curves over selected surface areas, was used for the adhesion measurements.

The drive for improved performance of microelectronic devices has led to the prevalence of copper metallization and the aggressive development of low-permittivity (low-κ) dielectric materials for use as interlayer dielectrics in BEOL interconnect structures. Progressive scaling of metal line widths coupled with the need to incorporate ultra low-κ (ULK) dielectrics, with κ<2.2, presents numerous challenges for integration and reliability. Perhaps the most significant challenge for the 90nm technology node and beyond is successful planarization of Cuinterconnect structures by chemical mechanical polishing (CMP). The present paper will discuss the general integration challenges and key structural reliability issues for chemical mechanical polishing of Cu-interconnects incorporating ULK dielectric materials.

Chemical–mechanical polishing, or planarization (CMP), has emerged as an increasingly important technology for integrated-circuit manufacturing. Consumables used during CMP interact in a complex manner with the polishing tool, the process conditions, and the wafer being polished. In this article, several advanced analytical methods are used to analyze the properties of slurries and pads under conditions similar to those found during CMP processing. Some of the key findings are that under these process conditions, pads can be stabilized with a heat treatment prior to installation on the polisher; pads absorb slurries at different rates, and slurries also react with the pads; and the mechanical properties of the pads are dependent on the orientation of the grooves on the pad. Dynamic rheometry was used to detect de-agglomeration in sheared slurries.