An X-ray microdiffraction dedicated beamline, combining white and monochromatic beam capabilities, has been built at the Advanced Light Source. The purpose of this beamline is to address the myriad problems in Materials Science and Physics that require submicron x-ray beams for structural characterization. Many such problems are found in the general area of thin films and nano-materials. For instance, the ability to characterize the orientation and strain state in individual grains of thin films allows us to measure structural changes at a very local level. These microstructural changes are influenced heavily by such parameters as deposition conditions and subsequent treatment. The accurate measurement of strain gradients at the micron and sub-micron level finds many applications ranging from the strain state under nano-indenters to gradients at crack tips. Undoubtedly many other applications will unfold in the future as we gain experience with the capabilities and limitations of this instrument. We have applied this technique to measure grain orientation and residual stress in single grains of pure Al interconnect lines and preliminary results on post-electromigration test experiments are presented. It is shown that measurements with this instrument can be used to resolve the complete stress tensor (6 components) in a submicron volume inside a single grain of Al under a passivation layer with an overall precision of about 20 MPa. The microstructure of passivated lines appears to be complex, with grains divided into identifiable subgrains and noticeable local variations of both tensile/compressive and shear stresses within single grains.

In advanced multi-level metallization schemes, the application of copper as interconnect metal requires the prevention of Cu diffusion into the active area and into interlevel dielectrics by total encapsulation of Cu with barrier films. Critical requirements for diffusion barriers are very small thicknesses, low resistivity, low deposition temperature and conformality on high aspect ratio trenches and vias. For this application, we have studied TiN films deposited by atomic layer chemical vapour deposition (ALCVD) at 400°C and 350°C. This paper discusses the ALCVD TiN films properties and compares them to the properties of TiN deposited by ionized physical vapour deposition (I-PVD).

The ALCVD TiN deposited at 400°C exhibits a resistivity comparable to I-PVD TiN resistivity. However, the ALCVD films deposited at 350°C show higher resistivity. The Cl residue in ALCVD films is 1.5% at 400°C and 3% at 350°C. The microstructure is fine-grained. A very high level of conformality on trenches characterizes the ALCVD TiN films. We believe this property gives a clear advantage over the sputtered I-PVD TiN since its coverage in high aspect ratio trenches and vias is expected to be limited for the future devices interconnection scheme.

We have investigated the stress interaction between via and polygranular cluster in the pure Al line using 1-dimensional computer simulation. The conventional belief was that the fastest stress evolution at the via occurs when the polygranular cluster is just below (or above) the via. However, the electromigration induced stress at the via would be faster when a cluster is apartfrom via because the stress interaction between via and clusters may assist electromigration. We simulated the time that the via reaches a certain stress value as a function of the distance of the cluster. It gives a specific distance where the time was minimum (i.e the fastest stress evolution). We named the position as the Fastest Stress Enhancing Polygranular cluster Position (FaSEPP). As a function of the current density, the FaSEPP decreases.

Poly(tetrafluoroethylene) (PTFE)/siloxane nanocomposites have been prepared as ultra low-k dielectrics. These new nanocomposites show excellent high-temperature mechanical properties compared to unfilled PTFE while their dielectric constant almost remains unchanged. Specifically, the data from the dynamic mechanical study indicates that these nanocomposites have the mechanical behavior similar to that of crosslinked polymers. Small-angle neutron scattering (SANS) has been carried out to characterize the phase morphology of the PTFE/siloxane nanocomposites and the size of the inorganic networks. It has been shown that no phase separations or orientations appear in these nanocomposites in the range of 12 to 469 nm. These SANS results suggest that these materials are single-phase nanocomposites that are very homogeneous and isotropic. They are basically PTFE-based molecular composites.

We have developed a methodology and a prototype tool for making computationally efficient circuit-level assessments of interconnect reliability. A key component of this process has been the development of simple analytic models that relate the reliability of the complex structures in layouts to the simpler straight, junction-free lines of uniform width that are typically used in lifetime tests. We have considered interconnect trees as the fundamental reliability units, where trees can have multiple junctions and limbs, and can also have width variations. We have developed analytic methods for identifying trees which are immune to failure, and have demonstrated that computationally simple techniques lead to the identification of a large fraction of the trees in a circuit as immune to failure (i.e., that they are ‘immortal’). These trees therefore need not be considered in further analyses. Using simulations and analytic treatments we have also developed default models which allow estimation of the reliability of the remaining trees. These models have been tested and validated them through experiments on simple tree structures with junctions and line-width transitions. Our prototype circuit-level reliability analysis tool projects the reliability of circuits based on specific layouts, and provides a rank listing of the reliability of mortal trees. This allows the user to accept the assessment as is, to carry out more accurate but computationally-intensive analyses of the least reliable trees, or to modify the layout or process to address reliability concerns and reanalyze the reliability.

Depth profiled positronium annihilation lifetime spectroscopy (PALS) has been used to probe the pore characteristics (size, distribution, and interconnectivity) in thin, porous films, including silica and organic-based films. The technique is sensitive to all pores (both interconnected and closed) in the size range from 0.3 nm to 300 nm, even in films buried under a diffusion barrier. PALS may be particularly useful in deducing the pore-size distribution in closed-pore systems where gas absorption methods are not available. In this technique a focussed beam of several keV positrons forms positronium (Ps, the electron-positron bound state) with a depth distribution that depends on the selected positron beam energy. Ps inherently localizes in the pores where its natural (vacuum) annihilation lifetime of 142 ns is reduced by collisions with the pore surfaces. The collisionally reduced Ps lifetime is correlated with pore size and is the key feature in transforming a Ps lifetime distribution into a pore size distribution. In thin silica films that have been made porous by a variety of methods the pores are found to be interconnected and an average pore size is determined. In a mesoporous methyl-silsesquioxane film with nominally closed pores a pore size distribution has been determined. The sensitivity of PALS to metal overlayer interdiffusion is demonstrated. PALS is a non-destructive, depth profiling technique with the only requirement that positrons can be implanted into the porous film where Ps can form.

A new characterization tool based on ultrasonic force microscopy (UFM) has been developed to image the nanometer scale mechanical properties of aluminum/low-k polymer damascence integrated circuit (IC) test structures. Aluminum and polymer regions are differentiated on the basis of elastic modulus with a spatial resolution ≤ 10 nm. This technique reveals a reactive-ion etch (RIE)-induced hardening of the low-k polymer that is manifested in the final IC test structure by a region of increased hardness at the aluminum/polymer interface. The ability to characterize nanometer scale mechanical properties of materials used for IC back-end-of-line (BEOL) manufacture offers new opportunities for metrological reliability evaluation of low-k integration processes.

A new class of copper(II) precursors containing silylated β-diketonate ligands has been developed for the chemical vapor deposition (CVD) growth of copper for applications in ultralarge scale integration interconnect schemes, including conformal seed layer for gigascale Cu integration and ultrathin Cu lines with enhanced conductivity characteristics. Cu(tmshd)2 (tmshdH = 2,2,6,6-tetramethyl-2-sila-3,5-heptanedione) has been studied as a representative compound and is appreciably more volatile than nonsilylated compounds such as Cu(tmhd)2 or Cu(tmod)2 (tmhdH = 2,2,6,6-tetramethyl-3,5-heptanedione; tmodH = 2,2,7-trimethyl- 3,5- octanedione). The CVD process employs Cu(tmshd)2 as the metalorganic precursor and hydrogen as the reducing and carrier gas. These films were deposited using a custom made, cold wall, stainless steel CVD. Copper films were produced at a substrate temperature of 250 – 320 °C, hydrogen flow rates of 20 - 100 sccm, deposition pressure of 0.2 - 1 Torr, and a source temperature of 120 – 135 °C. The films were analyzed by X-ray photoelectron spectroscopy, cross section scanning electron microscopy, transmission electron microscopy, four-point resistivity probe, Rutherford backscattering spectrometry and Auger electron spectroscopy.

A low κ dielectric barrier/etch stop has been developed for use in copper damascene application. The film is deposited using methane, silane and argon as precursors in a HDP-CVD reactor. The film has a dielectric constant of 4.2 which is lower than the dielectric constant of conventional SiC or plasma silicon nitride (>7). Film characterization including physical, electrical, adhesion to ILD films, etch selectivity, and copper diffusion barrier properties show that this film is a better barrier than silicon nitride for low κ copper damascene interconnects. This film consists of a refractive index in the range of 1.7 to 1.8, a compressive stress of 1.0-1.5×109 dynes/cm2, and a leakage current of 5.0×10−10 A/cm2 at 1 MV/cm. When integrated in-situ with HDP-FSG, an effective dielectric constant of 3.5 can be achieved.

We describe a method for determining the local strain state of passivated aluminum metal lines from single grains within 2.6 µm × 7.0 µm × 0.75 µm sized regions along the line. X-ray microbeam diffraction is used to obtain localized measurements of thermal and electromigration-induced strain during 37 hours of electromigration in a passivated 2.6 µm-wide, 300 µm-long pure Al conductor line at a current density of 4.2×105 A/cm2 and temperature of 270°C. Diffraction from single grains is used to measure both the in-plane and normal components of strain and their evolution during electromigration at several positions along the line.

High-resolution X-ray reflectivity and small angle neutron scattering measurements are used as complementary techniques to characterize the structure and properties of porous thin films for use as low-k interlevel dielectric (ILD) materials. With the addition of elemental composition information, the average pore size, porosity, pore connectivity, matrix density, average film density, film thickness, coefficient of thermal expansion, and moisture uptake of porous thin films are determined. Examples from different classes of materials and two analysis methods for small angle neutron scattering data are presented and discussed.

Chemical-Mechanical Polishing has been revealed as an attractive technique for poly-Si of trench planalization. Major issue of the process integration is pattern erosion after over polishing. A new process with silica slurry containing organic surfactant is reported in this paper. A patterned wafer after conventional CMP process is eroded by over polishing, however, the new process conducts small erosion for wide trenches. The organic surfactant is well known as a inhibitor for the protection of poly-Si from alkaline, and the new slurry shows a large pH dependency of the viscosity. The experimental work has been focused on the viscosity, and the mechanism of the small erosion is discussed. This new process should be useful for recessing poly-Si by CMP, because it keeps the erosion level very low.

A plasma deposited SiOC very low k (VLK) interlayer dielectric (ILD) film has been developed which can be tuned to 2.5 = k = 3.0, demonstrates very good thermal stability, excellent adhesion properties, acceptable hardness, and an indication that it may be extendible to k < 2.5. This paper will disclose properties of this SiOC film which are important to a VLK ILD application.

A study was carried out to investigate the effect of current density and pulse waveform on the filling of line trenches and contact vias with aspect ratio of 2:1 for sub-0.25 µm device manufacturing using normal pulse plating of copper. The growth pattern of the copper films deposited using 0.05 and 0.10 A/cm2 current density gave no significant difference. Small grains were seen to have nucleated uniformly across the line trenches and via holes after 1 second of electroplating. With increasing the deposition time to 2 seconds, a slight buildup of the film thickness was observed in both trenches and vias without significant increase in the size of the copper grains. Grain growth involving the coalescence of small grains occurred after 5 seconds of plating and a further buildup in thickness and fill up of the trenches and vias occurred after 10 seconds of deposition.

When the patterned wafers were plated with a pulse waveform of 3 ms on and 0.5 ms off, the filling of trenches could not be complete after 30 seconds of electroplating. A complete filling of the trenches was achieved within 30 seconds of deposition using a pulse waveform of 6 to 8 ms on and 1 to 2 ms off. When the on-period was increased above this range to 9.9 ms, voids were observed at the centre of the via holes.

A model is proposed to describe the temperature dependence of the aluminum oxynitride (AlxOyNz) diffusion barrier formation during a silver self-encapsulation process. These barrier layers form in the temperature range of 500-725 °C during anneals of the Ag/Al bilayers on oxidized Si substrates in an ammonia ambient. Experimental results show that temperature has a significant effect on the kinetics of this process. In this investigation, the diffusion of Al atoms through the Ag layers during self-encapsulation process is modeled using an analytical solution to a modified diffusion equation. This model shows that higher anneal temperatures will minimize the retardation effect by i) reducing the chemical affinity between Al and Ag atoms, and ii) allowing more Al atoms to surmount the interfacial energy barrier between the metal layer (Ag) and the newly formed AlxOyNz diffusion barriers. The theoretical predictions on the amount of segregated Al atom correlate well with experimental results from Rutherford backscattering spectrometry. This model in addition confirms the self-passivation characteristics of AlxOyNz diffusion barriers formed by Ag/Al bilayers annealed between 500∼725 °C.

The adhesion between several materials implemented in Cu/low-k integration is studied. Adhesion issues at different interfaces are important with regard to the reliability of back-end processing. Layered test structures are processed to study different interfaces. A tangential shear tester allows quantifying the adhesion force at the interface and provides a relative measurement to compare various materials. Failed interfaces are analyzed using auger electron spectroscopy (AES) and scanning electron microscopy (SEM). Among all studied structures, the strongest interface is seen between a barrier (Ti(N), Ta(N), WxN) and Cu. A weaker interface proves to be between a low-k dielectric and Cu. However, the presence of a barrier increases the adhesion. The weakest interface occurs between an oxide cap and the low-k material, with a lower adhesion when the low-k material is fluorinated. The low-k/cap oxide interface forms a critical issue with regard to Cu/low-k integration processing such as chemical mechanical polishing (CMP). All test structures show no significant degradation of the adhesion after a thermal cycle up to 400°C.

A methodology to characterize nanoporous thin films based on a novel combination of high-resolution specular x-ray reflectivity and small-angle neutron scattering has been advanced to accommodate heterogeneities within the material surrounding nanoscale voids. More specifically, the average pore size, pore connectivity, film thickness, wall or matrix density, coefficient of thermal expansion, and moisture uptake of nanoporous thin films with non-homogeneous solid matrices can be measured. The measurements can be performed directly on films up to 1.5 µm thick while supported on silicon substrates. This method has been successfully applied to a wide range of industrially developed materials for use as low-k interlayer dielectrics.

Chemical mechanical planarization (CMP) has been widely used for planarization of ILD, STI, plug and wiring processes. In post metal CMP cleaning processes, there are still many problems to be solved. There are several surfaces of materials, such as wiring materials, barrier materials, dielectric materials etc., on the wafer that must be cleaned at the same time,. It is also important to clean these different surfaces without any chemical or mechanical damage. We have confirmed that the Electrolyzed D.I.water is effective in post CMP cleaning for controlling the surface condition during cleaning and leaving a robust surface after CMP. We describe the Electrolyzed D.I.water system and present some results on the cleaning capability and control of the metal surface for application to cleaning after a metal CMP process.

For the benefit of reducing capacitance in multilevel interconnect technology, low-k dielectric HSQ (hydrogen silsesquioxane) has been used as a gapfill material in Al-metallization- based non-etchback embedded scheme. The vias are consequently fabricated through the HSQ layer followed by W plug deposition. In order to reduce the extent of via poisoning and achieve good W/Al contact, thin Ti/TiN stack films are typically deposited before via plug deposition. In this case, HSQ makes direct contact with the Ti layer. The reliability of the Ti/HSQ structures at elevated temperatures has been systematically studied in this work by using a variety of techniques. These results are also compared with those from Ti/TEOS (Tetraethylorthosilicate) structure, where TEOS is a conventional intra-metal dielectric. When the temperature is below 550 °C, a significant number of oxygen atoms are observed to diffuse into the titanium layer. The primary source of oxygen is believed to come from the HSQ film. When the temperature is above 550 °C, HSQ starts to react with Ti. At 700 °C, a TiO/Ti5Si3/HSQ stack structure forms. The Ti/HSQ system exhibits a higher reactivity than that of the Ti/TEOS system.

Fluorinated amorphous carbon (a-C:F) thin films were deposited by inductively coupled plasma enhanced chemical vapor deposition (ICP-CVD) with increasing CF4:CH4 gas flow rate ratio, and then annealed with increasing annealing temperature (100, 200, 300, and 400.). We have found the reduction mechanism of the dielectric constant and the thermally stable condition for the a-C:F films. On the basis of the results, the optimal condition to satisfy both the low dielectric constant and the thermal stability is followed as; the a-C:F films have to have the compatible F content to make a compromise between the two properties; the C-Fx bonding configuration has to exist as a form of C-F2 & C-F3 instead of C-F; The films should be somewhat cross-linked structure.