Hua Gen Peng

Impact of reductive N2∕H2 plasma on porous low-dielectric constant SiCOH thin films

Porous low-dielectric constant (low-κ) SiCOH thin films deposited using a plasma-enhanced chemical-vapor deposition have been comprehensively characterized before and after exposure to a reactive-ion-etch-type plasma of N2 and H2 chemistry. The low-κ film studied in this work is a carbon-doped silicon oxide film with a dielectric constant (κ) of 2.5. Studies show that a top dense layer is formed as a result of significant surface film densification after exposure to N2∕H2 plasma while the underlying bulk layer remains largely unchanged. The top dense layer is found to seal the porous bulk SiCOH film. SiCOH films experienced significant thickness reduction, κ increase, and leakage current degradation after plasma exposure, accompanied by density increase, pore collapse, carbon depletion, and moisture content increase in the top dense layer. Both film densification and removal processes during N2∕H2 plasma treatment were found to play important roles in the thickness reduction and κ increase of this porous ...

Pore Sealing by NH3 Plasma Treatment of Porous Low Dielectric Constant Films

Porous interlayer dielectric films with interconnected pores pose a serious challenge for their integration into next-generation microchips. The opening of interconnected pores in the surface region needs to be sealed to prevent intrusion of atomic layer deposition precursors used to create metal diffusion barriers. In this paper, we report the formation of a thin, nonporous surface layer on a porous methyl-silsesquioxane-based dielectric film by NH 3 plasma treatment. Depth-profiled beam positronium annihilation lifetime spectroscopy was applied to conveniently examine the formation of the dense layer. A nonporous surface layer was readily identified by the curtailment of positronium escape into vacuum through the surface. Among plasma treatments at temperatures ranging from 25 to 300°C for duration of 3-600 s, the best result was achieved at 300°C for 10 s. A very thin skin layer, ∼ 10 nm, could be formed with little damage to the bulk of the low-κ film. This thin skin layer further proved to improve the performance of Ta barriers for Cu diffusion. Chemical analysis, infrared spectroscopy, and sputtering secondary ion mass spectroscopy were also performed to examine how the plasma treatment altered the dielectric film.

Advanced chemical vapor deposition silicon carbide barrier technology for ultralow permeability applications

Plasma-enhanced chemical vapor deposition (PECVD) processes have been developed to produce prototype barrier coatings for protection from detrimental gases. The strategy used is based on a combination of molecular precursor design and advanced plasma processing and represents a route to an effective, barrier solution. Silicon carbide room temperature deposition processes have been established on several reactor systems. The impact of process-operating factors on the structure and barrier performance has been analyzed and a wide range of tunability has been found. A metrology has been developed to estimate the optical, mechanical, and application-relevant barrier properties. In addition, coatings have been analyzed for subnanometer structural defects by positronium annihilation lifetime spectroscopy (PALS). None of the barriers present evidence of any mesopores or open porosity. Furthermore, the amount of nanostructural defects in layers has been found to depend on both plasma chemistry and power. Based on...

Deducing nanopore structure and growth mechanisms in porogen-templated silsesquioxane thin films

Adjusting the functional group of a porogen is found to have a tremendous effect on the pore structre of porous low dielectric constant films with silsesquioxane as the matrix precursor. The pore size and interconnection length measured by positronium annihilation lifetime spectroscopy can be used to deduce the pore shape and its evolution with porosity from templates of isolated porogen molecules through film percolation. Inert, self-linkable, and amphiphilic porogens are demonstrated to randomly aggregate three-dimensionally, linearly polymerize, and form micelles, respectively.

Depth-profiling pore morphology in nanoporous thin films using positronium lifetime annihilation spectroscopy

Positronium annihilation lifetime spectroscopy (PALS) using a positron beam is a proven technique to characterize porosity in amorphous thin film materials. The capability to control the depth of the implanted positrons is unique to beams as compared to traditional bulk PALS techniques. By increasing the positron beam energy, positrons are implanted deeper into the film. Control of the positron implantation depth in beam-PALS allows analysis of sub- micron films, investigation of depth-dependent film inhomogeneities, determination of pore interconnection lengths, and access to buried films under barrier layers. Details on PALS depth profiling and an example of applying the technique to a plasma-enhanced-chemical-vapor- deposited (PECVD) porous film are presented.

Determining Pore Structure and Growth Mechanisms in Templated Nanoporous Low-k Films

Templating is one of the most popular methods for generating nanocomposite and nanoporous films and the resultant pore size and pore interconnection length depend strongly on porogen concentration/porosity among other factors. Positronium Annihilation Lifetime Spectroscopy (PALS) analysis has been performed on a series of films produced using increasing concentrations of a type of cyclodextrin (CD) porogen in a modified silsesquioxane host matrix. PALS reveals the relationship between the resulting pore structure (both size and interconnection length) and porosity, which can be used to deduce pore shape. At low porogen concentration, isolated pores are resolved, but the pore size is consistent with a cluster of two or three CD molecules, rather than an individual one. As the porosity increases, the aggregation of the porogen domains appears to be more 3-dimensional (pseudo-random) with gradual increase in pore size. Computer simulations using a random pore growth model show consistent trends for pore size growth, but the agreement is poor for interconnection length. It is a key demonstration of the usefulness of PALS in untangling the fundamental pore structure and its evolution in porosity. PALS characterization of porosity provides novel feedback in the understanding and design of nanoporous materials.

Compatibility of high pressure cleaning mixtures with a porous low dielectric constant film: A positronium annihilation lifetime spectroscopic study

High pressure CO2 based cleaning mixtures have recently been proposed as an environmentally benign approach for postplasma etch residue removal. These mixtures must remove etch residues without damaging the low-k dielectric film that will be used to isolate interconnect structures in future generation devices. In this work, the compatibility of a CO2-based mixture with a porous low-k film is evaluated. Positronium annihilation lifetime spectroscopy (PALS) is used to monitor the change in pore size and film chemistry in a porous methyl silsesquioxane film after treatments under several different elevated pressure conditions. Spectroscopic ellipsometry and infrared spectroscopy are used to complement the PALS technique in order to better understand cleaning mixture effects on the dielectric film. CO2–TMAHCO3–methanol mixtures cause negligible changes in pore dimensions and bulk composition of the film. The high pressure treatments cause a small decrease in positronium formation which may be attributed to co...