Willi Volksen

Low Dielectric Constant Materials

Modern computer microprocessor chips are marvels of engineering complexity. For the current 45 nm technology node, there may be nearly a billion transistors on a chip barely 1 cm2 and more than 10 000 m of wiring connecting and powering these devices distributed over 9-10 wiring levels. This represents quite an advance from the first INTEL 4004B microprocessor chip introduced in 1971 with 10 μm minimum dimensions and 2 300 transistors on the chip! It has been disclosed that advanced microprocessor chips at the 32 nm node will have more than 2 billion transistors.1 For instance, Figure 1 shows a sectional 3D image of a 90 nm IBM microprocessor, containing several hundred million integrated devices and 10 levels of interconnect wiring, designated as the back-end-of-the-line (BEOL). Since the invention of microprocessors, the number of active devices on a chip has been exponentially increasing, approximately doubling every two years. This trend was first described in 1965 by Gordon Moore,2 although the original discussion suggested doubling the number of devices every year, and the phenomenon became popularly known as Moore’s Law. This progress has proven remarkably resilient and has persisted for more than 50 years. The enabler that has permitted these advances is known as scaling, that is, the reduction of minimum device dimensions by lithographic advances (photoresists, tooling, and process integration optimization) by ∼30% for each device generation.3 It allowed more active devices to be incorporated in a given area and improved the operating characteristics of the individual transistors. It should be emphasized that the earlier improvements in chip performance were achieved with very few changes in the materials used in the construction of the chips themselves. The increase of performance with scaling * Corresponding author. E-mail: gdubois@us.ibm.com. † IBM Almaden Research Center. ‡ Stanford University. Willi Volksen received his B.S. in Chemistry (magna cum laude) from New Mexico Institute of Mining and Technology in 1972 and his Ph.D. in Chemistry/Polymer Science from the University of Massachusetts, Lowell, in 1975. He then joined the research group of Prof. Harry Gray/Dr. Alan Rembaum at the California Institute of Technology as a postdoctoral fellow and upon completion of the one-year appointment joined Dr. Rembaum at the Jet Propulsion Laboratory as a Senior Chemist in 1976. In 1977 Dr. Volksen joined the IBM Research Division at the IBM Almaden Research Center in San Jose, CA, where he is an active research staff member in the Advanced Materials Group of the Science and Technology function.

Application of Complex Macromolecular Architectures for Advanced Microelectronic Materials

The distinctive features of well-defined, three-dimensional macromolecules with topologies designed to enhance solubility and amplify end-group functionality facilitated nanophase morphologies in mixtures with organosilicates and ultimately nanoporous organosilicate networks. Novel macromolecular architectures including dendritic and star-shaped polymers and organic nanoparticles were prepared by a modular approach from several libraries of building blocks including various generations of dendritic initiators and dendrons, selectively placed to amplify functionality and/or arm number, coupled with living polymerization techniques. Mixtures of an organosilicate and the macromolecular template were deposited, cured, and the phase separation of the organic component, organized the vitrifying organosilicate into nanostructures. Removal of the sacrificial macromolecular template, also denoted as porogen, by thermolysis, yielded the desired nanoporous organosilicate, and the size scale of phase separation was strongly dependent on the chain topology. These materials were designed for use as interlayer, ultra-low dielectric insulators for on-chip applications with dielectric constant values as low as 1.5. The porogen design, chemistry and role of polymer architecture on hybrid and pore morphology will be emphasized.

Light-induced orientation in a high glass transition temperature polyimide with polar azo dyes in the side chain

We report on both polar and nonpolar light-induced orientation of a polyimide of high glass transition temperature (Tg ≈ 210 °C) with nonlinear optical azo dye molecules in the side chain. This photoinduced orientation is shown to occur at room temperature, i.e., at least 190 °C below the Tg value of the polymer, which indicates that the photoisomerization-induced movement of the nonlinear optical chromophores induces, in turn, a movement of the polyimide main chain. This allows for an efficient orientation of the dye molecules in spite of the stiffness of the polyimide main chain. A nonpolar orientation is induced by polarized light irradiation alone, whereas polar orientation is achieved by application of a dc field during the photoisomerization process. Further light irradiation in the absence of a dc field destroys the previously induced stable polar order. A detailed theoretical study of this light-induced depoling process is also presented.

Re‐evaluation of the thermal stability of optically nonlinear polymeric guest‐host systems

Guest‐host polymer systems with potential use in electro‐optic devices are discussed. The polymer host is a polyimide and the guest chromophores are 2,4,5‐triarylimidazoles (lophines). Poling stabilities have been obtained by extrapolating the second harmonic generation decay using a stretched exponential function and extrapolated lifetimes greater than a year at 80 °C have been obtained. In addition, an apparent relationship between the stability of poled order and the glass transition temperature is discussed.

Effect of plasma interactions with low- κ films as a function of porosity, plasma chemistry, and temperature

Integration of new low-κ interlayer dielectrics (ILD) with current damascene schemes is a continuing issue in the microelectronics industry. During integration of the ILD, processing steps such as plasma etching, resist strip, and chemical-mechanical planarization are known to chemically alter a layer of the dielectric. Here, porous organosilicate glass (OSG) ILD films, which—according to the 2004 edition of the International Technology Roadmap for Semiconductors—are projected for use in the 65 and 45 nm nodes, are investigated. spectroscopic ellipsometry, x-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy are used to characterize the modified layer of the ILD after exposure to O2 or H2 resist strip plasmas. The effects of the two types of plasma etch chemistries on the formation of the modified layer were found to differ significantly. These effects include both the degree of modification (i.e., chemical composition) and depth of the modified layer. A key difference between the...

Application of the Protection/Deprotection Strategy to the Science of Porous Materials

The strategy of introducing protecting groups in organic chemistry has enabled major progress in multistep synthesis. [ 1 , 2 ] We believe that applying such a powerful concept to the processing of porous materials could signifi cantly extend the range of their applications. In microelectronics, porous thin fi lms have been used to both increase microprocessor performance and reduce power consumption. The extendibility of this approach relies on the successful integration of highly porous materials (ultralowk , ULK) at ever smaller dimensions. As of today, materials with a dielectric constant ( k ) as low as 2.4 are commonly used in manufacturing. [ 3 ] However, below this dielectric constant, increased pore size and interconnectivity lead to high sensitivity to wet and dry processes, which ultimately results in device failure. Here, we show that the porous structure can be fi lled with an organic polymer, which then acts as a protective agent during the various aggressive processing steps. We have demonstrated the effi cacy of this approach using a highly porous ( k = 2.0) organosilicate dielectric fi lm. The fi lled composite fi lm was almost impervious to processing damage and its porosity was fully regenerated after integration, while the unprotected, porous fi lm suffered severe structural and physical damage. We believe that this protection strategy will facilitate the integration of materials at k < 2.4 in future electronic devices. [ 4 ] In addition, using this concept it is possible to selectively block pores of different size and/or further independently modify the external and internal thin-fi lm surfaces. Therefore, it holds great promise for the selective functionalization of porous materials in areas such as membranes, biosensors, and catalysis. [ 5 , 6 ]

Pore size distributions in nanoporous methyl silsesquioxane films as determined by small angle x-ray scattering

Small angle x-ray scattering (SAXS) measurements were performed on nanoporous methyl silsesquioxane films that were generated by the incorporation of a sacrificial polymeric component into the matrix and subsequently removed by thermolysis. The average pore radii ranged from 1 to 5 nm over a porosity range of ∼5–50%. The distribution in pore size was relatively broad and increases in breadth with porosity. The values and observations obtained by SAXS are in good agreement with field emission scanning electron microscopy.

Porosity effect on the dielectric constant and thermomechanical properties of organosilicate films

This letter reports a study of the porosity effect on material properties of methylsilsesquioxane films, including the dielectric constant, thermal conductivity, and thermal stress behavior. In a porosity range from 0% to 50%, both the dielectric constant and thermal conductivity decreased with increasing porosity and no significant change was observed at the percolation point where pores became interconnected. In comparison, the stress–temperature slope also decreased with porosity, but as the porosity approached the percolation point, the slope showed a large drop of 40%, indicating a significant degradation of the thermomechanical properties due to percolation of pores. Assuming the coefficients of thermal expansion remain at 17 ppm/°C within the porosity range, the change in the stress–temperature slope corresponds to a decrease of the biaxial modulus from 7 to 5 GPa around the percolation point.

Light-induced orientation in azo-polyimide polymers 325 degrees C below the glass transition temperature

We report on light-induced nonpolar orientation of sidechain nonlinear-optical polyimides [glass transition temperatures (Tg) up to 350 °C] containing no flexible connectors or tethers. The nonlinear-optical azo-dye chromophore is incorporated through the donor substituent as a part of the polymer backbone. This impressive photoinduced orientation occurs at room temperature, i.e., at least 325 °C below the Tg of one of the polymers that we investigated. Furthermore, it is shown that, after photoinduced ordering, this polymer must be heated to 350 °C to induce main-chain movement and to erase the orientation, whereas the direction of orientation of the chromophores can easily be controlled at room temperature simply by choice of the appropriate polarization of the irradiating light. This light-induced orientation process is shown to be useful for storing images in waveguides.

Effect of precursor history on residual stress and relaxation behaviour of high temperature polyimides

Abstract Using a wafer bending technique, residual stress and its relaxation were investigated for four different kinds of high temperature polyimides: rodlike PMDA-PDA, semi-rigid BPDA-PDA, semi-flexible PMDA-ODA, and flexible BTDA-ODA. Residual stress was measured in situ on silicon wafers during thermal imidization of the polyimide precursors and subsequent cooling of the resulting polyimides as a function of temperature over the range of 25–400°C. The stress of the cured films at room temperature was significantly relaxed by the moisture uptake of the films rather than their creep behaviour. Both residual stress and moisture-induced stress relaxation in the cured polyimide films were strongly dependent upon the molecular nature (that is, molecular chain rigidity, degree of molecular orientation and packing), as well as the precursor origin. In addition, the diffusion coefficients of water in the cured polyimide films were estimated by best-fitting stress relaxation against time profiles.