Controlled/living radical polymerization: Features, developments, and perspectives

Organic semiconductors that can be fabricated by simple processing techniques and possess excellent electrical performance, are key requirements in the progress of organic electronics. Both high semiconductor charge-carrier mobility, optimized through understanding and control of the semiconductor microstructure, and stability of the semiconductor to ambient electrochemical oxidative processes are required. We report on new semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices. Relatively large crystalline domain sizes on the length scale of lithographically accessible channel lengths (∼200 nm) were exhibited in thin films, thus offering the potential for fabrication of single-crystal polymer transistors. Good transistor stability under static storage and operation in a low-humidity air environment was demonstrated, with charge-carrier field-effect mobilities of 0.2–0.6 cm2 V−1 s−1 achieved under nitrogen.

Liquid-crystalline semiconducting polymers with high charge-carrier mobility.

The ever increasing requirements for electrical performance of on-chip wiring has driven three major technological advances in recent years. First, copper has replaced Aluminum as the new interconnect metal of choice, forcing also the introduction of damascene processing. Second, alternatives for SiO2 with a lower dielectric constant are being developed and introduced in main stream processing. The many new resulting materials needs to be classified in terms of their materials characteristics, evaluated in terms of their properties, and tested for process compatibility. Third, in an attempt to lower the dielectric constant even more, porosity is being introduced into these new materials. The study of processes such as plasma interactions and swelling in liquid media now becomes critical. Furthermore, pore sealing and the deposition of a thin continuous copper diffusion barrier on a porous dielectric are of prime importance. This review is an attempt to give an overview of the classification, the character...

Low dielectric constant materials for microelectronics

The cost-effective production of flexible electronic components will profit considerably from the development of solution-processable, organic semiconductor materials. Particular attention is focused on soluble semiconductors for organic field-effect transistors (OFETs). The hitherto differentiation between "small molecules" and polymeric materials no longer plays a role, rather more the ability to process materials from solution to homogeneous semiconducting films with optimal electronic properties (high charge-carrier mobility, low threshold voltage, high on/off ratio) is pivotal. Key classes of materials for this purpose are soluble oligoacenes, soluble oligo- and polythiophenes and their respective copolymers, and oligo- and polytriarylamines. In this context, micro- or nanocrystalline materials have the general advantage of somewhat higher charge-carrier mobilities, which, however, could be offset in the case of amorphous, glassy materials by simpler and more reproducible processing.

Organic semiconductors for solution-processable field-effect transistors (OFETs).

“Life is branched” was the motto of a special issue of Macromolecular Chemistry and Physics1 on “Branched Polymers”, indicating that branching is of similar importance in the world of synthetic macromolecules as it is in nature. The significance of branched macromolecules has evolved over the last 30 years from just being considered as a side reaction in polymerization or as a precursor step in the formation of networks. Important to this change in perception of branching was the concept of “polymer architectures”, which formed on new starand graft-branched structures in the 1980s and then in the early 1990s on dendrimers and dendritic polymers. Today, clearly, controlled branching is considered to be a major aspect in the design of macromolecules and functional material. Hyperbranched (hb) polymers are a special type of dendritic polymers and have as a common feature a very high branching density with the potential of branching in each repeating unit. They are usually prepared in a one-pot synthesis, which limits the control on molar mass and branching accuracy and leads to “heterogeneous” products with a distribution in molar mass and branching. This distinguishes hyperbranched polymers from perfectly branched and monodisperse dendrimers. In the last 20 years, both classes of dendritic polymers, dendrimers as well as hb polymers, have attracted major attention because of their interesting properties resulting from the branched architecture as well as the high number of functional groups.2 The challenging synthesis of the dendrimers attracted especially scientists with a strong organic chemistry background and led to beautifully designed macromolecules, which allowed a deeper insight into the effect of branching and functionality. Dendrimers have been considered as perfect “nano-objects” where one can control perfectly size and functionality, which is of high interest in nanotechnology and biomedicine. hb polymers, however, were considered from the beginning as products suitable for larger-scale application in typical polymer fields like coatings and resins, where a perfect structure is sacrificed for an easy and affordable synthetic route. Thus, the first structures that were reported paralleled the chemistry used for linear polymers like typical polycondensation for polyester synthesis. More recently, unconventional synthetic methods have been adopted also for hb polymers and related structures. Presently, a vast variety of highly branched structures have been realized and studied regarding their properties and potential application fields. Excellent reviews appeared covering synthesis strategies, properties, and applications, like the very recent tutorial by Carlmark et al.,3 the comprehensive book on hyperbranched polymers covering extensively synthesis and application * E-mail: voit@ipfdd.de; lederer@ipfdd.de. Chem. Rev. 2009, 109, 5924–5973 5924

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Hyperbranched and highly branched polymer architectures--synthetic strategies and major characterization aspects.

For faster, smaller, and higher performance integrated circuits, a low dielectric constant insulator is required to replace silicon dioxide. Here the properties of a new dielectric—SiLK resin, a solution of a low-molecular-weight aromatic thermosetting polymer—are reviewed and examples of its application in the fabrication of interconnect structures, such as the one shown in the Figure, are given.

Development of a Low‐Dielectric‐Constant Polymer for the Fabrication of Integrated Circuit Interconnect

A new class of organic dielectrics, benzocyclobutenes, 1, are described and their application to the fabrication of thin film multichip modules is detailed. Key properties for3, a siloxy containing BCB derivative include low dielectric constant (2.7), low loss (0.008 at 1 MHz), low water absorption (0.25% after 24 h water boil) and high degree of planarization (>90% from one layer coverage). All other properties meet the requirements necessary for fabrication of thin film MCM structures.

Benzocyclobutene (BCB) dielectrics for the fabrication of high density, thin film multichip modules

This paper addresses the drift of copper ions (Cu/sup +/) in various low-permittivity (low-/spl kappa/) polymer dielectrics to identify copper barrier requirements for reliable interconnect integration in future ULSI. Stressing at temperatures of 150-275/spl deg/C and electric fields up to 1.5 MV/cm was conducted on copper-insulator-silicon capacitors to investigate the penetration of Cu/sup +/ into the polymers. The drift properties of Cu/sup +/ in six industrially relevant low-/spl kappa/ organic polymer insulators-parylene-F, benzocyclobutene, fluorinated polyimide, an aromatic hydrocarbon, and two varieties of poly(arylene ether)-were evaluated and compared by capacitance-voltage, current-time, current-voltage, and dielectric time-to-failure measurements. Our study shows that Cu/sup +/ drifts readily into fluorinated polyimide and poly(arylene ether), more slowly into parylene-F, and even more slowly into benzocyclobutene. Among these polymers, the copper drift barrier property appears to be improved by increased polymer crosslinking and degraded by polar functional groups in the polymers. A thin nitride cap layer can stop the drift. A physical model has been developed to explain the kinetics of Cu/sup +/ drift.

Kinetics of copper drift in low-/spl kappa/ polymer interlevel dielectrics

Benzocyclobutene (DVS-BCB) polymer as an interlayer dielectric (ILD) material

A suitable cross-linkable matrix precursor and a poragen can be treated to form a porous cross-linked matrix having a Tg of greater than 300 °C. The porous matrix material has a lower dielectric constant than the corresponding non-porous matrix material, making the porous matrix material particularly attractive for a variety of electronic applications including integrated circuits, multichip modules, and flat panel display devices.

Paul H. Townsend

Papers

Development of a Low‐Dielectric‐Constant Polymer for the Fabrication of Integrated Circuit Interconnect

Benzocyclobutene (BCB) dielectrics for the fabrication of high density, thin film multichip modules

Kinetics of copper drift in low-/spl kappa/ polymer interlevel dielectrics

Benzocyclobutene (DVS-BCB) polymer as an interlayer dielectric (ILD) material

Composition containing a cross-linkable matrix precursor and a poragen, and a porous matrix prepared therefrom