Polyimides dielectric studies

Recently, the same series of six polyimides was studied by positron annihilation spectroscopy to determine die fractional free volume directly. In all three H/F analogue pairs, the increased free volume of the fluorinated polymer accounted for around 50% of the observed decrease in refractive index and dielectric constant. This result confims an astonishingly large free volume contribution predicted by our earlier estimates.Future work will investigate the generality of this result to other polymer systems. 

Conditions have been defined for applying polyimide coatings onto the silicon wafer as passivation and/or dielectric. Processing variables studied included the critical areas of adhesion, cure cycle and thermostability. Aminosilane was shown to be effective adhesion promoter. The rate of imidization was followed by F.T.I.R. employing time lapse technique. 

Because of the structural variety possible with polyimides, many smdies have sought to understand their structure-property relationships, often focusing on one specific target property. Such studies have included those aimed at understanding thermal expansion behavior, optical properties electronic structure, dielectric constant and loss, PTIR analysis, adhesion, water absorption, and molecular ordering, as well as others. The references cited... 

Adhesion of polyimides to inorganic substrates is of great importance to the microelectronics industry [1, 2]. The polyimide films are deposited most often by spin coating the polyamic acid (PAA) usually from a TV-methylpyrrolidone (NMP) solution onto the substrate surface followed by thermal imidization at temperatures up to 400<>C. The most studied polyimide is the pyromellitic dianhydride-oxydianiline (PMDA-ODA), which exhibits excellent mechanical and dielectric properties, but not so good adhesion characteristics. The latter has been generally overcome by application of an adhesion promoter, such as y-aminopropyltriethoxysilane [3-7]. The reactions of APS (coated from water solution) with the silicon dioxide surface as well as with polyamic acid have been well characterized by Linde and Gleason [4] however, we do not have such detailed information available on APS interaction with other ceramic surfaces. 

For a number of years, polymers such as polyimide, have been subjected to widespread research, because of their increasing importance as dielectric materials for the fabrication of microelectronic devices (1). In particular, the adhesion of metal or polyimide films deposited on polyimide substrates and vice versa, is of considerable importance in most applications, and many studies ranging from adhesion testing to detailed spectroscopic analysis of interfaces have been reported previously (2,3.. 5.6). 

Polyimides have excellent dielectric strength and a low dielectric constant, but in certain electrolyte solutions they can electrochemically transport electronic and ionic charge. Haushalter and Krause (5) first reported that Kapton polyimide films derived from 1,2,4,5-pyromellitic dianhydride (PMDA) and 4,4 -oxydianiline (ODA) undergo reversible reduction/oxidation (redox) reactions in electrolyte solutions. Mazur et al., (6) presented a detailed study of the electrochemical properties of chemically imidized aromatic PMDA- derived polyimides and model compounds in nonaqueous solutions. Thin films of thermally... 

In this paper, we report the studies on the adhesion between metals and fluorocarbon polymer films. Fluorocarbon polymer has a dielectric constant of 2.1, lower than that of polyimide, 3.2-3.5, and is attractive to packaging. We have studied the adhesion of Cu to bulk Teflon, a polytetrafluoroethylene (PTFE) polymer, and found enhanced adhesion using a presputtering treatment of the Teflon prior to the deposition of Cu (4). Further analysis shows that the morphological changes of the Teflon due to the sputtering treatment could be a major contributor to the enhanced adhesion observed (5). 

Just as polymers may be used to form printable semiconductors, so they may be used to form dielectrics as well. Indeed, polymer dielectrics are in widespread use in conventional microelectronics as well. For printed electronics applications, polymer dielectrics are therefore a natural choice for use in printed transistors. Several families of polymer dielectrics have been studied and used in printed transistors. These include various polyimides and other polymer dielectrics such as pol)rvinylphenol (PVP). In general, these dielectrics are characterized by the following properties ... 

Thermal compatibility — To increase electrical robustness, many commonly studied dielectric materials, including the polyimides and PVP above are annealed after printing. The purpose of this anneal is varied. In some materials, it serves to cause the evaporation of residual solvent. In other materials (for example, the polyimide and PVP above), it is used to cause a chemical conversion such as a cross-linking event. In every case, it is important that the requisite thermal process be compatible with the substrate and all layers that have already been printed at the time of annealing. 

The organic dielectrics known as polyimides have been studied extensively by a variety of bulk characterizational techniques as a perusal of the literature will illustrate. Little has been published on their surface properties. X-ray photoelectron spectroscopy (ESCA) has been extremely useful for polymer characterization (, 7, ), In a previous paper ( ), we have reported the ESCA spectra of structurally different polyimides derived from both commercially available polyamic acid resins (DuPont s PI5878, PI2525, PI2550), and from laboratory synthesized polyamic acid resins. 

Some general conclusion from these studies are (1) Cu/PI TFML structures have excellent thermal and mechanical stability under extremes of temperature, humidity, and radiation (2) the adhesion of polyimide is highly dependent on interface chemistry and surface preparation (3) PI rapidly absorbs and desorbs water, which has an appreciable effect on its dielectric properties and thus the electrical charactersitics of TFML interconnections the electrical design tolerances must accommodate these variations or the package must be hermetically sealed (4) properly baked and sealed TFML packages can maintain MIL-STD internal moisture levels of less than 5000 ppm at 100°C. 

That work has been extended to provide even further reductions in the dielectric constants of aromatic condensation polyimides by physically incorporating selected diamic acid additives into low dielectric constant polyimide systems. The monomer selection for the synthesis of these additives was based on the results of the Langley structure-property studies on lowering the dielectric constant of polyimides.CL)... 

Ea, above and below Tg. Three case studies illustrate the range of applicability of the bending beam setup and factors contributing to the stress state. The first is a comparison of two polymers for interlayer dielectrics PMDA-ODA (pyromellitic acid dianhydride - oxydiamine) and a bis-benzocyclobutene. The second is of a neat epoxy resin commonly used for microelectronics encapsulation (epoxidized ortho-cresol novolac cured with a phenolic novolac). The third is a screen-printable polyimide coating used for protection of the integrated-circuit chip. An outline of our stress model is sketched, and example results are presented. 

Three case studies are examined which illustrate the use of the bending beam stress experiment. The first is a comparison of two polymers for interlayer dielectrics. The second is of a neat epoxy resin commonly used for microelectronics encapsulation. The third is a polyimide coating used for protection of an integrated-circuit chip. 

Film refractive index n was determined using an Abbe refractometer at room temperature. The dielectric constant e of the material at a frequency near 1 MHz is evaluated roughly from the refractive index to be e=l.ln2.[7] These results are listed in Table 1. Optically estimated e s of the nonaromatic polyimides were approximately 2.6, whereas those of semi-aromatic and aromatic polyimides were around 2.8 and 3.1, respectively.[6] The birefringence An (optical anisotropy) of sample films was evaluated by means of ellipsometry. All the nonaromatic polyimides examined in this study possessed small birefringence below 10"4. 

Xie et al. [2005] studied the influence of BT 100-nm particles on the dielectric properties of polyimide (PI) matrix. BT is commonly used, due to its high dielectric permittivity. The dielectric permittivity (e ) of PI/BT composites versus / increases... 

Adhesion of metals to polymers has been an intensively studied subject over the past decades This is due to the wide application of polymers to electronic packaging and, to a lesser extent, to device inter-connect The increasing demand in density for devices and speed for packaging, in turn, prompts searches for polymers with reduced dielectric constants than that of the widely used polyimide. Some fluorocarbon polymers, notably Teflon, have lower dielectric constants, 2.1, vis-i-vi the values of 3.0-3.5 for polyimides. The fluorocarbon polymers, however, have very weak adhesion to metals. An enhancement in adhesion is thus a primary requirement for the application of such polymers to technologies. A wide range of studies have been made in the past to understand and enhance the adhesion between metals and fluorocarbon polymers In this paper we review some of our earlier work, and present new observations related to the enhanced adhesion between metals and fluorocaiton polymers. We present results address three contributions to enhanced adhesion between metals and fluorocarbon polymers chemical, mechanical, and thermal. 

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