Fluorinated compounds for advanced IC interconnect applications: a survey of chemistries and processes

The semiconductor industry is now in the early stages of an unprecedented change in materials set for the integrated circuit (IC) interconnect structure. The traditional layers of aluminum conductors and silicon dioxide dielectrics are being replaced by copper thin films and a variety of low k candidates, respectively. In many cases, fluorine confers desirable properties on either the precursors or the final films. At the same time, fluorine presents some potentially adverse effects, which have led to a so-called “fear-of-fluorine” in interconnect applications. This paper will review the proposed uses of fluorinated compounds in the interconnect structures, covering both precursors and the resulting thin films. Both the status of technical studies, and the prospects for commercial implementation, will be addressed.     

Meissner Anisotropy in Deuterated (TMTSF)2Clo4

Both the Meissner-signal (flux expulsion on cooling through T_c) and the shielding signal (obtained by turning on a field in the superconducting state) have been observed in deuterated single crystals for fields oriented both along and normal to the chain axis. A possible isotope effect on T_c is discussed. We find complete diamagnetism in normal fields and incomplete (～ 40 %) diamagnetism in parallel fields. A dramatic drop of the Meissner-effect in parallel fields well below H_c1 is observed and not yet well explained.     

Numerical methods for light propagation in large LC cells: a new approach

Accurate numerical methods for the propagation of light in large 3D samples with strong lateral variation of the director field require prohibitive amounts of time. We consider and compare a standard spectral method and the Finite Difference in Frequency Domain method, showing that the CPU time can be reduced by one or two orders of magnitude using a perturbation approach or a recently developed Reduced Order Method. The equations obtained are applied to liquid crystal cells with in-plane switching, illuminated by a large incoherent source. The developed formalism, based on numerically exact equations, is particularly suitable for treating magnetic or optically active media and for extending to such media the well known approximations based on the 4 × 4 (Berreman) or 2 × 2 (Jones) matrices.     

An Investigation into the Migration of Segments in Crosslinked Fluorinated Polyimide Adhesive

Crosslinked fluorinated polyimides (CFPI) were successfully synthesized to study and explore the effect of cross-linkage on the migration of fluorinated segments and on the adhesion strength. Characterization by dynamic thermomechanical analysis (DMA) and thermo gravimetric analysis (TGA) confirmed good thermal properties of CFPI. X-ray photoelectron spectroscopy (XPS) results showed that the ratio of fluorinated component (6FDA-ODA) concentration of the surface to the bulk decreased with the crosslink density. The water contact angle of CFPI was lower than that of non-crosslinked fluorinated polyimide, indicating that the migration of fluorinated groups to the surface was reduced by the presence of cross-linkage. Therefore, CFPI, with no fluorine segregation on the surface, exhibited excellent wetting of adherent surfaces and adhesion strength, which was proved by lap shear strength (LSS) measurements and scanning electron microscopy.     

Synthesis and characterization of 9,9‐bis(4‐hydroxyphenyl and 4‐aminophenyl)dibenzofluorenes: Novel fluorene‐based monomers

Two novel 9,9‐difunctionalized fluorene‐type monomers, 9,9‐bis(4‐hydroxyphenyl‐ and 4‐aminophenyl)‐2,3:6,7‐dibenzofluorenes, are synthesized by the reaction of dibenzenzofluorenone with phenol and aniline. These monomers are used for the preparation of polyester and polyimide as the typical polymers to evaluate the property change such as thermal stability caused by the benzene rings fused to the fluorene skeleton with keeping good solubility, in comparison with the polymers derived from simple fluorenone. In fact, these two new polymers have the fairly enhanced thermal stability and refractive index value along with satisfactory solubility in organic solvents, enough to emphasize the fusion effect. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2602–2605     

Nonvolatile write‐once read‐many‐times memory behaviors of polyimides containing tetraphenyl fluorene core and the pendant triphenylamine or carbazole moieties

To better understand the structure–property relationships, two novel aromatic diamines containing tetraphenyl fluorene (TPF) moiety through triphenylamine (TPA) unit and carbazole (Cz) unit modification are designed and synthesized, respectively. Four thermally stable and excellent solubility polyimides are prepared and characterized. The excellent film‐formation ability and thin film stability are investigated by X‐ray diffraction (XRD) and atom force microscopy (AFM) measurements, respectively. The memory devices are fabricated, PIs films with low water uptakes sandwiched between indium‐tin oxide (ITO) ground electrode and Al top electrode, and exhibit nonvolatile write‐once read‐many‐times (WORM) memory behaviors with low threshold voltages, due to increasing the retention time through regulating the energy level. The current conduction mechanisms of all devices are linearly fitted by theoretical conduction model. Molecular simulations are used to demonstrate switching mechanism and the memory effects. The experimental results provide a sight for the design‐adjustable switching voltage of memory devices. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1630–1644     

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.     

Sulfur Precursor Reactivity Affecting the Crystal Phase and Morphology of Cu2−xS Nanoparticles

For plasmonic copper-deficient Cu_2−xS nanoparticles (NPs), accurate control of the crystal phase and morphology is highly desirable as both of which are known to determine the localized surface plasmon resonance (LSPR) wavelength and amplitude. Here, how the sulfur precursor reactivity in the synthesis of Cu_2−xS NPs affects the resulting crystal phase and morphology is examined. Djurleite Cu_1.94S, roxbyite Cu_1.8S, digenite Cu_1.8S as well as covellite CuS nanodisks were synthesized by using 1-dodecanethiol, N,N-dibutylthiourea, and crystal sulfur 1-octadecene/oleylamine solutions and their crystal phase dependent LSPR properties were exhaustively discussed. In addition, crystal phase interconversion between covellite CuS and djurleite/roxbyite Cu_2−xS was realized in the presence of the above sulfur precursors. On the other hand, djurleite Cu_1.94S nanorods rather than nanodisks were prepared by replacing 1-dodecanethiol with more reactive tert-dodecanethiol. The structural and morphological Cu_2−xS NPs here holds great promise in the application of photothermal therapy, photocatalysis, surface-enhanced Raman scattering (SERS), and many others.     

Hyperbranched polyimide application in liquid crystal alignment layers

Several hyperbranched polyimides (HBPIs) were applied in liquid crystal (LC) alignment layers and exhibited outstanding performance for LC alignment. The maximum pretilt angle was above 8°, and the minimum pretilt angle was 4.2°. The results of atomic force microscope measurement disclosed that a lot of grooves were aligned parallel to the rubbing direction and found that the grooves were not main factor for LC alignment. The LC alignment and pretilt angles are unambiguously associated with the intrinsic HBPI chemical structures. The results of thermal gravimetric analysis and ultraviolet–visible spectra showed that the HBPIs had good thermal stability and excellent transmittance. T₅ and T₁₀ were higher than 360°C and 400°C, respectively. Copyright © 2012 John Wiley & Sons, Ltd.