The structural transformation and properties of spin-on poly(silsesquioxane) films by thermal curing

Liu, Wei-Chih; Yang, Chung-Wei; Chen, Wen‐Chang; Dai, Bau–Tong; Tsai, Ming-Yen

doi:10.1016/s0022-3093(02)01373-x

Cited by 73 publications

(30 citation statements)

References 13 publications

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“…Two significant changes are observed in Fig 2 as the MSSQb transforms to the MSSQF : the disappearance of the SiOH absorption band at 890 cm −1 and the reduced cage/network structural ratio at 1000– 1150 cm −1 by thermal curing. That the cage structure is transformed to the network structure by thermal curing has been reported previously 21–25. The characteristic polyimide peaks of CO stretching (1776 and 1722 cm −1 ) and CN stretching (1380 cm −1 ) are shown in the spectrum of PI1K , which indicated the complete imidization reaction.…”

Section: Resultssupporting

confidence: 76%

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Synthesis and characterization of polyimide/oligomeric methylsilsesquioxane hybrid films

Lin

Chen

2004

Polymer International

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In this study, polyimide/silsesquioxane hybrid materials were synthesized from aminoalkoxysilane‐capped poly(pyromellitic dianhydride‐co‐4,4′‐oxydianiline) (PMDA‐ODA) and oligomeric methylsilsesquioxane (O‐MSSQ) precursors. The O‐MSSQ moiety was used to obtain well characterized nano‐inorganic cage and network structures in the hybrid materials. The effects of molecular structures and composition on the morphologies and properties of the prepared hybrid materials were studied. The phase separation of the prepared hybrid materials could be controlled by varying the molecular weight of the polyimide moiety, the SiOH end group content of the O‐MSSQ or the coupling agent. Homogeneous and transparent hybrid thin films were obtained from the low molecular weight polyimide moiety with a coupling agent, 3‐aminopropyltrimethoxysilane (APrTMS). However, microphase separation occurred if the molecular weight of the polyimide moiety was enhanced or was prepared without a coupling agent, as evidenced by atomic force microscopy (AFM), field emission scanning electron microscopy (FE‐SEM), and electron spectroscopy for chemical analysis (ESCA). The high SiOH content of the O‐MSSQ could enhance the bonding density between the organic and inorganic moiety and thus retard phase separation. The thermal and mechanical properties of the prepared hybrid materials were largely improved compared with the parent polyimide, PMDA‐ODA, and were demonstrated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and thermal‐stress analysis. The hybrid materials showed adjustable refractive index and dielectric constant by varying the O‐MSSQ content. The birefringence of the PMDA‐ODA was reduced by incorporating the O‐MSSQ moiety. This work revealed that the polyimide/O‐MSSQ hybrid materials could have potential applications as optical films or low dielectric constant materials. Copyright © 2004 Society of Chemical Industry

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Section: Resultssupporting

confidence: 76%

“…Silsesquioxanes with a well‐defined nanoscale size have been used as an inorganic moiety for hybrid materials 17–20. They have been regarded as a new class of low dielectric constant materials or optical waveguide materials 21–25. However, polysilsesquioxanes could exhibit unacceptable cracking propagation in film processing.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of polyimide/oligomeric methylsilsesquioxane hybrid films

Lin

Chen

2004

Polymer International

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“…However, the ATR‐FTIR spectra for films with GPTMS pretreated using H 2 O for 4, 12, and 14 d showed no difference regardless of GPTMS pretreatment time. On the other hand, after 12 d of pretreatment with 0.1 m HCl, the peak at 1105 cm −1 increased in intensity, leading to a sharp peak for films deposited after 14 d. The peak at 1105 cm −1 is representative of the stretching mode of an Si–O–Si bond, suggesting that not only is more GPTMS present in the film, but that it is also present in the form of an organosilicate network . Furthermore, for the film deposited with 14 d of 0.1 m HCl pretreatment, a sharp peak at 910 cm −1 appears, which is attributed to unopened epoxide rings …”

Section: Resultsmentioning

confidence: 98%

Selective Deposition of Compositionally Graded Hybrid Adhesive Films

Giachino

Watson

Dubois

et al. 2015

Adv Materials Inter

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different water solubilities, hydrolysis, and polycondensation rates. Nevertheless, for hybrid fi lms deposited from aqueous solutions, it is often believed that the composition of the resulting fi lm is representative of the species that are the majority in solution. However, this is not always the case especially when dealing with dynamic and kinetically driven systems. For example, our previous work has shown that synthesizing hybrid fi lms from heterogeneous solutions is an innovative strategy to control the interfacial and bulk properties of the deposited fi lms. [ 19,20 ] Here we show that by using a dip coating technique, the minority of the species in solution, due to their chemical state, become the predominant species on the deposited fi lm. This selective deposition of minority species adds another dimension that allows for the control of the molecular structure of a fi lm deposited from dynamic systems involving, for example, copolymerization of functional organosilanes, macromonomers, and metal alkoxides. We highlight the effectiveness of this technique by depositing compositionally graded hybrid organic-inorganic fi lms, capable of forming a high-performance bond at the interface between an organic layer and an oxide substrate. We show that when synthesizing these fi lms, changes in the chemical structure of the precursors in solution that would appear insignifi cant actually result in a dramatic enhancement of the physical properties of the deposited fi lms.We use an aqueous and dilute sol-gel approach using an epoxy-functionalized silane, 3-(glycidoxypropyl)trimethoxysilane (GPTMS), and a zirconium alkoxide, tetran -propoxyzirconium (TPOZ). [19][20][21]23,24 ] In order to deposit fi lms with a compositionally graded molecular structure that are organic-rich toward the top, the molecular weight of the organic and inorganic networks formed by the GPTMS and TPOZ precursors in solution need to be optimized prior to deposition. Due to the interlaced inorganic and organic chemistry in this system, it is both dynamic and kinetically driven, therefore careful pretreatment of the precursors is necessary in order to allow for proper crosslinking of the molecular networks. We show that precise pretreatment of the GPTMS with hydrochloric acid (HCl) is fundamental to achieve an organosilicate network with a molecular weight optimized to enrich the top surface of the fi lm. By coupling a thin-fi lm delamination technique with chemical characterization of the fi lms, we correlated the underlying molecular structure to the adhesive/cohesive properties of the fi lms. We found that increasing the condensation of a very small fraction of the Hybrid organic-inorganic materials that are compositionally graded are excellent candidates for addressing the challenges related to the bonding of polymeric layers and inorganic substrates. Often, the synthesis of these hybrid materials involves the use of kinetically driven and dynamic solution systems where obtaining the desired hybrid molecular structures in the deposited fi...

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“…Then volatilization of highly symmetric low molecular weight molecules comprising cage/open cage structures evaporation of the elements non yet linked into the network by crosslinking reactions [3,6], leading to a random network-like structure [7,8].…”

Section: Introductionmentioning

confidence: 99%

“…In their works, Wei-Chih Liu et al[7] identifies in the Silres MK FTIR spectra characteristic peaks for Si-CH 3 , Si-OH and more interesting, succeed to distinguish and explain Si-O-Si forming cage structure and Si-O-Si forming random network. The cleavage of the Si-CH 3 bond results in the collapse of the cage structure and then the formation of the dense Si-O-Si network structure.…”

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confidence: 99%

A Kinetic Analysis of a Thermal Curing Reaction of a Silicon Resin in Solid State

Vivier

Santamaria²,

Pellerej³

et al. 2014

Characterization of Minerals, Metals, and Materials 2014

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The curing mechanism of a silicon resin, pure or mixed with catalyst is discussed here. The silicon resin is a polymethylsilsesquioxane containing hydroxyl and ethoxy side groups which ensure the condensation. Side-products of this condensation are water and ethanol. The solid curing catalyst used is the aluminium acetylacetonate. Former studies have been developed on liquid solutions of silicon resins and catalysts in solvent, ensuring the complete contact between species -with maximum efficiency-, this work proposes a solid state mixing and questions the real utility of the catalyst. This work is divided in three parts: the first one is about resin behavior and reactions occurring under non-isothermal conditions, using different methods as Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). The second step deals with kinetic analysis under isothermal conditions at different T. The last part is about stability in time of the system resin and catalyst.

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The structural transformation and properties of spin-on poly(silsesquioxane) films by thermal curing

Cited by 73 publications

References 13 publications

Synthesis and characterization of polyimide/oligomeric methylsilsesquioxane hybrid films

Synthesis and characterization of polyimide/oligomeric methylsilsesquioxane hybrid films

Selective Deposition of Compositionally Graded Hybrid Adhesive Films

A Kinetic Analysis of a Thermal Curing Reaction of a Silicon Resin in Solid State

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