New hybrid low-k dielectric materials prepared by vinylsilane polymerization
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New hybrid low-k dielectric materials prepared by vinylsilane polymerization Jung-Won Kang, Byung Ro Kim, Gwi-Gwon Kang, Myung-Sun Moon, Bum-Gyu Choi, Min-Jin Ko, LG Chem. Ltd./Research Park, Corporate R & D, Daejon Korea
Abstract Spin-on Low-K materials are potentially very attractive as interconnection materials in a wide range of semiconductor structures. In this work, new organic-inorganic hybrid materials synthesized by vinylsilane polymerization were proposed. According to compositions and additional fabrications, dielectric constants of these materials were evaluated to be 2.3~3.1. The hardness was 2.0GPa after 430oC curing. These materials had good adhesion strength such that fracture toughness on silicon wafer was 0.22 MPa*m0.5 without any adhesion promoters. This result indicates that these organicinorganic hybrid materials are very promising candidates for low-K dielectrics.
Introduction Reducing interline capacitance and line resistance is required to minimize RC delays, reduce power consumption and crosstalk in 100nm node technology [1]. For this purpose, various inorganic- and organic polymers have been tested to reduce dielectric constants in parallel with the use of copper as the metal line. However, requirements related to integration of low-k materials are so diverse and stringent that it is difficult to satisfy the whole requirements. Lowering the dielectric constants, in particular, causes the detrimental effect on mechanical properties and then leads to film damage and/or delamination during chemical-mechanical planarization(CMP) or repeated thermal cure cycles. To overcome this issue, new carbon-bridged hybrid materials synthesized through vinyl polymerization and sol-gel reaction were proposed. Organic-inorganic hybrid was selected because of the potential of combining distinct properties of both organic and inorganic components within a single molecular composite. While organic components offer structure flexibility, inorganic ones have an advantage in thermal and mechanical stability. Polymerization with other materials was attempted to improve mechanical properties. Porogen loading inside the materials was carried out to lower dielectric constant.
O O HO Si Si O Si O O MeO Si OMe O O Sol-Gel reaction Si OMe Si OMe O O O O +
H H2O
thermal cure > 350oC
O O HO Si Si O Si O O O O Si OMe Si O O O O
Figure 1 General process scheme preparing PVSSQ gels by the sol-gel reaction followed by thermal curing.
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Result and Discussion Sol-gel polymerization of VTMS(vinyltrimethoxysilane) monomer proceeded by a series of hydrolysis and condensation reaction under acidic condition (Figure 1). A starting mixture containing VTMS, water, catalyst and solvent was heated at 60 ℃ for overnight. Under this condition the VTMS were partially hydrolyzed and condensed. To prepare dielectric films, a sol-gel product was spincoated at spinning rate of 2000rpm for 20s onto a silicon(001) substrate. After deposition, the coatings were dried for 1 min at 120 ℃ on a hot plate. Subsequent annealing was
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