Influence of the Cure Process on the Properties of Hydrogen Silsesquioxane Spin-On-Glass

Többen, D.; Weiganda, P.; Shapiro, M. J.; Cohen, S.

doi:10.1557/proc-443-195

Cited by 21 publications

(17 citation statements)

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“…[3][4][5][6][7][8][9][10][11][12] Used as gap-filling dielectric in advanced metallization, HSQs built-in microporosity results in reduced dielectric constant and thus lowers coupling capacitance between tightly pitched metal lines. The successful integration of HSQ into IC interconnnects requires a careful choice of materials together with heat-treatment optimization.…”

mentioning

confidence: 99%

Thermal Curing of Hydrogen Silsesquioxane

Siew

Sarkar

et al. 2000

J. Electrochem. Soc.

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Recent progress in semiconductor technology includes the utilization of advanced metallization schemes and low k dielectrics in integrated circuit (IC) design. 1,2 As critical dimensions decrease, intermetal dielectrics (IMD) with low dielectric constant (k < 3) play an increasingly important role in developing and producing high speed, high performance ICs. Low k dielectrics reduce interconnect RC [resistance (R) ϫ capacitance (C)] delay, power consumption, and offer many advantages such as reduced line-to-line capacitance and interconnnect cross-talk noise.Hydrogen silsesquioxane (HSQ), commercially available in solution as FOx ® flowable oxide, is one of the most intensively studied low k spin-on dielectrics (SOD) concerning both its basic properties as well as integration-related issues. 3-12 Used as gap-filling dielectric in advanced metallization, HSQs built-in microporosity results in reduced dielectric constant and thus lowers coupling capacitance between tightly pitched metal lines. The successful integration of HSQ into IC interconnnects requires a careful choice of materials together with heat-treatment optimization. However, properties of HSQ films, particularly dielectric properties are strong function of curing parameters, i.e., time, temperature, etc. It is therefore of current research interest to carry out an in-depth study of the curing characteristics of this SOD, to achieve a better understanding of how thermal curing affects the properties of HSQ.HSQ is a subset of polyhedral oligomeric silsequioxane (POSS) macromers, a family of ordered three-dimensional polymers whose structure resembles a cage (Fig. 1a). 3 With the empirical formula of (HSiO 3/2 ) 2n (n ϭ 2, 3, 4, etc.), there are one and one-half (sesqui) stoichiometry of oxygen bound to silicon in a caged structure of HSQ. The structure of HSQ resin, however, is composed of mixture of Si-O network and cage-like network (Fig. 1b), i.e., a random structure of partially formed cages of various sizes as the chemical reactions which produce the resin do not produce completely formed cages. HSQ has no terminal Si-OH or Si-OR groups and it polymerizes after bake and cure by opening of the cages. Therefore, HSQ is cured from a near cage-like structure to a three-dimensional network which provides mechanical integrity to the film for subsequent wafer processing. 4 ExperimentalThin film characterization.-HSQ films (about 4,000 Å) were prepared by spin-coating Dow Corning FOx ® solution onto 8 in. Si wafers followed by heating on three hot plates at 150, 200, and 335ЊC for 1 min each. After that, these films were cured in a furnace at different curing temperature for different durations. The curing conditions used for this study are listed in Table I. The thickness of HSQ films was measured using ellipsometer prior to and after thermal curing. Recent studies reported the importance of an inert environment during the HSQ cure at around 400ЊC in order to prevent oxidation. 4,5 Hence, in this study the HSQ cure employs double ramp rates to prevent tem...

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confidence: 99%

Thermal Curing of Hydrogen Silsesquioxane

Siew

Sarkar

et al. 2000

J. Electrochem. Soc.

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“…As visualized in Figure 3(b), the film cured at 600°C shows a significantly increased integrated area of the hydroxyl absorption feature with respect to the film cured at 700°C, indicating an increased silanol content. [34] The presence of hydroxyl in non-oxidatively cured HSQ-based films has been previously observed by other groups, [20] who have hypothesized that the hydroxylation originates from rapid water uptake of the incompletely polymerized films after curing. In comparison to the thermal oxide, the film cured at 800°C retained a vibrational feature at 878 cm −1 wavenumber (circled feature in Figure 3(a)), which has previously been assigned to the Si-H bending vibrations [31,35] in a Si-rich oxide.…”

Section: Film and Interface Chemistrymentioning

confidence: 72%

“…The process generally relies on the deposition of a liquid hydrogen silsesquioxane (HSQ) containing precursor solution, followed by a thermal polymerization, forming a fully inorganic, SiO 2 ‐like surface film, which offers potential advantages in processing cost, ease of application, reduction of hazardous reaction products or film quality with respect to the incumbent deposition processes . Further, due to the gradual transformation from the resinous precursor to an inorganic ceramic, the process offers a wide range of possible coating properties, ranging from loosely bonded, hydrogenated films to highly polymerized and virtually hydrogen‐free coatings …”

Section: Introductionmentioning

confidence: 99%

“…[1] Further, due to the gradual transformation from the resinous precursor to an inorganic ceramic, the process offers a wide range of possible coating properties, ranging from loosely bonded, hydrogenated films to highly polymerized and virtually hydrogen-free coatings. [19,20] Our recent studies of SOG curing in air [21,22] showed an extensive degradation of the substrate surface due to thermal oxidation at the coating/substrate interface. The buildup of a thick thermal oxide at the interface impaired the corrosion performance and coating adhesion of samples cured above 400°C and restricted the curing temperature and achievable degree of coating polymerization.…”

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confidence: 99%

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Properties and performance of spin‐on‐glass coatings for the corrosion protection of stainless steels in chloride media

Lampert

Jensen²,

Din

et al. 2018

Materials & Corrosion

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Spin‐on‐glass deposition was investigated as viable alternative to increase the durability and performance of 316L steel in chloride environment. The buildup of a detrimental interface oxide was prevented by non‐oxidative thermal curing of the coatings, which leads to a transformation to an inorganic, SiO2‐like material. The degree of polymerization was found dependent on the curing temperature; however, even curing at the maximum investigated curing temperature of 800 °C led to still incomplete transformation, showing less SiO2‐like character with respect to thermally grown oxide or fused silica. Electrochemical analysis by cyclic polarization indicated that the coatings behave as imperfect barrier coatings, which may enhance the passive properties of the substrates; however, there is still some statistical scatter in the quality of the coatings. While there is a tendency for an increase of the upper limit of the breakdown potential, there is also a decrease of the lower limit. It was found that such lower quality coatings showed, in association with substrate defects, unevenly distributed coating flaws, which may act as initiation points of pitting corrosion and decrease the corrosion resistance of coated substrates. Further, the films showed instability in aqueous environment due to imperfect polymerization.

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“…Introduction of the dual damascene process with a Cu layer and low-relative dielectric constant (low-k) film into the ULSI process is very effective in solving this problem. Thus, many low-k films have been proposed using several materials and deposition methods [2][3][4].…”

Section: Introductionmentioning

confidence: 99%