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  • Original Paper: Sol-gel and hybrid materials for dielectric, electronic, magnetic and ferroelectric applications
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Novel adamantane-based periodic mesoporous organosilica film with ultralow dielectric constant and high mechanical strength

Abstract

In this work, a novel bridged organosilane precursor, adamantane-bridged organosilane (ADBO), was synthesized successfully which was employed to prepare adamantane-based (ADH-based) periodic mesoporous organosilica (PMO) thin film in the presence of porogen and acid catalyst via evaporation-induced self-assembly (EISA) after spin-coating procedure. The resultant ADH-based PMO thin films were characterized by FTIR, NMR, TEM, and small-angle XRD. The ADH-based PMO thin film with weight ratio of porogen to ADBO (0.75:1) possesses low dielectric constant (1.55 ± 0.04@1 MHz), excellent Young’s modulus (6.69 ± 0.54 GPa), and ideal hydrophobic property (90.2° of water contact angle) simultaneously. These outstanding properties of ADH-based PMO film can be ascribed to lower polarity, lower density, and rigid cavity structure of adamantane, which suggests its potential application as high-performance low-κ material in next-generation microelectronics.

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References

  1. Kohl PA (2011) Low-dielectric constant insulators for future integrated circuits and packages. Annu Rev Chem Biomol 2:379–401

    Article  Google Scholar 

  2. Baklanov MR, Maex K (2006) Porous low dielectric constant materials for microelectronics. Philos Trans R Soc A 364:201–215

    Article  Google Scholar 

  3. Shamiryan D, Abell T, Iacopi F, Maex K (2004) Low-k dielectric materials. Mater Today 7:34–39

    Article  Google Scholar 

  4. Hatton BD, Landskron K, Hunks WJ, Bennett MR, Shukaris D, Perovic DD, Ozin GA (2006) Materials chemistry for low-k materials. Mater Today 9:22–31

    Article  Google Scholar 

  5. Maex K, Baklanov MR, Shamiryan D, lacopi F, Brongersma SH, Yanovitskaya ZS (2003) Low dielectric constant materials for microelectronics. J Appl Phys 93:8793–8841

    Article  Google Scholar 

  6. Wang WD, Lofgreen JE, Ozin GA (2010) Why PMO? Towards functionality and utility of periodic mesoporous organosilicas. Small 6:2634–2642

    Article  Google Scholar 

  7. Wang WD, Grozea D, Kohli S, Perovic DD, Ozin GA (2011) Water repellent periodic mesoporous organosilicas. ACS Nano 5:1267–1275

    Article  Google Scholar 

  8. Yang QH, Liu J, Zhang L, Li C (2009) Functionalized periodic mesoporous organosilicas for catalysis. J Mater Chem A 19:1945–1955

    Article  Google Scholar 

  9. Lin CX, Qiao SZ, Yu CZ, Ismadji S, Lu GQ (2009) Periodic mesoporous silica and organosilica with controlled morphologies as carriers for drug release. Micro Mesopor Mat 117:213–219

    Article  Google Scholar 

  10. Wang XQ, Lu DN, Austin R, Agarwal A, Mueller LJ, Liu Z, Wu JZ, Feng PY (2007) Protein refolding assisted by periodic mesoporous organosilicas. Langmuir 23:5735–5739

    Article  Google Scholar 

  11. Rebbin V, Schmidt R, Fröba M (2006) Spherical particles of phenylene-bridged periodic mesoporous organosilica for high-performance liquid chromatography. Angew Chem Int Ed 45:5210–5214

    Article  Google Scholar 

  12. Tani T, Mizoshita N, Inagaki S (2009) Luminescent periodic mesoporous organosilicas. J Mater Chem 19:4451–4456

    Article  Google Scholar 

  13. Hunks WJ, Ozin GA (2005) Challenges and advances in the chemistry of periodic mesoporous organosilicas (PMOs). J Mater Chem 15:3716–3724

    Article  Google Scholar 

  14. Wills AW, Michalak DJ, Ercius P, Rosenberg ER, Perciano T, Ushizima D, Runser R, Helms BA (2015) Block copolymer packing limits and interfacial reconfigurability in the assembly of periodic mesoporous organosilicas. Adv Funct Mater 25:4120–4128

    Article  Google Scholar 

  15. Hoffmann F, Cornelius M, Morell J, Fröba M (2006) Silica-based mesoporous organic–inorganic hybrid materials. Angew Chem Int Ed 45:3216–3251

    Article  Google Scholar 

  16. Liu HC, Su WC, Liu YL (2011) Self-assembled benzoxazine-bridged polysilsesquioxanes exhibiting ultralow-dielectric constants and yellow-light photoluminescent emission. J Mater Chem 21:7182–7187

    Article  Google Scholar 

  17. Hatton BD, Landskron K, Whitnall W, Perovic DD, Ozin GA (2005) Spin-coated periodic mesoporous organosilica thin film-towards a new generation of low-dielectric-constant materials. Adv Funct Mater 15:823–829

    Article  Google Scholar 

  18. Jiang T, Zhu B, Ding SJ, Fan ZY, Zhang DW (2014) High-performance ultralow dielectric constant carbon-bridged mesoporous organosilica films for advanced interconnects. J Mater Chem C 2:6502–6510

    Article  Google Scholar 

  19. Huang YQ, Economy J (2006) New high strength low-k spin-on thin films for IC application. Macromolecules 39:1850–1853

    Article  Google Scholar 

  20. Edelstein D (2008) Extendibility of Cu/low-k/airgap BEOL. Electrochem Soc 28:2073

    Google Scholar 

  21. Guo Y, Mylonakis A, Zhang ZT, Yang GL, Lelkes PI, Che SN, Lu QH, Wei Y (2008) Templated synthesis of electroactive periodic mesoporous organosilica bridged with oligoaniline. Chem-Eur J 14:2909–2917

    Article  Google Scholar 

  22. Landskron K, Ozin GA (2005) Periodic mesoporous organosilicas: self-assembly from bridged cyclic silsesquioxane precursors. Angew Chem Int Ed 44:2107–2109

    Article  Google Scholar 

  23. Gao L, Wei F, Zhou Y, Fan XX, Wang Y, Zhu JH (2009) Periodic mesoporous organosilica materials: self-assembly of carbamothioic acid-bridged organosilane precursors. Chem-Eur J 15:8310–8318

    Article  Google Scholar 

  24. Schachtschneider A, Wessig M, Spitzbarth M, Donner A, Fischer C, Drescher M, Polarz S (2015) Directional materials-nanoporous organosilica monoliths with multiple gradients prepared using click chemistry. Angew Chem Int Ed 127:10611–10615

    Article  Google Scholar 

  25. Seino M, Wang WD, Lofgreen JE, Puzzo DP, Manabe T, Ozin GA (2011) Low-k periodic mesoporous organosilica with air walls: POSS-PMO. J Am Chem Soc 133:18082–18085

    Article  Google Scholar 

  26. Lu HY, Teng CL, Kung CH, Wan BZ (2011) Preparing mesoporous low-k films with high mechanical strength from noncrystalline silica particles. Ind Eng Chem Res 50:3265–3273

    Article  Google Scholar 

  27. Goethals F, Levrau E, Pollefeyt G, Baklanov MR, Ciofi I, Vanstreels K, Detavernier C, Driessche IV, PVD Voort (2013) Sealed ultra low-k organosilica films with improved electrical, mechanical and chemical properties. J Mater Chem C1:3961–3966

    Google Scholar 

  28. Yuan H, Xu JQ, Xie LL (2011) Ultra low-dielectric-constant methylated mesoporous silica films with high hydrophobicity and stability. Mater Chem Phys 129:1195–1200

    Article  Google Scholar 

  29. Rathore JS, Interrante LV, Dubois G (2008) Ultra low-k films derived from hyperbranched polycarbosilanes (HBPCS). Adv Funct Mater 18:4022–4028

    Article  Google Scholar 

  30. Zhang JW, Zhang GP, Gao YJ, Sun R, Wong CP (2016) Ultra-low-κ HFPDB-based periodic mesoporous organosilica film with high mechanical strength for interlayer dielectric. J Mater Sci 51:7966–7976

    Article  Google Scholar 

  31. Zhang GP, George TF, Assoufid L, Mansoori GA (2007) First-principles simulation of the interaction between adamantane and an atomic-force-microscope tip. Phys Rev B 75:035413

    Article  Google Scholar 

  32. Fort RC, Schleyer PV (1964) Adamantane: consequences of the diamondoid structure. Chem Rev 64:277–300

    Article  Google Scholar 

  33. Tong J, Zhang H, Gu J, Li L, Ma C, Zhao J, Wang C (2016) Poly (ethylene glycol)-block-poly (propylene glycol)-block-poly (ethylene glycol)-assisted synthesis of graphene/polyaniline composites as high-performance supercapacitor electrodes. J Mater Sci 51:1966–1977

    Article  Google Scholar 

  34. Landskron K, Hatton BD, Perovic DD, Ozin GA (2003) Periodic mesoporous organosilicas containing interconnected [Si(CH2)]3 rings. Science 302:266–269

    Article  Google Scholar 

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Acknowledgements

This work was financially supported by National Natural Science Foundation of China (Grant No. 21201175, 61505123, and 21601065), NSFC––Guangdong Jointed Funding (U1601202), NSFC––Shenzhen Robot Jointed Funding (U1613215), Guangdong and Shenzhen Innovative Research Team Program (No. 2011D052, KYPT20121228160843692), Key Laboratory of Guangdong Province (2014B030301014), and R&D Funds for basic Research Program of Shenzhen (Grant No. JCYJ20120615140007998, 20150401145529012, and 20150525092940976) and Shenzhen Fundamental Research Program (Grant No. JCYJ20160331191741738 and JSGG20160229194437896).

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Correspondence to Guoping Zhang, Fangfang Niu or Rong Sun.

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The authors declare that they have no conflict of interest.

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Highlights

  • Design a novel bridged organosilane precursor, introdcuing adamantane (ADH) with rigid cavity structure

  • Prepare adamantane-based (ADH-based) periodic mesoporous organosilica (PMO) through evaporation-induced self-assembly (EISA)

  • The best ADH-based PMO possesses low dielectric constant (1.55 ± 0.04@1 MHz), excellent Young’s modulus (6.69 ± 0.54 GPa), and ideal hydrophobic property (90.2° of water contact angle) simultaneously

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Zhang, G., Zhang, J., Niu, F. et al. Novel adamantane-based periodic mesoporous organosilica film with ultralow dielectric constant and high mechanical strength. J Sol-Gel Sci Technol 85, 703–711 (2018). https://doi.org/10.1007/s10971-018-4582-5

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  • DOI: https://doi.org/10.1007/s10971-018-4582-5

Keywords

  • Periodic mesoporous organosilica
  • Low electric constant
  • Mechanical property
  • Thin film