Photocatalytic Patterning of Monolayers for the Site-Selective Deposition of Quantum Dots onto TiO₂ Surfaces

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Abstract

A novel photochemical mechanism is reported for the site-selective deposition of quantum dots onto nanocrystalline TiO₂ films. The patterning mechanism involves the combination of surfactant-mediated self-assembly and monolayer photolithography. In the self-assembly process, CdS and CdSe quantum dots were attached to TiO₂ surfaces through bifunctional mercaptoalkanoic acid (MAA) linkers. MAAs were adsorbed to the TiO₂ surface as the deprotonated carboxylates, primarily through monodentate coordination to Ti⁴⁺ sites. CdSe quantum dots were bound to the terminal thiol groups of surface-adsorbed MAAs, with a surface adduct formation constant, K_ad, of (2.1 ± 0.7) × 10⁴ M^-1. The color and optical density of the quantum dot-functionalized TiO₂ films were tunable. Monolayer photopatterning involved the TiO₂-catalyzed oxidative degradation of surface-adsorbed mercaptohexadecanoic acid (MHDA). A mechanism is proposed wherein MHDA degradation occurs through both oxidative decarboxylation and the formation of interchain disulfides. These MHDA photodegradation processes regulate the extent to which CdSe quantum dots adsorb onto the TiO₂ surface. Illumination through a photomask yielded optically patterned, quantum dot-functionalized TiO₂ films that were characterized by scanning electron microscopy and energy-dispersive X-ray analysis.

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This article has been cited by 20 ACS Journal articles (5 most recent appear below).

• 

  Facile Patterning of Hybrid CdSe Nanoparticle Films by Photoinduced Surface Defects

  Yushin Park, Mary Jane Felipe, and Rigoberto C. Advincula
  ACS Applied Materials & Interfaces2011 3 (11), 4363-4369

  • Facile Patterning of Hybrid CdSe Nanoparticle Films by Photoinduced Surface Defects

    Yushin Park, Mary Jane Felipe, and Rigoberto C. Advincula
    ACS Applied Materials & Interfaces2011 3 (11), 4363-4369

    The photopatterning of CdSe quantum dots (QDs) films is facilitated by preparing defect-rich QDs on selective sites on the film. A key step is UV irradiation in the presence of a polar solvent such as methanol in situ as a “developer” which readily ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Attachment of CdSe Nanoparticles to TiO₂ via Aqueous Linker-Assisted Assembly: Influence of Molecular Linkers on Electronic Properties and Interfacial Electron Transfer

  Jeremy S. Nevins, Kathleen M. Coughlin, and David F. Watson
  ACS Applied Materials & Interfaces2011 3 (11), 4242-4253

  • Attachment of CdSe Nanoparticles to TiO₂ via Aqueous Linker-Assisted Assembly: Influence of Molecular Linkers on Electronic Properties and Interfacial Electron Transfer

    Jeremy S. Nevins, Kathleen M. Coughlin, and David F. Watson
    ACS Applied Materials & Interfaces2011 3 (11), 4242-4253

    CdSe nanoparticles (NPs) capped with cysteinate (Cys), 3-mercaptopropionate (MP), and mercaptosuccinate (MS) were adsorbed to TiO2 from basic aqueous dispersions. Native capping groups served as molecular linkers to TiO2. Thus, the materials-assembly ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Formation of Molecular Monolayers on TiO₂ Surfaces: A Surface Analogue of the Williamson Ether Synthesis

  Jixin Chen, Ryan Franking, Rose E. Ruther, Yizheng Tan, Xueying He, Stephanie R. Hogendoorn, and Robert J. Hamers
  Langmuir2011 Article ASAP

  • Formation of Molecular Monolayers on TiO₂ Surfaces: A Surface Analogue of the Williamson Ether Synthesis

    Jixin Chen, Ryan Franking, Rose E. Ruther, Yizheng Tan, Xueying He, Stephanie R. Hogendoorn, and Robert J. Hamers
    Langmuir2011 Article ASAP

    Strategies to modify metal oxide surfaces are important because of the increasing applications of metal oxides in catalysis, sensing, electronics, and renewable energy. Here, we report the formation of molecular monolayers on anatase nanocrystalline TiO2 ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Aggregation-Induced Increase of the Quantum Yield of Electron Injection from Chalcogenorhodamine Dyes to TiO₂

  Kacie R. Mulhern, Michael R. Detty, and David F. Watson
  The Journal of Physical Chemistry C2011 115 (13), 6010-6018

  • Aggregation-Induced Increase of the Quantum Yield of Electron Injection from Chalcogenorhodamine Dyes to TiO₂

    Kacie R. Mulhern, Michael R. Detty, and David F. Watson
    The Journal of Physical Chemistry C2011 115 (13), 6010-6018

    We used transient absorption spectroscopy to characterize excited-state electron injection from a 2,7-bis(dimethylamino)-9-(2-thienyl-5-carboxy)selenoxanthylium dye (1-Se) and a 2,7-bis(dimethylamino)-9-(3-thienyl-2-carboxy)selenoxanthylium dye (2-Se) to ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Comparison of Adsorption of Mercaptopropyltrimethoxysilane on Amphiphilic TiO₂ and Hydroxylated SiO₂

  J. Zuo and E. Torres
  Langmuir2010 26 (19), 15161-15168

  • Comparison of Adsorption of Mercaptopropyltrimethoxysilane on Amphiphilic TiO₂ and Hydroxylated SiO₂

    J. Zuo and E. Torres
    Langmuir2010 26 (19), 15161-15168

    Alkylsilane 3-mercaptopropyltrimethoxysilane (3MPT) monolayers with a functional end group −SH were used to immobilize Ag colloidal nanoparticles on photoinduced amphiphilic TiO2 and hydroxylated SiO2 surfaces. The differences in the adsorption of 3MPT ...

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