Realization of expeditious layer-by-layer siloxane-based self-assembly as an efficient route to structurally regular acentric superlattices with large electro-optic responses

Peiwang Zhu, Milko van der Boom, Hu Kang, Guennadi Evmenenko, Pulak Dutta, Tobin J Marks

Research output: Contribution to journalArticle

74 Citations (Scopus)

Abstract

A new, expeditious siloxane-based layer-by-layer assembly process for the formation of intrinsically polar organic electro-optic thin films is described using highly reactive-SiCl2I- functionalized, silyl-protected donor-acceptor azo-benzene chromophore derivatives and octachlorotrisiloxane as a deprotecting reagent/interlayer precursor. This all-"wet-chemical" two-step process can be efficiently implemented in a vertical dipping procedure to yield polar films consisting of 40 alternating chromophore and capping layers. Each nanoscale bilayer (chromophore + polysiloxane layer ≈ 3.26-nm thick) can be grown in ≈40 min - at least 1 order of magnitude more rapidly than previous siloxane-based solution deposition methodologies. Chromophore monolayer deposition from solution reaches completion in ≈15 min at 55°C. The adherent, structurally regular assemblies exhibit appreciable electro-optic responses (χ(2) ∼ 180 pm/V and r33 ∼ 65 pm/V determined by SHG measurements at 1064 nm) and high chromophore surface densities (≈40 Å2/chromophore) and have been characterized by a full complement of physicochemical techniques: optical spectroscopy, aqueous contact-angle measurements, specular X-ray reflectivity, atomic force microscopy, and angle-dependent polarized second-harmonic generation.

Original languageEnglish
Pages (from-to)4982-4989
Number of pages8
JournalChemistry of Materials
Volume14
Issue number12
DOIs
Publication statusPublished - Dec 1 2002

Fingerprint

Siloxanes
Superlattices
Chromophores
Electrooptical effects
Self assembly
Angle measurement
Harmonic generation
Benzene
Silicones
Contact angle
Monolayers
Atomic force microscopy
Derivatives
X rays
Thin films

ASJC Scopus subject areas

  • Materials Science(all)
  • Materials Chemistry

Cite this

Realization of expeditious layer-by-layer siloxane-based self-assembly as an efficient route to structurally regular acentric superlattices with large electro-optic responses. / Zhu, Peiwang; van der Boom, Milko; Kang, Hu; Evmenenko, Guennadi; Dutta, Pulak; Marks, Tobin J.

In: Chemistry of Materials, Vol. 14, No. 12, 01.12.2002, p. 4982-4989.

Research output: Contribution to journalArticle

@article{28f2a4efd8814fa4ab3e00a78a12ad58,
title = "Realization of expeditious layer-by-layer siloxane-based self-assembly as an efficient route to structurally regular acentric superlattices with large electro-optic responses",
abstract = "A new, expeditious siloxane-based layer-by-layer assembly process for the formation of intrinsically polar organic electro-optic thin films is described using highly reactive-SiCl2I- functionalized, silyl-protected donor-acceptor azo-benzene chromophore derivatives and octachlorotrisiloxane as a deprotecting reagent/interlayer precursor. This all-{"}wet-chemical{"} two-step process can be efficiently implemented in a vertical dipping procedure to yield polar films consisting of 40 alternating chromophore and capping layers. Each nanoscale bilayer (chromophore + polysiloxane layer ≈ 3.26-nm thick) can be grown in ≈40 min - at least 1 order of magnitude more rapidly than previous siloxane-based solution deposition methodologies. Chromophore monolayer deposition from solution reaches completion in ≈15 min at 55°C. The adherent, structurally regular assemblies exhibit appreciable electro-optic responses (χ(2) ∼ 180 pm/V and r33 ∼ 65 pm/V determined by SHG measurements at 1064 nm) and high chromophore surface densities (≈40 {\AA}2/chromophore) and have been characterized by a full complement of physicochemical techniques: optical spectroscopy, aqueous contact-angle measurements, specular X-ray reflectivity, atomic force microscopy, and angle-dependent polarized second-harmonic generation.",
author = "Peiwang Zhu and {van der Boom}, Milko and Hu Kang and Guennadi Evmenenko and Pulak Dutta and Marks, {Tobin J}",
year = "2002",
month = "12",
day = "1",
doi = "10.1021/cm020438t",
language = "English",
volume = "14",
pages = "4982--4989",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "12",

}

TY - JOUR

T1 - Realization of expeditious layer-by-layer siloxane-based self-assembly as an efficient route to structurally regular acentric superlattices with large electro-optic responses

AU - Zhu, Peiwang

AU - van der Boom, Milko

AU - Kang, Hu

AU - Evmenenko, Guennadi

AU - Dutta, Pulak

AU - Marks, Tobin J

PY - 2002/12/1

Y1 - 2002/12/1

N2 - A new, expeditious siloxane-based layer-by-layer assembly process for the formation of intrinsically polar organic electro-optic thin films is described using highly reactive-SiCl2I- functionalized, silyl-protected donor-acceptor azo-benzene chromophore derivatives and octachlorotrisiloxane as a deprotecting reagent/interlayer precursor. This all-"wet-chemical" two-step process can be efficiently implemented in a vertical dipping procedure to yield polar films consisting of 40 alternating chromophore and capping layers. Each nanoscale bilayer (chromophore + polysiloxane layer ≈ 3.26-nm thick) can be grown in ≈40 min - at least 1 order of magnitude more rapidly than previous siloxane-based solution deposition methodologies. Chromophore monolayer deposition from solution reaches completion in ≈15 min at 55°C. The adherent, structurally regular assemblies exhibit appreciable electro-optic responses (χ(2) ∼ 180 pm/V and r33 ∼ 65 pm/V determined by SHG measurements at 1064 nm) and high chromophore surface densities (≈40 Å2/chromophore) and have been characterized by a full complement of physicochemical techniques: optical spectroscopy, aqueous contact-angle measurements, specular X-ray reflectivity, atomic force microscopy, and angle-dependent polarized second-harmonic generation.

AB - A new, expeditious siloxane-based layer-by-layer assembly process for the formation of intrinsically polar organic electro-optic thin films is described using highly reactive-SiCl2I- functionalized, silyl-protected donor-acceptor azo-benzene chromophore derivatives and octachlorotrisiloxane as a deprotecting reagent/interlayer precursor. This all-"wet-chemical" two-step process can be efficiently implemented in a vertical dipping procedure to yield polar films consisting of 40 alternating chromophore and capping layers. Each nanoscale bilayer (chromophore + polysiloxane layer ≈ 3.26-nm thick) can be grown in ≈40 min - at least 1 order of magnitude more rapidly than previous siloxane-based solution deposition methodologies. Chromophore monolayer deposition from solution reaches completion in ≈15 min at 55°C. The adherent, structurally regular assemblies exhibit appreciable electro-optic responses (χ(2) ∼ 180 pm/V and r33 ∼ 65 pm/V determined by SHG measurements at 1064 nm) and high chromophore surface densities (≈40 Å2/chromophore) and have been characterized by a full complement of physicochemical techniques: optical spectroscopy, aqueous contact-angle measurements, specular X-ray reflectivity, atomic force microscopy, and angle-dependent polarized second-harmonic generation.

UR - http://www.scopus.com/inward/record.url?scp=0036906684&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0036906684&partnerID=8YFLogxK

U2 - 10.1021/cm020438t

DO - 10.1021/cm020438t

M3 - Article

VL - 14

SP - 4982

EP - 4989

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 12

ER -