skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Evaporation-Induced Self-Assembly of Metal Oxide Inverse Opals: From Synthesis to Applications

Journal Article · · Accounts of Chemical Research
ORCiD logo [1];  [2];  [2]; ORCiD logo [3]
  1. Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States, Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States, Materials Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, 3584 CG Utrecht, The Netherlands
  2. Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States
  3. Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States, Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States

Inverse opals (IOs) are highly interconnected three-dimensional macroporous structures with applications in a variety of disciplines from optics to catalysis. For instance, when the pore size is on the scale of the wavelength of visible light, IOs exhibit structural color due to diffraction and interference of light rather than due to absorption by pigments, making these structures valuable as nonfading paints and colorants. When IO pores are in an ordered arrangement, the IO is a 3D photonic crystal, a structure with a plethora of interesting optical properties that can be used in a multitude of applications, from sensors to lasers. IOs also have interesting fluidic properties that arise from the re-entrant geometry of the pores, making them excellent candidates for colorimetric sensors based on fluid surface tension. Metal oxide IOs, in particular, can also be photo- and thermally catalytically active due to the catalytic activity of the background matrix material or of functional nanoparticles embedded within the structure. Evaporation-induced self-assembly of sacrificial particles has been developed as a scalable method for forming IOs. The pore size and shape, surface chemistry, matrix material, and the macroscopic shape of the IO, as well as the inclusion of functional components, can be designed through the choice of deposition conditions such as temperature and humidity, types and concentrations of components in the self-assembly mixture, and the postassembly processing. These parameters allow researchers to tune the optical, mechanical, and thermal transport properties of IOs for optimum functionality. In this Account, we focus on experimental and theoretical studies to understand the self-assembly process and properties of metal oxide IOs without (bare) and with (hybrid) plasmonic or catalytic metal nanoparticles incorporated. Several synthetic approaches are first presented, together with a discussion of the various forces involved in the assembly process. The visualization of the deposition front with time-lapse microscopy is then discussed together with analytical theory and numerical simulations to determine the conditions needed for the deposition of a continuous IO film. Subsequently, we present high-resolution scanning electron microscopy (SEM) of assembled colloids over large areas, which provides a detailed view of the evolution of the assembly process, showing that the organization of the colloids is initially dictated by the meniscus of the evaporating suspension on the substrate, but that gradually all grains rotate to occupy the thermodynamically most favorable orientation. High-resolution 3D transmission electron microscopy (TEM) is then presented together with analysis of the wetting of the templating colloids by the matrix precursor to provide a detailed picture of the embedding of metallic nanoparticles at the pore–matrix interface. Finally, the resulting properties and applications in optics, wetting, and catalysis are discussed, concluding with an outlook on the future of self-assembled metal-oxide-based IOs.

Research Organization:
Harvard Univ., Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Department of Defense, Army Research Office; National Science Foundation Graduate Research Fellowship
Grant/Contract Number:
SC0012573
OSTI ID:
1872497
Alternate ID(s):
OSTI ID: 1875422; OSTI ID: 1903513; OSTI ID: 1903554
Journal Information:
Accounts of Chemical Research, Journal Name: Accounts of Chemical Research Vol. 55 Journal Issue: 13; ISSN 0001-4842
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (57)

Optical costs and benefits of disorder in biological photonic crystals journal January 2020
Slow Photons for Photocatalysis and Photovoltaics journal February 2017
Slow light in photonic crystals journal August 2008
Bio-inspired self-replenishing and self-reporting slippery surfaces from colloidal co-assembly templates journal December 2021
Dye-Sensitized Solar Cell Based on a Three-Dimensional Photonic Crystal journal July 2010
Stable Ordered FePt Mesoporous Silica Catalysts with High Loadings journal June 2008
Enhanced condensation heat transfer using porous silica inverse opal coatings on copper tubes journal May 2021
New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica journal November 2017
Optical Properties of Inverse Opal Photonic Crystals journal August 2002
Nanocrystalline Precursors for the Co-Assembly of Crack-Free Metal Oxide Inverse Opals journal January 2018
Microscopic origins of the crystallographically preferred growth in evaporation-induced colloidal crystals journal August 2021
Tunable Anisotropy in Inverse Opals and Emerging Optical Properties journal February 2014
Tailored Disorder in Photonics: Learning from Nature journal June 2021
Encoding Complex Wettability Patterns in Chemically Functionalized 3D Photonic Crystals journal August 2011
Bio-inspired slippery surfaces with multifunctional anti-icing performance journal September 2021
Directional Wetting in Anisotropic Inverse Opals journal June 2014
Combining Bottom-Up Self-Assembly with Top-Down Microfabrication to Create Hierarchical Inverse Opals with High Structural Order journal June 2015
Wide-Angle Spectrally Selective Absorbers and Thermal Emitters Based on Inverse Opals journal October 2019
Wetting in Color: Colorimetric Differentiation of Organic Liquids with High Selectivity journal December 2011
Colorimetric Ethanol Indicator Based on Instantaneous, Localized Wetting of a Photonic Crystal journal December 2019
Tunable Structural Color Surfaces with Visually Self-Reporting Wettability journal September 2016
Connecting Hindered Transport in Porous Media across Length Scales: From Single-Pore to Macroscopic journal October 2020
Dilute Pd/Au Alloy Nanoparticles Embedded in Colloid-Templated Porous SiO 2 : Stable Au-Based Oxidation Catalysts journal July 2019
Opal and inverse opal photonic crystals: Fabrication and characterization journal January 2007
Direct observation of drops on slippery lubricant-infused surfaces journal January 2015
Photonic crystals: putting a new twist on light journal March 1997
Fabrication of Photonic Microbricks via Crack Engineering of Colloidal Crystals journal December 2019
Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites journal March 2022
Design and functionality of colloidal-crystal-templated materials—chemical applications of inverse opals journal January 2013
Fabrication of Au- and Ag–SiO2 inverse opals having both localized surface plasmon resonance and Bragg diffraction journal October 2015
The Role of Thickness Transitions in Convective Assembly journal September 2006
Three-Phase Co-assembly: In Situ Incorporation of Nanoparticles into Tunable, Highly Ordered, Porous Silica Films journal November 2013
Raspberry colloid-templated approach for the synthesis of palladium-based oxidation catalysts with enhanced hydrothermal stability and low-temperature activity journal January 2021
Engineered disorder in photonics journal December 2020
Amplified Photochemistry with Slow Photons journal July 2006
An Antibody-Immobilized Silica Inverse Opal Nanostructure for Label-Free Optical Biosensors journal January 2018
Multiple solvent-response behavior of metal-organic inverse opals journal March 2018
Liquid-Impermeable Inverse Opals with Invariant Photonic Bandgap journal December 2014
Transparency and damage tolerance of patternable omniphobic lubricated surfaces based on inverse colloidal monolayers journal July 2013
Assembly of large-area, highly ordered, crack-free inverse opal films journal May 2010
Photo-tuning of highly selective wetting in inverse opals journal January 2014
Gold-Nanoparticle-Infiltrated Polystyrene Inverse Opals: A Three-Dimensional Platform for Generating Combined Optical Properties journal June 2006
Highly Ordered Inverse Opal Structures Synthesized from Shape‐Controlled Nanocrystal Building Blocks journal December 2021
Inverse Opal Photonic Crystals as an Optofluidic Platform for Fast Analysis of Hydrocarbon Mixtures journal May 2018
Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity journal September 2011
On the Origin of Sinter‐Resistance and Catalyst Accessibility in Raspberry‐Colloid‐Templated Catalyst Design journal September 2021
Color from hierarchy: Diverse optical properties of micron-sized spherical colloidal assemblies journal August 2015
Inverse Opal Films for Medical Sensing: Application in Diagnosis of Neonatal Jaundice journal November 2020
Dynamics of evaporative colloidal patterning journal September 2015
Decoding reactive structures in dilute alloy catalysts journal February 2022
From colloidal particles to photonic crystals: advances in self-assembly and their emerging applications journal January 2021
Achieving High Selectivity for Alkyne Hydrogenation at High Conversions with Compositionally Optimized PdAu Nanoparticle Catalysts in Raspberry Colloid-Templated SiO 2 journal November 2019
Entropic Control of HD Exchange Rates over Dilute Pd-in-Au Alloy Nanoparticle Catalysts journal June 2021
Structural Color of Colloidal Clusters as a Tool to Investigate Structure and Dynamics journal November 2019
Modular Design of Advanced Catalytic Materials Using Hybrid Organic-Inorganic Raspberry Particles journal December 2017
Direct-Write Freeform Colloidal Assembly journal August 2018
Hierarchical structural control of visual properties in self-assembled photonic-plasmonic pigments journal January 2014