On-Surface Self-Assembly of Stimuli-Responsive Metallo-Organic Films: Automated Ultrasonic Spray-Coating and Electrochromic Devices

Naveen Malik, Neta Elool Dov, Graham De Ruiter, Michal Lahav, Milko van der Boom

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

We demonstrate the on-surface formation of homogeneous and uniform electrochromic films via ultrasonic spray coating. This fully automated process is capable of fabricating metallo-organic films on transparent conducting oxides (TCOs) on glass or flexible poly(ethylene terephthalate) (PET) with surface areas of up to 36 cm2 and film thicknesses of half a micron. The assembly process involves alternatingly spray-coating dilute solutions of structurally well-defined iron polypyridyl ([Fe(mbpy-py)3]2+) complexes and bis(benzonitrile)palladium dichloride (Pd(PhCN)2Cl2) onto conductive substrates, where the latter palladium salt was used as the inorganic cross-linker. The on-surface self-assembled three-dimensional networks are intensely colored and were subsequently integrated into laminated electrochromic devices (ECDs) containing a lithium-based gel electrolyte. The ECDs retain their intense color in the ground state, having a ΔTmax of 40-49% at λmax ≈ 600 nm, and can be operated for up to 1500 redox cycles. The fluorine-doped tin oxide counter electrode coated with poly(3,4-ethylene-dioxythiophene)polystyrene sulfonate (PEDOT:PSS) as a charge-storage layer resulted in these stable devices. A significant decrease in the potential window of ΔE ≈ 2.5 V was achieved by using a metal grid on PET as the counter electrode. The operation of the electrochromic films is diffusion-controlled, and the diffusion coefficients (Df) reflect their molecular densities. During these studies, we found that ClO4- is a suitable counterion of the lithium-based electrolytes for optimal ECD performance.

Original languageEnglish
Pages (from-to)22858-22868
Number of pages11
JournalACS Applied Materials and Interfaces
Volume11
Issue number25
DOIs
Publication statusPublished - Jun 26 2019

Fingerprint

Electrochromic devices
Self assembly
Ultrasonics
Lithium
Coatings
Palladium
Electrolytes
Electrodes
Polyethylene Terephthalates
Fluorine
Tin oxides
Polyethylene terephthalates
Oxides
Ground state
Film thickness
Polystyrenes
Ethylene
Gels
Iron
Salts

Keywords

  • coordination chemistry
  • electrochromic devices
  • electrochromics
  • metallo-organics
  • self-assembly
  • spray-coating
  • thin films

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

On-Surface Self-Assembly of Stimuli-Responsive Metallo-Organic Films : Automated Ultrasonic Spray-Coating and Electrochromic Devices. / Malik, Naveen; Elool Dov, Neta; De Ruiter, Graham; Lahav, Michal; van der Boom, Milko.

In: ACS Applied Materials and Interfaces, Vol. 11, No. 25, 26.06.2019, p. 22858-22868.

Research output: Contribution to journalArticle

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abstract = "We demonstrate the on-surface formation of homogeneous and uniform electrochromic films via ultrasonic spray coating. This fully automated process is capable of fabricating metallo-organic films on transparent conducting oxides (TCOs) on glass or flexible poly(ethylene terephthalate) (PET) with surface areas of up to 36 cm2 and film thicknesses of half a micron. The assembly process involves alternatingly spray-coating dilute solutions of structurally well-defined iron polypyridyl ([Fe(mbpy-py)3]2+) complexes and bis(benzonitrile)palladium dichloride (Pd(PhCN)2Cl2) onto conductive substrates, where the latter palladium salt was used as the inorganic cross-linker. The on-surface self-assembled three-dimensional networks are intensely colored and were subsequently integrated into laminated electrochromic devices (ECDs) containing a lithium-based gel electrolyte. The ECDs retain their intense color in the ground state, having a ΔTmax of 40-49{\%} at λmax ≈ 600 nm, and can be operated for up to 1500 redox cycles. The fluorine-doped tin oxide counter electrode coated with poly(3,4-ethylene-dioxythiophene)polystyrene sulfonate (PEDOT:PSS) as a charge-storage layer resulted in these stable devices. A significant decrease in the potential window of ΔE ≈ 2.5 V was achieved by using a metal grid on PET as the counter electrode. The operation of the electrochromic films is diffusion-controlled, and the diffusion coefficients (Df) reflect their molecular densities. During these studies, we found that ClO4- is a suitable counterion of the lithium-based electrolytes for optimal ECD performance.",
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