Premium
Electrodeposition of Silver Vanadate Films: A Tale of Two Polymorphs
Author(s) -
Vali Abbas,
Sarker Hori P.,
Jee HyungWoo,
Kormányos Attila,
Firouzan Farinaz,
Myung Noseung,
Paeng KiJung,
Huda Muhammad N.,
Janáky Csaba,
Rajeshwar Krishnan
Publication year - 2019
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201900558
Subject(s) - electrosynthesis , vanadate , ammonium metavanadate , materials science , electrochemistry , aqueous solution , inorganic chemistry , semiconductor , cyclic voltammetry , chemical engineering , vanadium , chemistry , electrode , optoelectronics , engineering
Abstract Two polymorphs of AgVO 3 , namely the α‐ and β‐ forms, were prepared and their physical, structural, optical, electrochemical, and photoelectrochemical characteristics were compared using a battery of experimental and theoretical tools. A two‐step method, previously developed in the our laboratory for the electrodeposition of inorganic semiconductor films, was applied to the electrosynthesis of silver vanadate (AgVO 3 ) films on transparent, conducting oxide surfaces. In the first step, silver was cathodically deposited from a non‐aqueous bath containing silver nitrate. In the second step, the silver film was anodically stripped in an aqueous medium containing ammonium metavanadate. The anodically generated silver ions at the interface underwent a precipitation reaction with the vanadate species to generate the desired product in situ. Each of these steps were mechanistically corroborated via the use of electrochemical quartz crystal microgravimetry, used in conjunction with voltammetry and coulometry. As‐deposited films were crystalline and showed p‐type semiconductor behavior. Theoretical insights are provided for the electronic origin of the α→β phase transformation in AgVO 3 and the disparate optical band gaps of the two polymorphs. Finally, implications for the application of this material in solar cells are provided.