Iridium(IV) oxide

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Iridium(IV) oxide
Names
Other names
Iridium dioxide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.031.572 Edit this at Wikidata
UNII
  • InChI=1S/Ir.2O/q+4;2*-2 checkY
    Key: NSTASKGZCMXIET-UHFFFAOYSA-N checkY
  • InChI=1/Ir.2O/q+4;2*-2
    Key: NSTASKGZCMXIET-UHFFFAOYAQ
  • [Ir+4].[O-2].[O-2]
Properties
IrO2
Molar mass 224.22 g/mol
Appearance blue-black solid
Density 11.66 g/cm3
Melting point 1,100 °C (2,010 °F; 1,370 K) decomposes
insoluble
+224.0·10−6 cm3/mol
Structure
Rutile (tetragonal)
Octahedral (Ir); Trigonal (O)
Hazards
Flash point Non-flammable
Related compounds
Other anions
 iridium(IV) fluoride, iridium disulfide
Other cations
 rhodium dioxide, osmium dioxide, platinum dioxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Iridium(IV) oxide, IrO2, is the only well-characterised oxide of iridium. It is a blue-black solid. The compound adopts the TiO2 rutile structure, featuring six coordinate iridium and three coordinate oxygen.[1]

It is used with other rare oxides in the coating of anode-electrodes for industrial electrolysis and in microelectrodes for electrophysiology research.[2]

As described by its discoverers, it can be formed by treating the green form of iridium trichloride with oxygen at high temperatures:

2 IrCl3 + 2 O2 → 2 IrO2 + 3 Cl2

A hydrated form is also known.[3]

Application[edit]

Iridium dioxide can be used as an anode electrode for industrial electrolysis and as a microelectrode for electrophysiological studies.[4]

Iridium dioxide can be used to make coated electrodes.[5]

Mechanical Properties[edit]

Oxide materials are typically hard and brittle, which means it can fracture under stress without significant prior deformation[6]. Iridium oxide is also a stiff material and do not easily deform under stress[7]. Since iridium oxide’s applications focus on electrode coating and catalytic materials for electrolysis, the discussion of mechanical properties is related to these applications.

Young’s Modulus[edit]

Young’s modulus is a material property that measures the stiffness of the material. By experimentally measuring Young’s modulus, people could understand how much a material will deform under a specific load, which is essential in designing structures and preventing deformations[8]. For iridium oxide films, the young’s modulus data is crucial for accurate modeling and design of electromechanical devices where the mechanical properties of the electrode material significantly affect device performance.

Therefore, researchers used the cantilever bending method to determine Young’s modulus of iridium oxide thin film[7]. First, iridium oxide was deposited onto a silicon wafer and fabricated to cantilever beams. Using an atomic force microscope (AFM), a fine tip is aligned to the free end of the beam and a tiny force is applied. The force exerted and the resulting deflection were precisely measured to calculate the stiffness and then the Young’s modulus of iridium oxide. The experimental measurement of the young’s modulus of Iridium oxide thin film is reported to be 300 ± 15 GPa[7]. Compared to metal Iridium, which has a young’s modulus of 517 GPa[9], the oxidation of iridium lower the stiffness of the material.

Fracture and Delamination of Iridium Oxide Film on Substrate[edit]

Fracture and delamination are well-known problems when fabricating devices that incorporate iridium oxide film. The delamination is typically due to stresses that develop between the IrO2 layer and its substrate during manufacturing processes.

One potential cause of delamination is lattice mismatch between iridium oxide and the substrate material. Iridium oxide has a tetragonal lattice with lattice parameters of 4.5Å and 3.15Å[10]. In contrast, popular substrates like gold and platinum have lattice constants of approximately 4.08 Å and 3.92 Å, respectively[11][12]. The difference in lattice parameter can lead to strain at the interface between the iridium oxide layer and the substrate, resulting in fracture and delamination of the iridium film. Iridium oxide sputtered on liquid crystal polymer could be a potential way to avoid delamination[13].

Another cause of delamination is the incorporation of high temperature processes during fabrication, such as annealing. Annealing involves heating iridium oxide to a high temperature but under melting point (around 750-900 °C) and then cooling it, relieving internal stresses and improving the iridium oxide’s crystallinity and mechanical properties[14]. However, if the lattice parameter of the iridium oxide layer changes significantly compared to the substrate following annealing, it can result in a greater lattice mismatch, which increases the surface tension and assist the formation of long cracks (similar to mechanically stressed cracks reported by Mailley et al.[15]). The cracks create a breakpoint where the surface strain is relieved, leading to delamination and other types of mechanical failure.

Even if the iridium oxide film remains intact under equilibrium conditions, it may still delaminate during operation. Cogan et al. reported that sputtered iridium oxide films could delaminate after several cyclic voltammetry cycles, which suggests that the film could delaminate under operational loads[16]. The team then limits the maximum potential bias to 0.9V and no visible delamination occurs.

References[edit]

  1. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  2. ^ Cogan, Stuart F. (August 2008). "Neural Stimulation and Recording Electrodes". Annual Review of Biomedical Engineering. 10 (1): 275–309. doi:10.1146/annurev.bioeng.10.061807.160518. PMID 18429704.
  3. ^ H. L. Grube (1963). "The Platinum Metals". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. NY: Academic Press. p. 1590.
  4. ^ Cogan, Stuart F. (August 2008). "Neural Stimulation and Recording Electrodes". Annual Review of Biomedical Engineering. 10 (1): 275–309. doi:10.1146/annurev.bioeng.10.061807.160518. ISSN 1523-9829. PMID 18429704.
  5. ^ "改性二氧化铱电极研制--《无机盐工业》1998年03期". www.cnki.com.cn. Retrieved 2021-05-21.
  6. ^ Dillingham, Giles; Roberts, Rose (2023). Advances in Structural Adhesive Bonding (Second Edition) (2nd ed.). Woodhead Publishing. pp. 289–325. ISBN 9780323984379.
  7. ^ a b c Rivas, Manuel; Rudy, Ryan Q.; Sanchez, Bradley; Graziano, Milena B.; Fox, Glen R.; Sunal, Paul; Nataraj, Latha; Sandoz-Rosado, Emil; Leff, Asher C.; Huey, Bryan D.; Polcawich, Ronald G.; Hanrahan, Brendan (2020-08-01). "Iridium oxide top electrodes for piezo- and pyroelectric performance enhancements in lead zirconate titanate thin-film devices". Journal of Materials Science. 55 (24): 10351–10363. doi:10.1007/s10853-020-04766-5. ISSN 1573-4803.
  8. ^ "Significance Of Young's Modulus - The Structural Blog". thestructuralblog.com. 2020-05-10. Retrieved 2024-05-12.
  9. ^ "Young's Modulus, Tensile Strength and Yield Strength Values for some Materials". www.engineeringtoolbox.com. Retrieved 2024-05-12.
  10. ^ Bestaoui, N.; Prouzet, E.; Deniard, P.; Brec, R. "Structural and analytical characterization of an iridium oxide thin layer". Thin Solid Films. 235 (1–2): 35–42. doi:10.1016/0040-6090(93)90239-l. ISSN 0040-6090.
  11. ^ Uddin, Jamal (2018). "Terahertz multispectral imaging for the analysis of gold nanoparticles' size and the number of unit cells in comparison with other techniques". International Journal of Biosensors & Bioelectronics. 4 (3). doi:10.15406/ijbsbe.2018.04.00118.
  12. ^ "nglos324 - platinum". www.princeton.edu. Retrieved 2024-05-12.
  13. ^ Wang, K.; Chung-Chiun Liu; Durand, D.M. "Flexible Nerve Stimulation Electrode With Iridium Oxide Sputtered on Liquid Crystal Polymer". IEEE Transactions on Biomedical Engineering. 56 (1): 6–14. doi:10.1109/TBME.2008.926691. ISSN 0018-9294. PMC 2738844. PMID 19224713.{{cite journal}}: CS1 maint: PMC format (link)
  14. ^ Dong, Qiuchen; Song, Donghui; Huang, Yikun; Xu, Zhiheng; Chapman, James H.; Willis, William S.; Li, Baikun; Lei, Yu. "High-temperature annealing enabled iridium oxide nanofibers for both non-enzymatic glucose and solid-state pH sensing". Electrochimica Acta. 281: 117–126. doi:10.1016/j.electacta.2018.04.205. ISSN 0013-4686.
  15. ^ Mailley, S.C; Hyland, M; Mailley, P; McLaughlin, J.M; McAdams, E.T. "Electrochemical and structural characterizations of electrodeposited iridium oxide thin-film electrodes applied to neurostimulating electrical signal". Materials Science and Engineering: C. 21 (1–2): 167–175. doi:10.1016/s0928-4931(02)00098-x. ISSN 0928-4931.
  16. ^ Cogan, Stuart F.; Ehrlich, Julia; Plante, Timothy D.; Smirnov, Anton; Shire, Douglas B.; Gingerich, Marcus; Rizzo, Joseph F. "Sputtered iridium oxide films for neural stimulation electrodes". Journal of Biomedical Materials Research Part B: Applied Biomaterials. 89B (2): 353–361. doi:10.1002/jbm.b.31223. ISSN 1552-4973. PMC 7442142. PMID 18837458.{{cite journal}}: CS1 maint: PMC format (link)
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