Phosphorus doped TiO2 as oxygen sensor with low operating temperature and sensing mechanism

Abstract Nano-scale TiO 2 powders doped with phosphorus were prepared by sol–gel method. The characterization of the materials was performed by XRD, BET, FT-IR spectroscopy, Zeta potential measurement and XPS analysis. The results indicate that the phosphorus suppresses the crystal growth and phase transformation and, at the same time, increases the surface area and enhances the sensitivity and selectivity for the P-doped TiO 2 oxygen sensors. In this system, the operating temperature is low, only 116 °C, and the response time is short. The spectra of FT-IR and XPS show that the phosphorus dopant presents as the pentavalent-oxidation state in TiO 2 , further phosphorus can connect with Ti 4+ through the bond of Ti O P. The positive shifts of XPS peaks indicate that electron depleted layer of P-doped TiO 2 is narrowed compared with that of pure TiO 2 , and the results of Zeta potential illuminate that the density of surface charge carrier is intensified. The adsorptive active site and Lewis acid characteristics of the surface are reinforced by phosphorus doping, where phosphorus ions act as a new active site. Thus, the sensitivity of P-doped TiO 2 is improved, and the 5 mol% P-doped sample has the optimal oxygen sensing properties.

[1]  K. Zakrzewska,et al.  Gas sensing mechanism of TiO2-based thin films , 2004 .

[2]  S. Oswald,et al.  Depth distribution and bonding states of phosphorus implanted in titanium investigated by AES, XPS and SIMS , 1998 .

[3]  Noboru Yamazoe,et al.  Effects of additives on semiconductor gas sensors , 1983 .

[4]  L. Castañeda Effects of palladium coatings on oxygen sensors of titanium dioxide thin films , 2007 .

[5]  Zhi Zheng,et al.  Synthesis and Characterization of Phosphated Mesoporous Titanium Dioxide with High Photocatalytic Activity , 2003 .

[6]  Dong Yang,et al.  Visible-light photocatalytic regeneration of NADH using P-doped TiO2 nanoparticles , 2006 .

[7]  K. Hadjiivanov,et al.  Study of phosphate-modified TiO2 (anatase) , 1989 .

[8]  Maolin Zhang,et al.  Improvement and mechanism for the fast response of a Pt/TiO2 gas sensor , 2010 .

[9]  W. Göpel,et al.  Intrinsic defects of Ti O 2 (110): Interaction with chemisorbed O 2 , H 2 , CO, and C O 2 , 1983 .

[10]  S. Han,et al.  Micro-bead of nano-crystalline F-doped SnO2 as a sensitive hydrogen gas sensor , 2005 .

[11]  R. Debnath,et al.  Inhibiting effect of AlPO_4 and SiO_2 on the anatase → rutile transformation reaction: An x-ray and laser Raman study , 1992 .

[12]  A. Maldonado,et al.  Sensing properties of chemically sprayed TiO2 thin films using Ni, Ir, and Rh as catalysts , 2008 .

[13]  Zonghao Huang,et al.  Theoretical and experimental study on the electronic structure and optical absorption properties of P-doped TiO2 , 2010 .

[14]  Il-Doo Kim,et al.  Pd-doped TiO2 nanofiber networks for gas sensor applications , 2010 .

[15]  U. Lampe,et al.  Metal Oxide Sensors , 1995, International Conference on Solid-State Sensors, Actuators and Microsystems.

[16]  J. Ying,et al.  SnO2−In2O3 Nanocomposites as Semiconductor Gas Sensors for CO and NOx Detection , 2007 .

[17]  G. L. Sharma,et al.  Mechanism of highly sensitive and fast response Cr doped TiO2 oxygen gas sensor , 1997 .

[18]  Xin Du,et al.  Effects of F doping on TiO2 acidic sites and their application in QCM based gas sensors , 2010 .

[19]  M. C. Bhatnagar,et al.  Effect of Nb metal ion in TiO2 oxygen gas sensor , 1996 .

[20]  Oleg G. Poluektov,et al.  Improving Optical and Charge Separation Properties of Nanocrystalline TiO2 by Surface Modification with Vitamin C , 1999 .

[21]  H. Ahmad,et al.  Low operating temperature of oxygen gas sensor based on undoped and Cr-doped ZnO films , 2010 .

[22]  N. McIntyre,et al.  XPS Characterization of the Corrosion Films Formed on Nanocrystalline Ni–P Alloys in Sulphuric Acid , 1996 .

[23]  T. Morimoto,et al.  Molecularly adsorbed water on the bare surface of titania (rutile) , 1987 .

[24]  Jing Du,et al.  Electrostatic spray assisted vapour deposition of TiO2-based films , 2004 .

[25]  Wojtek Wlodarski,et al.  Gas Sensing Properties of P-type Semiconducting Cr-doped TiO2 Thin Films , 2002 .

[26]  R. Lappalainen,et al.  Determination of P/Al ratio in phosphorus-doped aluminium oxide thin films by XRF, RBS and FTIR , 1995 .