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X-Ray Photoelectron Spectroscopy (XPS)

INTRODUCTION AND OBJECTIVE:


Hybrid Nano-device Research Group (HNRG), Electrical Engineering Department, Indian Institute of Technology-Indore (IIT-I), under the kind supervision of Dr. Shaibal Mukherjee has been working in the state of the art Dual Ion Beam Sputtering (DIBSD) grown semiconductor thin films. The group has successfully grown ZnO and MgZnO based films for possible applications in optoelectronics and aims to grow ZnO/MgZnO nanowires and high K-dielectrics. Hence, it is imperative to characterize the films for possible anomalies, for which X-ray photoelectron spectroscopy will be an extremely valuable asset. The group therefore intends to work closely with CSR-UGC DAE (Indore), a center of international reputation and publish articles in journals and conferences of high quality. In this way MHRDs vision of empowering Indian Universities and Institutes like IIT-I in terms of research will be well served.

CHARACTERIZATIONS STUDIES WITH XPS i. Identification of Elements present:

Investigation of the sample for identification of the elements present will be carried out. A wide scan over the sample will provide strong peaks for the elements present. The slope of the background will also be studied for 1-10nm thickness.

ii. Chemical State Information:


All elements in the periodic table show chemical shift, which can vary from a fraction of an electron volt up to several eVs. The shifts observed in XPS have their origin in either initial-state or finalstate effects. Such chemical shifts will indicate the influence of gas ratios in XPS spectra of ZnO films which could be analyzed to investigate the chemical states of Zn and O and their percentage in ZnO film. For ZnO and MgZnO films, the influence of Ar2, O2 and N2 can be studied for possible oxygen vacancy and interstitial studies by analyzing Low Binding Peak (LP), Middle Binding Peak (MP) and High Binding Peak (HP) of O1s state. This would provide a stoichiometric analysis of ZnO/MgZnO for different ambient conditions. Also, ZnO and MgZnO films grown on Si substrates can be studied for the presence of SiO2, Si2O, SiO etc. [X.Q.Wei et.al., Physica B 388, 2007].

iii. Depth Profiling Using XPS:


Depth profiling of the sample in terms of XPS quantities can be obtained by combining a sequence of ion gun etch cycles interleaved with XPS measurements from the current surface. An electron gun etches the surface for a definite period of time, which is then switched off and XPS spectra are obtained. With this uniformity of elemental composition as a function of ion beam etching can be obtained. This would provide a through surface analysis with etch rate and time.

iv. Valence Band Offset (VBO) Measurement:


The valence-band offset (VBO) of MgxZn1xO with respect to ZnO is not only an important parameter for MgxZn1xO/ZnO quantum well structure, but also related to other properties of MgxZn1xO. Acceptor levels in p-type MgZnO alloy are strongly dependent on the valence-band maximum (VBM) positions. The lower VBM position will result in deeper acceptor level, which influences electrical properties of MgZnO alloy. Therefore, it is necessary to measure the VBO of MgZnO/ZnO heterostructure, especially of MgO/ZnO heterostructure. [Y.F. Li et.al., Appl. Phys. Lett.,
92, 192116, 2008].

v. Charge Compensation Effects:


The XPS technique relies on electrons leaving the sample. Unless these emitted electrons are replaced, the sample will be charge relative to the instrument causing a retarding electric field at the sample surface. Without effective charge compensation, the measured energy for a photoelectric line may change as a function of kinetic energy of the electrons. Charge compensation with and without the presence of neutralization with binding energy can be studied for ZnO and MgZnO samples. References:
[1] J.F. Watt and J. Wolstenholme, An Introduction to Surface Analysis by XPS and AES, Wiley, 2003. [2] R. Deng et. al., X-ray photoelectron spectroscopy measurement of n-ZnO/ p-NiO heterostructure valence-

band offset, Appli. Phys. Lett., 94, 2009.


[3] K. Saravanakumar et. al., XPS and Raman Studies on (002) oriented Nanocrystalline ZnO Films Showing

Temperature Dependent Optical Red Shift, Adv. Studies Theor. Phys., Vol. 5, 2011.
[4] M. Chen et. al., X-ray photoelectron spectroscopy and auger electron spectroscopy studies of Al-doped

ZnO films, Appl. Surface Sci., Vol.158, Iss.1-2, 2000.


[5] K. Kotsis et. al., Ab initio calculations of the O1s XPS spectra of ZnO and Zn oxo compounds, Phys.

Chem. Chem. Phys., 2006, 8, 1490-1498.

[6]

Y Zhang et. al., X-ray photoelectron spectroscopy study of ZnO films grown by metal. organic chemical vapor deposition, Journal of Crys. Growth, 252, 2003.

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