Analysis of Adsorbates on Polished Zinc Selenide

Emily Mellott and Alison R. Noble, Ph.D.

Department of Chemistry and Biochemistry, Messiah College, Mechanicsburg PA 17055

Self-Assembled Monolayers (SAMs)

The SAM head group has an affinity for the substrate and chemisorbs to the substrate forming an orderly and well packed monolayer.

Surface oxides
The polished and fracture surfaces were characterized by Xray Photoelectron Spectroscopy (XPS) after various surface treatments. The presence of surface oxides on polished ZnSe was explored as well as the impact of chemisorption of thiolate and carboxylate monolayers on the zinc and selenium oxides.
Fig. 6: Schematic of how XPS works
http://wiki.utep.edu/pages/viewpage.action?pageId=39195028

The Auger peaks (Fig. 10) were used to determine Auger parameters. The Auger parameter, , (Table 2) for zinc on the clean polished ZnSe slide was similar to the Auger parameter that McGee et al. found for ZnO. The Auger Parameter for the fracture surface (Table 2) was nearer to that of ZnSe powder indicating a chemical environment closer to ZnSe rather than ZnO. Fig. 11 shows the two Se Auger peaks confirming the formation of a Se oxide.

Fig. 1. Diagram of SAM structure

http://en.wikipedia.org/wiki/Self-assembled_monolayer

SAMS can be utilized to prepare functionalized surfaces. Applications of SAMs: analytical sensors, orientation of liquid crystals, lubrication, protection against corrosion, catalysis, optics, and medical devices. In this project, the chemisorption of two types of functionalized alkanes (thiol and carboxyl) to the surface of zinc selenide (ZnSe) was explored.
Fig. 2: Chemical structure of palmitic acid, with a carboxylic acid headgroup, and hexadecanethiol, with a thiol headgroup
www.chemspider.com

XPS data collected on the thiol and carboxyl adsorbates and a clean slide showed that the O 1s peak and the Se 3d 5/2 oxide peak were much larger for the clean slide indicating the formation of an oxide. XPS measurements were taken on a freshly fractured surface to determine the composition of ZnSe that had only been exposed to ambient conditions for a very short time. XPS measurements were recorded on a freshly fractured surface that was UV/ozone (UVOC) cleaned for 20 minutes to determine how the UVOC treatment affects the freshly fractured surface.

Changes in Oxide
The oxygen 1s peak is smaller for polished slides on which SAMs have been formed as compared to clean polished slides (Fig. 12). Some attenuation due to an overlayer would be expected, but atomic percentages indicate that the ZnSe with a SAM is more like stoichiometric ZnSe than the clean slide. A control experiment ruled out the possibility that this difference is due to the solvent, ethanol, indicating that the SAM may be etching the surface oxide as it assembles.

Zn and Se Oxides
High resolution spectra of the fracture surface show a significant oxygen peak and a small selenium oxide peak (Fig. 7 and 8). After UVOC of the fracture surface, the oxygen 1s peak (Fig. 7) and the selenium 3d 5/2 oxide peak increased (Fig. 8). In conclusion, the freshly fractured surface has an oxide, and the oxide increased with exposure to the UVOC. This result is not entirely surprising as UVOC cleaning produces ozone which is very reactive, and zinc is a transition metal which often has a native oxide.

Why Zinc Selenide (ZnSe)?

ZnSe is useful as an optics element in many spectral devices including CO2 lasers and infrared spectrometers. ZnSe is an intrinsic semiconductor that is transparent over a wide range of the visible spectrum and has low absorption in the IR region of the electromagnetic spectrum. Fine-grained polycrystalline ZnSe has good mechanical properties and a relatively low cost. The formation of surface oxides complicates the chemisorption of SAMs on ZnSe.
Fig. 4. AFM image of polished ZnSe slide

Fig. 12: Clean slide (purple) O 1s peak is much larger than that of the slides with SAMs palmitic acid (green) and hexadecanethiol (red) .

Future Direction
Form and characterize various chain length carboxylate SAMs on ZnSe to determine film thickness and establish ideal monolayer packing Investigate functional group selectivity for SAMs on ZnSe Use SAMs to promote liquid crystal orientation in an electro-optical sensor Model the monolayer formation using XPS modeling software

Fig. 3: Polycrystalline ZnSe slides

Characterization of SAMs on ZnSe

Infrared Spectroscopy
The FTIR spectrum of a thiolate (hexadecanethiol) SAM on ZnSe (Fig. 5) The characteristic low intensity methylene peaks at 2916 cm-1 and 2851 cm-1 are shown in Fig. 5

Fig.7 : The O 1s (531.5 eV) is much larger for the clean polished (purple peak) surface and UVOC surface (red peak) than for the fracture (green peak) surface.

Fig. 8: The selenium oxide peak is the smaller higher binding energy peak (59 eV). It is smallest for the fracture surface (green). The fracture surface had a much a larger selenium peak (55 eV).

Fig.9 : The Zn 2p 3/2 (1022 eV) appears to be attenuated from the fracture (green peak) surface to the clean (purple peak) surface.

Acknowledgements
Department of Chemistry and Biochemistry

Attenuation of the Zn 2p 3/2 peak on the clean slide compared to the fracture surface (Fig. 9) also indicates the presence of a surface oxide. The Zn Auger peak is more sensitive to chemical shift than the photoelectron peak, so an Auger spectrum was collected to confirm the presence of zinc oxide (ZnO).

Auger Peaks

Contact Angles
Static contact angles of a 10 L drop of water were measured on the ZnSe surface after the chemisorption of a SAM. The results of the contact angle measurements for the thiolate and carboxylate SAMs (reported as the mean of three measurements) are summarized in Table 1. The surface wetting properties of these SAMs are similar to those seen in other SAM systems.
Table 1: Static Contact angles of water for SAMs on ZnSe Fig. 10 : The Zn Auger peak (523 eV) is similar for clean polished slides but different in shape and position for the fracture surface (green peak). Fig. 5: The CH2 asym. (l) and sym. (r) IR stretches of a thiolate SAM

Penn State Center for Nanoscale Science NSF-MRSEC (DMR-0820404) Penn State Materials Research Institute Laboratory staff

References
(1) Gavrushchuk, E. M. Polycrystalline Zinc Selenide for IR Optical Applications. Inorganic Materials. 2003, 39, 883-898. (2) McGee, T.F.; Cornelissen, H.J. X-Ray Photoelectron Spectroscopy of Etched ZnSe. Applied Surface Science. 1989, 35, 371-379.

Table 2: Calculated Auger Parameters

Fig.11 : Selenium Auger Peaks (125, 127 eV)