Materials Characterization

X-Ray Diffractometer (XRD) X-Ray diffraction is a well understood physical phenomenon during which an x-ray traveling along an angle of Theta incident to a plane will interact with the atoms on the substrates surface, which causes the incoming ray to be diffracted into multiple directions. An XRD uses this principle in order to analyze the samples crystal structure. In order to achieve this, an XRD shoots an x-ray beam at an angle of theta onto the substrate, where it becomes diffracted. As the diffracted x-rays leave the surface of the plane they interact with one another creating specific diffraction patterns. In order to better understand this process, the Advanced Certificate in Powder Diffraction at Birkbeck College illustrates the basic mechanism with Figure 1.

Figure 1- X-ray diffraction of an incident x-ray beam with a characteristic wavelength of incoming at an angle of incident to the substrate. The resulting diffraction interference depends on the spacing between rows of atoms noted as d. The resulting diffracted rays travel at an angle of 2 with respect to the original x -ray beam.

As you can see from Figure 1, the x-ray diffraction patterns can either constructively or destructively interfere as they leave the substrate. This interference patterns depends exclusively on the spacing between the rows of crystal planes. This spacing can be then measured by using Brags Law, Equation 1. 1) where d is the average spacing between layers or rows of atoms, is the angle of incidence and is the characteristic wavelength of the x-ray beam. It is important to notice that this process will not damage the sample and can be conducted at ambient conditions, therefore this is a great characterization technique often used in industry for the characterization of crystal materials. After the diffraction pattern is created an x-ray detector, located at an angle of theta opposite to the incoming x-ray beam, then reads the intensity of the diffracted x-rays and plots them into a 2D graph. These graphs have an angle of 2Theta on the x-axis and intensity on the y-axis value. The high peaks that can be observed on these plots represent x-ray beams that constructively interfered while leaving the surface, the smaller peaks are known as background noice, which is generated by all the diffractions that destructively

interfered with one another. The position with respect to 2theta of this high intensity peaks then can be interpreted using the JCPDS tables, which contain the expected positions for specific crystal structures. For instance, one of the crystal structures that we analyzed is Lead Zirconate Titanate, better known as PZT. Figure 2 displays an XRD scan conducted on one of the PZT samples we prepared. Using the JCPDS, we could determine that indeed this sample has, in its majority, a pervoskite crystal structure. However, it is important to note that the samples we synthesized were not very good, and even though they present the desired basic pervoskite crystal structure they also show some irregularities as well as an undesired pyrocholore peak at around 2Theta equal to 28.

Figure 2, XRD analysis of spin-coated PZT deposited on Platinum substrate.

X-Ray Photoelectron spectroscopy The X-Ray Photoelectron spectroscopy is a materials characterization technique that is based on the principle of stimulated photon emission first proposed by Einstein, in which an atom that has being bombarded with photon energy will absorb this energy and become excited. If the energy of the photon is enough to overcome the binding energy of the electron to the nucleus, this electron will then be ejected from its orbit in the form of a photoelectron. A detector will then capture the emitted electron and measure its kinetic energy. By knowing the specific frequency at which the photon is colliding with the sample and the initial energy of the photon, and by using Equation 2, one can find the binding energy of the electron to its nucleus. 2) where KE is the kinetic energy of the emitted electron, h is Planks constant, is the frequency of the photon source (x-ray), BE is the binding energy of the electron and is the working function of the spectrophotometer. The binding energy is unique for each element and furthermore it even depends on the overall chemical state of the atom. Therefore the energy at which an electron is ejected from an element will

have a different kinetic energy than that ejected from the same element on a different oxidation state (double bonds, triple bonds). Furthermore, the XPS analysis can determine the relative composition of elements inside a sample. On a regular XPS scan the data obtained is a graph with Binding Energy as the x-axis and CPS on the y-axis. The elemental composition of a material can be determined by matching the specific peaks occurring at different binding energies. The relative composition of each element then can be determined by comparing the Full Width Half Maximum (FWHM) expression. It is important to note however that even though photons can penetrate well into the substrate, the emitted electrons will lose some of this characteristic kinetic energy by interacting with the atoms that surround them as they leave the substrate. Therefore one must take into account the fact that this technique is mostly considered a surface characterization technique, since can only find the binding energy of the electrons corresponding to elements located on the uppermost 10nm of the substrate surface profiling. One way to go around this physical barrier is to etch the sample while inside the XPS machine. This has to be done inside the machine, since the etching of a sample may lead to unwanted reactions that might occur if this process takes place at ambient conditions. The ultra-high vacuum system existing inside the XPS analyzer provides a perfect environment to conduct this practice known as depth profiling. However, for this same reason it is very expensive to operate and maintain an XPS machine; and even though the information gathered from this technique can be very relevant, the cost of operation makes this a less appealing characterization technique in an industrial setting. Still, because of the accuracy of the results generated by the XPS, this technique is widely used for research purposes, to the point that it has become an indispensible technique used for the development of new synthesis techniques. This analysis helps researches know if the sample they have generated actually has the composition desired from their synthesis.

Figure 3- XPS survey scan of PZT deposited on a platinum substrate.