Erasmus Mundus Master of Materials Science (EMMS) 2010

X-ray diffraction service

Studies in powder, thin films, bulk samples

Submitted: Lingfei Zhang Email: zhanglingfei1980@gmail.com

Statement of Purpose
This internship is carried out in line with the mandatory requirement of Erasmus Mundus Master in Materials Science (EMMS) program to complete a 10 ECTS training in industry or academic service. The applicant was offered to a position in Central Analytical Lab at the University of Aveiro to conduct user service and self research on various X-ray diffraction (XRD) subjects. This internship aims to train the student with a solid knowledge and first-hand experience in operating the X-ray diffraction in powder, thin-film, bulk sample measurement and residual stress measurement. The software skills in operating the instrument, data collection and data analysis as well as result interpretation are given throughout the period. After the internship the training should result in operating the instrument independently and taking measurement in various mode and ambient conditions by the student. Equally important, the student is also encouraged to train with own project in Quantitative phase analysis by XRD.

Acknowledgement
This internship was carried out under the guidance of supervisors, Professor Artur Ferreira and Dr Rosario Soares. First of all I thank Professor Artur Fereirra for offering me such as wonderful opportunity to do internship at LCA. This opportunity to work with XRD closely as technician has been long dreamed and Professor Ferreira helped me bring it into reality. Throughout the period Professor Ferreira had gave me great help in analysis and discussion though he had an extreme busy schedule.

In the meantime, mostly I worked with Dr Rosario Soares when I was in LCA and she helped me wholeheartedly without any reservations. The experience working with such a wonderful person is memorable and beneficiary. Dr Soares has trained me in all kinds of experiments and I would specially thank her for giving me training in residual stress measurement.

The last but not the least to thank Professor Margarida Almeida and Professor Vitor Amaral who encourages me to do this internship which turns out to be an incredible opportunity and enormous experiences are collected from this work.

Finally, I also want to express my thanks for the staffs at LCA who also offered me a lab and equipments to conduct some research for the internship.

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Table of Contents
Chapter 1: System introduction ...............................................................................................2 1.1 X-ray background.........................................................................................................2 1.2 X-ray instrument PANalytical Xpert...........................................................................3 1.3 User software................................................................................................................4 1.4 Auxiliary sample environments ..................................................................................8 Chapter 2: X-ray diffraction service and study.....................................................................10 2.1 Powder diffraction with XPert Accelerator .............................................................10 2.2 Calibrating instrument resolution.............................................................................11 2.3 Thin film/bulk and grazing angle scattering ............................................................16 2.3.1 Small angle scattering in Gonio mode of thin film or bulk ..........................18 2.3.2 Non-Gonio Grazing incidence scattering of thin film ...................................19 Chapter 3: Residual stress measurement.............................................................................23 3.1 Basic principle............................................................................................................23 3.2 MRD characteristics and specimen alignment........................................................24 3.3 Study examples ..........................................................................................................27 Chapter 4: XRD Quantitative Phase Analysis .......................................................................31 4.1 Introduction ................................................................................................................31 4.2 Specimen preparation................................................................................................33 4.3 Results and discussion .............................................................................................34 Bibliography.............................................................................................................................38

Chapter 1: System introduction

1.1 X-ray background
X-ray was firstly discovered by German physicist Rntigen in 1896 [1] for which he was awarded with the first Nobel Prize in physics in 1901. Later the research was followed up with a lot of works developed by Charles Barkla who discovered gas scattering of X-ray and each element has characteristics X-ray [2] in 1898. However at the time the X-ray wavelength was not able to be determined yet therefore the measurement performed by Charles Barkla was based on the X-ray absorbance in matter. Not after long time, Max von Laue, Paul Knipping and Walter Friedrich discovered, for the first time, X-ray diffraction by crystals and determine the X-ray wavelength. The X-ray diffraction was developed rapidly most notably by father and son William Bragg jointly which gave the birth to X-ray crystallography. Mosley later discovered that X-ray was characterized with the elemental Z number which was associated with the innermost k-level electron being excited and falls back to the orbit during which the energy was released. It was found that the spectrum of emitted X-ray is a continuous with a few sharp characteristics peaks corresponding to the electronic energy level of innermost layer electron as seen in Figure 1. It is also noticed that a continuous background was lying underneath the characteristics peak and the background was specialized with term Bremsstrahlung radiation. Bremsstrahlung is a German word for Brake radiation and the incident electron that carries more energy than needed to excite the orbit electron will release the energy in a continuous way when the charged particles are stopped suddenly by potential field. In X-ray diffraction study, the Bremsstrahlung spectrum was normally filtered out leaving the sharp characteristics energy with a narrow wavelength distribution in order to perform the X-ray diffraction. It is also noted that there are not only one peak but instead two peaks as result of K1 and K2 energy levels in case Copper used as target material. The ratio between intensity K1 and K2 is 0.5.

Figure 1: Bremsstrahlung spectrum [3]

The position of characteristic peaks are well known and determined because that is only related to the innermost core electron which is stable inside the atom without being affected by any physical or chemical reaction. For different materials the K line has different wavelength for instance Cu target will emit X-ray of 1.540598 and 1.544270 ; etc. The X-ray radiation in laboratory X-ray machine is not changeable. However at modern Synchrotron research centre the X-ray is generated by Cerenkov radiation from tangent direction of high speed moving electrons in accelerator. The wavelength is tuneable as function of speed of accelerated particles. This could produce a tailored made condition to study special problems with element scattering contrast for neighbouring elements such as Ni and Fe. Meanwhile, the resolution and brilliance of synchrotron X-ray is one or more order magnitude higher that Lab X-ray. In one word, synchrotron X-ray become cleaner in background and versatile research tools as state-of-the-art compared to lab X-ray these days.

1.2 X-ray instrument PANalytical Xpert

The instrument used in this study was made by Philip. Ltd, Netherland. The model is PAN Analytical XPert diffractometer with Xpert Accelerator and Thin film detector. The instrument has a versatile ability to study conventional powder diffraction, and a programmable slit option for constant illuminated area in thin film study. The diffractometer is also possible to conduct non-Gonio scan mode by fixing the incident angle at around 1o while the diffracted optics moving in omega plane. This condition is known as Grazing incidence angle scattering

which is mostly useful to study upper layers deposited on crystalline substrates.

For the first time use, the instrument should be turned on with two switches on the wall and the most important thing is to switch on the refrigerating system in order to keep the system cooling otherwise it is risk to melt down the target which cause serious problem in machine. After the main power and refrigerating system are turned on, one should press down to turn on the instrument power-on button. The instrument working voltage and current should be set to 40kV and 50mA respectively. However this has to be done in instrument control software as to be seen later on. Once the current and voltage reach desirable level the instrument is ready to start measurement.

The instrument was constructed as a incident beam optics with 0.04rad Soller collimator to direct the beam to an anti-scatter slit ranging from 1/8o to 2o. The beam was shed onto a pre-tuned sample stage and then diffracted into detector known as XPert accelerator. The system is not only used in Gonio mode which is theta-2theta coupled in order to maximize the X-ray detection statistics for measurements that do not require to start below 3,5o. But also available to run with programmable slit starting at low angle ~1o in order to eliminate the over counting problem due to bigger illuminated area due to low incident angle. The programmable slit will control automatically the incident beam optics in order to ensure the X-ray illuminated length is constant, e.g. 10mm. Last but not the least, is XPert MPD is also possible to run at Grazing incidence ~1o sing 2theta mode, fixing the incidence but moving the diffracted beam optics. This is a specialized design to avoid the deep penetration of thin film sample which are mostly deposited on oriented substrates by increase the travelling path within the thin film.

1.3 User software

The instrument control is mostly based on PANalytical software called XPert Data Collector Graphic User interface. The software is used to set the X-ray tube voltage and current before starting measurement as well as parameters in performing fine calibration and measurement. The intensity of diffracted beam versus angle is collected in real-time and plot on screen to allow user to monitor the progress of measurement.

The instrument also provides user software in data for viewing and data reduction. Data viewer is a simple straightforward program to display the data in multiple datasets. HighScore is used to identify the phase with built-in PDF database. The PDF database is also accessible by program ICDD PDF and this is currently the most complete XRD pattern for minerals and inorganic compounds and its main usage is to predetermine the peak and compare the phase by locating the peaks position. XPert stress is specialized program for determining the residual stress by evaluating the peak shifts. The powder XPert MPD diffractometer at LCA provides not only state-of-the-art instrument but also user-friendly and first class software support with inorganic structure database ICDD and phase analysis software HighScore. ICDD contains almost 400,000 minerals from different sources such as experiments and simulation. The pattern is classified into different qualities. Each mineral is assigned with a ICDD ID number by which user can fast track the crystal structure information and XRD pattern. Also ICDD allows the user to search for any possible known structure based on restriction of elements composition. HighScore is very useful tool data manipulation and reduction software for background determination, data displaying for various formats, profile fitting and phase identification. It is ideally for the following purpose of XRD analysis [4]: * Qualitative phase analysis. * Semi-quantitative phase analysis using RIR values or the autoscaler method. * Crystallite size and/or lattice strain determinations by the SCHERRER method of by fitting individual profiles and the WILLIAMSON-HALL plot. * Processing of multiple scans (add, subtract, merge, extend, scale and edit). * Mass absorption coefficient and penetration depth calculations. * Retrieval and display of reference data by (combinations of) several criteria * Pattern treatment possibilities: - Divergence slit intensity conversions - Background determination/subtraction by three functions. - Peak hunting based on counting statistics.

- K2 stripping after LADELL or RACHINGER algorithms. - Fast Fourier transform or sliding polynomial smoothing. - Step-size interpolation.

The normal procedure to displaying Scans is given the suppliers website [4]: Open raw data (.RD, .xrdml, etc) file in Highscore. Inserting scans into an existing Highscore (.HPF) project. Displaying and changing scan properties in the object inspector pane. Different ways to display multiple scans in the main graphics pane. Zooming in on areas of interest. Document settings.

Phase Identification is most important task that HighScore can do in daily XRD analysis; however various pattern pre-treatments need to be carried out before phase ID can be performed. These can be fully automated and performed as a macro program, but it is usually necessary to customize this program for your particular samples to obtain the correct results. The recommended steps are: Pattern Treatments Prior to Identification 1. Determine background. The auto function is usually acceptable, and the bending factor and granularity can be varied to get the best fit for the background. (This step can be

done unseen when peak search is performed, but the algorithm used is different and there is no user input. 2. Peak search to find peaks with high significance. the peak list tab of the lists pane. 3. Strip K2 peaks. (This is done unseen when search match is performed, which is The accepted peak data is given in

often preferred because the graphics will then show the original data.) Search and Match and Phase Identification Search matching is used to find candidate phases from the reference database to explain the peak features in the measured scan.

Advisable to set-up restrictions so that only a sensible subset of the full database is searched.

The way in which the candidates are scored can be adjusted with various parameters either before search match is carried out, or afterwards (buttons on the bottom taskbar).

Candidate phases can be shown in the main graphics pane with the scan data. When a phase is accepted (either by dragging from candidate list to accepted list, or by right-click or accept pattern), the scores of the remaining candidate phases change accordingly.

Unmatched peaks are indicated in analyze view by a v marker at the top of the scan. The residual unmatched peaks can be viewed in the additional graphics pane. This process can be automated by checking the identify box in the automatic tab of the search and match window, but need to have a good restrictions set and must check result is sensible!

Peaks can be labeled using Tools / Label Peaks.

Reporting / Extracting the Data The software will create Word or RTF format reports which can be fully customized in Report / Edit Report Definition. the right hand panel. the parameters. Select items required on the left hand panel and drag into

To modify the default items in the left hand panel, click the item to view

When you have modified the parameters, click the <<More button to view the

save icon. Save the new parameter set with a new name. Limitations of the HighScore Software The HighScore software does not have the capability to carry out Rietveld Analysis. The HighScore software does not have the capability to create different users. The Since

only way to achieve this is to set-up each user with an individual windows login. there are so many users of this system, this is not feasible. The HighScore software is very customizable. By all means create your own

parameter sets, but it is very important to give them your name as well as an identifier because they will be available for everyone.

1.4 Auxiliary sample environments

In LCA, XPert Philips MPD machine has two goniometers that share the same X-ray source. The second Goniometer is used to run measurement at non-ambient conditions at a high temperature range up to 1500oC with vacuum option and low temperature range to liquid nitrogen (77K). This is a significant advantageous since a lot of structural transformation will take place when the structure was heated up or cooled down. The option to apply vacuum by rotary pump and turbo pump can produce vacuum with pressure down to 10-4 mbar. This enables user to study phase transition to minimize contamination effect on diffraction pattern from oxidation in air. The general outlook of the furnace and sample stage is seen in Figure 2.

Sample stage

X-ray window

Figure 2: (a) X-ray transparent cover lid of the furnace made of Kapton;

(b) variable temperature chamber and sample stage

The furnace is equipped with a cover lid made of Kapton which is commonly used as windows materials at X-ray source. Relatively high mechanical and thermal stability (excellent insulating properties) as well as its high transmittance to X-rays make it the preferred material for high temperature or low temperature variable experiment. In high temperature experiments, The powder was place in the centre of sample stage as shown in Figure 2(b). It is important to know that some time the measurement has to be carried out in vacuum to avoid unwanted oxidization. Therefore a two stage pumping system is also installed with first stage rotary pump and second stage of turbo pump. The maximum vacuum this system can provide up to 10-4 mbar.

The variable temperature measurement is fully automatic and user could modify their measurements via a macro specific program in the control software. The measurement parameters such as temperature ramp rate from RT to first measurement temperature are typically 5oC/min or 10oC/min. It is necessary to set up a so-called stability time typically 5-10 mins in order to let the temperature stabilized at desirable temperature and start measurement afterwards. The data collection time is similarly defined by step angular size and time at each angular step from a few mins to a few hours. After one measurement is completed, the program will drive the furnace to ramp the furnace temperature to next programmed value at a steady rate. Then a repeated strategy is applied to the next temperature until all pre-set temperatures measurement is completed. The furnace will naturally cool down upon finish of the programmed measurement.

Chapter 2: X-ray diffraction service and study

The internship at LCA is divided into two roles. First of all routine user service is practised at a weekly basis. The user will access LCA in person and deliver the samples to us. The samples are collected and arranged in measurement based on first come first serve basis. However in some cases priority will be also given to emergent user or a study with special consideration. The user when accessing the LCA for measurement must submit a datasheet indicating the sample name, measurement conditions such as 2theta scanning angle range, the time to scan at per step and steps angle. These three parameters will determine the total data collection time which varies from a few minutes to a few hours. In some cases, when profile refinement is necessary in addition to the phase identification, the data collection will take as long as 13h for a very good spectrum. After measurement, the data collected in XDRML format will be converted into two-column ASCII format XY file for most graphic editor or XRD analysis software to accept. And the data was feedback to user by email.

2.1 Powder diffraction with XPert Accelerator

The powder diffraction measurement is performed in the following scheme. The X-ray tube and detector is coupled to form Gonio geometry for best statistics. The sample holder is made of aluminium with glass blade base or Silicon. The silicon sample holder is specially cut to gives a flat background. In contrary, aluminium sample holder shows characteristics peaks at well known peak positions which can be dealt with in data post-processing.

The measurement starts with a user made program known as a macro file containing the user specified information and parameters to allow the instrument to execute the measurement automatically. The program is to set the scan start angle and end angle as well as the angle step. The time at each step will also be preset as if affects the statistics and total data collection time. Once the user modifies the specified program the program should be saved and used later on for a user specified measurement. The next step is to go to menu measure ->program. This opens a dialogue asking the user to select the previously defined user program with measurement conditions.

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2.2 Calibrating instrument resolution

In X-ray diffraction the peaks are always observed with certain amount of broadening instead of being a sharp single line which is predicted by mathematical crystallography. Briefly speaking the broadening of the peak is associated with the particle size and strain of the sample and a qualitative evaluation will determine whether the samples are crystalline (sharp peaks ,bigger particles), nanoparticles (wide peaks, small particles) or only local correlation (wide bumps, no peaks, amorphous). The quantitative evaluation of peak broadening for instance by Scherrer formula is to estimate particle size and strain in specific (hkl) direction while Williamson-Hall plot will be able to determine an average particle size and strain.

However, the experimentally observed peak broadening is not only coming from contribution of the samples microstructural characteristics but also from the geometry of instrument hardware. This could be seen and calibrated with strictly synthesized and certified standard sample such as LaB6 with nearly ideal crystallized state. Therefore the contribution from the standard sample is approximated to zero and the peak broadening which is very small is regarded only as from the instrument-specific contribution. The experimental broadening of the peak is actually a convolution between two broadenings from instrument and sample specific respective. When evaluating the sample microstructures the instrument broadening should be taken into account and subtracted.

The instrument broadening is calibrated conventionally by two approaches. One is to fit and model the diffraction peaks at each 2theta and calculate the Full-Width at Half Maximum (FWHM). The FWHM is determined also two different ways either by determining the lateral breadth of the peak at half-maximum or the integral breadth obtained from dividing the height by the peak area. In our work, we choose the first way to model the FWHM. The FWHMs are plotted as function of 2theta and the curves are fitted using the conventional diffractometer resolution function developed by Caglary and et al [5] as shown in equation (1).

FWHM 2 = U tan 2 + V tan + U + P / cos2

(1)

However (1) is regarded as only valid for low-resolution powder diffraction since the instrument resolution in 1950s was not very good. Nowadays, the instrument resolution
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function has been developed and added with many other terms in order to simulate the peak asymmetric behaviour and other effects of instruments. However due to limit of space an detailed introduction to various types of resolution functions can be found in GSAS manual [6]. The second approach to determine the resolution function is based on Whole-pattern fitting method also known as Rietveld refinement. Rietveld refinement is a method taking into account not only the interplanar spacing but also many other parameters such as temperature factor, atomic coordinates, atom occupancies, sample relative wt% in case of mixture and size and strain effect from the peak broadening. Most programs are free-of-charge such as GSAS and Fullprof and commercial one such as TOPAS provide a separate interface to refine the profile function coefficients by Rietveld method. In the following paragraph we are about to demonstrate the instrument resolution function determined by peak-by-peak fitting and Rietveld refinement.

The LaB6 sample is from certified NIST standard power SRM 660a with precisely defined lattice parameter and (hkl) list positions. The XRD pattern is seen in Figure 3 without sample broadening due to structural defect strain and crystallite size effect. It is apparent that the sample has small dependent broadening with its sharp peaks. However one zoom the peaks and reveal different broadening at each peak. This is attributed to the effect of instrument. The broadening is characterized and quantified by FWHM as previously introduced. Note that the sample was measured in Aluminium sample holder therefore the diffraction from the sample holder is unavoidable as marked in Figure 3. These are not included in the fitting to instrument resolution function.

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18000 16000

Alum inium sam ple holder

14000 12000

intensity

10000 8000 6000 4000 2000 0 20 40 60 80 100

2theta

Figure 3: XRD pattern for NIST standard powder LaB6 SRM660

Figure 4 shows the result of FWHM variation of peaks from running LaB6 sample using 1/4o fixed slit and 1/2o anti-scatter slit in incident beam optics as well as 5.5mm slit in diffracted beam optics. The resolution was fitted with Caglary equation as shown in red and the parameters U, V, W are determined U=0.0368, V=-0.04493 and W=0.07381 respectively. We noticed that the fitting is not very good at lower 2 angle but it continues to improve when 2 is higher.
0.085
Chi^2/DoF = 5.5358E-6 R^2 = 0.89473 U V W 0.0368 0.00573 -0.04493 0.00948 0.07381 0.0035

0.080

0.075

FWHM(deg)

0.070

0.065

0.060

0.055

0.050 20 30 40 50 60 70 80 90 100 110

2theta

Figure 4: resolution curve for 1/2o anti-scatter slit and 5.5mm slit

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However profile function in (2) was considered as mainly for low and intermediate resolution of Neutron diffractometer [6] and Nowadays, a more successful function employs a multi-term Simpson's rule integration given by C.J.Howard [7]. This function is based on Pseudo-Voigt function described by Thompson which was used in TOF data. The broadening of the peak are now divided into two components of Gaussian and Lorentzian variance. The equation seen in (2) was only descriptive to Gaussian variance whilst the Gaussian broadening is defined [6]:
g = (8ln 2) 2

The profile function parameter determined based on C.J.Howard [7] is done within GSAS program where the profile function parameters are refined as part of Rietveld refinement. The sample is supposed to be free from any structural defect and the sample particle size is large with crystallite size estimated by Scherer formula to be roughly 10,000. Therefore the lattice can be approximated to give a sharp diffraction peak as shown in Figure 5.

Figure 5: whole pattern fitting of the LaB6 diffraction peak with CW profile function 2 wRp=0.1453 or Rp=0.1058, Chi**2=5.405

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Figure 6: higher angle range of LaB6 diffraction peak with CW profile function 2

Figure 7: Low angle range of the LaB6 diffraction peak with CW profile function 2

After refinement is completed one should check the profile function parameter in GSAS profile function panel to record the parameter for future use or create an instrument file containing such parameters. The parameters from above refinement are seen in Figure 8.

Figure 8: GSAS profile function parameter for XPert MPD at LCA

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2.3 Thin film/bulk and grazing angle scattering

Thin film is an important class of materials and the XRD technology has to be specially modified to suit the effect study of the structure. One of the challenges is the alignment of thin film or bulk samples have to be adjusted due to the thickness of the sample. Unlike the powder, thin film or bulk samples has to be placed on a sample stage on which the sample must be correctly placed in Z-direction as shown in Figure 3.1. The X-ray could miss the sample if the sample is either too high or low in Z-direction. Provided X-ray beam is only ~1mm wide and the alignment is very important to optimize the X-ray beam onto the centre of the sample surface.

Figure 9: schematic illustration of thin film or bulk sample measurement (a) correct position; (b) sample stage is too low (c) sample stage is too high

Figure 9 implies that the sample stage position must be calibrated before carrying out measurement. The sample stage position in Z direction without film or bulk using precise screw meter is recorded as reference to adjust the sample stage height after the sample is placed in position. Since the thickness of the thin or thick film or bulk materials vary from one to another. Therefore it is necessary to use the height meter to determine the Z-position of each sample top surface before measurement. This will ensure that only the centre of the sample will be illuminated by X-ray as shown in case (a) of Figure 9.

The thin-film study also requires different detector known as MPSS-thin film in Data Collector program. The thin-film detector has different technology compared to Accelerator detector in the following aspects; First, thin-film detector has gas-filled detecting chamber in
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which the gas molecules are ionized to register the intensity of the X-ray whilst the Accelerator has solid state detector which is faster and more stable than gas-filled device. Secondly, the thin film detector has a group of parallel collimator in front of the diffracted beam Therefore, thin film detector could accept only very well collimated and parallel X-ray diffracted from the sample. This is important to reduce the inaccuracy of dependence of the sample height. When user study the thin film one should first disconnect the MPSS Accelerator and unscrew the MPSS accelerator. Then one should replace with MPSS-thin film detector as shown in Figure 10 (a) and (b). The use of thin film detector requires use of as shown in red square of Figure 10(a). In addition to this, the anti-scatter slit which is used in powder diffraction mode should be removed in order to control the beam illuminated area by programmable slit inside the before the anti-scatter slit slot as shown in (b) of Figure 9.

Figure 10(a): Thin film detector with beam slit(red)

Figure 10(b): the anti-scatter slit has been removed for programmable slit control

Last but not the least thing to remember is the inaccuracy of zero angle offset should be checked before running experiments from starting angle lower than 1o. The calibration is done by using direct incidence of X-ray beam into detector to determine whereabouts of the maximum beam intensity. The calibration should be always done with beam attenuator in place to prevent beam attenuation accident. At beginning, all previous beam zero offsets should be cleared to zero. Then performing 2theta mode scan with 10o range at 0,02o step, after the maximum beam position is found one should move the cursor to locate the peak where beam is maximum and accept this as current zero offsets. Secondly performing Omega scan with 2,5o range at 0,02 step. When the fine calibration is complete, accept the new position of zero offset and the instrument
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is ready for low angle measurement.

2.3.1 Small angle scattering in Gonio mode of thin film or bulk Small angle scattering has another issue in incidence beam optics. The set-up is different from conventional powder diffraction starting from higher angle. In this case, the incident beam optics is required to use programmable slit with constant illuminating length on the sample as shown below. Figure 11 shows that the programmable slit will be able to control the X-ray illuminated area (bars shown in red) on the sample. This is needed since the incident X-ray photons will illuminate the sample holder at very low angle incidence with setup for higher angle incidence. In case of using constant programmable slit, the illuminated area will be constrained only on the sample area by varying the slit width (2<1) at low angle as illustrated by Figure 11.

Figure 11: Schematic illustration of programmable slit in constant illuminated length scanning

The software setup to activate the programmable slit operation for small angle incidence follows the procedures and parameter as illustrated in Figure 12. In this case, the starting angle is 1 and the end angle is 25, other parameters such as time per step and step size are also available in Figure 12.

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Figure 12: software setup for programmable slit of 10mm

2.3.2 Non-Gonio Grazing incidence scattering of thin film Grazing incidence scattering is specially developed for study of thin film sample deposited on substrate for instance. The reason of using grazing incidence is due to that the intensity of Silicon single crystal substrate is very intense. The intensity from the substrate could submerge the intensity of the peaks from the thin film sample itself. In Gonio mode, the source X-ray tube and the detector are coupled to do 2 scan in order to maximum the signal to noise ratio at particular angular position. However in grazing incidence scattering, the Gonio mode is no longer used and the source X-ray tube and detector are de-coupled. This implies that only the detector will scan signal from start end to the end angle for instance 3o to 70o but the source X-ray tube remain fixed at very low incident angle such as 0.5~1o. This gives two advantages namely 1) glancing angle will only allow X-ray to penetrate a small depth of the thin film therefore the diffraction from the substrate could be effectively eliminated or suppressed; 2) to avoid seeing any strong peaks from Silicon substrate due to the peaks of silicon are mostly showing up from 20-70 degrees and the intensity from substrate peaks will be minimized due to de-coupled 2theta scan. The principle of grazing incidence is illustrated in Figure 13.

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Figure 13: Bragg reflection in Gonio mode (a) vs. off-specular reflection (b) in grazing incidence mode

The Disadvantage of grazing incident scattering is the statistics is not as good as to Gonio mode. Since the most signal will scattered at reflection angle due to Bragg equation and therefore the experiment should take considerable longer in order to get good and comparable statistics in Gonio mode. The Grazing incident angle scattering also required additional care in instrument alignment in terms of zero angles. The alignment is performed in following steps: 1) Move the source X-ray and detector into parallel position. However the position of detector may not truly parallel to the source X-ray tube due to misalignment. This will be found out and calibrated in the next step 2) Place an attenuator before the source X-ray tube to reduce the intensity otherwise the incident X-ray is directly into the detector will cause saturation of the detector due to intensity spike. 3) Perform a scan around current zero angle with 1o to determine the true zero position with maximum incident intensity. Determine the new position of maximum intensity and determine the offset needed to current zero angular position. 4) Accept the new zero angular position.

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The calibration is critically important since in grazing incident scattering experiment the zero offset is usually comparable or even larger to the grazing incidence angle if not properly calibrated. In our study, we discovered that the zero position offset is 0.075 deg. This about 1/10 compared to the grazing angle of 1o. So it must be correctly calibrated. The corresponding software setup to perform glancing angle scattering is shown in Figure 14.

Figure 14: software setup for grazing incidence to study thin film

In Figure 14, one can see that the detector configuration has been changed from XPert Xcelerator to MPSS_thin_film which was introduced in instrument specification in Chapter 1. The Scan Axis has been changed to 2Theta from Gonio mode. In the meantime, in Other Gonio angle configuration, the Omega angle has also been defined as 1o. This Omega is the angle between the incident X-ray beam and the plane of sample as shown in Figure 13. In Grazing angle scattering, the signal-to-noise ratio is also an important term to be considered. It is known that the closer to Gonio mode the better statistics is likely to be. However as shown in figure above, increased angle will also increase the penetration depth of X-ray into the thin film and the reflection from the substrate will be also included if the X-ray hit the substrate. The X-ray attenuation depth is defined as depth when X-ray intensity has dropped to 37% of that at the surface. The depth can be related to the materials properties of mass adsorption coefficient and density of the materials in cm-g-s (cgs) unit system x = 1/() (cgs) (3)

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In case of Multicomponent Systems containing more than one element, the total absorption coefficient is the sum of individual elements mass adsorption coefficient i multiplied by the weight fraction Ci respectively.

s = Ci i

(4)

In one of user measurement studies, the materials of thin film is assumed to be PbTiO3, the weight fraction wt% between Pb, Ti and O is 0.70, 0.15 and 0.15. For lead the absorption coefficient at X-ray incident wavelength energy E=8.05 keV, (8.05 keV) = 231.13 cm2/g. For Titanium: (8.05 keV) = 201cm2/g and oxygen (8.05 keV)=11cm2/g [8]. Therefore, s=(CPb)(Pb)+(CTi)(Ti)+(CO)(O) =(0.70)(231.13)+(0.15)(201)+ (0.15)(11) =193.59 cm2/g. The attenuation length of the PbTiO3 is determined from (3) to be 6.538 m. The maximum grazing incidence angle is determined to be 1o. Therefore the thickness of the PbTiO3 film is determined by Pythagoras principle t=6.538 m *sin1o =0.114 m or ~114 nm.

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Chapter 3: Residual stress measurement

In modern engineering study, residual stress or internal stress as consequence of material processing mostly due to insufficient annealing or welding-induced dislocation within elastic limit has caused a wide interests in materials study. The internal stress varies across the materials and balances each other to main the shape. However under certain external loading conditions the stress may either benefit to strength the materials or deteriorate the material strength. Therefore insight knowledge of residual stress is important to material processing particularly in metal and alloys. Conventional mechanical measurement is only a reflection of bulk properties as an average of all residual stress and that is why the same materials can have different mechanical properties as internal stress will counter-balance the external load. Therefore a local probe of stress detection and measurement is necessary.

X-ray is capable to study interplanar spacing and the variation of interplanar spacing is an direct evidence of strain and hence the stress which causes the strain. Once the strain is measured from variation of atomic spacing change the stress can be calculated based on the Youngs modulus of that material. The advantage of using X-ray is that the stress distribution across the sample can be mapped out. But the X-ray can also penetrate the sample surface into certain depth depending on X-ray incident energy and materials from less than hundreds microns up to few mm. This gives X-ray an ability to look into the materials where the stress can not be studied by any other means. However we should not forget that neutron diffraction has been developed in recent decades due to high resolution diffractometer has come into force. Compared to X-ray, neutrons are not scattered due to electronic cloud but the nuclei and hence will travel further into materials. This is complementary to X-ray in lab in studying residual stress deeper inside the materials. More recently, Synchrotron X-ray has also been developed which delivers even stronger capability to study deeper inside materials by its high energy x-ray with extremely high resolution. In one word, stress X-ray measurement is one of the most important tools these days to engineering and material science.

3.1 Basic principle

The basic principle of measuring residual stress within the crystal lattice is based on the

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determination of crystal lattice misalignment or strain. However the residual stress measurement has to assume that strain is found within its elastic limit. Therefore stress measurement is an extrinsic measurement and not direct measurement. Strain is an intrinsic property instead.

To determine the stress, the strain in the crystal must be precisely measured for specific crystalline orientations (hkl) relative to the sample surface. Therefore X-ray stress measurement requires the sample is crystalline, fine grained and produces diffraction for any orientation of the sample surface [9]. The sample could be metal or ceramics. The X-ray stress measurement is carried out by two diffractions from the same sample surface at higher angle for at least two orientations respective to the incident X-ray beam. The angle is defined as the angle between the samples normal to the scattering plane in Figure 15.

Figure 15: definition of angles in X-ray stress measurement, S: source, D:detector

In principle any interplanar spacing variable can be used to determine the strain and hence the stress. However in practice the higher angle the greater precision of the determination of stress. The 2theta angle is mostly chosen greater than 120o. Table 1 (reference) lists the recommended peak index (hkl) and radiation to study residual stress in various materials.

3.2 MRD characteristics and specimen alignment

The MRD diffractometer is illustrated in Figure 16. The MRD has more degree of freedom compared to MPD. In addition to Omega and 2theta scan, MRD is able to vary the angle between the sample plane and the Omega plane.

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Figure 16: photographic representation of stress measure.

The alignment is critical to a good measurement. If the sample zero positions cannot be aligned properly the sample will show orientational effect which causes a split results between negative and positive sin2 plot. The general steps to calibrate the sample zero offsets for alignment is summarized below.

1. First of all, user should go to tool-> sample offset-> clean all offsets. This is necessary to remove all previous offsets for other measurements and set all to zero for new alignment. NB. The alignment is necessary every time a new sample is to be measured. 2. Z (height) calibration: The height of the sample should be in the middle of the beam; therefore scan should be made around current Z position within a range of 4mm with step of 0.05mm. Note Cu attenuator should be inserted before scan is made since the beam will be incident directly to the detector. The attenuator will prevent detector from shutting down due to saturation of direct beam incidence. The scan should give a curve from maximum intensity to zero intensity and the Z position should be chosen in the middle of the curves which are indicated by red line by Figure 17.

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Figure 17: Z position fine calibration

3. After Z calibration, Omega scan should be carried out within range of 10o with step of 0.1o. The scan is to ensure that surface of the sample is not affecting to the results. The typical Omega scan gives scan of constant intensity meaning no preferred orientation. 4. Z and Omega scan are made at 2=0, however since we need to choose one reflection (hkl) to measure the lattice strain as function of , therefore the further alignment has to be done at 2=2hkl. The choice of reflection (hkl) is not random, the reflection should be used at higher angle due to X-ray resolution is the best. It is more likely to see the peak shift. 5. The alignment at 2=2hkl is Omega scan again within 10o with step of 0.25. A constant intensity should be expected if the sample is not textured. At 2=2hkl, scan is last step of alignment in order to ensure the maximum counts at specific angle. The typical scan should gives a curves as seen in Figure 18 and the new position should be chosen where the maximum counts locate as indicated by the read line. In case the red line is not located at the peak maximum, user should right click mouse and select move mode in order to re-locate the peak and the machine will re-position the detector for new zero offset.

Figure 18: fine optimization

6. From step 2 to 4, new offsets are found due to scans made to align the sample to obtain best counting statistics. The new offsets should be introduced into the software as new zero
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points of detector. This is done by tool -> sample offsets -> Set new offsets.

Once all above-mentioned 6 steps are completed successfully, the instrument is ready to take measurement. The user should go to file >open program to edit the measurement parameters such as the range of scan, number of scan at each positive and negative side of the cradle. Steps of Gonio scan at each to determine the peak position and the time at each step. A typical scan takes 30 mins in order to determine the peak shift by either manual or automatic peak determination. However we discovered that the statistics matters in the determination and we recommend 13 scans at positive and negative sides, 0.02o for Gonio scan and 2 seconds per steps in order to determine the peak position more reliably and effectively. The corresponding time is almost 2h.

3.3 Study examples

In order to train the skills in measurement of residual stress, two samples are provided by a colleague. The samples geometry is a thick disc with two different thicknesses. The radiuses of the discs are R1 and R2 respectively. The sample was sintered from green density of approx. 50% and the sintered density is close to 100%. The volume shrinkage was then determined to be about 50%. Due to tremendous volume shrinkage the materials will be compressed into the centre of disc and the closer to the centre the bigger compressive force, this motivated us to study the residual stress distribution along the radial direction assuming that the residual stress is uniform in plane and only a function of distance to the centre. It is known that X-ray has limited penetration from hundreds of m to few mm dependent on the incident energy in different materials. Therefore, conventional lab X-ray could only study the residual stress up to a small distance from the surface of sample. The assumption is made that only in-plane stress exists in bi-axial model and there is no stress components normal to the sample surface within the X-ray penetration depth. Because of this lab X-ray is regarded mostly as surface residual stress study tool. Synchrotron X-ray at higher energy can extend the penetration to cm however it is difficult to access and expensive for most users.

The samples are studied with two residual stress measurement each at the centre of the disc and some distance away from the centre along radial direction. For sample 1, the location was chosen at R/2; while for sample 2 the location was chosen at 7/9R. This choice was made to see
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how much the residual stress drop at percentage as function of distance to the centre. The measurement was taken for the peak at higher angle due to good angular resolution for X-ray, the peak we chose to study is (112) at ~98o. The was chosen with positive and negative values around the 0, at each side, 6 angles were selected. The total number of scans for (112) d-spacing shift due to variation was 13. The dependent (112) peak scans results for sample 1 is demonstrated in Figure 19.

Figure 19: typical dependent (112) peak scan

Figure 19 shows apparently that the (112) peak has shifted significantly as function of . This is a clear indication that the sample has a tremendous lattice strain due to residual stress. Since the scan was done for positive and negative , therefore the peak position is determined by averaging the two scans. Once the peak positions are determined by manual or Lorentz peak profile functions, the peak positions are ready to be taken as input to calculate the residual stress provided the materials Youngs modulus is available. The results of the residual stress are calculated using sin2 method. The plot is made for lattice spacing change as function of sin2, and the slope is used to evaluate the residual stress while the sign of the slope is to evaluate the stress is either compressive (negative slope) or tensile stress (positive slope). The sin2 plot for sample 1 at the centre of sample is shown in Figure 20.

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Figure 20: residual stress determination for sample 1 by sin2 plot

Similarly, another location was study at R/2, where R is radius of the disc. According to our expectation the sample should show less residual stress further away from the centre due to less material compressed during sintering process. The results show agreement with our expectation. The same measurement was also performed for another sample with different geometry. The sample 2 is thicker than sample 1 but the diameter is smaller. The residual stress measurement were performed at the centre of the disc and location with distance of 7/9R2 to the centre. The d-spacing shift as function of is not shown. The residual stress was determined by sin2 plot respectively in Figure 21.

Figure 21: residual stress determination for sample 2 by sin2 plot

The residual stress distribution along radial direction for sample 1 and sample 2 are shown in
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Figure 22 (a) and (b) respectively.

-3.2 -4.0 -4.8 -5.6 -6.4 -3.0

residual stress(GPa)

(a) 1/2R1 centre of disc

residual stress(GPa)

-3.6 -4.2 -4.8

(a)

7/9R2

centre of disc

radial distance of the sample discs

Figure 22: Compressive residual stress distribution in radial directions

The results from sample 1 and sample 2 show that the residual stress is always bigger, perhaps maximized in the centre of the hard ceramics body due to sintering process in which the materials shrinks and compressed towards to the centre. It shows that sample 1 has experienced 23% decrease of residual stress at 50% radius from the centre while sample 2 has only 16% decrease of residual stress at 77% radius from the centre. Sample 1 shows a bigger gradient in residual stress distribution. This is connected to the sample 1 thickness which is bigger than that of sample 2. The thinner sample will produce more uniform distribution of the residual stress across the radius direction. However when we compared the maximum residual stress between sample 1 and sample 2 we found that sample 1 show always higher residual stress. This is perhaps due to the total weight of sample 2 is less than sample 1 which reduce the total residual stress in the sample.

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Chapter 4: XRD Quantitative Phase Analysis

4.1 Introduction
X-ray diffraction has been used for quantitative phase analysis (QPA) for recent decades. The development was facilitated especially with the Rietveld method [10] and computer program. In past days, the quantitative phase analysis is based on Reference-Intensity-Ratio (RIR) method developed by ICDD [11]. This method is to compare the intensity of the primary peak to that of corundum (113) peak measured under the same experimental conditions. However the accuracy based on single peak comparison is not very optimistic and the RIR method has become obsolete.

There are primary two approaches in QPA called traditional method and Rietveld method [10]. Both methods are based on calculation of the peak reflection intensity which is function of many parameters. The reflection intensity from (hkl) of phase j is written as below: I hkl = I j fj V
2 j

Lhkl Fhkl , j Phkl , j Aj

(5)

Where, I: incident beam intensity, fj: phase volume fraction, Vj: cell volume, Lhkl,j: Lorentzian polarization, Fhkl,j: structure factor, Phkl,j: Texture factor, Aj: absorption factor. From (5) we see that the intensity of diffraction peak is directly proportional to the phase volume fraction. The parameters in (5) should be well known before any QPA analysis. However the definition between Rietveld software will be different. In [12], the texture factor is 1 when the texture is random; while for Gonio geometry and flat sample surface the absorption factor is 1/2, is linear absorption coefficient of the mixture.

The most popular method to do quantitative phase analysis is based on internal reference by adding a known amount of well known phase to a mixture of unknown phases and measure the peak intensity ratio. Therefore the amount of unknown phase j can be calculated based on the ratio between its peak intensities and intensity of the internal reference. The equation is represented by the intensity of Ihklj reflection of phase j and weight fraction of that phase wtj as well as intensity Ihklinternal and weight fraction of internal reference wtinternal, in (6)

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I hkl j I
h 'k 'l ' int ernal

=K

wt j wtint enral

(6)

However traditional method also presents several unavoidable limits [12] such as the methodology to determine the peak intensity is often done to the height instead of peak integral; Only one or few peaks are used and this will produce error when preferred orientation is present; In case of peak overlapping the peak integral is even difficult to be extracted intensity. Another reason why RIR method has become obsolete is that the value from the ICDD PDF file may not be the representative of the real phase in the study. All of these principal error sources urge the scientist to develop a new way of QPA, Rietveld refinement [10]. The Rietveld method is different from old days that the peak is only fitted with mathematical profile functions. Instead Rietveld is a model dependent approach containing all crystal structure and sample microstructure information. However Rietveld method also has limitations. When the structural information is not completed even for just one phase, the refinement work cannot be completed. The incorrect structural information will also affect the quantitative phase analysis in a significant way since the profile intensity is solely determined by the crystal structural information. Recalling the usual intensity of Rietveld formula [12, 13]: (7) Sj(2i-2k,n) is line broadening term which determines the shape of the peak, normally 4 types of shape functions are available in Bragg-Brentano namely, Gaussian, Cauchy, Voigt and Pseudo-Voigt as well as Pearson VII; Pk,n is texture factor, A is absorption factor; which determines the height of the peaks; LK is Lorentz-Polarization faction which is depending on instrument geometry, monochromatic take off angle (a), detector, beam size/sample volume and sample positioning (angular); Fk,n2 is structure factor incorporated with temperature factor; bkgi is the background function; Vn is the volume of unit cell [14]. Where Sn are now the scale factor for the phase j and comparing this to intensity formula for the hkl reflection in (5), the volume fraction or weight fraction of phase j can be written like S j j S (8) f j = N j and wt j = N Si i Si
n =1

i =1

N: the total number of phases in mixture, Sj is scale factor, i is density of phase, Sii is
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phase density of the phase.

The first prerequisite to carry out a good QPA is the software. Currently there are several software either from commercial suppliers or free-of-charge to do QPA. The most known software is TOPAS developed by Alan Coelho and commercialized by Bruker AXS. The other one which is known and tested in this work is SIROQUANT developed by SIETRONICS Australia. The advantage of using SIROQUANT is to simulate the reflection profile pattern based on whole pattern decomposition. Similar another program called QUANTO is also based on principle of combining Rietveld refinement and whole-pattern decomposition method [15]. The commercial software is not available in this work. Therefore there is also free software such as GSAS [6], Fullprof [16] and MAUD [17]. The author has little experience in Fullprof therefore the analysis later on will only be conducted and compared between GSAS and MAUD. In Table 1, a list of main features and other info are presented for most typical program in powder diffraction analysis.
Table 1: popular commercial and free software for Rietveld and Quantitative phase analysis Program Rietveld QPA TOPAS (commercial) Yes Yes TOPAS (academic) Yes Yes HighScore Plus Yes Yes GSAS Yes Yes Fullprof Yes Yes MAUD Yes Yes SIROQUANT No Yes QUANTO No Yes

Price (EURO) >10,000 700 >10,000 free free free 5000 free

4.2 Specimen preparation

The sample in this case study is a mixture of well crystalline sample containing ZnO, SnO2 and V2O5 supplied by Aldrich ltd. The mixture was made by low speed micro ball milling in Mg stabilized ZrO2 jar of 50ml at 400 rpm with 12 various sizes Zirconia balls. The time of ball milling is set to be 30 mins in total. After ball milling the powder is homogeneously mixed and the sample was measured with different weight to create a standard reference sample for verification of the QPA results from different programs.

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4.3 Results and discussion

Table 2 shows the phase and wt% of mixture used in the QPA study. The weight are measured respectively in a balance with 4 digit precision0.0001g. The last two columns are computed wt% by Rietveld program GSAS and MAUD. We noticed that GSAS found the best agreement for ZnO phases while MAUD has found best agreement for SnO2 and V2O5 phases. Besides human experience related error, as Rietveld refinement is a specialty task required at least two years experience in order to give the reliable analysis. The author has worked with Rietveld refinement for last 5 years but it is still very challenging when the agreement is not found. Nevertheless, Table 2 gives us a complication that how to use the QPA for analysis with more accurate results in future. The refined diffraction spectra are plotted in Figure 23.

Table 2: Mixture of phases for QPA and results from Refinement

phases ZnO SnO2 V2O5 mixture

weight(g) 3.292 8.1958 1.4076 12.8954

wt% GSAS% MAUD% Fullprof% 25.52848 21 32 12.46 63.556 48 60.3 82 10.91552 29 7.7 5.5 -

Figure 23: refinement of ZnO-SnO2-V2O5, wRp=0.0833, Rp=0.0625, Chi**2=5.459

As seen in Figure 23, the refinement has reached a very good convergence between the observed diffraction spectrum (+) and calculated diffraction spectrum (----). The pink curve is

34

the difference between the observed and calculated spectrum. The blue, red and black marker underneath indicates the peak position for each phase, V2O5, SnO2 and ZnO respectively. Figure 23 shows that the agreement is found perfectly from 2=35o. The main discrepancy between the observed and calculated spectra is from lower angle diffraction. Compared to the results in Table 2, we noticed that the most profound discrepancy is from SnO2 and V2O5 at lower angle. Therefore we zoomed in this area for a close inspection.

Figure 24: regional plot of (200),(001) and (101) peaks

Figure 24 shows that the main inaccuracy of QPA is from the mismatch of peaks corresponding to V2O5 and SnO2. The peak at (001) is seen significantly underestimated for SnO2 however it is noticed in Figure 23, the position of V2O5 peaks overlap with most SnO2 peaks and it is difficult to see from peak intensity only since the peaks are fitted well at higher angle. But the wt% refinement results show that intensity from V2O5 are overestimated while the intensity should be assigned to SnO2.

One other likely explanation of the large discrepancy is that the statistics of the data is not good enough to rule out fluctuation such as seen at peak (001). The highest intensity point could be a intensity spike due to instrument which is not real from the sample. The only way to remove all ambiguities from instrument response is to collect the data over longer time where a intensity statistics is expected to be improved in order to give a smooth pattern. The typical
35

recommended time at MPD for QPA refinement is 5-10 hours depending on the samples complexity. We only run the sample for one hour.

Because the statistic of previous scan is not good enough to run QPA, we run the sample for 20 h and the result was shown using GSAS and MAUD in Table 3. The Rietveld plot is also shown in Figure 25. We noticed that the result in Table 3 shows that QPA result has increased significantly to the expected values as previously weighed for comparison.

Table 3: Mixture of phases for QPA and results from 2nd Refinement

phases ZnO SnO2 V2O5 mixture

weight(g) 3.292 8.1958 1.4076 12.8954

wt% GSAS% MAUD% Fullprof% 25.52848 27 29.75 12.46 63.556 48 61.29 82 10.91552 23 8.96 5.5

However GSAS has not improved and wt% of ZnO and V2O5 only swap their values. This may indicate the instability of GSAS in QPA by Rietveld refinement but the root reason of the discrepancy in QPA for different Rietveld program should be given more research to choose the program. In this case, MAUD show that although the quality of Rietveld fit is not excellent, sig=13, and Rw=17% compared to GSAS as seen in Figure 26, Rw=7%. However the wt% is very close to expected result compared to GSAS. We see that the wt% for V2O5 is lower than the experimental result in Figure 25. This is also predictive since the first 3 peaks belonging to V2O5 is not fit well in Figure 25 after many cycles. In MAUD, the peak profile parameter is refined automatically. This is where user may modify the profile in order to match the first 3 peaks in Figure 25 without changing the QPA result. Figure 26 shows that although GSAS has given a very nice fit to the experimental pattern but the QPA result from GSAS has caused a significant error in Table 3. Nevertheless a comparative study of GSAS, MAUD and Fullprof for mixture of ZnO, SnO2 and V2O5 shows that the MAUD has better adaptability in QPA when the profile statistics improved significantly.

36

Figure 25: QPA result of 20h scan by Rietveld method (MAUD)

Figure 26: QPA result of 20h scan by Rietveld method (GSAS)

According to [12], the accuracy of Rietveld method in QPA is affected by the preferred orientation or texture of the phase. This reminds us that for powder samples a proper preparation and measurement conditions such as spinning the sample stage to avoid preferred orientation is fundamental and important to a good QPA. Micro absorption also reduces the intensity of scattered X-ray causing erroneous QPA. Therefore the corrections of preferred orientation or texture and micro adsorption should be made whenever is possible.

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