School of Physical and Geographical Sciences PHY-30007 Physics Project 2007-08

Title Phys2007/17 Spectroscopic investigation of radiation damage in crystals Student WEJ Burgess Supervisor Dr. A Mahendrasingam Date of submission 20
th

March 2008

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Abstract This investigation explores the point defect creation in ionic crystals via means of x-ray irradiation. Specifically the alkali halide class of ionic crystals (Crystals formed by the ionic bonding of elements from the alkali metals and halogen groups) , the effect of irradiation conditions on defect creation, the models of a particular group of point defects; f-centres, and the spectroscopic verification of those models, and the lifetime and decay of this particular group of point defects. Dedication and Acknowledgements
In pursuing this investigation I received large amounts of help and supervision from many faculty members and wish to acknowledge them within this section Dr Craig D. Adam for his guidance in the theory of crystallography and empirical data gathering technique as well as instruction in the use of the equipment involved. Dr A.Mahendrasingam for supervision, overall support, and guidance in practical x-ray generation theory Mel Cheney for help, administration and guidance within the lab and organising crystal irradiations as well as infinite co-operation within the sometimes difficult work schedule.

Phil Callaghan for help and co-operation in access to laboratory equipment. Dave Evans for his work in irradiating crystals and liaising with the rest of the faculty about booking x-ray machine run time.

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Table of Contents Title Page Abstract Dedication and Acknowledgements Chapter 1 Extended Introduction Chapter 2 Theory Experimental Technique Results Chapter 3 Conclusions and Suggestions for Further Work Bibliography Appendices Appendix A; Safety Appendix B; Layout of a *.hrf spectroscopic file Appendix C; Sample work schedule Appendix D; Graphs of Data

Pg 1 2 2

12 16 19

27 28

29 30 33 35

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Chapter 1 Extended Introduction Within the field of crystal defects there is one type of defect in particular that is strongly observed within spectrographic methods; the f-centre. The f-centre is a type of point defect. Point defects are single site deviations from the crystals regularly repeating structure. For example, sodium chloride, an ionic crystal in the alkali halide group is arranged in the following manner;

Figure 1; NaCl Crystal Structure reproduced from Wikipedia (Wiki Commons) no permission required. That is, a close packed face centred cubic structure. The other alkali halide that is explored in this investigation is potassium bromide.

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Figure 1a; KBr Crystal Structure NaCl Crystal Structure reproduced from Wikipedia (Wiki Commons) no permission required. As can be seen KBr has the same structure as NaCl and this structure is common to the alkali halide range. Hence a point defect, in reference to sodium chloride, would be a removal of a sodium or chlorine ion from its lattice site. From this there are a few classifications of point defect; Vacancies, Interstitials, Schottky Defects, and Frenkel Pairs. Vacancies are points in the crystal structure, known as the lattice, where an atom or molecule, atom in the case of sodium chloride, is missing from the lattice. This missing atom/molecule can either be removed from the crystal or can be still be present within the crystal solid at an interstitial site. An interstitial defect is a defect where an atom/molecule, atom in the case of sodium chloride, is between lattice sites, usually by making the atom in question electrically neutral and therefore not ionicially bound, and is found in a space between lattice sites. This changes the crystals entropy and methods which measure entropy can be used to observe the changes in the crystal. Whilst interstitials can occur from vacant atoms or molecules, other foreign substances can be found at interstitials either placed there by contamination, or purposely by doping methods as in semiconductors. A Schottky defect is a process, named after Walter H. Schottky, where pairs of atoms in an ionic solid, in the case of sodium chloride a pair of one chlorine ion and one sodium ion, leave their lattice sites, conserving the crystals charge neutrality, and are found interstitially within the lattice. Once again this changes crystal entropy and measurements of this can lead to observables.

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A Frenkel defect, otherwise known as a Frenkel pair, named after Yaakov Frenkel, is explicitly a pair of interstitial and vacancy defects where the liberated atom or molecule, atom in the case of sodium chloride, occupies an interstitial site. The f-centre, which became the focus of this investigation, is a specific type of point defect, part of its mechanism is the creation of a Frenkel defect. And for the purposes of this investigation the creation of these point defects were by method of ionising radiation. Investigation into f-centres, farbe-centres or colour-centres in English, began in the first half of the twentieth century. It is almost universally accepted that De Boer (J.S 1937) first described a model of an f-centre defect. Its physical import was to explain a visible phenomenon using quantum mechanics. Since then, (Simpson J, 1949) has carried out calculations specific to f-centres within alkali halides. Also a very robust treatment of the fcentre model in alkali halides is found in a paper by Herman and Barnett (Herman, 1982) Hence it was the object of this investigation, in the main, to reproduce some of the findings of these works and thus provide spectrographic evidence of these models. This investigative shift from point defects in general to f-centres in particular was due to advice from supervisors and it being the principle defect created by irradiation which is observable by visible spectroscopy. The specific structure of an f-centre defect is discussed in the main body of the report, under theory, but for the purposes of introduction the link between the defect and irradiation shall be established. An f-centre is a specific type of Frenkel defect, where an interstitial defect and a vacancy defect occurs, and to preserve lattice neutrality an electron fills the vacancy left by the, now, interstitial atom. What specifically occurs, using a solid state model of an ionic solid, is that when an ionic crystal is irradiated the lattice is supplied with enough energy to promote one (or more) of its valance atoms to the conduction band. This leaves an ion within the lattice without its valance electrons and hence free from the lattice and allowing it to move to an interstitial site. This is described in detail by Henderson (Henderson, 1972) in depth in the chapter, The production of defects in solids However the most important findings from the chapter are the displacement probability step and the schematic representation of the band gap in alkali halides.

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Figure 2; Probability of displacement curve/step reproduced from (Henderson, 1972) without permission This shows that the probability of creating the Frenkel defect, which is the first step in the mechanism of creating an f-centre, is dependent on energy delivered to the lattice, which in this investigation is through the medium of ionising radiation such as x-ray or -ray radiation, with a step like behaviour (IE either the lattice receives enough energy to produce a defect, or it does not and any energy below the step is dispersed in phonon modes) softened to a curve due to environmental factors such as temperature which translates as kinetic energy on the lattice/atomic level.

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Figure 3; Schematic of band gap in alkali halides reproduced from (Henderson, 1972) without permission As the schematic shows, the mechanism of creating the f-centre (shown by f-centres occupying the band gap) involves promoting electrons from the valence band to the conduction band. Again this is considered as a step jump, but with the added complication of exciton; self trapped electrons (an electron with conduction band energy trapped within its valence band hole) within the band gap energy which will eventually decay to the conduction band. This is largely unimportant to the investigation. With the bulk of the ionising radiation energy being used to create a Frenkel pair, the second step is an electron from the conduction band filling the space left by the Frenkel atom. It does this to maintain lattice electrical neutrality hence in the case of sodium chloride, it is the Chlorine atom involved in the Frenkel pair and the electron taking its place. Hence the f-centre defect is exactly an electron taking the place of an anion within the ionic crystal lattice with the anion, in the case of defect creation by radiation, taking position in an interstitial site. Henderson shows this diagrammatically.

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Figure 4; Diagram of f-centre type defects reproduced from (Henderson, 1972) without permission A brief explanation of all the f-centre possibilities is the F-centre is the basic electron trapped within an anion site. The FA-centre is similar in that it is still an electron in an anion site but the presence of a differing cation neighbour changes the potential experienced by the electron which changes the defects behaviour, as will be explained within the next chapter on the f-centre theory. An F-centre is two electrons sharing an anion site. And an F2-centre is two f-centres that have degenerated into sharing two neighbouring anion sites. An H-centre is a Crowdion; a collection of interstitials with an X2-centre being a monovaliant example of an H-centre. For the purposes of this investigation only the F-centre is considered as a consequence of irradiation with the consideration of the degenerate Fcentres in the chapter on results. And that is what this investigation explored through spectroscopic observables since the fcentre produces observables which can only be explained by a quantum mechanical model which produces spectral lines. This is the De Boer model predicts; that an f-centre is a quantum mechanical system with energy level transitions at energies equal to EM waves. This produces certain optical behaviour observable visibly and spectroscopically. This is well described in Sodium Chloride by Herman and Barnett (Herman, 1982)

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Whilst Henderson considers the f-centre to be a particle (electron) trapped in an infinite square well (anion site) to illustrate several key points of the behaviour, which will be discussed fully in the next chapter under the subsection of theory, Herman and Barnett produce a more pleasing overview diagrammatically for sodium chloride;

Figure 5; Diagram of an f-centre in sodium chloride from (Herman, 1982) without permission Hence an f-centre has energy levels similar to that of a Bohr hydrogen atom and indeed De Boer used an inverse Bohr hydrogen model (A negative charge surrounded by a positive one as oppose to the hydrogen atom of a positive charge surrounded by a negative one) to predict the energy levels as in Herman and Barnett. As can be seen the transition between 1s and 2p (this is a contentious point within the theory, whether the 2s or 2p energy level is dominant in the f-centre, something which this investigation concerns itself with) is within the violet range of the EM spectrum. Spectroscopically this produces an absorption line (or experimentally a Gaussian curve) at that wavelength and optically turns the sodium chloride crystal the complementary colour of that wavelength which happens to be orange/brown as was attempted to photographically capture within the lab;

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Figure 6; Photo of an irradiated (f-centre populated) sodium chloride crystal The transition 2p to E=0 is what is referred to as the decay transition; effectively it is the destruction of the f-centre. The electron escapes the anion site, which is conventionally thought to occur through heating, although Barnett and Henderson ascribe ultra violet radiation to be the key process, this has been tested within the remit of this investigation. In actuality the total destruction of the defect occurs by the liberation of the electron from the f-centre, and the anion moving itself back to its site from its interstitial site through means of kinetic energy. So heating does play a large part in the decay process. The extent of which was investigated. As a complete aside, although the f-centre itself is electrically neutral it is affected by a voltage and will appear to drain from the crystal when a potential difference is applied across it, as show by Miller 2001

Figure 7: Photographic capture of f-centre drift due to an applied voltage reproduced from (Miller 2001) without permission

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Investigation of this was beyond the remit of the investigation and indeed beyond the equipment available. Whilst an attempt at applying a low voltage across a crystal sample occurred (less than 30V) no visible and no spectroscopic change was observed. It is presented merely as behaviour of the phenomenon being investigated.

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Chapter 2 Main Body of Report Following The Final Project Report Specification and Guide (Grennel, 2007) this chapter will be divided into subsections titled as follows: Theory, Experimental Technique, Results, and Discussion. Theory The bulk of the theory involved in this investigation is providing a realistic model of an fcentre which can predict observables, which in itself is relatively simple, there are many indirect assumptions made. For example there is the Fowler model, which appears in the book Physics of Colour Centres (B, 1968) and the Simpson model (Simpson J, 1949). The difference between the two models is in these indirect assumptions about an f-centre which changes the energy levels of the electron within one. To confuse the issue Herman and Barnett use their own methodology but result in energy levels similar to Fowlers in that the 1s-2p transition is observed and not 1s-2s. From here on I will be referencing Herman and Barnetts methodology since I will use their model to discuss results purely because of an exhaustive treatment of sodium chloride which appears in their paper which also happens to be the main alkali halide of this investigation. Henderson provides a simpler entry point into the topic by presenting the f-centre as a model that should be familiar to all physics undergraduates; the infinite potential square well, and although a poor simile to what is experimentally found, highlights the main theoretical points and the importance of the indirect assumptions used. Using the time independent, 3 dimensional, infinite square well potential, particle in the box model Henderson finds the solutions to the Schrodinger equation and energy levels as; ( )

Equations 1 and 2 Henderson (Henderson, 1972)

The model itself, as Henderson comments, is crude due to its wave function being limited to inside the anion site and assuming that the potential is perfectly symmetrical (which is not the case in the FA-centre due to a differing neighbouring cation), but it also illustrates the main bone of contention between all the models of f-centres; the value of a; the size of the anion site.

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In preparing for this investigation I considered a few possibilities for the constant a. The constant in itself is the width of the square well. It is this that varies across crystals and is the root of the observed differences in the colour centres of sodium chloride and potassium bromide, for example. While my methods (not presented in this report) considered a to be size of the chlorine Van der Wall sphere, the point between two sodium ions when their potentials were cancelled out by each other, and the size of a chlorine atom. As expected these produced totally unsuitable energy levels for the well model. Hermann and Barnett relate their constant (not precisely a since they use a spherical coordinate version of the Schrdinger equation) to the crystal lattice parameter, which is experimentally determined by other means. This provides a much more suitable energy level model as shown in figure 4. To produce the f-centres in the alkali halide ionic crystals, as stated in the project title, irradiation techniques were used. Principally hard x-rays were used although an investigation into using -ray was attempted. Hard x-rays are x-rays produced by firing soft x-rays produced from a cathode gun into a metal target. In this investigation the faculty x-ray machines were used which employ copper targets. These produce x-ray similar to:

Figure 8; Hard x-ray spectra reproduced from (Whiston, 1987)without permission Whilst not part of the investigation, the theory of hard x-ray creation is important in the discussion of observed results so I will provide summary here.

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The above spectrum is explained by considering it in two parts; Continuous or Bremstrulung (halting) radiation and Characteristic radiation. Continuous radiation is produced by the interaction of soft x-rays with the copper target in bulk; the x-rays are halted by the atomic potentials of the metal atoms and are scattered at differing wavelengths and intensity and have a wide range of energies. Characteristic radiation is produced with the soft x-rays exciting electrons within the metal atoms which promotes k-shell electrons which then releases specific wavelengths of x-ray energy k and k. The difference between the two, specifically their intensity and power will provide avenues of discussion of the observed results, specifically what happens to the crystal when the Continuous radiation is masked. So, as described in the extended introduction, f-centres are point defects which are created when a crystal is irradiated by ionising radiation such as x-ray and -ray radiation as discussed above. This leads to several observables, as discussed in the extended introduction and how they are investigated is discussed in the next subsection;

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Experimental Technique Due to the way in which the investigation was approached, an explanation of which is in Appendix A; Safety, there are a set of irradiation conditions which can be considered observables from the point of view of the investigation. These were; Time of irradiation, inclination of crystal in the x-ray beam and x-ray beam power consisting of two separate variables; beam current (set in mA up to 40mA) and beam voltage (set in keV up to 40keV). Due to time constraints time of irradiation was fixed at two hours per sample as well as inclination in the beam which was set at sixty degrees. This left two investigatable variables in the form of x-ray beam power. Namely the effect of beam current and beam voltage on the creation of f-centres in a crystal sample. Both these variables were set prior to irradiation so are the varying parameters. The observable is the number of f-centre defects. Whilst there are a few experimental techniques that allow measurement of how many f-centres a crystal sample contains, for example, by paramagnetic measurements, this investigation is interested in spectroscopic investigation. Hence it is the spectroscopic technique that will be discussed.

Figure 9; Spectrometer The spectrometer used was actually a monochromator IE it uses a Diffraction grating to split the illuminating light into discrete wavelengths (at user discretion down to single nanometre steps if required) which are then passed through the crystal and then hit a detector. It then records the intensity of light as a function of counts (a measurement peculiar to the monochromator itself) along with its wavelength in a *.hrf file which is useable in Microsoft Excel. An example of which is given in Appendix B along with a sample scatter graph of the data.

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Hence the procedure adopted in investigating irradiation conditions effect on f-centre creation, which was later extended to investigations into f-centre decay, was to scan the irradiated crystal in the monochromator, irradiate the crystal, and rescan the crystal (which had now taken on its characteristic f-centre colour as discussed above) and compare the two in Excel. This was first carried out with sodium chloride. A work schedule is included in Appendix C. Other crystals (discussed in results) were irradiated more pragmatically and have no scheduled plan. To aid discussion of experimental technique I shall be referring to this graph, one of the many sodium chloride scans taken;

25 keV 20 mA
Monochromator Counts
60000 50000 40000 30000 20000 10000 0 0 200 400 600 800 1000 1200 1400 Wavelength (nm) Unirradiated Irradiated

Figure 10; Sodium Chloride Monochromator Scan The blue line (labelled Unirradiated) is a monochromator scan through an unirradiated crystal. Since unirradiated sodium chloride (as are all alkali halides) is clear or white, it is essentially a scaled profile of the illuminating source which in this investigation was a tungsten filament source with the characteristic dip at 760nm due to glass absorption. The red line (labelled Irradiated) is a monochromator scan through an irradiated crystal IE a crystal containing colour centres such as pictured in figure 6. As explained in the extended introduction, the colour centre has an energy level transition equal to an optical wavelength. As shown in figure 5 there are three transitions in the optical range for a sodium chloride f-centre, of which two are visible, albeit obliquely, in figure 10; 329.4 nm and 458 nm. I say obliquely since the unfamiliar eye will only notice a slight difference between red and blue lines in the region of 500nm. Hence there should be a gap between the two lines at these points since light is absorbed by the f-centre at these wavelengths. Translation into model fits of data will be discussed in the results subsection all that is required for experimental technique is to show how the obtained data relates to observables.
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Similar methods were used to investigate the effect of time, or rather the decay, on fcentres. An irradiated crystal was left in a dark container (to begin with, as will be seen different crystals required different conditions) and scanned periodically, producing graphs such as figure 10. At this point its important to discuss the physical meaning of counts and how they relate to f-centre decay. Following the corpuscular theory of light, and that 1 photon is required to produce 1 transition in 1 f-centre defect it is tempting to equate the two linearly and say 1 count = 1 photon. Sadly this is not the case either physically or empirically due to data manipulation necessary to produce results. The graphs, as appear in figure 10 and will appear in the results and appendices sections, have been normalised IE one line has been scaled to fit the other. In all cases the irradiated crystal scan has been scaled to the unirradiated crystal IE so their graph lines match as closely as possible by multiplying the data set by a fixed number. The raw data unscaled would not show any defects (the activity shown in figure 10 between 400 and 600 nm) so when drawing conclusions from the data, it is empirically important to note that when defect activity is quoted it is done so as a figure of merit, e.g. an irradiation setting at x keV and y mA produces z defects, an irradiation setting at x1 keV and y1 mA produces z1 defects. If z1>z then one can say that x1 and y1 produce more defects than x and y but the z values are not exact counts of actual f-centres. This put limits on the scope of investigation but still allowed for quite a large amount of experimental activity. Also as a side investigation, differing methods were used to irradiate crystals, using a table top x-ray generator and a -ray source. This was done principally due to the intended x-ray machine being in use or being out of use. Whilst it introduced nothing intrinsically different to the investigation if either method had work then it would have supplied more data collection opportunities than using the main faculty x-ray machines. Sadly the power density of the table top x-ray source and the -ray source was too low to produce defects and will hence not be discussed in preceding sections.

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Results I will be discussing the results by dividing them into sub-sections. For readability ease, I will be putting raw data graphs into Appendix D, but all analysis methods and data conclusions will be presented here. The investigation divides itself into three parts; the effect of radiation conditions on the production of f-centres in sodium chloride, the decay of f-centres in sodium chloride, and the decay of f-centres in potassium bromide. The effect of radiation conditions on the production of f-centres in sodium chloride As discussed in experimental technique, the observables in this subsection were x-ray beam current and voltage which were the variable observables and the defect count. A full reproduction of all these scans appears in Appendix D. The defect count is defined as the difference in bounded areas of the line graphs of irradiated and unirradiated monochromator scans plotted over each other; the shaded region in the graph below;

Figure 11: Defect count as expressed as a shaded region Whilst there are other areas of difference, they can be attributed to experimental error, the expected area of defect, as shown by the Hermann and Barnett model, was between 300 and 600nm. Just to aid analyses this was the only area considered. The shaded area was then binned into a bar chart, to aid data analysis making a spectrographic profile of the form;

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25 keV 20 mA Defect Profile

Difference between bin counts
7000 6000 5000 4000 3000 2000 1000 0 300 315 330 385 400 415 430 445 460 475 490 505 520 535 550 565 580 Wavelength (nm)

Figure 12; Spectrographic profile of data What theoretically was expected was the presence of spectral absorption lines/peaks at the transition wavelengths predicted in Figure 5 IE peaks at 191.6, 329.4, and 458 nm which are the transitions from 1sE=0, 2pE=0, and 1s2p respectively. The 191.6 peak is not present due to it being below the minimum wavelength of the scan as discussed in Appendix B. whilst there are two peaks present in the defect profile; they appear to be at 290 and 480nm. This is clearly not in good agreement with Herman and Barnets results.
Herman and Barnett 1s2p 2pE=0 1sE=0 458nm 392.4nm 191.6nm Result 480nm 290nm Unavailable

Figure 13; Summary of results

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However, there does appear to be a systematic shift between the two sets of results. This would lead to the conclusion that, as discussed in the previous sections, that either the constant a, used in the model derivation is incorrect, which is physically illogical, or, as I believe to be the case, the 2p state is not a 2p state but a 2s state. Herman and Barnetts model does not allow a 2s state. However it does show that the assumption of 3 energy levels within the f-centre is valid. Other models such as the one discussed in (Varaskin, B, & G, 2006) the Bogan-Fitchen model complicate the model by considering the excited state to be a superposition of 2p and 2s states with the energy level being dependent primarily on the 2p state. Calculations for comparisons were made using the data within (Varaskin, B, & G, 2006) and the 1s2p* absorption wavelength was found to be 580nm. So there is sufficient evidence to show that the excited state in an f-centre is a superposition of 2s and 2p states. All of the defect profiles collected via spectroscopy, as shown in Appendix D, follows this model as summarised in Figure 13. The only notable deviation from this occurs in 40keV 30mA where the Gaussian curve around the spectral absorption line of 480nm has degenerated into a second peak at 530nm. This does not fit any investigated model and can be assumed to be experimental error. Moving onto the main point of the investigation in sodium chloride, the effect of irradiation conditions on f-centre creation is explored. As is shown in Appendices C and D, various irradiation settings, as explained in experimental technique have been investigated and their defect profiles were created. Simplifying the data to consider the peak of the 480nm Gaussian curve as the figure of merit related to the number of f-centres this value was plotted against the irradiation conditions, as shown in Appendix D and reproduced here, with Excel calculated trend lines;

Power v. Count
9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 200 400 600

Defect Counts

y = -1.7722x + 7990 R = 0.6357

800

1000

1200

1400

Power (eVW)

Figure 14; Irradiation Power (Voltage * Current) v Peak Defect Count

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Voltage v. Counts
9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 10 20 y = 55.032x + 4864.1 R = 0.1652

Defect Counts

30

40

50

Voltage (keV)

Figure 15; Irradiation beam voltage v Peak count defect

Current v. Counts
9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 10 20

Defect Counts

y = -54.131x + 7978.5 R = 0.652

30

40

50

Current (mA)

Figure 16; Irradiation beam current v Peak count defect

As shown from the trend lines, these results are counterintuitive; that beam power and current vary inversely with the creation of greater defect counts. However, the beam voltage seems to vary correctly with an increase in beam voltage, which increases the amount of high energy x-rays, increases defect counts, although the figure of merit identifying the trend R2, the amount of values explained by the trend, is low at roughly 16%

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As explained in the x-ray theory above. The method of production means that that the change in beam voltage does not directly mean a linear increase in power density delivered to the crystal. The beam voltage is related to the point SWL in figure 8. SWL is the soft wave length point, so increasing the beam voltage shifts the graphs peaks to the right, leading to higher energy x-rays overall, but still in the same ratios. It is unclear, due to an arms length approach to irradiation (as explained in Appendix A) what the peak energies are but it can be assumed, ignoring exciton modes, the characteristic wavelengths contribute the most to the irradiation of the crystal. Exciton modes cannot be ignored however, due to finding that changing x-ray generators, between one which allowed all wavelengths of x-rays through to the crystal to one which only allowed the characteristic wavelengths through led to no f-centres being created in the irradiated crystals. This may be due to the resulting beam power density being lower and fcentres, in the energy ranges concerned, are complicated by an addition exciton step. However this is far from clear. However one would, experimentally, expect a positive linear dependence of defects on power, since using the corpuscular theory of EM waves, which one can safely do for x-rays, the voltage would increase the range of x-ray photon (electron) energies, and the current would increase the number of photons. However, as is seen in figure 16, current acts inversely. And since the power graph (figure 14) is a product of voltage and current, and not the power density hitting the crystal which was unobserved and the R2 trend of the current is stronger than the voltage, it dominates the power graph making it unreliable and misleading. It is not all bad news, since the voltage graph (figure 15) confirms Hendersons probability of defect creation step requiring a minimum energy to create a defect (figure 2) (Henderson, 1972) since there is a minimum voltage for defect creation of about 0.0181 keV. This is not in good agreement with Hendersons figure of 0.2-0.3 eV per defect (Henderson, 1972), but that would correspond to the power density at crystal, which could account for the orders of magnitude difference. The decay of f-centres in sodium chloride As explained in experimental technique, a sodium chloride crystal was irradiated, at the xray generator maximum power (as shown in Appendix C work schedule) and left to decay away. Also as explained it was expected that room temperature and ultraviolet light would allow the f-centres to decay away; the ultraviolet light liberating the electron from the anion site, and the temperature providing the kinetic energy to replace the chlorine atom back in its anion site. The crystal was scanned at regular intervals of 2,4,2,4 days corresponding with lab sessions. The graph appears in Appendix D and is as follows;

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Time/Peak Decay Counts

16000 14000

Peak Decay Counts

12000 10000 8000 6000 4000 2000 0 0 200 400 600 800 1000 Time (hours) y = -3.3102x + 12487 R = 0.2684

Figure 17; Decay of f-centres over time in sodium chloride The graph was generated, as in previous sections from peaks values of 480nm Gaussian peak which can be safely attributed to f-centres. As is shown this is a definite trend of decay over time, although the figure of merit suggests it may not be linear. It shows a very slow decay, not even reaching half value within the six weeks of investigation. This was as expected due to the depth of the anion site potential. The decay of f-centres in potassium bromide The investigation into the f-centres of potassium bromide, as mentioned, was more pragmatically attempted with the investigation into the spectral absorption lines, and the decay of f-centres within a crystal being achieved concurrently for reasons which shall become clear in that the life time of f-centres in potassium bromide is very short, and also the number of defects created at x-ray generator maximum was fewer than in sodium chloride. The strongest potassium bromide defect profile was the one taken at 10 minutes which was the closest possible time to the crystal coming from the generator to the monochromator.

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Decay Profile 10 Minutes

Difference between Bin Counts
450 400 350 300 250 200 150 100 50 0 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 Wavelength (nm)

Figure 18; Decay profile of potassium bromide Many characteristics are apparent. Firstly the profile isnt as clean as with sodium chloride, mainly due to the low ratio of actual defects to noise (standard error of the square root of counts) However there are still the characteristic two Gaussian curves at 500 and 720nm. A paper concerning the spectral absorption lines of f-centres in potassium bromide (Pincherle, 1950) places the excitation line at 620nm. Once again this based on the assumption of the excitation line being either a 1s2p or a 1s2s and not a mixture of the two as later work suggests and thus there is a systematic shift of the peaks when considering it as a 1s2p model. What is apparent however is that the decay absorption peak, 500 nm is very large in comparison to the excitation line. This is due to the fast decay of the f-centres in potassium bromide of roughly an hour compared to the six weeks of sodium chloride.

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Time/Peak Defect
700 600

Peak Defect Count

500 400 300 200 100 0 0 10 20 30 40 50 60 70 Time (minutes) y = -4.4143x + 489 R = 0.3814

Figure 19; decay of f-centres in potassium bromide As is shown in figure 19, the decay trend is much steeper. This is attributable to the weaker anion potential well, which is further confirmation of the established f-centre model.

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Chapter 3 Conclusions and Suggestions for Further Work In conclusion I am reasonably happy with the outcomes of the investigation compared to its stated goals. Spectrographic techniques were used to obtain substantial amounts of data on the phenomena of f-centres in alkali halides and although the data obtained shows deviations from predicted values of theoretical models it does show agreement with the system of the model with deviations explained there in. Specifically verification of there being spectral absorption lines, the step model of defect creation, and the modes of decay. There were hindrances to the investigation, the time available, and general reliability, of xray generation equipment within the faculty. Whilst in a teaching and research environment management of time and facilities is paramount to the success of an investigation, and fault may lie in being too ambitious in the scope of the investigation, further attempts may be improved by a more hands on approach to irradiation and possibly other methods of irradiation, such as -ray irradiation would be more fruitful, not requiring machine time and having a better theoretical grounding within the undergraduate course. This of course is dependent on the faculty having -ray sources with sufficiently high power density to create f-centres, which as mentioned, were not available and possibly due to safety concerns wouldnt be allowed on site. Hence maybe a shift in investigation from empirical research to data verification, as in other 3rd year projects, may be better since it is clear that there is large amounts of work needed to fully investigate the link between quantum mechanical models and observed spectral lines; the dependence on 2s/2p states for example, and other facilities having access to more powerful irradiating techniques which would make data more reliable since for alkali halides other than sodium chloride irradiation at maximum power produced no or few defect counts as in potassium bromide. Suggestions for further work would include accelerating the f-centre decay through heating, which was attempted within the final weeks of the project but was halted due to x-ray machine problems. Also, paramagnetic verification of the number of f-centres contained in a sample would provide useful interpretative tools to the spectrometry obtained, since as mentioned there is no simple solution for relating defect profile counts to actual numbers of f-centres. Also extending the work to other alkali halides, and even silver bromide which has been mentioned in research as exhibiting f-centre behaviour, providing of course that they could reliably be irradiated.

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Bibliography
B, F. W. (1968). Physics of Colour Centres. London: Academic Press. Grennel, P. K. (2007, October 27). Phy-30007 Physics Project. Retrieved March 16, 2008, from Web CT: http://www.vle.keele.ac.uk Henderson, B. (1972). Defects in Crystaline Solids. London: Edward Arnold (Publishers) Ltd. Herman, Z. S. (1982). The Electronic Structure of F-Centres in Alkali Halide Crystals. Revista Brasileira de Fsica , 73-91. Pincherle, L. (1950). Energy Levels of F-centres. Telecomunications Research Establishment, Ministry of supply, Malven, Worcs , 648-657. Simpson J, H. (1949). Charge Distribution and Energy Levels of Trapped Electrons in Ionic Solids. Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, , 269-281. Varaskin, A. N., B, S. A., & G, P. V. (2006). Characteristics of F centers in the ground and excited states in alkali halide crystals. The physics of solid state , 453-459. Whiston, C. (1987). X-Ray Methods. London: John Wiley and Sons Ltd.

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Appendix A; Safety The main safety concern within this investigation was the inherent dangers of using radioactive sources in irradiating the crystals both with x-ray and -ray beams. Health and Safety procedures require certification before handling such sources is allowed. As such it was the case that I personally was not involved in the irradiation process beyond prescribing what was required as shown in Appendix C. Beyond the irradiation safety concerns there are general safety concerns working within the lab environment. Rather than recite verbatim the safety handbook available at http://www.phys.keele.ac.uk/ I will outline the main points; No working in the lab unsupervised, No eating or drinking within the lab, and in general be aware of the safety procedures involved when using pieces of equipment, electrical or otherwise.

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Appendix B; Layout of a *.hrf spectroscopic file HiResReferenceScanFile: B:\NACL0.HRF Date: 02-12-2008 Time: 14:57:57 StartWavelength: 300 EndWavelength: 1300 NumberOfPoints: 100 RemoteStart: N InputRange: OneMicroAmp DataReadings: Average IntegrationTime: 1000 msec DarkSubtracted: N Grating: 2 PMT Voltage: 700 volts 0, 300, 1, 310, 2, 320, 3, 330, 8 5 5 50

4, 340, 333 5, 350, 615 6, 360, 807 7, 370, 951 8, 380, 1163 9, 390, 1671 10, 400, 2259 11, 410, 2852
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This is an example of the raw data obtained from the monochromator. It is in an ASCII format but uses its own file extension, as referenced within this report as *.hrf. Whilst HiResReferenceScanFile: B:\NACL0.HRF is self explanatory; the filename of the raw data file, it is useful to discuss the technical data contained within as it relates to experimental technique although not important enough to be included within the experimental technique section. It is included as a guide to reproducing the data obtained at a later date. The StartWavelength: 300 refers to the starting point of the monochromator scan in nm. This is the lower limit on the equipment scan range. Likewise EndWavelength: 1300 is the end point of the monochromator scan in nm. Again this is the upper limit of the equipment scan range. NumberOfPoints: 100 means that the monochromator samples 100 points within the scan range. In the example this will mean the monochromator will sample at 100nm intervals. In data analysis terms it is better to consider these points as bin mid-point markers since the spectrum is continuous. In theory this can be as low as 1 and in practice as high as 1000 as the monochromator tends to lock up at this point. For most practical physical purposes a figure in the hundreds is optimum due to equipment limits. RemoteStart: N is irrelevant to this investigation and is one of the higher technical points of the micrometer. In theory it is possible to trigger the monochromator scan at the event of some observable. This was not used in this case and hence has a truth operator N, for no. InputRange: OneMicroAmp refers to the current setting on the detector of the monochromator. This is the default setting for the monochromator. DataReadings: Average this refers to the sampling method of the detector; at each data point an average reading of the counts observed by the detector is recorded. The other option, recommend for weak sources, is the Sum; the sum of the counts at the data point. IntegrationTime: 1000 msec is the time taken by the monochromator to sample the counts at each data point. The lowest possible time of integration is 250 milliseconds. The highest was 2000 milliseconds at which point the monochromator locked up. DarkSubtracted: N is an option to take a reading of the background light readings in the lab which contains the monochromator. Useful for weak sources it had little merit within the experimental technique of this investigation. Grating: 2 The monochromator is equipped with two diffraction gratings with 2 being the more sensitive. This is the reason why it was chosen for all uses of the monochromator within this investigation.

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PMT Voltage: 700 volts This is analogous to the tube voltage of a Geiger-Muller detector; it allows the sensitivity of the detector tube within the monochromator to be set so as to allow maximum sensitivity to the source without swamping the data output. 700 volts was the recommended setting. 0, 300, 8 is an example of the delimited data output of the detector. Recognised by Microsoft Excel it is a point number, wavelength (nm) and a count.

40 keV 4 mA
60000 50000 40000 Counts 30000 20000 10000 0 0 200 400 600 800 1000 1200 1400 Wavelength (nm)

Whilst not directly obtainable from the monochromator this Excel line graph plot is exactly as what was output from the monochromator, via a PCI card to the PC controlling it.

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Appendix C; Sample work schedule Standardised Settings for all irradiations 60 inclination 2-hour irradiation All NaCl crystal samples Week 6 Tuesday for 2pm; 40 keV 40 mA crystal 1 40 keV 40 mA crystal 2 Total; 4 hours Thursday for 2pm; Total; 2 hours Week 7 Tuesday for 2pm Total; 2 hours Thursday for 2pm Total; 2 hours Week 8 Tuesday for 2pm Total; 2 hours Thursday for 2pm Total; 2 hours Week 9 Tuesday for 2pm Total; 2 hours Thursday for 2pm Total; 2 hours 35 keV 40 mA crystal 1 40 keV 20 mA crystal 1 30 keV 40 mA crystal 1 35 keV 20 mA crystal 1 25 keV 40 mA crystal 1 30 keV 20 mA crystal 1 25 keV 20 mA crystal 1

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Week 10 Tuesday for 2pm Total; 2 hours 40 keV 40 mA crystal 1

For week 6 (and perhaps onward) could an oven or some form of heating apparatus be made available; Crystal 1 will have to be heated and checked via the spectrometer that it has returned to its starting condition. From week 6 could crystal 2 (after irradiation) be kept at ambient lab temperature and isolated (out of direct light, in its bag) since it will be used on a weekly basis for investigation into colour centre decay.

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Appendix D; Graphs of Data The effect of radiation conditions on the production of f-centres in sodium chloride The graphs in these sections are what was obtained from the monochromator *.hrf files plotted as line graphs in Microsoft Excel The bar graphs are the bin sampled defect data IE the area of difference between the two lines on the line graph between 300 and 600nm.

25 keV 20 mA
Monochromator Counts 60000 50000 40000 30000 20000 10000 0 0 200 400 600 800 1000 1200 1400 Wavelength (nm) Unirradiated Irradiated

25 keV 20 mA Defect Profile

Difference between bin counts 7000 6000 5000 4000 3000 2000 1000 0 300 315 330 385 400 415 430 445 460 475 490 505 520 535 550 565 580 Wavelength (nm)

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25 keV 40 mA
Monochromator Counts 60000 50000 40000 30000 20000 10000 0 0 200 400 600 800 1000 1200 1400 Wavelength (nm) Unirradiated Irradiated

25 keV 40mA Defect Profile

Difference between Bin Counts 7000 6000 5000 4000 3000 2000 1000 0 300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 Wavelength (nm)

30 Kev 20 mA Scan
Monochromator Counts 60000 50000 40000 30000 20000 10000 0 0 200 400 600 800 1000 1200 1400 Wavelength (nm) Unirradiated Crystal Irradiated Crystal

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30 keV 20 mA Defect Profile

Difference between bin counts 8000 7000 6000 5000 4000 3000 2000 1000 0 300 310 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520 530 540 550 560 570 580 Wavelength (nm)

30 keV 40 mA
Monochromator Counts 60000 50000 40000 30000 20000 10000 0 0 200 400 600 800 1000 Wavelength (nm) Unirradiated Irradiated

30 keV 40mA Defect Profile

Difference between bin counts 7000 6000 5000 4000 3000 2000 1000 0 300 310 320 330 415 425 435 445 455 465 475 485 495 505 515 525 535 545 555 565 575 585 595 Wavelength (nm)

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40 keV 4 mA
60000 Monochromator Counts 50000 40000 30000 20000 10000 0 0 200 400 600 800 1000 1200 1400 Wavelength (nm)

40 keV 4mA Defect Profile

Difference Between Bin Counts 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 300 310 320 330 340 400 410 420 430 440 450 460 470 480 490 500 510 520 530 540 550 560 570 580 590 600 Wavelength (nm)

40 keV 30 mA
60000 Monochromator Counts 50000 40000 30000 20000 10000 0 0 200 400 600 800 1000 Wavelength (nm)

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40 keV 30 mA Defect Profile

Difference Between Bin Counts 7000 6000 5000 4000 3000 2000 1000 0 300 315 330 415 430 445 460 475 490 505 520 535 550 565 580 595 Wavelength (nm)

35 keV 20 mA
60000 Monochromator Counts 50000 40000 30000 20000 10000 0 0 200 400 600 800 1000 1200 1400 Wavelength (nm)

35 keV 30 mA Defect Profile

Difference between bin Counts 7000 6000 5000 4000 3000 2000 1000 0 300 315 330 395 410 425 440 455 470 485 500 515 530 545 560 575 590 Wavelength (nm)

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As a summary of the data, and to show the dependence of x-ray beam power, voltage and current on f-centre defects it is assumed that the actual absorption line of the f-centre in the visible spectrum is at 480nm Gaussian peak as corresponds to the binned data in the defect profile counts graph. Hence this peak value is plotted against x-ray beam power (voltage * current) voltage and current.

Power v. Count
9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 200 400 600 800 1000 1200 1400 Power (eVW)

Defect Counts

Voltage v. Counts
9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 10 20 30 40 50 Voltage (keV)

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Defect Counts

Current v. Counts
9000 8000 7000 6000 5000 4000 3000 2000 1000 0 0 10 20 30 40 50 Current (mA)

The decay of f-centres in sodium chloride As mentioned in experimental technique and results, the decay of f-centres in NaCl was investigated by repeatedly scanning an irradiated crystal over a long time frame and as in the previous subsection of investigation, plotting line graphs of the monochromator obtained spectrum against the unirradiated spectrum and changing the observed difference in spectrum between 300 and 600nm as a bar chart of binned data.

Defect Counts

24 Hour Defect Profile

Difference between Bin Counts 16000 14000 12000 10000 8000 6000 4000 2000 0 300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 Wavelength (nm)

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Difference between bin counts -2000 0 0 12000 10000 12000 10000 12000 2000 4000 6000 8000 2000 4000 6000 8000

Difference between bin counts

Difference between bin counts

10000

-2000

2000

4000

6000

8000

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202 Hour Decay Profile

154 Hour Defect Profile

324 Hour Decay Profile

Wavelength (nm)

Wavelength (nm)

Wavelength (nm)

300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 600

300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 600

300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 600

Difference between bin counts -2000 0 0 12000 10000 12000 10000 12000 14000 2000 4000 6000 8000 2000 4000 6000 8000

Difference between bin counts

Difference between bin counts

10000

2000

4000

6000

8000

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564 Hour Decay Profile

444 Hour Decay Profile

612 Hour Decay Profile

Wavelength (nm)

Wavelength (nm)

Wavelength (nm)

300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 600

300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 600

300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 600

732 Hour Decay Profile

Difference between bin counts 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 600 Wavelength (nm)

780 Hour Decay Profile

Difference between bin counts 14000 12000 10000 8000 6000 4000 2000 0 300 315 330 345 360 375 390 405 420 435 450 465 480 495 510 525 540 555 570 585 600 Wavelength (nm)

As in previous sections, the Gaussian peak suggests, backed by theory, that the f-centre data bin was the 480nm so its value was plotted against time.

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Time/Peak Decay Counts

16000 14000 Peak Decay Counts 12000 10000 8000 6000 4000 2000 0 0 200 400 600 800 1000 Time (hours)

The decay of f-centres in potassium bromide These graphs follow the procedure and methods of the decay of f-centres in sodium chloride but over a shorter time scale.

Decay Profile 10 Minutes

Difference between Bin Counts 450 400 350 300 250 200 150 100 50 0 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 Wavelength (nm)

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Difference between bin counts 50 0 0 300 350 100 150 200 250 300 350 400 100 200 300 400 500 600 700

Difference between bin counts

Difference between bin counts

50

100

150

200

250

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Decay Profile 30 Minutes

Decay Profile 20 Minutes

Decay Profile 40 Minutes

Wavelength (nm)

Wavelength (nm)

Wavelength (nm)

300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300

300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300

300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300

Peak Defect Count 50 50 0 0 700 100 150 200 250 300 100 150 200 250 300 350

Difference between bin counts

Difference between bin counts

100

200

300

400

500

600

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Wavelength (nm) Wavelength (nm)

10

20

30

40

Time/Peak Defect

Decay Profile 60 Minutes

Decay Profile 50 Minutes

Time (minutes)

50

60

70

300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300

300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300