S.WS. McKEEVER Deparment of Phys, Oahome State University Thermoluminescence of solids CAMBRIDGE UNIVERSITY PRESS Cambridge London New York New Rochelle Melbourne SydneyContents frodston ‘What is theiolaninescnce? Eary observations of hermolumincience pr 1948) Applications 182, Age determination LA Geology 148. Othe aplcaions This book Theoretical background Elementary concepts 214.1. Energy bands and lean evel: rane materials 2. Nomerytaline entra 211.3. Traps and recombination centres 214 Transitions ao involving the decane hands Recombination posses 221, Direct ad inet resombination Radiative and soaradiatve recombination Model for thermoluninesenee 232, Additions tothe simple mode! 233, An alternative model 24, More complex modes “Themalminecene analysis Introduction Trap emptying 321, Equations forthe simple mod: order of kinetics 4322, Equations for other models Methods of analya su Pa 111 taal and whole curse unas 1.32 ek spe methods 3.33, Peak positon methods 334, Cunetiting 3.35, othe 336, Ener stebutions 337, Calculation ofthe raqncy fst, 338 summary Trop iling BL The simple mode! 3.42. Additions tothe simple mods Adina factors governing thermoluminescene Fourber discussions of supeaineaity 441.1, Molistage cation models 4112. More on competion mods 4.13. Tap eration models Sensitization 421. Comping trap models 422, Contre conversion models 423, Trap creation models adiation and thera) Optical ees 43. Opti! stilton Tunneling aid anomalous fading Quenching tests 4451. Thermal quenching 4452, Concentration quenching 453, Impurity quenching Defects and thermoluminscense General intsoduction The alka hades S21, Siactare and dots 522 tration oes 523. Thermoluminsseeace fom KCI, KBr, KI and NaCl iratiatod at 4K 5.24, Samples radiated a SDK. '525, Samples rated at room tempoature on us his i a i m Ms as 10 Contents 524, Theemoluminesene frown LiF Quart and iis S31 Strasture 532. Detets 533. Luminescence 534, Thermolumiaesonce; samples tated below room temperature 535, Samples radiated at room tenperatre ermolminesceace dosimetry (LD) General requitements fr TLD materials 611. Dose response 61.2 Energy response (613, Fading nd stability (614 Annealing prosedures 615, Other factors Specs examples 62: Liki Quoride, LF 622, Lithia borat, Li80. (623, Magnesium borate, MgB,O, (624 Magnesium oethoscats, MSO, 625. Caeium sulphate, C380, £626, Cakium fuorie, CaF 627. Berlin oxide BeO 162.8. Aluminio oxide, ALO, rao efess andl dose estimation Personal dounety (641, Introduction 642, Materia 643, Practical application Enviroumenta monitoring {651 Inrodstion 652, Materials 653, Prac appbeaton Modi aplstions| {66 Inrodution (6, Materials 663, Prac application (664 Specie examples To 190 7 2s au 26 an 2 a 2 aw 261 26a ermotminesceac dating Techniques in pottery dating 721, Inroition 722. Fine gain dating 723, Inlsion dating 724, Predose dating 725, Phototander dating General problems 73, Fading 72 Spurious themoluminesence 1723, Sensieation and supalinerity Dove rate evaluation 7A. Itradution 742. Thermoluminesence dosimetry 743, Alpha-coumting and K-analyis TAA, Otbertchniqus Speci dating applications 751, Sediments 182, Stones and rocks 1153, Shel, bones and tet 754, Authontsity ting Geological applications 122, Thermosminesence 1823, The use ofthe patra glow- room temperate) 922, Low tpertare (= room temperate) Heater design and temperature contol 93, Heater design 932, Temperature cone sat detestion 941. Photomuliplier tube: de: curteat mode 942, Photon counting Special considerations 91. Background susraction 952. Emision spca Comercial syste Append A: Minerals Appendix B: Commercial thrmoluminecence stems References a 36 36 Ls “ rn mIPreface Previous books dealing with thermoluminescence have tend to treat ‘only specialist aspects of is usage eg. dating, dosimetry, geology oF analysis of glow-curves, This is a refletion of the way in which thermoluminescenee research his developed over the last decade: is study has become fragmented cach fragment being talored to sit only the discipline to which i is being applied. AS a resul, the various disciplines have become somewhat insular, the advances in one ena hot nocesarily being transmitted to another (For instance, one might Find the occasional inappropiate application of diferent methods of tnalysis of glow-curves to problems associated with, say, geology oF tchasology ora lick of appreciation ofthe solid-state delet reactions ‘which ean fake placein phosphors when thermoaminescene is applied to measure radiation dose) “These facts do not appear to have imposed a limit on the rate of publication of papers dealing with thermolumineseence: several hun- ‘rad articles on this topie appear each year- Considering this, perhaps the time is now appropriate for a pause in the accelerated use of termolominescence in order to reflet upon its capabilities and to hecome more aware offs limitations, This book is intended asa step towards this gou, and towands the unification of the insular approaches by presenting the topic of thermoluminescence as a single subject. Extensive referencing of published works wasfelt to bean importa requirement and asa est ‘ver 1000 references are listed. By fully realizing the limitations ofthe technique we wil be able to make best use ofits capabilitis, The hook begins (chapter 1) by placing thermoluminescence in the ‘context of luminescence phenomena in general and then traces the historical development of the subject. culminating in ts modern-day usage in a wide variety of applications. Chapter 2s primarily intended far those readers who have no knowledges lo thermoluminescence More experienced readers may wish to miss ov sstons 2.1 and 22 of| this chapter and proceed directly with section 23, "Those readers primarily intrested in the use ofthe technique as an investigative tool in tra-level spectroscopy wil ind ehapter 340 be the ‘mos def of the chapters for their noc. Along with section 23, thisHeep ‘hper provides the reader withthe necessary information to pesform atic of sales on experimental glow-curves, ‘Asa general information chapter covering several aspects of thermo- luminesence production, chapter 4 deals with important phenomen suc as supralincarity, sensitization, fading and apical and quenching flees. This is followed by the ist of the “apliations’ chapters (5) or Which I chose, as illustrative material, to give a detailed account of 'iermoluminescence in alkali halides and SiO,, This chapter is intended to present the reader with a view of how the technigue can be used 10 infer information on a phosphors solid-state propetiss. Alkali halides and SiO, were chosen because these materia, more than any other, have been subjected to such an intense examination over the decades ‘hata wie variety of detailed information could be given, borrowing heavily from a rich literature on many other experimental techniques, ‘Chapters 6 and 7 dal with the most popula ofthe applications of thermoluminescence namely, dosimetry ind dating, The specialist reader may only need to read one or other of these chapters, ut to ‘obtain fll uscfulnes eom the book, ii recommended that both sre read, ‘Chapter 8 examines the application of theemoluminescenee to cology. Although much useful information has emerged in this context, the technique his tended to promise more than ican (0 fat deliver, Finally chapter 9deas with instrumentation, In some senses his isolated chapter in that i not truly necessary to read the others blo turning to iti all that is required iv information on experimental apparatus. Where relerence to earlier materi i desirable, appropriate ‘roseferences af given, is a great pleasure to extend my warm thanks to those who have ‘contributed so mich tothe writing f this book, Primarily my thanks Bo to Profesor RW. Cahn who fist suggested the book and tho fas provided constant encouragement and hell eit throughout is preparation. [am indebted ako to Dr PD. Townsend who puinstak- ingly read every page of the manuscript and whose constructive di cussions, comments and criticisms have greatly improved the book’ ‘content The usful remarks of Des HLM Rendell and LE, Hallibacton fon various sections of the hook are alo ately acknowledged Finally, I must extend a decp sense of gratitude to” my wife, whose patience, support and typing sils played major roks in the book’ production, (You can now hase yout husband back.) SWS. McKeever Obtahom State Unicersty July 1983, 1 Introduction Lt What is thermotuminescence? Volume 84 ofthe Physics Abstracts Subject Indes for 1981 ists ‘over 300 separate entries for papers concerning the topic of hermolumin- ‘scene, Brunch (1979) states that there ate over S00 articles published fer year on phenomena relating to thermoluminescence (generally fermod thermally stimulated relaxations, Newcomers t this fel and experienced research workers like may find such a high rate of publication surprising, This response may be feinforced when they realize that, a8 an experimental technique, thermoluminesence finds favour in sich diverse scientific disciplines as archaeology, geolozy, medicine, solid-state physics, biology and organic chemistry, to name jst some of the mainstream areas of study, The reader may jusiably {enquire what itis about thetmolunsinesence that makes it sucha well: used experimental method, enjoying widespread popularity and display ing cnormous versity, The answer to this enquiry is the essential theme addrewed in this hook, To answer the question fll it will be rnocessry to llustrate how the thermoluminescence characterises ofa ‘material relate directly tothe material's solid-state properties and how these solidstate properties are being utilized in the diverse elds ‘mentioned above, However, before delving into the detail necessary to ‘answer the question in fll an initial approach tothe problem must be ‘made by tating what thermoluminescence is. “Thermoluminescence is the emission of light from an insulator or semiconductor when its heated. This is ot tobe confused withthe ight Spontaneously emitted from a substance when itis beated toi ‘indescence, Thermoluminescence isthe thermally stimulated emission, ‘of light Following the previous absorption of energy from radiation. Inthisstatement can be found the three essential ingredients necessary forthe production ofthermoluminescence Fely, the material must be an insulator or semiconductor - metals do not exhibit huminescent properties. Secondly, the material must have at some time absorbed nergy during exposure to radiation, Thirdly, the luminescence emission is triggered by heating the material, In addition, there is one important ‘property of thermoluminescence which cannot be infeed from this atement as it stands at present, It is @ particular characteristic of thermoluminescence that, once ated to exit the ight emission, the2 Introduction ‘material cannot be made to emit theemoluminescence again by simply ‘cooling the specimen and reheating. In order to re-exhibit the lumines: cence the material ha to be reexposed to raation, whereupon raising the temperature will once again produce light emission, ‘The fundamental principles which govern the production of thermo= luminescence are essenilly the same as those which gover all luminescence proceses, and inthis way thermolsminescence is meely ‘one of a large family of luminescence phenomena. Therefore, before Progressing further in order to examine the process of thermolimines= feenceina more detailed manner, i insructive to pause for moment and fo take a wider perspective by examining where thermolumines- ‘ence Hes inthe context of luminescence phenomena in general 12 —Laminescence When radiation isincident ons material some ofits energy may bbeubsorbed and re-emitted slight of longer wavelength (Stokes La) Thisisthe process of luminescence. The wavelength ofthe emitted Bits characteristic of the luminescent substance and not of the inident radiation, Usually, most studies. of luminescence phenomena are ‘concerned withthe emission of visible light but other wavelengths can be ‘emitted, such asulr-violt or infra-red, tis only theemission of visible Tinh which is dealt with in this book "The various laminescence phenomend are given mums which reflst the type of radiation used 10 excite the emission, Thus we hive Photoluninescence excitation by optical or ultra-violet Hight), radiatum inecence (nuclear radiations, ie ays, fepartils, X-rays, el) and athodoluminescence (electron ear). In addition to excitation by radiation, luminescence ean also be generated by chemical energy {chemituminescence), mechanical energy (tiboluninescence, letrcal ‘energy elctroluminescence) biochemical energy (bioluminescence) and ‘even sound waves (sonoluminescence). Unless otherwise sated, the lunineseence referred to throughout this book will be concerned with excitation by radiation The emission of light takes place a characteristic time x, aftr the absorption ofthe radiation and this parameter allows us tosub clasiy the process of luminescence (Se figure 1.1). Thus we can distinguish between fluorescencein which, < 10" "sand phosphorescence in which 2.210" #s Garlick, 1949; Cure, 1960, The value of +, 10-%s provides a definition for the essentially spontaneous process of fuorescence emission, Thus, i figure 1.2, the AMuorescence emission is depicted astaking pce simultaneously with the bsorption of radiation and stopping immediately the radiation ceases Invrduetion 3 Phosphorescenceon the other hand is characterized by a delay between the eadiation absorption and the time ty, to reach fll intensity, Furthermore, the phosphorescence is seen to continu for some time alter the excitation has heen removed. Cleary ithe delay time risa the forder of I, itis easy to classify the emission as phosphorescence However, for delays of a much shorter time it is more difficult to Aistingush between Muorescence and phosphorescence, Phos Dhorescence itself may be conveniently subivided into two main types (Garlick & Wilkin, 1945; Randall & Wilkins, 1945,h: Cure, 1960) namely, short-perio (c,< 10s) and long-period (> 10"*s) phosphorescence. From a practical viewpoint the only clear way 10 Aistinguish between Nuoeescence and phosphorescence sto stady the ‘ntneenexestion snd embion , sivingishes between foresee and Purses Ponta eT4 tnodvetion effet oftemperatureupon the decay ofthe uminescene. Fluorescence, essentially independent of tmperatire, whereas the decay of phosphor ‘scence exhibits a strong femperatute dependence, Tn general, luminescence emission is explained by the transfer of nergy from radiation tothe electrons of the solid ths exciting the ‘lectrons from a ground state g tan excited state e(eanstion (in Figute 13a}, The emission ofa luminescence photon takes place when an ‘excited cestron returns 10 its round ae (Uransition (i) Thus, for Mhuoressence, the delay between transitions (and iis less than 10" and this process is temperature independent. According to Chen & Kirsh (1981) Jablonski (1935) gave the fist explanation of temperature: dependent phosphorescence. Here (igure 1p) the energy level diagram is moaifd bythe presence of metastable level m in the forbidden’ nergy gap between © and @ An electron excited from g to ¢ can nov bocome trapped atm where willremain units ven enough energy Etoreturn toefrom where itcan undergo a normal ansiion hack 0 Alwhch rabies pag nthe ening rae, te ie ch itera ens ane day of poonpborance eps Invroduetion 5 with the subsequent emission of light. Thus the delay observed in [Phosphorescence corresponds to the time the electron spends i the ‘eetron trap m, From thermodynamic arguments it ea be shown that ‘the mean time spent in the trap at temperature T is given by FexplEikT), a where sis constant and & i the energy diference between m and (called the trap depth): is Boltzmann's constant. Ths the phosphores- ence procs is exponentially dependent upon temperature ‘This simple picture of phosphorescence asd on the energy band theory of solids has boen used with success to account for the luminescence properties of several phosphors (ee. Johnson, 1939). However, the theory was not given a thorough formals until the work ‘of Randall & Witkins(1948a). These authors assumed that once the lestron had been fed fom strap (Le, onceit had made the transition m-ein igure 1.3) the probability oft turing tom is much less than the probability oft returning tothe ground state g. The intensity of [Phosphoresence emission a any iastant It) is proportional t the rate ff recombination (ie, the rate of ¢-z transition). In this cise, ¢-8 transitions are simply governed by m-e transitions and thus 10) is proportional tothe rte of eslease of electrons from the trap. Hence, 19) = ~ Cdnjar= Cais 2 where C isthe constant of proportionality and wis the number of clectrons trapped in m, Integrating (1.2) gives 1) =Iyexp(—1i9) wa) where xis given by equation (1.1) fs time und isthe intensity at Equation (1.3) isthe equation of the decay of phosphorescence at @ constant temperature fllowing the end of iradation, for ¢> 1 in Fee. Bet rnsion invent pdt reece Ubfposphorecence Symbols de no Ty) I6 Itrocton figure 1.2. At constant temperature, the decay is thus a simple ‘exponential or first-order decay. tis offen found in practice, however, that the decay of phosphors «ence is non-exponental. One reason for this might be the overlap of ‘Several first-order processes so that at anyone temperature several ra, ‘ach of dlferent E values, are being sampled A second reason, also dealt, With by Randall & Wilkins (1945), conceras the possibilty that once released from is trap, the electron may either returh tom, oF ecomine At gn this case the recombination rate is proportional not jst tothe numberof electrons but also to the amber of available recombination sites, The assumption that these are equal (both equal 1 7) gives My = Caria = 02 a where i a constant at constant T. Comparison of equation (1) with equation (.2) shows that the phosphorescence intensity is mow proportional ton rather than mand Integration gives 1) tanga 1 ws ‘This kind of decay is termed second-order. The constants telated to ‘themean ifetime randtoa vem which describes he elative possibiliis ofthe retrapping of electrons at m and their recombination at. Ths eonstant (2) wll be discussed in more detail ina later ston, Equation (11) shows that the mean lime + is exponentially dependent upon temperature, For phosphorescence the combined values of E and 7’ are such that + is very small and luminescence is ‘observed easly at the temperature Tat which the iradiation takes plice. However, if the traps deep enough, then values of Band, ate such that E47 and thus is very large. Tn fect, this means thatthe ‘ecto will emai trapped in level m indefinitely, or rather the rate of release of wrapped electrons dn/dt =~ is very small at Ty. For ‘example, for trap depth E = 1SeV and assuming that s= 105", then r="73 x 108 years at T=298 K. From a practical viewpoint this ‘means that laminescence would never be observed frm this trap at T, = 298K. of les. However, luminescence emission can be induced by Taising the temperature. For example, ithe temperature is fase a linear rate = da, there willeome temperature at which I) large enough forthe laminescence to he observed. As Tries, «decreases 1d consequently the intensity inreases asthe electrons become treo from the trap and recombination takes place. Eventually, as the tap bocomes depleted, 1) starts to decrease and the resultant intensity versus temperature cure is im the form of a peak. Because the Introduction 7 luminescence has heca stimulated by heating its thermoluminescence. [A thermoluminesoence peak is show in Figue 1.2 in comparison with the Nuorescence and phosphorescence emissions. In tis figure i i plotted agains time, whichis related to temperature by f =< Fora Suitably deep trap the thermoluminescence ean he triggered an indefinite time after the fradition ceases, This ime may range fom minutes to years A practical imiton the time between irradiation and theemoli= ‘minoscence readout set only by the age thesolar system at 4.6 x 10" years (igure 1.0, “The normal way of displaying thermoluminesoonce data i 1 plot luminescence intensity as function of temperature known ay tow curve. A typical glow-curve fr LiF, one ofthe most studied thermotu minescent phosphors, is shown in figure 4, The temperature at which ‘the peak maximum sppearssrelate othe trapdepth in figure 14, four peaks are shown (2-8) indicating that four diferent species of trap are being activated within this particular temperature ange, each with its ‘vn value of Ean sla general the larger the value ofthe higher the {emperatureat which the peaks will cur, However, this is by no means allays true as will be discussed later) The area under each peak is related to the numberof filled taps, which, in turn is relat to the amount of radiation initially imparted to the specimen, In this simple description of the thermoluminescence process i Fig 14 ashanti dpe wih Mea pee8 Invoduetion possible to observe al the essential elements of the initial statement on thermoluminescence made inthe preceding section, namely, ‘band mode! associated with semiconductors and insulators: the absor- tion of energy from radiation building wp « population of trapped ‘lecirons:and the thermally stimulated release of the electrons followed by recombination and lyminescence emission, Furthermore, it 8 Possible to se how a second irradiation i necessary if thermolumines- ‘cence isto e induced again after the first heating. 1.3 arly observations of thermoluminescence (pre-1948) According to Becker (1973) medieval alchemists were aware that certain minerals glowed faintly when heated inthe dark. However, possibly the fist siemifcally recorded observation of thermolumines- ence was marke in 1663 by Robert Boyle (Boyle, 1663) who noted “glimmering light from a diamond by "aking it to Bed with me, and hholdingita good while pon a warm part ofmy Naked Body’. Boylealso stimulated the lumineseence emission by more conventional means by using the heat rom aot iron, from fiction and fom a candle n 1676, Elshotz observe similar eet fom the mineral Morspar (se See 1975) Early interpeeations ofthe phenomena were that the heat ise vas being directly converted into ight. OMlenbur (1676). relerring to the thermoluminescence of 2 phosphor called “Phosphorus Smaragdinus, wrote that the material roeived its ight eom the Fite isc” Most of the other observations atthe time supported. thie oF similar views Du Fay (1726) thought that the luminescence was due toa Sulphur which actually burned on heating, but later he was 10 provide ‘shat was possibly te fist clear evidence thatthe observed phenomenon (ie, thermoluminessnce) was nothing more than delayed phosphores- conce(Du Fay, 1738) His experiments on natural quart shoted tha the {thermoluminescence cou be reactivated by exposure ofthe stmple 10 light, Heat only simulated the eminsion, but was not its cause. Dicibér® (1936) reports that, in 1821, Calloud, a chemist rom Annecy Jn France, discovered that heating sulphate of quinine produced an intensebe luminescence between 100 and IS0°C. This observation was confirmed shorily afterwards by Pelletier. In 1867. Becquere also ‘eported luminescence from Muara ast was heated (se Rutherford, 1913) Some years later, the rst account of thetmoluminescence from extraterrestrial minerals was written by Alevander Herschel Herschel, srandson of the great astzonomer William Herschel, observed that ‘Some fine dust and grains obtained fom the inner portion of the Middlesborough aerate, when the meteorite was first being chemically Invrodution 9 and microscopically examined, werefound, to my considerable surprise, toglow quite distincly, though not very brighily, with yellowsh-white light, when sprinkled th usual way fr these experimentson. pice of near redcheated iro inthe dark (Herschel, 1889). tis dificult to pinpoint exactly when the word thermoluminescence was irs used in th published hteratue, but itis cetinly used in 1895 bby Wiedemann & Schamdt (1895) in what Becker (1974) desribes as ‘Probably the first careful investigation of experimentally radiation- induced TH. (hermoluminescence) under its modern name.“ A major tilfrence Between the work of Wiedemann & Schmid and that of earlier investigators is that these authors induced the thermolumines: ence themselves by ifvadating the specimens with an eletron beam in the laboratory. This type of thermoluminescence is sometimes referred to as “artificial” whereas the earlier observations were on “natural thermoluminescence ie, that induced by natural radioactivity i the environment, Wiedemana & Schmidt studied a wide viet of synthe tilly produced phosphors. However, the fat that the thermolumines- ‘cencefrom natural specimens could be regenerated in he lboratory wis first published by Trowbridge & Burbank (1898) These authors drained ‘the natural thermoluminescence from Muorte by heating it and then re excited the thermoluminescence by exposing the specimen to X-rays. “The connection between phosphorescence and radiation was the subjgct of extensive examinations in the late nineteenth century (se Rutherford, Chadwick & Elis, 1987) and the study of radiation induced termoluminescence recived boost fom Marie Curie in 1908 when shewrotein her doctoral ess: "Certan bois, such as frie became luminous when heated they are thermo-luminescent Tht lninosty slisappears ater some time, but the capacity of becoming luminous lfesh through heat is restored to them bythe ation spark and also by the setion of radiation. Radian can thus estore to thew bods thei thermo-luminesent property. (Curie, 190) Infact, the ability of ays From radiom to restore thermoluminescence had also bovn observed by Wiedemann see Rutherford, 1913), ‘Acabout thistime the fies thorough study ofthe spectra ofthe emitted thermoluminescence was made by Morse (1905) The mineral fuorspar vas the subject of Morse's observations Lind & Bardwell (1923) continued the study of radition-indvced thermoluminescence by using radium to excite glow rom various gems and transparent minerals. This was followed in 1928by Wick, who made his own observation of natural thermoluminescence in voit (Wick, 1924) He and his colleagues proceeded to make a thorough stuly of X-10 Introdetion ray- and elctron-beam-induced thermoluminescenee in a selection of| hatural minerals (Wick & Gleason, 1924: Wick, 1927) and synthetic ‘hosprs (Wick & Slattery, 1927) In particular, Wick de Slattery (1928) ‘made an extensive investigation of X-ry-induced thermoluminescence in selection of the same synthetic phosphors as were studied by ‘Wiedemann & Schmidt 1895) Included in thee phosphors was CaSO, doped with manganese, Manganese became recognized a an expecially ‘good “Activator” of laminessence, and CaSO,:Mn in particular was an cexcclentthermoluminescent phosphor. This matedal was used by [Lyman (1935) to detect ulia-viole radiation by monitoring. the ‘hermolumineseence induced by exposure ofthe phosphor to light rom spark. The degree of transparency ofthe ar between the spark and the phosphor was deduced from the brightness of the thermoluminescence, Ina sense Lyman’s work was one ofthe earliest uses of hermolumines- cence in dosimetry. TW has already been noted that the temperature at which the thermoluminescence peak maximum occurs is related 10 the electron trap depth. This was recognized by Urbach (1930}asthe key theuse of ‘thormoluminescence to study irap depth distributions. However, it was ‘ot until the now-famous papers by the research group atthe University of Birmingham, England (Randall & Wilkins, 194840; Garlick & Gibson, 1948). that any real progress was madein this regard, Randall & ‘Wikins formalized the theory of thermoluminescence by considering the first-order mechanism of electron detrapping. is they assumed that once released oma rapthe electron will undergo recombination rather than retrapping. Thus, the intensity of luminescence emission is proportional to the rate of release of trapped eletrons (equation 12) Garlick & Gibson (1948) followed ths by considering the second-order cease, Here they assumed comparable rerapping and recombination probabilities and thus dealt with equation (14). By solving equations (12) and (14) Tor the non-isothermal case of a linear increase in temperature at rate P= dT, these authors were able to relate, in a precise manner, the temperature, shape and size ofa thermolumines: ‘ence peak to the trapping parameters E and s, and tothe number of| trapped electrons at the start of heating. Thus, Randall & Wilkins (0945.5 arrived at the following equation forthe shape of fist-onder ‘thermoluminescence glow peak 1 where nis the number of trapped electrons at temperature Ty Introduction u Similarly the equation for @ second-order glow peak as derived by Garlick & Gibson (1948) i rvoant-carys[ vain” ent enrar] 0) hete {Vis the number of available electron raps. From equations (16) and (7), simple expressions were proed from which the trapping parameters E and + could be derived from an «experimental glow-curve. Thus, from this pint on, thermoluminescence ‘grew in popularity as a relatively simple technique for obtaining information on tap distributions 14 Applications 11 Radiation dosimetry The increased use of thermoluminescence which became evie ‘dentin the late 19405 and eaely 1980s was only partly de tothe work of Randall & Wilkins and of Garlick & Gibsoo. Although a quantification of the thermolumineseence mechanism svas necessary in order 10 caleulate the tapping parameters, several ther applications of the Phenomenon were beginning to emerge at this time, The prime ‘motivators of this emergence of thermoluminescnce as practic research fl in several diferent fields of application were Farrington Daniels and his research group at the University of Wisconsin, USA, during the 1980, ‘Theabsorption of radiation increases the level of thermoluminescence observed from a specimen by filling the localized energy’ levels with trapped electrons. The absorption of heat from the environment, onthe other hand, tends to reduce the numbers of trapped electrons by thermally releasing them. Thus, the intensity of thermoluminescence from a specimen isthe result ofa competition between trap filing by radiation and trap emptying by thermal excitation, Ata given tempera ture oferadiation, many material display an intensity of thermolmin= ‘scence whichis proportional (or neatly so) to the amouat of radiation, absorbed ad thisled Daniels and colleagues to propose that thermolu- mminescence may be used as means of radiation dosimety. The first proper application of thermoluminescence to dosimetry was in 1953 when LiF was used 19 measure radiation following anatomic weapon test (quoted in Cameron, Suntharaingam & Kenney, 1968), LiF was found by Daniels hea particularly good material for use in radiation ‘dosimetry because ofits igh sensitivity, and small pellet ofthis material12 Introduction ‘were used a the Hospital of Oak Ridge Institue of Nuclear Studies to ‘measure internal radiation doses received by cancer patients treated with radioactive isotopes (Daniel, Boyd & Saunders 1953) By ving the patients swallow small LF pellets. which were recovered after passage through the digestive system, the accumulated dose received by the patients was obtained by measuring the thermoluminescence fom ‘the pellets and comparing with that produced in similar crystals which had been iradited with « known dose of radiation Following the pioncering work of Daniels and colleagues the application of thermoluminescence 1o radiation dosimetry has seen an ‘immense escalation of effort and avast literaturenow exstson this topic, (More than 50°, ofthe papers published onthermoluminescence each year are concerned with dosimetts) Most research has boen devoted 0 the Aiscovery and development of materials suitable for thermolumines- cence dosemeters. As early as 1957, Daniels had despaired of the unpredictable properties of LiF and had favoured Al,O, as a beter ‘dosemeter material Rieke & Daniels, 1957), LF didnot re-emerge asa first-class dosemeter until the work of Cameron and his colleagues nthe 1960s. It had been known since the work of Wiedemann & Schmidt (0595) thatthe presence of imputities within a erytal enbnees the ‘thermoluminescence response and soit was that the sensitivity of LiF ‘was found to be improved by the incorporation of impurities although at that ime the exact nature of the impurity eesponsible forthe enhanced luminescence in LiF was unknown) Te was also realized that some ofthe unpredictable behav ‘could be olfet by various pre- and postatradation ann ‘edures (eg, Zimmerman, Rhyner & Cameron, 1966) A commercial thermoluminescence dasemeter based on LiF became available shortly fallerwards. In collaboration with Cameron's research group, the Harshaw Chemical Company, Ohio, USA, developed the dosemeter TLD-100 which consists of LiF doped with approximately 170 mole ppm Mg and 10 mole ppm Ti. This material remains the most popular Thermolumineseent dosemeter in use today ‘Much research was (ad sills carted out on the development of ‘other dosemeters and for detailed history of the development of thermoluminescence dosimetry in general the reader is relerted 10 several recent books and review articles on the top (Horowitz, 1981; Becker, 1973; McKinlay, 1981; Obetholer & Scharmann, 1981) Since 1966 there have been seven intemational conferences on luminescence dosimetry, namely, Stanford (AUG, 1963): Gatlinburg (Aber, Becker & Robinson, 1968); Risp (Mejdahl, 1971): Krakow (Niewiadomski, 1974); Sao Paulo (Scharmann, 1977), Toulouse (Portal, 1980) and Inroduetion 13 Owawa (Stoebe, 1984) The published proceedings From thes symposia ‘resent a detailed picture ofthe development of thermoluminescence oximetry into what isemeping asa peterted method of radiation dose ‘measurement asit gradually ovsts the more traditional techniques hat use film badges and ionization chambers. 142 Age determination ‘Once the telationship between thermoluminescence intensity and absorbed radiation dose had heen established it was only a shor, ‘Slop to the use of thermoluminescenee as a means of age determination. ‘This application of thermoluminescence was also fist sugested by Daniels and colleagues (Daniel eta, 1953) who offered the premise that the natural thermoluminescence from rocks is directly related to the radioactivity from uranium, thorium and potassium present within the material. Ths radioactivity results in the accumulation of so-called ‘geological dose. I the rate of irradiation from the radioactive minerals is established, and i the rate of thermal release ofthe thermolumines- ‘cence during the rock's radiation ean be shown to be negligible, then the length of time over which the rock has been irradiated (Le, is ‘geological age) can be determined from: ‘age = absorbed dosedose rate as) Several attempts to determine the geological age of cxtain rock formations were carried out in the 1950s but the proper development of thermoluminescence as a means of age determination didnot begin in ‘earnest uni the discovery of natual thermoluminescence fom samples ‘of ancient pottery (Kennedy & Knopf, 1960; see also. Grogler Houtermans & Staufe, 1960. This observation le tothe immediate development of thermoluminescenee as means of archaeological ‘ating, The basic premises that the ingredients ofthe pottery fi, the lay) lose their accumulated geological dose when the pots fired during fits manufacture, Because of the high temperature experienced during firing the thermoluminescence levels re-set to zero. The newly formed potis now subjected to natural radiation from the radioactive cements, {chiefly uranium, thorium and potassium) naturally present in the ela and surroundings. Thus the pottery now aecumlates an absorbed dose ‘which i proportional to its archaeological agc'~ i.e, the time since firing. This age is aso calculated by equation (18) ‘The method of thermoluminescence dating progressed through the 1960s and 70s via the development of improved methods of extracting the thermoluminesceat grains from pottery in order to facilitate the calelation of the natural dose rate- Thus the uartz-inlusion (Femi 1966) and fine-grain (Zimmerman, 1967) methods were introduced. AM4 Intedution rather diferent method of dating, relying not on the thermolumines= cxnee due to the archaeological dose, D, but upon changes in the thermoluminescence sensitivity ofthe specimen induced by D,. vas intcoduced in 1971 (the so-called ‘pre-dose technique; Zimmerman, J, iia), In addition to these major innovations, thermolumineseence dating fas benefited from many valuable improvements in techn: |que which have helped to overcome & plague of complexities (e. Aieuties im dose’ rate evaluation, the problems of ‘spurious Juminescence- ic, not due to radiation - and of athermal fading). The result is that thermoluminescence dating is now establishing itself among archacolopsts asa respectable method of age determination ‘Several review articles on thermoluminescence dating have been writen, Among them books by Aitken (1978) and Fleming (1976) deserve particular attention. Both of these books are concerned. with methods of dating in archaeology and contain detiled chapters on ‘thermoluminescence whilst Atiken (1984) and Fleming (19794) devote ‘complete books tothe copc. In addition, a book by Fleming (19754) on, Authenticity testing in art contains a detailed treatment of the se of thermoluminescence to detect forgeries of ceramic artefact, Review articles by Seely (1975), Aitken (1978a) and Winde (1980) ate aso particularly helpful Specialist seminars on thermoluminescence are now held regularly (Aitken, 1978b; Mejdahl & Aitken, 1982) with the most recent one having taken place at Helsinggr, Denmark (Mejdahl eral, 19830) 143 Geology ‘The occurrence of natural thermoluminescence fom rocks as Jong been Known and several carly observations have already been ‘mentioned in this chapter for example the study of thermotumines- cence in uorteby Trowbridge & Burbank (1898) Caleitetoo was known to be a good thermoluminescent phosphor. According to Ellsworth U932)the natural glow trom this material was discovered accidentally by partes of prospectors in Ontario searching for radioactive minerals ‘When placed on aot camp stove at night the cakeite was observed to slow brightly. It would bea mistake, however, to think that Muoriteand falkite were somehow unigue among minerals. Daniels etal. (1983) sated that of over 3000 natural minerals studied (mostly granites and limestones approximately 75%, were found to exhibit natal therma- minescenee of such an intensity that it was easly measured. The remaining 25% were also thought to emit thermaluminescence, but of lower intensity and the senivity ofthe measuring apparatus a that Introduction 1s time was not high enough to detect it. Some ofthe recorded natural ‘hermoluminescence was bright enough to be “tiicient for reading 3 newspaper. Daniels and his colleagues were instrumental in proving the re lationship between the natural radioactivity and the natural thermolo- ‘minescence, although this connection had already been suggested earlior (Ellsworth, 1932) twas this relationship which led diretly tothe use of ‘thermoluminescence as a means of areving atthe geological age of the specimen. The principle assumption thatthe thermoluminescenceis ‘measure of the absorbed radiation dose since the specimen was last, ‘heated, which, inthe case ofa roc, sits time of formation. Zeller (1968) provides «use account of the principles involved However, age determination isnot the only way that thermotumines: cence is utilized in geology In some instances thermoluminescence i more sensitive for detecting traces of radioactivity than more con- ‘entional means eg, Geiger counter ora seintillation counter. Thus the technique has found widespread application in radioactive mineral prospecting, Some minerals are found to exhibit paticula glow-curve Shape when extracted from one area, but the same mineral gives an entirely diferent glow-curveif extracted from another. Thus thermolu ‘minescence has also found use in source identieation. Many more specialized example can be quoted ‘One aspect of geology in which thermoluminescences proving to be prtcularly useful is the study of meteorites and lunar material Herschel’s observation of thermoluminescence from the Miles borough meteorite emained unexploited until the potential usefulness ofthe technique in meteorite research was recognized by Houtermans And his colleagues in the late 1950s (GrOgler, Houtermans & Stauffer, 1958), More recently, the balance between radiation fling of traps and the thermal emptying of them has been used to provide information felevant tothe nearness ofthe meteorites othe sun whist in space fe, ‘heir orbit) and tothe time the meteorites have spent on earth (ie thet “terrestrial age). A useful review is piven by McKeever & Sears (1979). A elassifiation scheme for certain rate meteorites (perologi type 3) has Aho been devised on the bass oftheir thermoluminescence propetis, (Sears etal, 1980) Early speculation on the thermoluminescence from lunar material (eg. Sun & Gonzales, 1966; Sidran, 1968) was concerned primarily with, 4 possible explanation for Transient Lunar Phenomena (anomalous brightness rom specific regions ofthe moons surface), However, theirst measurements of the eficiencyofthermoluminescence fom the Apollo IT specimens in 1969-70 ruled out this form of luminescence a an