Scintillators for the detection X-rays, gamma rays, and thermal neutrons Dr. P. Dorenbos Section Radiation Detection & Matter Scintillators are materials that convert the energy of ionizing radiation into a flash of light. Scintillation material can be gaseous, liquid, glass-like, organic (plastics), or inorganic. In each case the material should be transparent to its own scintillation light. Inorganic wide band gap ionic crystals are the most widely used scintillators for detection of X-rays, gamma rays, and thermal neutrons. Gamma rays interact with a scintillator by means of 1) photoelectric interaction (dominant below 500 keV and interaction probability is proportional to Zeff3-4 where Zeff is the effective atomic number of the atoms in the compound), 2) Compton scattering (dominant around 1MeV and interaction probability proportional to the density), or 3) pair creation (dominant well above the threshold at 1.02 MeV). For efficient detection of gamma rays of energies 100 keV to 10 MeV, a scintillator should contain high atomic number elements (e.g. Ba, La, I, Lu, Cs, Pb, Bi) and posses a high density. Depending on application crystals of sizes that may range from a few cm3 up to 1 dm3 may be required. For the detection of thermal neutrons, thermal neutrons need to be captured by isotopes with high capture cross section. Most popular is 6Li with 6% natural abundance n + 6Li 7 Li 3 H + α + 4.79 MeV (1) The reaction energy of 4.79 MeV is shared between the triton and alpha particle, and both particle create an ionization track. The history on inorganic scintillator discovery is shown in Figure 1. ZnS played an important role in the discovery of the alpha-particle by the famous experiments of Ernest Rutherford. Around 1900 photon detectors were not yet available and for the detection of the scintillation flashes the eyes of young students were used. Matters changed after the development of the photomultiplier tube around 1945. Very soon NaI activated with Tl+ was discovered. Even today, NaI:Tl is still the most widely applied scintillator. CsI:Tl has higher density than NaI:Tl but it is much slower, 6 LiI:Eu was developed for thermal neutron detection and BGO is popular for its very high density. New scintillation research activities arose after the discovery of a sub-nanosecond fast scintillation decay component in BaF2 in 1982. The fast emission is caused by a then new luminescence phenomenon, i.e., core valence luminescence (CVL). PbWO4 was developed at CERN in Geneva. More than 75 thousand 23 cm long PbWO4 scintillator crystals are required for the electromagnetic calorimeter of the CMS (Compact Muon Selenoid) detector at LHC (Large Hadron Collider). In terms of light output (100 photons/MeV) it is a very poor scintillator. However, considering the very high energies of the gamma rays involved, the high density and the short decay time are much more important parameters. Past 15 years many Ce3+ activated scintillators have been developed. Lu2SiO5:Ce combines a high density with a fast scintillation response and is used in scanners for medical diagnostics. The newest scintillators LaCl3:10%Ce and LaBr3:5%Ce3+ were discovered at Delft University and provide record high energy resolution and ultrafast detection of gamma rays. It is available under the trade mark BriLanCe and generates much interest in the radiation detection world. 1 LaBr3:Ce LaCl3:Ce RbGd2Br7:Ce LuAlO3:Ce Lu2SiO5:Ce PbWO4 CeF3 (Y,Gd)2O3:Ce BaF2( fast) YAlO3:Ce Bi4Ge3O12 BaF2 (slow) CsI:Na CdS:In ZnO:Ga CaF2:Eu silicate glass:Ce LiI:Eu CsI CsF CsI:Tl CdWO4 NaI:Tl ZnS:Ag CaWO4 1900 1920 1940 1960 1980 2000 2020 year Fig, 1. The history of inorganic scintillator discovery (reproduced from M.J. Weber, J. Lumin 100 (2002) p.35) Table 1: Compilation of scintillation properties (density ρ , refractive index n, scintillation decay τ, emission wavelength λ, photon yield Y, energy resolution (FEHM) at 662 keV) of some well known scintillators. scintillator ρ (g/cm3) NaI(Tl) CsI(Tl) BaF2 slow comp. BaF2 fast comp, Bi4Ge3O12 (BGO) PbWO4 3.67 4.51 1.85 1.80 4.89 1.56 7.13 8.28 7.4 5.37 3.86 5.07 Lu2SiO5:Ce (LSO) YAlO3:Ce LaCl3:10%Ce LaBr3:5%Ce n λ (nm) Y (ph/MeV) 230 3340 415 540 42000 65000 2.15 2.20 1.82 1.95 630 0.6 300 10 47 27 310 220 480 470 420 370 9500 1400 8200 100 25000 18000 1.9 1.95 22 17 350 380 42000 70000 τ(ns) R @ 662 keV (%) 6.5 7 8 -7.7 -8 4 3.3 2.8 Scintillation light output and scintillation mechanisms 2 Figure 2 demonstrates the general principle of scintillation. An ionizing particle creates an ionization track in the host crystal, and electrons from the filled valence band are excited to the empty conduction band (arrow 1). The average energy to create one ionization is about 2.5Eg where Eg is the band gap of the scintillator. The value for β is larger than unity because in the electron-electron collisions during track creation momentum conservation does not allow for the creation of electron and holes of zero kinetic energy (=momentum). This means that for a wide band gap oxide crystal with Eg=8 eV, approximately 50,000 free electrons and free holes are created upon total absorption of 1 MeV gamma ray energy. 2 6 5 L × 1 4 6 3 Fig. 2 Principle of scintillation in activated wide band gap materials. After ionization, the hot electrons relax to the bottom of the conduction band (arrow 2) and the hot holes relax to the top of the uppermost valence band (arrow 3). Next the free electrons should recombine with the hole to emit a photon. Figure 2 illustrates the situation for an impurity activated scintillator. The activator ion creates energy levels within the forbidden gap of the host material, and the free electrons and holes recombine radiatively via an excited state of the impurity ion (arrow 4). The total light output is given by Yph = 106 SQ photons/MeV β Eg (2) where Yph is the number of photons emitted by the scintillator per unit of energy absorbed (usually photons/MeV). β is a constant that appears approximately 2.5. For the ideal situation, the transfer efficiency S and the quantum efficiency Q of the activator ion are 100% and then with Eg=8 eV the light yield will be 50000 ph/MeV. In the ideal situation also the transfer speed of free electrons and free holes to the impurity ion is instantaneous, i.e., faster than 1 ns. In that case the rise time of the scintillation pulse is very short and the scintillation decay time τs is determined by the life time τν of the activator excited state only. Figure 3 shows the light output of known scintillators and luminescent phosphors as function of the band gap of the host material. The solid curve is the theoretical maximal output obtained when S=Q=1. For the available oxide scintillators the yield is limited to below 30000 ph/MeV whereas based on Eq. (2) values of 50,000 ph/MeV should be possible. 3 The situation is much better for LaCl3:Ce and LaBr3:Ce. They appear, in terms of light output, ideal scintillators with yields close to the theoretical maximum. Proceeding to increasingly smaller band gap materials we arrive at the most popular scintillator NaI:Tl. With 42000 ph/MeV, NaI:Tl appears only 50% as efficient as the theoretical maximum. Pure NaI at liquid nitrogen temperature is known to yield much higher light output of 80000 ph/MeV. The highest light outputs are reported for the sulfides which have the smallest band gap. ZnS:Ag, used for α particle detection by Rutherford, has a light yield of 90000 ph/MeV, which is about the same as for CaS:Ce used in the first generation of cathode ray tubes for TV screens. 140 Yield (photons/keV) 120 bromides oxides fluoride sulfides chlorides iodides 100 ZnS:Ag 80 NaI:(80K) 60 LaBr3:Ce 40 NaI:Tl CsI:Tl K2LaCl5:Ce LaCl3 Lu2S3:Ce 20 β=2.5 YAlO3:Ce Lu2SiO5:Ce BaF2 0 2 3 4 5 6 7 8 9 CaF2:Eu 10 11 12 13 14 Egap Fig. 3 Scintillator light output of various scintillators as function of the band gap of materials. The solid curve indicates the theoretical limit. Most scintillators and phosphors do not reveal the theoretical maximum light yield. There are many causes for electron-hole losses in scintillators. Figure 2 shows that electrons and holes may recombine without emitting a photon (arrow 5). This may occur in the intrinsically pure lattice but also due to the presence of defects or unintended impurities that are sometimes called ``killer centers'' (arrows 6). Other mechanisms competing with the wanted scintillation process are illustrated in Figure 4. It shows that a hole in the valence band is trapped in the activator ion (arrow 1), but the electron is trapped somewhere else (arrow 2). When the electron trap is shallow (< 0.5 eV), the trapping is not stable at room temperature. Thermal activation of the electron back to the conduction band and subsequent transfer to the hole trapped on the activator ion (arrow 3) may lead to delayed luminescence (arrow 4). Depending on the depth of the electron trap, this afterglow may last several ms or it may persist much longer. Lu2SiO5:Ce3+, for example, shows a strong afterglow lasting for several hours. For materials with even large trapping depth the trapping is permanent at room temperature. Those types of materials can be used for dosimeters. The number of filled traps is proportional to the amount of radiation dose received. By heating the material the electrons can be liberated from their traps. Recombination of the electron with the hole then yields luminescence (thermo-luminescence). The TL intensity is a direct measure for the received dose. A hole in the valence band tends to be shared between two adjacent anions and a molecular like defect is created in the lattice. In alkali-halides the molecular complex is known as a Vk center. By thermal activation the Vk center may jump from one site to an adjacent site. It tends to trap an 4 electron. If this occurs, a self trapped exciton (STE) is created. The STE is a neutral defect and may also migrate relatively easily by thermal activation through the lattice. The self trapped exciton can also decay under the emission of a photon. 3 2 4 1 Fig. 4. The role of trapped holes in the scintillation process a) c) b) LaC 3 l % 0.6 Ce LaC 3 l % 10 Ce LaC 3 4% Ce 400 K 400 K 400 K 200 K 175 K 135 K 250 300 350 400 450 wavelength (nm) 500 550 100 K 250 300 350 400 450 wavelength (nm) 500 100 K 550 250 300 350 400 450 500 550 wavelength (nm) Fig. 5. X -ray excited emission in LaCl3 with 0.6%, 4%, and 10% Ce3+ as function of temperature in K Figure 5 shows X-ray excited emission spectra of LaCl3 with Ce concentration of 0.6%, 4%, and 10% Ce. At 135 K and 0.6%, Ce3+ emission is observed as the double peaked emission at 337 nm and 358 nm. In addition a 0.70 eV broad band emission is observed peaking at 400 nm. This emission is caused by STEs. Upon heating to 400 K, the STE emission disappears and the Ce emission gains intensity. The explanation is as follows. At low temperature the free holes have two options: 1) they self-trap to form a Vk center or 2) they are trapped by Ce3+ to form Ce4+. This all happens on the sub-nanosecond timescale. At 135 K, the Vk center mobility is low and it 5 will trap the electron to from the STE that provides the broad band emission. Electrons trapped by Ce4+ give the characteristic Ce3+ emission doublet. Upon heating the crystal, the STE becomes mobile and transfers its energy to Ce3+. Ce3+ emission with an effective lifetime dictated by the transfer rate from the STE is observed. When the concentration increases the role of STEs becomes less and for 10% Ce3+ almost all emission is as Ce3+ emission. Figure 6 (left panel) shows that the scintillation pulse of LaCl3 contains a fast component and a slow component. Scintillation decay curves of NaI:Tl and Lu2SiO5:Ce3+ (LSO) are also shown for comparison. intensity (arb. units) Intensity (a.u.) 10000 3+ LaCl3:10%Ce 3+ LaCl3:30%Ce NaI:Tl LaBr3:0.5%Ce 1000 NaI:Tl 100 LaBr3:4%Ce 10 Lu SiO :Ce 2 5 1 0 200 400 600 800 1000 time (ns) 0 50 100 150 200 250 300 time (ns) Fig. 6. γ excited decay curves of various scintillators. Energy resolution and non-proportionality Figure 7 shows pulse height spectra of a 137Cs source, emitting 662 keV gamma rays and 32 keV X-rays, measured with a NaI:Tl scintillator and a LaBr3:0.5% Ce3+ on a standard photomultiplier tube. One of the most important properties of a scintillator applied for gamma ray spectroscopy is the resolution with which the energy of gamma rays can be determined. Figure 7 shows that it is much better for LaBr3:Ce than for the traditional NaI:Tl. 1.2 (5) counts (arb. units) 1.0 (1) 0.8 (3) 0.6 (4) 0.4 (2) b) 0.0 EC(662) 477 keV 0.2 a) 0 100 200 300 400 500 600 700 800 energy (keV) Fig. 7. 137Cs pulse height spectra with a) LaBr3:0.5%Ce3+ and b) with NaI:Tl+ 6 The energy resolution R is usually specified as R= ∆E = 2.35σ ( E ) E (3) where ∆E is the full width at half maximum intensity (FWHM) of the total absorption peak at gamma energy E and σ(E) is the standard deviation in the pulse height. The energy resolution achievable with a NaI:Tl photomultiplier combination is about 6.4%. The scintillator LaBr3:0.5% Ce3+ reveals a much better resolution of 3.3%. This together with the much faster decay time of the LaBr3:Ce3+ scintillator, makes LaBr3:Ce3+ and also LaCl3:10% Ce3+ a scintillator that is superior to NaI:Tl+. Formally the energy resolution can be written as 2 2 2 R 2 = Rstat + Rnp2 + Rinh + Rdet (4) where Rstat is the contribution from the statistics in the number Ndph of detected photons. Rnp is a contribution connected with non-proportionality in the scintillation light yield with gamma ray or electron energy. Rinh is a contribution from in-homogeneities or non-uniformities in the scintillator, the light reflector or the quantum efficiency of the photon detector. Rdet is a contribution from noise and variance in the gain of the photon detector. The last two contributions are related to crystal growth and detector technology. The first two are fundamental in nature and intrinsic to the scintillator. Rstat follows Poisson statistics Rstat = 2.34 1+ v ( M ) N dph (5) Where v(M) is the variance in the gain of the photomultiplier tube and is about 0.1. Figure 8 shows the energy resolution of scintillators at 662 keV as function of Ndph . These are the number of generated photoelectrons in the case of PMT readout. The solid curve represents Rstat given by Eq. (1). As required by Eq. (4) energy resolutions are always larger than Rstat. Data on YAlO3:Ce3+, LaCl3:10% Ce3+ and LaBr3:0.5% Ce3+ are very close to Rstat indicating that the other three contributions in Eq. (4) are insignificant. The situation for the well known scintillators NaI:Tl, CsI:Tl, and Lu2SiO5:Ce3+ is much different. The observed resolution appears twice as large as Rstat indicating important other contributions. The poor resolution of NaI:Tl, CsI:Tl, and Lu2SiO5:Ce3+ is caused by a response of the scintillator that is not proportional with the energy of the gamma ray. Figure 9 shows the proportionality curves for several scintillators. The light yield in photons/MeV at gamma ray energy Eγ relative to the light at energy 662 keV is shown as function of Eγ. For a proportional response, the curve should be a constant line at value 1. That of YAlO3:Ce3+ and LaBr3:Ce3+ are indeed close to one between 30 keV and 1 MeV. On the other hand for Lu2SiO5:Ce3+, 7 gamma rays or X-rays of 10 keV are 40% less efficient in producing scintillation light than at 662 keV energy. For NaI:Tl 30 keV gammas are 20% more efficient than at 6 MeV. 1.2 NaI:Tl 9 BaF2 1.1 Lu2SiO5:Ce YAlO3 1.0 7 6 CsI:Tl relative yield Energy resolution at 662 keV 8 NaI:Tl 5 YAlO3:Ce 4 0.9 LaBr3 0.8 LaCl3:Ce 3 0.7 LaBr3:Ce Lu2SiO5 2 CdZnTe 0.6 1 Ge 1000 10000 100000 0.5 Ndq 10 100 1000 energy (keV) Fig. 8. Left panel. The energy resolution (FWHM) of scintillators at 662 keV. The solid curve is the calculated Poisson statistical contribution. Ge and CdZnTe are semiconductor detectors. For Ge the energy resolution of 0.2% at 662 keV is 5 times better than expectations from Poisson statistics. The is because the variance in the number of generated and detected electron hole pairs in the ionization track does not follow Poisson statistics. Fig. 9 Right panel. Proportionality curves of scintillators, i.e., normalized scintillation yield as function of gamma ray energy. The non-proportionality with gamma ray energy is directly related with non-proportionality with electron energy. Suppose Y(Ee) is the light output of a scintillator as function of electron energy Ee. After the absorption of a gamma ray with energy 662 keV, a cascade of events takes place both in the atom that the gamma particle interacted with and in the ionization track formed by the primary electron. For a gamma particle labeled 1, the cascade eventually results into a collection of n secondary electrons (also called δ-rays) with energies E1, E2, .., En that each create a branch n of the ionization track with . ∑E i = 662keV . Another gamma particle labeled 2 creates another i m collection of m secondary electrons E1, E2, .., Em. Again the sum ∑E i = 662keV . Since the i light yield is not proportional with electron energy, the two gamma’s of the same energy do not produce equal amount of photons. The creation of energetic secondary electrons is a statistical process and leads to fluctuating light output and therefore to a contribution Rnp in Eq. (3). Only when a scintillator is proportional the light output does not depend on secondary electron distribution. This is the situation for YAlO3:Ce3+, LaCl3:Ce3+, and LaBr3:Ce3+ at energies above 30 keV. Scintillation decay time and the luminescence centers Decay time of the scintillation pulse is the most important parameter when a scintillator is used for fast timing. It depends on the transfer speed of charge carriers from the ionization track to the luminescence center and by the lifetime of its excited state. In the ideal case of infinitely fast (i.e. 8 faster than 1 ns) energy transfer to the luminescence center, the scintillation decay is determined by the decay rate Γν =1/τν of the excited state. The decay rate is given by Γν = 1 τν ∝ n ( n2 + 2) λ 2 3 f µ i 2 (6) The decay rate decreases with the third power of the wavelength λ of emission and increases with the refractive index n of the host material. The last factor in Eq. (6) is the matrix element that connects the initial state (this is the excited state of the activator ion) with the final state via the electric dipole operator µ. This is non-zero only for electric dipole allowed transitions. The number of activator ions that show electric dipole allowed transitions suitable for scintillation applications is limited. These are the transitions between the 5d and the 4f orbitals in the lanthanides, Ce3+, Pr3+, and Eu2+ and the transitions between the 6s6p and 6s2 configurations in the so-called 6s2-elements Tl+, Pb2+, and Bi3+. These are precisely the activator ions encountered in applied scintillators. Transitions in Tl+, Pb2+, and Bi3+ are from a 6s6p spin triplet 3PJ state to the 6s2 spin singlet 1S0 ground state. Those transitions are spin forbidden, yet partly relaxed by the spin-orbit interaction, leading to relatively long scintillation decay times. The scintillation decay time in NaI:Tl is 230 ns (see Figure 6) and 300 ns for BGO. For fast timing purposes the 6s2-elements are not suitable as activator. Eu2+ is also relatively slow (~1 µs). Figure 10 shows X-ray excited emission spectra of Ce3+, Pr3+, and Nd3+ in various compounds. Ce3+ emits in a characteristic doublet at wavelengths depending on the type of compound. It is usually around 300 nm in fluorides and it tends to shift to longer wavelengths with smaller value for the band gap of the host crystal. For Lu2S3:Ce3+ the emission is in the red at 600 nm. Pr3+ shows a more complex emission with four main bands. When in the same compound as Ce3+ the emission to the ground state is always at 1.5 eV higher energy than Ce3+. That of Nd3+ emits at 2.8 eV higher energy. wavelength [nm] 800 600 0.8 Ce 400 200 3+ Lu2S3 LiYF4 3+ Pr 3+ Y3Al5O12 2 4f -4f LiLuF4 2 0.4 0.8 Pr Nd quantum efficiency [%] yield [arb. units] 0.4 0.8 Ce 80 Nd 3+ LaF3 3 3 4f -4f 30 40 3 50 -1 wavenumber [10 cm ] 60 silicon photodiode TMAE 40 20 0 20 3+ 60 photomultiplier tube 0.4 10 3+ 200 400 600 800 1000 wavelength [nm] Figure 10. Left panel. X-ray excited luminescence in Ce3+, Pr3+, and Nd3+ doped compounds. Figure 11 Right panel. Wavelength range of Ce3+, Pr3+, and Nd3+ 5d-4f emission in compounds compared with typical quantum efficiency curves of a photomultiplier tube, a photodiode, and the photosensitive gas TMAE. 9 In addition to the relatively broad 5d-4f emissions in Pr3+ and Nd3+, these ions also reveal narrow emission bands caused by transitions between 4f levels. These emissions are dipole forbidden and very slow (ms). The life time of the Ce3+ 5d state depends on the type of compound and is found between 15 and 60 ns. Because of the shorter wavelength of emission, see Eq. (6), the lifetime of Pr3+ is roughly two times shorter and that of Nd3+ is four times shorter than that of Ce3+. Figure 11 shows the observed range of values for the 5d-4f emission of Ce3+, Pr3+, and Nd3+ in compounds together with the quantum efficiency curves of a photosensitive gas TMAE, a bialkali photomultiplier and an photodiode (PD). Depending of the type of compound the emission of Ce3+ may match nicely with the maximum quantum efficiency of a PMT or of a (A)PD. Altogether Ce3+ is an unique activator ion. It combines: 1) a fast 5d-4f emission, 2) absence of slow 4f-4f emission, 3) an almost unity Q=1 internal quantum efficiency, 4) the proper wavelength of emission, 5) it is also an excellent hole trap, and finally 6) it can be substituted on La3+, Gd3+, and Lu3+ sites that are constituents of high density host crystals. Anatomy of a pulse height spectrum Figure 12 shows the pulse height spectrum of 24Na measured with LaBr3:Ce, the highest energy resolution scintillation available today, coupled to a photomultiplier tube (PMT). Although the source emits only gamma photons of 2.75 MeV and 1.37 MeV, the spectrum is very rich in features that are, in order of decreasing energy, numbered 1 to 15. Starting on the high energy side we first observe the total absorption peak (1) at 2.75 MeV caused by a) photoelectric absorption, b) Compton scattering followed by photoelectric absorption of the scattered gamma ray, c) pair creation followed by absorption of the two 511 keV annihilation quanta. The maximum energy EC(Eγ) transferred to the electron in Compton scattering is EC = 2 Eγ2 511 + 2 Eγ (7) and it gives the Compton edge at EC(2.75)=2.52 MeV which is denoted by feature (3) in Fig. 13. When a gamma ray undergoes multiple Compton scattering interaction in the scintillator it contributes to the counts in the tail at (2). Part of the 2.75 MeV gamma rays is absorbed by pair creation. The created positron looses its kinetic energy and subsequently annihilates with an electron creating two 511 keV gamma rays that may or may not escape from the crystal. Features (7) and (5) at 1732 keV and 2243 keV are the double and single 511 keV escape peaks. 511 keV annihilation quanta Compton scattered in the scintillator with escape of the scattered gamma ray lead to features (6) and (4) on top of the Compton background from 2.75 MeV gamma rays. Those features extend to 2073 keV, i.e., 170 keV below the single 511 keV escape peak (5), and to 2584 keV, i.e., 170 keV below the total absorption peak (1). The pulse height spectrum is flat between 1450 keV and 1650 keV (8). This is the only part of the spectrum that is composed of one single contribution, i.e., from Compton scattering of 2.75 MeV gamma rays only. Peak (9) is the total absorption peak of 1.37 MeV gamma rays. Pair creation leads to the faint double (14) and single (12) 511 keV escape peaks. 10 6 counts (arb.units) 9 4 15 11 14 12 2 3 7 13 10 1 8 0 0.0 0.5 1.0 1.5 6 2.0 5 4 2.5 2 3.0 Energy (MeV) Fig. 12. The 24Na gamma ray pulse height spectrum measured with LaBr3:Ce. Features 1 to 15 are discussed in the text. The horizontal dashed line indicates the Compton background from 2.75 MeV gamma rays. Dashed vertical lines indicate the location of Compton edges. The Compton edge (11) starts below at EC(1.37)=1.16 MeV with a tail (10) due to multiple Compton scattering. Absorption of 1.37 and 2.75 MeV gamma rays outside the scintillator either by pair creation or Compton scattering and subsequent detection of 511 keV annihilation gamma ray or the Compton scattered gamma ray leads to the 511 keV back scatter peak (13) and the Compton back scatter events (15) at around 250 keV. 11