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N R A School of Ion Beam Analysis and Accelerator Applications Nuclear Reaction Analysis Resonances Gábor Battistig Research Institute for Technical Physics and Materials Science (MTA - MFA) Budapest, Hungary [email protected] 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 1 N R A School of Ion Beam Analysis and Accelerator Applications Inelastic nuclear collision with nuclear excitation Nuclear reaction in general A(a,b)B Isotope specific! Projectile energy must be higher than Coulomb barrier AA Aa Ab AB Z A Z a Zb Z B Ea E A Eb EB Q Q ( M a M A M b M B )c 2 Q 0 Exoterm Q 0 Endoterm 13-24 March, 2006, ICTP, Trieste, Italy 1 Z AZ ae2 Ec Z A Z a AA 3 [ MeV ] R M B Mb Eth Q M B Mb Ma G. Battistig, MTA – MFA Budapest, Hungary 2 N R A School of Ion Beam Analysis and Accelerator Applications Ion-Gamma reaction : Ion-Ion reaction : 19F(p,g)20Ne 19F(p,a)16O Ion-Neutron reaction : Q=12.845 MeV Q=8.115 MeV 19F(p,n)19Ne Q=-4.020 MeV Particle Induced Activation Analysis (PAA) : 19F(p,n)19Ne 19F b Energy levels and cross sections in nuclear reactions 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 3 N R A School of Ion Beam Analysis and Accelerator Applications Natural abundance of stable sotopes 1H - 99.985% 3He - 0.0001% 6Li - 7.56% 9Be - 100% 10B - 19.8% 12C - 98.89% 14N - 99.64% 16O - 99.76% 19F - 100% 23Na - 100% 24Mg - 78.99% 27Al - 100% 28Si - 92.23% 31P – 100% 50Cr – 4.35% 2H - 0.015% 4He - 99.999% 7Li - 92.44% 11B - 80.2% 13C - 1.11% 15N - 0.36% 17O - 0.04% 18O 25Mg 26Mg - 10.0 % - 0.20% - 11.01% 29Si - 4.67% 30Si - 3.10% 52Cr – 83.79% 53Cr – 9.5% 13-24 March, 2006, ICTP, Trieste, Italy 54Cr – 2.36% G. Battistig, MTA – MFA Budapest, Hungary 4 N R A School of Ion Beam Analysis and Accelerator Applications Most used particle induced nuclear reactions of light elements Proton induced reactions Q [MeV] 3He induced Deuteron induced reactions Q [MeV] reactions Q [MeV] 4He 6Li(p,a)3He 2H(d,p)3He 10B(a,p)13C 4.02 7Li(p,a)4He 17.35 9Be(p,a)6Li 2.13 10B(p,a)7Be 1.15 11B(p,a)8Be 8.58 15N(p,ag)12C 4.97 18O(p,ag)15N 3.98 19F(p,ag)16O 8.11 23Na(p,ag)24Mg 11.69 27Al(p,g)28Si 11.59 29Si(p,ag)30P 5.59 52Cr(p,ag)53Mn 7.56 3He(d,a)1H 12C(d,p)13C 13C(d,p)14C 14N(d,p)15N 14N(d,a)12C 16O(d,p)17O 16O(d,a)14N 19F(d,a)17O 13-24 March, 2006, ICTP, Trieste, Italy 4.03 18.35 2.72 5.95 8.61 13.57 1.92 3.11 10.03 2H(3He,p)4He 18.35 6Li(3He,p)8Be 6.79 9Be (3He,p)11B 0.32 9Be(3He,a)8Be 18.91 12C(3He,p)14N 4.78 12C(3He,a)11C 1.86 18O(3He,p)20F 6.87 18O(3He,d)19F 2.50 18O(3He,a)19O 12.51 induced reactions Q [MeV] 4.06 11B(a,p)14C 0.78 14N(a,p)17O -1.19 19F(a,p)22Ne 1.67 31P(a,p)34S 0.63 G. Battistig, MTA – MFA Budapest, Hungary 5 N R A School of Ion Beam Analysis and Accelerator Applications Principle 100 12 C(d,p )13 C 0 150°lab Q=2.77 MeV Sample 4He+, 3He+, 2H+, 1H+, etc Absorber foil s(mb sr-1) 80 40 20 0 Detector 16O(d,p )17O 1 60 0 200 400 600 800 1000 1200 Energie (keV) 14 16O(d,p )17O 0 12 Energy 13-24 March, 2006, ICTP, Trieste, Italy 10 s (mb sr -1) Counts 12C(d,p )13O 0 16O(d,p )17O 1 150°lab Q=1.05 MeV 8 6 4 2 0 0 200 400 600 800 Energie (keV) G. Battistig, MTA – MFA Budapest, Hungary 6 1000 1200 N R A School of Ion Beam Analysis and Accelerator Applications Experimental setup Vacuum chamber Vacuum chamber LN2 trap Surface barrier detector LN2 trap Sample Filter foil Ion beam Sample Ion beam Anular surface barrier detector 13-24 March, 2006, ICTP, Trieste, Italy g detector Filter foil G. Battistig, MTA – MFA Budapest, Hungary 7 N R A School of Ion Beam Analysis and Accelerator Applications Experimental results 600 nm SiO2 layer; 900 keV, Deuteron beam Yield: Nb NA ds ( ) N a d Well known reference sample is needed for quantification !!! 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 8 N R A School of Ion Beam Analysis and Accelerator Applications Experimental results 170 nm AlxN layer, 1.7 MeV d beam Many reactions, many, sometimes overlapping peaks. Total amount of the given isotope can be determined. 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 9 N R A School of Ion Beam Analysis and Accelerator Applications Thin sample : interferences 900 keV 2H+ on TiOxNy film Numerous overlapping peaks from 14N(d,p 0-7) and 14N(d,a ) reactions. 0,1 2500 2000 Counts 1500 Reaction Q-values are known In principle, interferences can be accounted for. In practice we avoid having to. 16 O reference 16 14 film containing O and N 1000 500 0 100 200 300 400 Channels 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 10 N R A School of Ion Beam Analysis and Accelerator Applications Reference samples YU NU NR YR Anodic isotopic Ta2O5 thin films for Certified sources. 16O 16O and 18O and 18O films available from different For thin targets, the cross section ratios of 12C(d,p)13C, D(3He,p)4He, 14N(d,a)12C, 14N(d,p)15N, 15N(d,a )13C and 15N(p,a )12C to that of 16O(d,p )17O have been obtained by 0 0 1 using stoichiometric frozen gas targets of CO2, NO and D2O. This enables the reliable and robust Ta2O5 reference targets to be used as a reference for NRA determinations of D, 12C, 14N and 15N. Davies, J. A., T. E. Jackman, et al. (1983). "Absolute calibration of 14N(d,a) and 14N(d,p) reactions for surface adsorption studies." Nucl. Instr. and Meth. 218: 141-146. Sawicki, J. A., J. A. Davies, et al. (1986). "Absolute cross sections of the 15N(d,a0)13C and 15N(p, a )12C reaction cross sections." Nucl. Instr. and Meth. B15: 530-534. 0 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 11 N R A School of Ion Beam Analysis and Accelerator Applications Depth Profiling : Principle x dx E inc q C(x) • A channel of width dEc at energy Ec in the spectrum corresponds to a slice of width dx at depth x in the sample, with Ec and dEc being inversely related to x and dx through a linear combination of the stopping powers for the incident and outgoing particle • The number of particles accumulated into that histogram bin is proportional to C(x), dx, and s(Ex), where Ex is the energy of the incident beam when it gets to depth x; s (x) E Area A dE Y Ns ( E ) Cxs ( E ) C ( x)s ( E )dx x 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 12 N R A School of Ion Beam Analysis and Accelerator Applications Cross section ds/d (mb. sr-1) Depth profiling Depth profiling nitrogen in titanium via 14N(d,a )12C 1 1.5 1.0 0.5 0.0 600 800 1000 1400 1200 Energy (keV) Spectra Concentration profile d) b) 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 13 N R A School of Ion Beam Analysis and Accelerator Applications Ion implantation of SiC RBS + channeling = lattice disorder 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 14 N R A School of Ion Beam Analysis and Accelerator Applications RBS + NRA = More information W. Jiang et al. / Nucl. Instr. and Meth. in Phys. Res. B 161±163 (2000) 501 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 15 N R A School of Ion Beam Analysis and Accelerator Applications Thin sample : summary dE/dx not needed Shape of s(E,q) much more important than absolute value. Precision standards are used rather than precision cross sections (Standardless NRA?) Approximate relative cross sections are needed to help in experimental design (isotopes …) Reaction Q values are needed - these are easily accessible and well known. 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 16 N R A School of Ion Beam Analysis and Accelerator Applications Resonances cross section [mb/sr] Differential Differenciális Hatáskeresztmetszet [µb/sr] 18O(p,a)15N cross section Cross section in the resonance: Breit-Wigner (Lorenz) function 6 10 5 10 4 10 334 keV 152 keV 3 10 629 keV 216 keV s R (E) K 2 10 10 18 0 10 -1 10 -2 10 -3 10 -4 10 -5 2 ( E ER ) 4 2 1 10 2 O(p,a) N 15 Q = 3.9804 MeV = 135° 100 200 300 400 500 600 Proton Energy Energia [keV] Proton [keV] 13-24 March, 2006, ICTP, Trieste, Italy 700 800 900 G. Battistig, MTA – MFA Budapest, Hungary 17 N R A School of Ion Beam Analysis and Accelerator Applications Most used Narrow Resonances in Depth Profiling Reaction Resonance energy Resonance width 18O(p,a)15N 100 eV 29Si(p,g)30P 15N(p,a)12C 30Si(p,g)31P 18O(p,a)15N 27Al(p,g)28Si 23Na(p,g)24Mg 27Al(p,g) 28Si 52Cr(p,g)53Mn 13C(p,g)13N 152 keV 413.9 keV 429 keV 620.4 keV 629 keV 632.23 keV 676.7 keV 991.86 keV 1005 keV 1748 keV 13-24 March, 2006, ICTP, Trieste, Italy 120 eV 68 eV 2000 eV 6.7 eV <70 eV 70 eV 50 eV 135 eV G. Battistig, MTA – MFA Budapest, Hungary 18 N R A School of Ion Beam Analysis and Accelerator Applications Depth Profiling by Resonance The resonance is scanned through the target depth by scanning the incident beam energy. Resonance samples the given isotope at depth E0 E R x dE dx 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 19 N R A School of Ion Beam Analysis and Accelerator Applications Principle of depth profiling with narrow resonances 18 O(p,a)15N resonance at 152 keV Sample energy loss E in the sample Beam energy ER + E The resonance occurs at depth xin the sample 154 13-24 March, 2006, ICTP, Trieste, Italy The resonance samples the 18 O at depth x =E/dE/dx FWHM ~ 100 eV 153 152 151 average beam energy in sample [keV] G. Battistig, MTA – MFA Budapest, Hungary 150 20 N R A School of Ion Beam Analysis and Accelerator Applications An excitation curve Yield Concentration profile C(x) Corresponding excitation curve N(E) Beam Energy [keV] N ( E ) G ( E ) * ( E ) * T ( E ) * S C ( x) n S C ( x) k n f (u ) *n n 0 13-24 March, 2006, ICTP, Trieste, Italy G(E) (E) T(E) S<C(x)> beam + Doppler energy spread rersonance lineshape beam energy straggling „straggling” of C(x) G. Battistig, MTA – MFA Budapest, Hungary 21 N R A School of Ion Beam Analysis and Accelerator Applications Excitation curve G(E) beam - Gaussian, + Doppler energy spread due to the thermal vibration of the target atoms s D (E ) 2 (E) 2MAE Ma kT rersonance lineshape - Lorantzian s R (E ) K 2 2 (E E R ) 4 13-24 March, 2006, ICTP, Trieste, Italy 2 G. Battistig, MTA – MFA Budapest, Hungary 22 N R A School of Ion Beam Analysis and Accelerator Applications T(E) beam energy straggling E f(u) Energy loss u f(u;x) tends towards a Gaussian for large x s (f (u )) S 2Z A 2 0.2 mg/cm protonok 152 152 keVkeV-os protons in CH2 stragglingje CH2-ben 2 " Tetszoleges egység The charged particles lose their energy in independent collisions with electrons. 0.3 mg/cm 2 0.4 mg/cm 2 0.6 mg/cm 2 0.8 mg/cm 2 1 mg/cm x 0.0 13-24 March, 2006, ICTP, Trieste, Italy 0.5 1.0 1.5 2.0 Energyveszteség loss [keV] Energia [keV] G. Battistig, MTA – MFA Budapest, Hungary 23 N R A School of Ion Beam Analysis and Accelerator Applications „Straggling” * S<C(x)> ‘ straggling ’ of C(x) On average, m energy-loss events per unit length * * f(u) * f(u) f(u) f(u) For thickness x mx events on average f(u)*f(u) g(u;x) 0 g u ; x n *n P ( mx ) f (u ) n n 0 Pn mx e mx 13-24 March, 2006, ICTP, Trieste, Italy u (mx )n n! G. Battistig, MTA – MFA Budapest, Hungary 24 N R A School of Ion Beam Analysis and Accelerator Applications Experimental excitation curves Si18O2 /Si sample, thermally grown, 20 mC /point Beam energy spred + Doppler broadening: 100 eV Resonance width: 100 eV Ta218O5 /Ta sample, anodically oxidised, 20 mC /point 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 25 N R A School of Ion Beam Analysis and Accelerator Applications Tilting the sample – increases the virtual thickness of the layer x ' x 13-24 March, 2006, ICTP, Trieste, Italy 1 cos G. Battistig, MTA – MFA Budapest, Hungary 26 N R A School of Ion Beam Analysis and Accelerator Applications Depth resolution 0.5 10 A + Narrow resonance width Large dE/dx (~ 100 keV) „negligible cross section outside the resonance – Background-free 20 A 30 A 0.3 Yield Beütés 0.4 40 A 0.2 SiO 2 x 0.1 Straggling – beam broadens by depth Multiple Scattering at tilted sample 0.0 152 153 ProtonEnergy Energia[keV] [keV] Proton Depth resolution vs Depth : tilt angle line: straggling circles: MS crosses: overall 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 27 N R A School of Ion Beam Analysis and Accelerator Applications Depth Profiling by Resonance - Summary As for thin samples, plus need for accurate S(E) low energy – large stopping – high depth resolution Stronger requirement for shape accurate s(E,q) for accurate depth profiling Straggling and Multiple scattering gradually decreases resolution 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 28 N R A School of Ion Beam Analysis and Accelerator Applications Typical experimental results 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 29 N R A School of Ion Beam Analysis and Accelerator Applications Isotopic tracing study of the microscopic mechanisms of oxygen transport in the oxide growing during dry oxidation of silicon. 18O depth profile SiO2 Silicon 16 O 2 then 18 88 O2 88 88 8 exchange exchange 18O depth profile Experimental excitation curve growth 800 600 400 200 0 150 155 160 165 Energy [keV] 170 175 180 Interpretation of the spectra in terms of 18O depth profile, demonstrating surface exchange and that the growth takes place at the SiO2/Si interface through interstitial oxygen movement: direct confirmation of the Deal and Grove model for growth x > 10 nm. No isotopic exchange in the matrix (natural abundance, 0.2%) except near the surface. 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 30 N R A School of Ion Beam Analysis and Accelerator Applications depth profile Coups (u.a) Yield 18O 150 160 170 180 190 200 210 Energy [keV] Energie (keV) Sequential oxidations in 100 mb 16O2 (40 h) at 1100°C, yielding 1600 Å Si16O2 then in 18O2 (5 h, 10 h and 24 h: additional 100, 285 and 405 Å). Excitation curve registration with target tilted to 60°. I. Trimaille et al. GPS, Paris 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 31 N R A School of Ion Beam Analysis and Accelerator Applications Isotopic tracing by sequential oxydation of SiC (40 h) then 18O2 (5 h, 10 h and 24 h) 6H-SiC C terminated surface 1,0 0,8 CoupsYield (u.a) Coups(u.a) Yield 6H-SiC Si terminated surface 18 2 [ O](%) 16O 0,6 0,4 0,2 0,0 0 150 152 154 156 158 160 162 164 Energy [keV] Energie(keV ) 150 155 160 165 170 175 180 185 Energy [keV] Energie(ke V) 100 200 Epaisseur (Å) Thickness [Å] 300 Sequential 16O2/18O2 oxidations, same conditions as for Si. SiC is a polar crystal: silica grows on both faces, similarly to the Si case, but the Si and C faces produce slow and fast growth. Isotopic tracing measurements of this type allow one to investigate with great sensitivity the near surface and interface properties of the silica produced by oxidation of SiC. 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 32 N R A School of Ion Beam Analysis and Accelerator Applications Hydrogen profiling with a nuclear resonance 1H(15N,ag)12C Hydrogen implantation profile in silicon (1016 cm-2, 40 keV) from W.A. Lanford, NIMB66(1992),68 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 33 N R A School of Ion Beam Analysis and Accelerator Applications Study of thin hafnium oxides deposited by atomic layer deposition J.-J. Ganem, NIM B 219–220 (2004) 856 Excitation curves measured using the 151 keV 18O(p;ac)15N resonance on 3.5 nm (a) and 7.5 nm (b) HfO2 samples oxidized in 18O2 atmosphere at 425 C just after: deposition (black circles), post-deposition N2 anneal at 425 C (open circles) and post-deposition N2 anneal at 800 C (open squares). After deposition the films present chlorine contamination and a lack of oxygen. They are unstable toward thermal oxidation since a high oxygen transport and exchange mechanisms occur during the process. Oxygen diffusion can be significantly reduced after a thermal anneal in N2 atmosphere. 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 34 N R A School of Ion Beam Analysis and Accelerator Applications Ultrathin silicon oxynitride film formation Experimental excitation curves of the 18O(p,a)15N reaction for samples with (a) deferent 15N areal densities, sequentially oxidized in 16O2 (60 min) and in 18O2 (90 min). The arrows indicate the energy position of the surface (dashed) and of the SiO2/Si interface (solid) in each sample; (b) no N prior to oxidation, oxidized under the same conditions as samples in (a). N amounts as low as 1/30 of a monolayer at the surface of Si wafers hamper the oxidation of Si, and the higher the N concentration, the thinner the oxynitride films; (ii) (ii) during the film growth, N and O are responsible for the atomic transport, while Si remains immobile; (iii) N, which is initially present at the surface of the Si wafer, migrates during oxidation, remaining at the near-surface and at the near-interface regions of the film. (i) 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 35 N R A School of Ion Beam Analysis and Accelerator Applications Silicon isotopic tracing with the 415 keV 29Si(p,c) narrow resonance near 29Si(p, c)30P excitation curves from an enriched silicon single crystal before and after thermal oxidation, showing loss of silicon during the oxidation process. I.C. Vickridge et al, NIM B 161±163 (2000) 441 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 36 N R A School of Ion Beam Analysis and Accelerator Applications Annealing of ZrAlxOy Ultrathin Films on Si in a Vacuum or in O2 E. B. O. da Rosa et al., Journal of The Electrochemical Society, 148 G695-G703 (2001) ZrAlxOy films were deposited at a rate of 0.3 nm/min by reactive sputtering using a Zr80-Al20 atomic composition target in an oxygen-containing plasma directly on Si(001) substrates. Postdeposition annealings were performed ex situ at 600°C for 10 min, either in high vacuum (p10-5 Pa) or in 710-3 Pa of dry 98.5% 18O2. Areal densities of Al and Si were estimated from the areas of the excitation curves of the 27Al(p,g)28Si and 29Si(p,g)30P nuclear reactions around the resonance energies at 404.9 and 414 keV. The as-deposited film has an approximate composition Zr4AlO9. Normalized excitation curves of the 18O(p,a)15N nuclear reaction around the resonance at 151 keV before and after thermal annealings and the used experimental geometry.(b) Normalized 18O concentration vs. normalized depth for the as deposited and 18O2-annealed samples. Solid lines represent the as-deposited sample, empty circles and triangles correspond to vacuum and 18Oannealed samples, respectively. 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 37 N R A School of Ion Beam Analysis and Accelerator Applications (a) Excitation curves of the 27Al(p,g)28Si nuclear reaction around the resonance at 404.9 keV before and after thermal annealings and the used experimental geometry. (b) Normalized 27Al concentration vs. normalized depth for the as-deposited and vacuumannealed samples. 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 38 N R A School of Ion Beam Analysis and Accelerator Applications (a) Excitation curves of the 29Si(p,g)30P nuclear reaction around the resonance at 414 keV before and after thermal annealings. (b) Normalized 29Si concentration vs. normalized depth for the as-deposited, 18O2- and vacuumannealed samples. 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 39 N R A School of Ion Beam Analysis and Accelerator Applications Summary • Isotope specific – unique tool for studying transport processes • Absolute concentration by well-known reference samples (no need of exact knowledge of cross section) • Narrow resonances: almost atomic depth resolution at the surface 13-24 March, 2006, ICTP, Trieste, Italy G. Battistig, MTA – MFA Budapest, Hungary 40