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Diffusion starts to become a problem when device is exposed to high temperatures e.g. After ion implantation (annealing at 900.1000degC for 30 s) diffusion can strongly be influenced by co-implantation of electrically ineffective ions. Diffusion is realized by jumps of interstitials or vacancies / divacancies simultaneous change of a ring of atoms needs too high energy.
Diffusion starts to become a problem when device is exposed to high temperatures e.g. After ion implantation (annealing at 900.1000degC for 30 s) diffusion can strongly be influenced by co-implantation of electrically ineffective ions. Diffusion is realized by jumps of interstitials or vacancies / divacancies simultaneous change of a ring of atoms needs too high energy.
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Diffusion starts to become a problem when device is exposed to high temperatures e.g. After ion implantation (annealing at 900.1000degC for 30 s) diffusion can strongly be influenced by co-implantation of electrically ineffective ions. Diffusion is realized by jumps of interstitials or vacancies / divacancies simultaneous change of a ring of atoms needs too high energy.
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structures are getting smaller in all technological developments (e.g. nano-design) especially in semiconductor technology: device structures are even smaller than diffusion length of dopants (45 nm technology of CPUs) diffusion starts to become a problem when device is exposed to high temperatures e.g. after ion implantation (annealing at 900.1000C for 30 s) diffusion can strongly be influenced by co-implantation of electrically ineffective ions (e.g. carbon co- implantation in B:SiC) 2 Atomic change of sites & diffusion diffusion in solids = material transport in lattice as a result of atomic change of sites for a single atom: random path diffusion always important for processes at elevated temperatures, such as: - ordering and disordering processes in alloys (formation of precipitation) - doping of semiconductors - defect annealing after plastic deformation and ion implantation - sintering - layer growth at surIaces, . proved: diffusion is realized by jumps of interstitials or vacancies/divacancies simultaneous change of a ring of atoms needs too high energy. It has never been observed. 3 Most simple mechanism: j ump of a vacancy jump of a vacancy (Leerstelle) = movements of an atom to the vacancy site jump rate v v = reciprocal mean duration of stay of a vacancy at a given lattice site the jump rate follows an Arrhenius law: Z . number oI next neighbors I 0 . jump attempt Irequency E v m ... migration energy k . Boltzmann constant v 0 v exp( / ) m Z E kT v = I typical frequency I 0 ~ 10 12 s -1 thus temperature T 1 where 1 step per second is observed: for metals with T melt =1300 K: already at 300K vacancy mechanism of diffusion works well 1 v / K 380 / eV m T E = 4 Vacancy model of diffusion self-diffusion in metals and alloys, in many ionic crystals, and in ceramic materials often occurs via vacancy mechanism atomic fraction of vacancies in thermal equilibrium typical values of C v in metals are 10 -4 . 10 -3 near the melting point (not in semiconductors) F F v F F exp( ) exp( ) , ... vacancy formation entropy and enthalpy S H C S H kT kT = 5 divacancy mechanism of diffusion at very high temperatures (near melting point) number of divacancies becomes considerably large vacancy mechanism of diffusion is accompanied by divacancy mechanism however vacancy mechanism dominates below 2/3 T m 6 I nterstitial diffusion interstitial (Zwischengitteratom) diffusion is more complicated structure of lattice and size of atoms is obviously important for jump difference: self- and impurity diffusion interstitial diffusion is often activated already at very low temperatures, i.e. migration energy extremely low - in Au and Nb: self-interstitials move below 1K ! self-interstitial annealing after low-temperature electron irradiation of Cu: v i >> m m E E r e s i d u a l
R e s i s t i v i t y dR dT 7 I nterstitial diffusion when interstitials exist in a large concentration: interstitial diffusion especially important when small atoms diffuse: e.g. hydrogen in metals but also self-diffusion (e.g. in Si, since diamond lattice is relatively open) ring vacancy interstitial mechanism not important for self-diffusion in dense metallic lattice (there: vacancy mechanism) self-interstitials in metals have a much larger formation enthalpy compared to vacancies 8 Hydrogen diffusion in metals hydrogen is very small: rapid diffusion technological application: storage of hydrogen in metals for use in fuel cells (e.g. in Ti) permeation of hydrogen through Pd membrane: method for purification isotopic effects are found: D H >D D >D T deviation of D H below RT from Arrhenius low was explained by quantum effects (tunneling) 9 I nterstitial diffusion in metals C, N, and O often dissolve interstitially in metals (e.g. in Nb) comparison with Nb self- diffusion shows orders of magnitude difference interstitial diffusivity near melting point may be as high as in liquids 10 I nterstitial diffusion in metals diffusivity of interstitially dissolved atoms can be very different D differs by 20 orders of magnitude slope is determined by migration enthalpy (Wanderungsenthalpie) 11 Dissociative interstitial-substitutional exchange mechanism: F rank-Turnbull mechanism atom starts from regular lattice site, moves to interstitial position, and diffuses as interstitial relatively fast (B in Si) vacancy is required; diffusion ends at the vacancy site also called: dissociative mechanism example: fast diffusion of Cu in Ge i s B V=B + 12 I nterstitial-substitutional exchange mechanism without vacancies: Kick-out mechanism impurity atom B starts from interstitial site, diffuses there and kicks out an atom at regular lattice site, which by itself starts interstitial diffusion diffusion of B ends at a regular lattice site, but can start there again, after being kicked out again example: rapid diffusion of Au, Pt, and Zn in Si; also several dopants in Si A i A i i A +B =B A A ... self-interstitials + 13 Abnormal fast diffusion in Si abnormal fast diffusivity in Si is due to interstitial-substitutional exchange mechanism (kick-out mechanism) 14 Summary of diffusion mechanisms 1. direct interstitial mechanism (video) 2. vacancy mechanism (video) 3. Frank-Thurnbull mechanism (video) 4. Kick-out mechanism (video) 15 Macroscopic description: Fick`s laws 1. Fick`s law (A. Fick 1855) describes diIIusion ('current I of atoms) along a concentration derivation/gradient dn/dx: 2. Fick`s law (diIIusion equation) describes in addition time dependence is second order, linear partial differential equation solution requires starting and boundary conditions d D ... diffusion coefficient d n I D x = 2 2 n n D t x c c = c c D is measured in m 2 /s (often in cm 2 /s) typical values: gases (normal conditions): 10 -5 . 10 -4 m 2 /s liquids (RT): 10 -9 m 2 /s solids: 10 -9 . 10 -24 m 2 /s example: Au self-diffusion at RT: D =10 -24 m 2 /s this means about 10 -10 m/day: 1 atomic distance 16 description of temperature behavior can often be described by an Arrhenius relation the pre-exponential factor D 0 can be written as: the so-called Arrhenius plot of diffusion shows log (diffusivity) = f (1/T); when Q is temperature independent, a straight line with slope Q k B -1 is found Diffusion is strongly temperature-dependent 0 exp( ) ... activation enthalphy of diffusion B Q D D k T Q = 0 0 ' 0 ' exp( ) ... diffusion entrophy ... geometry factors, jump frequency B S D D k S D A = A 17 Thin-film solution thin layer of diffusing species (amount M per unit area) is located at x=0 of a semi-infinite sample (self-exhausting source) concentration after time t is then described as the quantity is the typical diffusion length Dt Special solutions of the diffusion equation 2 ( , ) exp( ) 4 M x c x t Dt Dt = t The er ror function solution if at t = 0 the concentration of diffusing species is c(x,0) = 0 and if for t > 0 the concentration at x = 0 maintained to be c (0, t) = c s = const., the solution of the diffusion equation is: these conditions describe the in-diffusion of a diffusor into semi-infinite solid with a non- volatile (non-exhausting) source (e.g. diffusor from gas phase) ( , ) where 1 2 s x c x t c erfc erfc z erf z Dt | | = = | \ . 18 Tracer method Only method for self-diffusion, but works in general radioisotopic tracer atoms are deposited at surface of solid by e.g. electro-deposition isothermal diffusion is performed for a given time t often quartz ampoules are used (T<1600C) sample is then divided in small slices either mechanically, chemically or by sputtering techniques mechanically: for diffusion length of > 10 m; D>10 -11 cm 2 /s sputtering oI surIace: Ior small diIIusion length (at low temperatures) 2nm . 10m for the range D = 10 -21 . 10 -12 cm 2 /s Experimental determination of diffusion coefficient 19 example: diffusion of Fe in Fe 3 Si from such figures the diffusion constant can be determined with an accuracy of a few percent stable isotopes can be used as well, when high-resolution SIMS is used this technique is more difficult Experimental determination of diffusion coefficient 20 sophisticated method: growth of layer structure of material of interest including o-layers of diffusing impurity example: B diffusion in Si with and without Si implantation (upper panel) after implantation: strong enhancement of diffusion due to implantation-induced defects lower panel: enhancement of diffusion by implantation defects is suppressed when C is present at high concentration Si self-interstitials are strongly suppressed due to presence of C B diffusion is impeded (diffuses via kick-out mechanism) diffusion profiles were analyzed numerically by MC methods different diffusion mechanism can be separated this way Diffusion studies using MBE o-layers and SI MS Rene Scholz, Ph.D. Thesis, Halle 1999 21 Typical schematic of a dynamical SI MS instrument. High energy ions are supplied by an ion gun (1 or 2) and focused on to the target sample (3), which ionizes and sputters some atoms off the surface. These secondary ions are then collected by ion lenses (5) and filtered according to atomic mass (6), then projected onto an electron multiplier (7, top), Faraday cup (7, bottom), or CCD screen (8). SI MS: Secondary Ion Mass Spectroscopy 22 Table-top SI MS System 23 Diffusion depends on lattice structure and defect density diffusivity is much higher along grain boundaries and dislocations diffusion also depends on crystal lattice structure, i.e. the phase of an alloy (fcc and bcc Fe) 24 The Ki r kendall effect when two metals A and B are in direct contact, A atoms diffuse into B, and vise versa diffusion may be different, so at one side vacancy clusters are formed, the other material swells welding copper brass 25 26 Zn diffusion in GaP Zn diffusion in GaP (also in GaAs) creates a large number of monovacancies in contradiction to all existing diffusion models further research required to fully understand diffusion Positron annihilation result 27 Literature 'DiIIusion in Condensed Matter, J. Krger, P. Heitjans, R. Haberlandt Friedr. Vieweg & Sohn Verlagsgesell. mbH Braunschweig 1998 Analytical solutions of diffusion equation ,The Mathematics of DiIIusion', John Crank, Oxford University Press; 2. Ed. (1979, Reprint 2004. ,DiIIusion - Methoden der Messung und Auswertung', W. Jost, Verlag von Dr. Dietrich Steinkopff, Darmstadt 1957