CHINESE JOURNAL OF PHYSICS

VOL. 15, NO. 2

SUMMER, 1977

(Proceedings of the US-ROC Solid State Physics Seminar)

Lattice Vacancies and Interstitials in Silicon*

G. D. W
ATKINS

Department of Physics Sherman Fairchild Laboratory Lehigh University Bethlehem, Pa. 18015, USA

(Received March 1977)

A review is given of what is known about the simple intrinsic lattice point defects in silicon. This information has come primarily from high energy electron irradiation studies at cryogenic temperatures (4.2 K, 20.4 K) and observation in situ by electron paramagnetic resonance (EPR). Isolated vacancies have been observed as well as divacancies and higher aggregates of vacanies. Also a large number of vacancy-impurity pairs have been identified. Isolated interstitial silicon atoms have eluded detection but a variety of interstitial-impurity pairs, and possibly di-interstitials, have been studied. Current interests center around the effect of electron-hole recombination at the defects on their mobility, stability, and reaction kinetics. Evidence will be cited that t he energy released upon recombination at a vacancy can cause it to diffuse athermally through the lattice. The failure to detect isolated interstitial silicon has also been attributed to its lack of stability in the presence of ionizing radiation.

I. INTRODUCTION great deal of interest surronds the properties of the intrinsic lattice defects in a semiconductor A such as silicon. In the first place, as in any crystalline solid, these defects are believed to play
an important role in high temperature processes such as impurity and self-diffusion, crystal growth, dislocation climb, etc. In addition, they may play a direct role in the semiconducting properties of

the material. The deterioration of silicon solar cells in space due to radiation damage in the Van Allen belt, or the intentional radiation of devices to control minority carrier lifetimes are examples. In addition to these practical considerations, the study of these defects is of fundamental
scientific importance because it impinges directly upon an area of our weakest theoretical understanding at present. The proper theoretical treatment of a highly localized state in a semiconductor, the d eep level problem remains one of the outstanding unsolved problems in solid state physics. Currently a number of theoretical groups are tackling this difficult problemcr-10. The simple lattice * Research supported in part by the Office of Naval Research (contract N00014-76-C-1097). This is the text of a review talk to be given at the joint U.S.-Republic of China Solid State Physics conference to be held in Taipei, Taiwan, April 7-13, 1977. (1) J. Callaway and A. J. Hughes, Phys. Rev. 156, 860 (1967); Phys. Rev. 164, 1043 (1967). (2) K. H. Bennemann, Phys. Rev. 137, A 1497 (1965); Conference on Calculations of the Properties of Vacancies and Interstitials, Skyland, Va., 1966, NBS Misc. Publ. No. 287 (U. S. GPO, Washington, D. C., 1967) p. 127. ( 3 ) R.P. Messmer and G. D. Watkins, Phys. Rev. Letters 25, 656 (1970); Phys. Rev. 7, 2568 (1973); in Radiation Damage and Defects in Semiconductors (The Inst. of Physics, London 1973) p. 255. ( 4 ) G. D. Watkins and R. P. Messmer, Phys. Rev. Letters 32, 1244 (1974); in Computational Methods for Large Molecules and Localized States in Solids, edited by F. Herman, A. D. McLean, and R. K. Nesbet (Plenum Press, N. Y. 1973) p. 133. ( 5 ) S. T. Pantelides and C. T. Sah, Phys. Rev. BlO, 621, 638 (1974). ( 6 ) M. Jaros, J. Phys. C: Solid State Phys., 8, 2455 (1975). ( 7 ) W. Menzel, K. Mednick, C.C. Lin, and C. Franklin, J. Chem. Phys. 63, 4708 (1975). S. G. M. Schltiter, J. R. Chelikowsky, M. L. Cohen, Phys. Rev. B13, 1654 (1976). I:; L. A. Hemstreet, Bull. Am. Phys. Sot. II, 21, 437 (1976). (10) G. T. Surratt and W. A. Goddard, Bull. Am. Phys. Sot. II 21, 407 (1976). 92

G. D. WATKINS

93

interstitials and vacancies are the fundamental la~ice excitations of the perfect solid (in analogy to electrons and holes as electronic excitations). As such, they contain the most fundamental and direct information relevant to this problem. Probing the electronic and. vibronic structure of these simple defects can provide the experimental input vital to guide and confront theory. Finally, these simple defects can be considered the elementary building blocks for larger defect arrays such as voids, dislocations, grain boundaries, and even the external surfaces of a crystal. As such they may provide valuable insights into the understanding of the electronic properties of these larger defects, which are always present. Similarly, they may Supply clues to understanding the electronic propeties of amorphous semiconductors, which in many respects can be considered crystals with a saturated defect concentration. In this paper, we wiI1 review what has been Iearned about lattice vacancies and interstitiaIs in silicon. In general, the presence of these defects could be detected in a variety of ways as they affect the various properties of the material. However, the principal experiiental approach that has made possible the identification of these defects and the unraveling of their properties has been ele:tron paramagnetic resonance (EPR). In this paper, I will concentrate therefore primarily on the information obtained from these studies. In these studies, the intrinsic defects were introduced into the lattice by high energy (-1 MeV) electron irradiation at cryogenic temperatures (-4.2 K, -20.4 K). In this way, silicon atoms are simply knocked out of their lattice positions by a direct Coulomb Rutherford scattering of the atomic nuclei by the electrons, forming simple interstitial silicon atoms and lattice vacancies. The cryogenic temperatures serve to freeze in the primary defects for study. II. LATTICE VACANCIES A. EPR Observation Isolated stable single lattice vacancies have been detected by EPR directly after 1.5 MeV irradiation at 4.2K or 20.4KC11-16. They have been observed in two different charge states, V+ and V-, and the corresponding spectra seen in a ptype silicon crystal (aluminum doped -lOlo cm-*) are shown in Fig. 1. In Fig. la, the spectrum for V+ is optimized when the sample is illuminated by light hvzO.35 eV. Such light, in p-type material, produces free holes which are trapped by the neutral vacancy to form V+, indicating an electrical level close to the valence band edge, as illustrated in the inset of the figure. On the other hand, band gap light (hv21.2 eV> can produce free electrons which when trapped by the nevtral vacancy can give V-. This is illustrated in the inset of Fig. lb, along with the EPR spectrum for V-, whose intensity is optimized by band gap light. In the insets of Fig. I, an additional double minus charge state is also indicated. This is deduced from studies in n-type iaterial where light is also found to be required to generate the EPR V- spectrum. From these studies, we conclude therefore that the vacancy can assume four charge states in the forbidden gap. In semiconductor language, there are three levels in the gap: a single (-/O) and a double (=/-) acceptor Ieve and a single donor (O/+) level. Microscopic models deduced for the defects are also shown in the figure. For V+ the electronic wavefunction is spread equally over the four silicon neighbors to the vacancy and a tetragonal distortion, illustrated as a pairing by twos in the figure, has occurred. For V-, the vacancy takes on the interesting configuration in which the unpaired electron is shared primarily between two of the four neighbors. This is evidence that an additional dihedral distortion has taken place. These (I I) G. D. Watkins, in Defects and Their Structure in Non-Metallic Sokds, edited by B. Henderson and A. E. Hughes, (Plenum Press, London 1976) p. 203. (12) G. D. Watkins, J. Phys. Sot. Japan 18, Suppl. II, 22 (1963). (13) G. D. Watkins, in Radiation Damage in Semiconductors (Dunod, Paris, 1965) p. 97.. (14) G.D. Watkins, in Radiation Damage and Defects in Semiconductors, (Inst. of Physics, London 19;3) p. 228. (15) G. D. Watkins, in Lattice Defects in Semiconductors, 1974 (Inst. of Physics, London, 1975) p. 1. (16) G. D. Watkins, IEEE Trans. Nuclear Science NS-16, 13 (1969).

94

LATTICE VACANCIES AND INTERSTITIALS IN SILICON

(a) V

hv (O35ev

&

$75

7&J

71125

7iXl

_7;T5

72bo

72;s

72&-j

MAGNETIC FIELD.(GAuss) Fig. 1. Vacancy spectz$ Hll<IoO>, PO= 20 GHz. (a) V+ at 4.2 K; (b) V- at 20.4.

models follow directly from analysis of the anisotropy of the EPR g-values andthe *Y3i(I= l/2) hyperfine interactions with the near neighbor atoms. The hyperfine interactions give rise to the satellites (a, b, etc.) shown in the figure and reveal the distribution of the wavefunction. In this analysis, approximately 65% of the wavefunction appears to be distributed between the four neighbors to the vacancy. The remainder of the wavefunction is more diffuse.
B. Electronic Structure

The EPR results have suggested a very simple linear combination of atomic orbital-molecular orbital (LCAO-MO) modelclar15 for the various charge states of the vacancy. This is illustrated in Fig. 2. Here the atomic orbitals are the broken bonds (a, b, c, d) of the four atoms surrounding the vacancy. In the symmetry Td of the undistorted vacancy a singlet (a,) and triplet (tz) set of molecular orbitals are formed. For V+ (Fig. 2a), two electrons go into the a, orbital, paired off, and the third goes into the te orbital. Because of the degeneracy, a tetragonal Jahn-Teller distortion results, as shown, loering the symmetry to Da.+ The resulting orbital (bL) is spread equally over the four atoms as seen in the 2gSi hyperfine interactions for the V+ spectrum. The axial <lOO> anisotropy in the g-tensor reveals the tetragonal distortion. In forming V, Fig. 2b, the next electron goes into b,, paired off, further enhancing the tetragonal Jahn-Teller distortion. In this state the defect is diamagnetic and no EPR is observed. In forming V-, Fig. 2c, the added electron goes into the degenerate e orbital and a further Jahn-Teller distortion occurs. The distortion is of b, symmetry (in Ded) with atoms b and c pulling together and a and d separating slightly. The unpaired electron is now localized on only two of the four atoms, consistent with the observation in the V- spectrum. We conclude the following: The concept of a d efect mole,-ulec17 is valid. Approximately
(17) C.

A. Coulson and M. J. Kearsley, Proc. Roy. Sot. A241, 433 (1957).

---.,.._

G. D. WATKINS

9.5

(alI

o+b+c+d

4 - 2d -2V

c-b o-d -a+d

Fig. 2. Simple LCAO-MO treatment for the lattice vacancy. 65% of the wavefunction is accounted for as distributed between the dangling bonds on the atoms adjacent to the vacancy. The success of these one-electron models implies that the electron-electron interactions that tend to favor parallel spin coupling (Hunds rules for atoms, etc.) are smalP*. We are, in effect, in the strong crystal field regime. We fill each level before going on to the next. When degeneracy occurs, A Jahn-Teller distortion results which imposes a new crystal field, decoupling the electrons again. C. Jahn-Teller Effects By studying the response of the defects to applied. uniaxial stress, it has been possible to estimate the magnitude of these Jahn-Teller distortionP. They. have been found indeed to be very large, the estimates for the associated stabilization energies ranging as high as several electron volts. The energies appear to increase as the vacancy picks up electrons going from V+ to V0 to V-, etc. This has an interesting consequence which is illustrated very schematically in Fig. 3.

Fig. 3. Schematjc of vacancy energy levels (a) before and (b) after Jahn-Teller relaxation.

-.%- -

96

LATTICE VACANCIES AND INTERSTITIALS IN SILICON

The energies for unrelaxed vacancies might be expected to be something like that in Fig. 3a, the energies increasing substantially with electronic charge due to Coulombrepulsion between the highly loealized electrons. Allowing the lattic to relax for each charge state, however, lower their corresponding levels and compresses them together (a manifestation of the increasing Jahn-Teller energies with inrceasing electronic charge). In this way we can visualize why so many stable charge states can be crowded into a gap of only 1.2eV. In effeet, the lattiee vacancy is a soft, polarizeable defect which, each time you add an electron, ean relax in such a way as to keep the electrons apart and minimize their Coulombic repulsion. It is clear, therfore, that in a theoretical treatment of the vacancy, it is absolutely essential to include these distortions as an integral part of the model because the electrical level position and wavefunction of the defect level, the importance or not of many electron correlation effects--in fact, the existence or not of a localized state at all-depend critically upon the distortionscl. This is one of the reasons why the deep-level problem is so difficult. In effect, the problem can probably only be treated, or even qualitatively understood, in terms of a complex multi-configurational coordinate diagram for defect levels and band states. A S is well known, this leads to Stokes shifts for optieal excitation and luminescence, different energy level positions as determined by equilibrium vs. kinetie studies, and eomplex behavior for carrier eapture eross sections as the carriers move over these many-dimensional energy surfaces. Another important consequence of these large relaxation energies is that they imply large lattice energy release upon capture and recombination of carriers at the defect. On a configurational coordinate model, the released electronin energy is converted to kinetic energy of the local atoms as they are propelled toward their new equilibrium positions after an electronic transition. This energy may be converted to phonons which radiate harmlessly away from the defect. It could also however, remain localized long enough to permanently alter the the properties of the defect. In particular, it might cause it to migrate in the lattice or affect its stability. We will return to consider this in Section IV. D. Vacancy Mobility In p-type material, the vacancy disappears upon annealing at X0-180 Kclel. As the vacancy disappears, new EPR centers emerge that are identified as vacancies trapped by impurities and other defects. The annealing is, therefore, the result of long-rang migration of the vacancy. In ptype .material the stable charge state of the vacancy is neutral (VO), see Fig. 1. The measured activation energy for the annealing, 0.33 f 0.03 eVcle), is, therefore, identified as the activation energy of migration for V. In n-type material, the vacancy disappears at 70-80 K, again with the emergence of trapped vacancy spectrac). The activation energy 0.18f0.02 eV for this process is identified with the migration energy for V, the stable charge state in n-type material (see Fig. 1). The vacancy is therefore not a stable defect at room temperature. The activation energy for migration is surprisingly small, being an order of magnitude lower than that for self- and impuritydiffusion (-4-5 eV). As a result there is a substantial unresolved controversy at present in trying to understand the role of the lattice vacancy in diffusion(l*~lQ~. Another important observation is the significant change in abtivation energy of motion with charge state of the vacancy. E. Vacancy Interactions with Other Defects A large assortment of vacandy-impurity pairs emerge when the vacancy anneals. Some of the, ones that have been identified by EPR are illustrated in Fig. 4. In Fig. 4a and 4b the vacancy is shown trapped next to substitutional germanium. Both the (V- Ge)+ and (V.Ge)- charge states have been studied(Q. The distribution of the wavefunction is altered slightly between the four neighbors from that for V+ and V- (Fig. 2), but otherwise, the electronic structure, Jahn-Teller distortions, etc., are very similar. The presence of germanium is evidenced by the (21+1)= 10 hyperfine lines for 7SGe (I = 9/2, 7.6% abondant). ~ --__ (18) F. A. Huntley, II. Mehrer, and A. Seeger, in Lullice Dejecrs in Semiconducfors 1974 (The Inst. of Physics, London 1975) p. 557.
(19) J.A.

Van Vechten, in Laflice Defects in Semiconductors 1974 (The Inst. of Physics, London 1975) p. 212.

G. D. WATKINS

97

Q Q? Q? Q (-jy) @-b (-pQc+@?Q

a.(V*Ge)+

b.WGef

c.( v-01-

d.WY)

e.(V Al)-*

f.WB)

(V-Sn)

h.(Vi)+-

Fig. 4. Vacancy-defect pairs identified in silicon. The vacancy-oxygen pair results from the trapping of a vacancy by interstitial oxygen, a common impurity in silicon. Shown (Fig. 4c) is the stable configuration for (V.O)-ceo-Zs~. Vacancies trapped by the group V atoms Peer), As@~), Sbc25 take on the configuration shown in Fig. 4d. A photoexcited state of the aluminum-vacancy pair has been observed< pa), Fig. 4e, as has the ground state of a boron-vacancy pair@), Fig. 4f. The boron atom is deduced to reside at the next nearest neighbor site, as shown. The tin-vacancy pair c2*), Fig. 4g, takes on the interesting configuration in which the tin atom resides halfway between two atom sites and bonds partially with all six resulting dangling bonds. The divacancyc*~-Je~, composed of two nearest neighbor vacancies, has also been observed and is illustrated in Fig. 4h. It is sometimes produced as a primary damage event where the recoiling silicon atom also knocks out its neighbor. It is also produced as two vacancies get together during . vacancy anneal. Like the vacancy it has four stable charge states (VV+, VV, VV-, VV ) and EPR has been observed in the single plus and minus state. For all of these defects, simple one-electron molecular orbital models similar to those of Fig. 2 provide an adequate description of the structure. For most, Jahn-Teller distortions occur as evidenced in the figure by bond reformation by atom pairs which, in turn, produce minimum multiplicity for the ground state (i. e., S=1/2 or 0), as for the isolated vacancy. The only exception is the tinvacancy pair, which has S=l in its ground state. In the figure the localization of the unpaired spin is indicated in black. Again, hyperfine interactions and g-shifts are consistent with atomic dangling bond character for the wavefunction, with -65% localized in each case on the near atoms to the vacancy. In Fig. 5 the stability of the various vacancy and vacancy-defect pairs is schematically indicated (20) G. D. Watkins and J. W. Corbett, Phys. Rev. 121, 1001 (1961). (21) G. Bemski, J. Appl. Phys. 30, 1195 (1959). (22) K.L. Brower, Phys. Rev. B4, 1968 (1971). (23) K. L. Brower, Phys. Rev. B5, 4274 (1972). (24) G. D. Watkins and J. W. Corbett, Phys. Rev. 134A 1359 (1964). (25) E. L. Elkin and G. D. Watkins, Phys. Rev. 174, 881 (1968). (26) G.D. Watkins, Phys. Rev. 155, 802 (1967). (27) G. D. Watkins, Phys. Rev. B13, 2511 (1976). (28) G. D. Watkins, Phys. Rev. B12, 4383 (1975). (29) G. D. Watkins and I. W. Corbett, Phys. Rev. 138, A543 (1965). (30) J. W. Corbett and G. D. Watkins, Phys. Rev. 138, A555 (1965). (31) C. A. J. Ammerlaan and G. D. Watkins, Phys. Rev. B5, 3988 (1972). (32) J. G. deWit, C. A. J. Ammerlaan, and E. G. Sieverts, in Lattice Defecfs in Semiconductors. 1974 (The Inst. of Phys., London 1975) p. 178.

98

LATTICE VACANCIES AND INTERSTITIALS IN SILICON

Fig. 5. Schematic of vacancy and vacancy-impurity pair annealing stages. as would be observed in -15 min isochronal annealing studies. It ts clear that the stable vacancyrelated defects that may exist at room temperature in silicon, or in a silicon device, do not include the isolated single vacancies. Instead the vacancies exist only as trapped by impurities or other defects. The divacancy has served as a model for identifying higher aggregates of vacanciescSS**). In particular, tri-vacancies and quadrivacancies have been identified by EPR, with and without oxygen impurity incorporation, and appear as chain-like arrays in the {IOO) plane as if building upon and continuing the divacancy of Fig. 4h. An EPR center has also been identified as a penta-vacancyc)), but it departs from this planer pattern.

III. INTERSTITIALS Very little is known about the isolated interstitial silicon atom. In the primary damage event, of course, interstitials and vacancies must be formed in equal numbers. It is presently believed that interstitial silicon must,be unstable, at least under the conditions of irradiation in ptype material, and migrates until trapped by impurities even at i4.2K. The principal evidence for this is the E P R identification of interstitial aluminumcrs and boronca6 produced by irradiation at 4.2K, presumably formed when the mobile interstial silicon atom is trapped, trading places with the group III impurity and ejecting it into the interstitial site(). This is illustrated in Fig. 6. Indirect evidence At somewhat higher temperatures (5 100 K), interfor gallium trapping has also been observedcls. stitial trapping by the neutral impurities carbon and oxygen also becomes important. This has been

-c 5

l subs.

Fig. 6. Model for low temperature damage. (33) K. L. Brower, in Rudiafion Efects in Semiconductors, edited by J. W. Corbett and G. D. Watkins (Gordon and Breach, New York 1971) p. 189. (34) Y. H. Lee and J. W. Corbett, Phys. Rev. B13, 2653 (1976); Phys. Rev. B9, 4351 (1974). (35) Y. H. Lee and J. W. Corbett, Phys. Rev. B8, 2810 (1973). (36) G.D. Watkins, Phys. Rev. B12, 5824 (1975).

G. D. WATKINS

99

established from localized mode infrared absorption studiesCs7) and also, in the case of carbon, directly by EPR(=. In n-type silicon there is some very indirect and tentative evidence that interstitial silicon may. be somewhat more stable, not migrating and disappearing until -140 K. This evidence comes from EPR studiescaD of the divacancy after 20.4K irradiation which appears perturbed by some nearby defect in n-type material. It has been suggestedcsgl that this nearby defect, which disappears -140K, could te the interstitial silicon atom, less mobile in its charge state associated with n-type material. An EPR spectrum found to anneal in this temperature region has therefore correspondingly been tentatively suggested to be that of isolated interstitial silibon(15). However, much more research is required before these suggestions -can be properly evaluated. Therefore, many unanswered questions remain about the properties of the isolated interstitial silicon atom. What is its stable configuration? What is the mechanism for its remarkable mobility in ptype material? A major conceptual step in response to these questions has been afforded by theoretical molecular orbital calculations in clusters of atoms(4O341) simulating the interstitial in the silicon lattice. The actual calculations were performed for interstitial carbon in the isostructural lattice diamond, but the insights derived have been applied to the silicon problem. It was found that the lowest energy configuration was not with the atom in the normal tetrahedral interstitial site but rather in a bonded interstitialcy configuration. Two configurations-(i) a (11 l> bondcentered one with the extra atom nestled midway between two normal nearest atoms; and (ii) a <lOO> splitinterstitial, where two atoms form a <lOO> oriented dumbelI on a single lattice site-were very close in energy and found to be the most stable configurations (see Fig. 7). Assuming that one of these is the stable configuration, the other would be the saddle point for migration and their closeness in energy implies an easy path for diffusion.

a) <ll l> bond-centered b) <lOO> split Fig. 7. Possible interstitialcy configurations in the diamond lattice. Interestingly, the configuration for interstitial carbon in silicon has been interpreted to bk consistent with a <lOO> spIit-interstitial model, with one of the dumbbell pair atoms being the carboncsa. Interstitial boron on the other hand appears to have a configuration suggestive. of a distorted <ill) bond-centered interstitial@Q. Also, suggestions have recently be& made that certain EPR spectra observed in neutron-irradiated silicon(4B) and that emerge upon higher temperature, annealC4J may involve diinterstitials. For these also, a (lOO> dumbbell configuration for the interstitial constituents is suggested. (37) See the review by R.C. Newman, Infra-red Studies of Crystal Defects (Taylor and Francis, Ltd., London, 1973). p. 124 ff. (38) G. D. Watkins and K. L. Brower, Phys. Rev. Letters 36, 1329 (1976). (39) G. D. Watkins, in Symposium on Radiation Effebts on Semiconductor Components, Toulouse 1967 (Journess dElectronique, Toulouse 1967) Al-l. G. D. Watkins, R. P. Messmer, C. Weigel, D. Peak, and J. W. Corbett, Phys. Rev. Letters 27, 1573 (1971). (40) ,(41) C. Weigel, D. Peak, J. W. Corbett, G.D. Watkins and R.P. Messmer, Phys. Rev. B8, 2906 (1973). (42) Y. H. Lee, N. N. Gerasimenko, J. W. Corbett, Phys. Rev. Bid, 4506 (1976). (43) K.L. Brower, Phys. Rev. Bid, 872 (1976).

100

LATTICE VACANCIES AND INTERSTITIALS IN SILICON

At present, therefore, the best experimental evidence on the possible interstitial silicon configurations comes indirectly from the study of these trapped interstitials. (It is interesting to note that the EPR spectrum tentatively identified with the isolated interstitial silicon atom in n-type siliconcls) also has the correct symmetry to be associated with the <lOO> split interstitial of Fig. 7b). In Fig. 8, we summarize some of what is known about the stability of interstitial-impurity pairs as would be observed in -15 min isochronal annealing studies. In the figure we have included the interstitial carbonsubstitutional carbon pairs(44) and the similar aluminum-aluminumcr*~ and galliumgalliumcts pairs that form when the corresponding interstitial impurity begins to diffuse through the lattice. Again, as for the vacancy, interstitials are present at room temperature only as trapped .by other defects. The properties of the isolated silicon interstitial still remain clounded in mystery.

Fig. 8. Schematic of interstitial impurity annealing stages.

IV. DEFECT STABILITY UNDER ELECTRONIC EXCITATION There is growing evidence suggesting that defects can migrate at cryogenic temperatures during irradiation. The presence of the trapped interstitials in a 4.2K irradiation in p-type material is a dramatic example. Evidence has also been cited, however, for vucuncy motion in that vacancies trapped by oxygerV, germanium(IS), and tincPBj have also been observed after a 20.4 K irradiation. The concentrations of these trapped vacancies are often only a few percent of the isolated vacancy concentration, but still this is orders of magnitude greater than the random probability of defect formation next to the impurity. In the case of the vacancy, the activation energies for motion are known (section II) and appear to be too large to account for this motion as due to a thermally activated process alone. This suggests that the ionization accompanying the radiation may serve to enhance the motion as electrons and holes are alternately captured by the defect. Recently the first direct observation of this effect has been reported@Q. Using the 1.06~ excitation from a Nd YAG laser, it was demonstrated that isolated vacancies can be induced to migrate at 20.4 K in p-type material, as evidenced by, the observation of boron-vacancy pairing as the vacancy EPR spectrum was induced to disappear. Vacancy-boron pair break-up was also detected indicating that the reaction kinetics were also being modified by the excitation. These results appear to confirm that the large Jahn-Teller relaxations associated with the vacancy serve as a reservoir of energy which can be released upon electronic. excitation or electron or hole capture and assist in the motion of the defect. This is a very exciting result and points, for the first time, to the possibility of direct and detailed unraveling of the microscopic processes involved using EPR as the probe. The motion of the silicon interstitial is more difficult to study, however. because it has not been possible to freeze in this defect in its isolated state. Still, some of the trapped interstitials may represent indirect windows to the properties of the silicon interstial in that they appear to display similar interstitialcy character. Using the 1.06 y excitation, we have recently shown that interstitial
_ (44) K.L. Brower, Phys. Rev. B9, 2607 (1974).

i_

.-

_.,

G. D. WATKINS

101

boron can be made to reorient from one <II 1) interstitialcy configuration to another at 20.4 K, while thermally, in the dark, the activation barrier was measured to be 0.6 eVcss. This demonstrates that at least 0.6 eV energy can indeed be converted from the electronic excitation (-L2eV) into the necesssry kinetic energy of the surrounding atoms to overcome the barrier. The model of the defect (Fig. 7a) implies that reorientation is equivalent to migration, but this remains to be demonstrated experimentally. This therefore is an exciting new area of study. Understanding the role of electronic excitation on the mobility and stability of the defects holds promise of helping unravel the complex radiation damage processes going on in silicon. Perhaps more important, understanding in this simple model system ma? provide the key to unraveling similar processes in a wide variety of other semiconducting materials. GaAs and GaP are good examples, for instance, where similar effects may be operative the deterioration of their devices under injectioon conditionsc*5+). V. SUMMARY A great deal has been learned about lattice vacancies and their interactions with other defects. Isolated vacancies have been identified as have divacancies and higher aggregates of vacancies. A large number of vacancy-impurity pairs have also been identified. For all, simple one-electron molecular orbital models made up from the dangling broken bonds around the vacancy serve to satisfactorily describe their electronic structure. Large Jahn-Teller relaxations are characteristic of these defects. Isolated interstitial silicon atoms have so far eluded positive detection but a wide variety of interstitial-impurity pairs, and possibly di-interstitials, have been observed. For many of these, interstitialcy bonded configurations are observed, consistent with theoretical predictions based upon molecular orbital calculations of finite atom clusters. Neither the isolated interstitial nor the vacancy is stable at room temperature and they therefore are encountered at room temperature only in trapped or aggregated states. Evidence exists that both of these primary defects are mobile at cryogenic temperatures in the presence of ionizing radiation. Interstitial silicon is particularly mobile and, at least in ptype silicon, is observed only in its trapped states. The lattice vacancy can also be made to migrate, but less efficiently. The mechanism in each case is believed to be the vibronic coupling of the defect to the lattice which manifests itself in large Jahn-Teller relaxations in the case of the vacancy and the large lattice rearrangements associated with the interstitialcy configurations of the interstitial.

(45) P.M. Petroff and L. C. Kimerling, B. Am. Phys. Sot. II 21, 256 (1976). (46) D.V. Lang and L.C. Kimerling, B. Am. Phys. Sot. II 21, ,437 (1976).

YLr;

__