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Defects in Semiconductors:
Some Fatal, Some Vital
Hans J. Queisser* and Eugene E. Haller
i-- --7
Fig. 1. Range of electri-
from p-type to n-type material, they change from being majority to
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cal resistivities of pure inority carriers. The transistor inventors made the important, seren-
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process steps is a marvelous example of the meticulous control of of the cold war when collaborations between former Soviet and
defects within Si. Westem scientists made research with isotopically controlled semi-
Some unwanted electrically active centers in a semiconductor can conductors feasible. During the past few years, defect studies with
be passivated (or neutralized) by the formation of neutral pairs of the these special materials have generated a host of results (26), two of
impurities with interstitial lithium or hydrogen. The technique of which will have to suffice for illustrating the possibilities.
drifting Li+ ions in the electric field of a reverse-biased diode had Oxygen in Si or Ge is not an electrically active dopant impurity. It
been used for many years to passivate acceptors in p-type Si and Ge. plays, however, a crucial role in gettering transition metal ions in Si,
The process leads to millimeter- or centimeter-wide depletion layers in forming shallow donors with H in Ge, and in other processes.
that are widely used in solid-state ionization detectors for x-rays, Oxygen assumes a bond-centered interstitial position in these mate-
gamma rays, and energetic particles (17). The development of ultra- rials. In that position it is infrared active, forming sharp absorption
pure Ge with one dopant impurity per 1012 Ge atoms (a tour de force lines near 862 cm-I in Ge (8.06 cm-' is equivalent to 1 meV).
resulting in an electrically "twelve-nines" pure substance) has made Because natural Ge consists of five stable isotopes with sizable
Li+ drifting in this semiconductor obsolete and has made possible the concentrations, the oxygen atoms have a variety of nearest neighbor
fabrication of Ge detector diodes with depletion zone volumes of atom combinations, each ont leading to slightly different vibrational
several hundred cubic centimeters (18). All modem high-energy frequencies. The resulting absorption spectrum shows 11 distinct lines
resolution x-ray detectors used, for example, on transmission and (Fig. 6A). The close proximity of these lines forbids any detailed
scanning electron microscopes are fabricated from Li+ ion-drifted studies of line splittings caused by the interaction of the various
p-type Si. The resolution of these devices is superior to those made possible vibrational modes (v,, v,, and v,). Growth of isotopically
from high-purity Si because Li+ ions passivate shallow as well as pure, oxygen-doped Ge crystals drastically simplified the spectrum to
deep-level dopants and defects (19). just one line (Fig. 6B) and allowed the determination of the interac-
During the development of ultrapure Ge, hydrogen was discovered tions between the v,, v,, and v, modes (27).
to be an impurity that could either activate or passivate impurities and Self-diffusion is the most fundamental, atomic, random walk
defects. For example, oxygen, silicon, and carbon were found to form process in a solid. In semiconductors it is the starting point for the
shallow-dopant complexes with hydrogen (20). Multivalent acceptors understanding of all dopant diffusion processes. Radioactive isotopes
and deep-level impurities became partially or fully passivated by have typically been used to follow the random walk of host atoms.
combining with hydrogen (21). In the early 1980s, hydrogen was Both the short half-life of the most suitable radio isotope (31Siwith a
found to enter Si and to passivate acceptors and donors (22). Almost half-life of 2.6 hours) and the near-surface effects have made an
every device processing step that involves wet chemicals (even boil- accurate determination of the Si self-diffusion coefficient rather ten-
ing in water) bill introduce-hydrogeninto Si. Deliberate introduction tative. Epitaxial growth of a multilayer structure consisting of natural
of hydrogen with proton implantation is used to form highly resistive and ,*Si together with secondary ion mass spectrometry (SIMS)
layers to isolate neighboring devices or to confine electrical currents enabled the first direct determination of Si self-diffusion profiles (28).
to specific areas. Separating a thin layer from an underlying substrate A single diffusion enthalpy of 4.75 ? 0.04 eV characterizes the
can be achieved with implantation of large doses of hydrogen. An self-diffusion process within these limits. This result is attractively
entire new body of solid-state chemistry describing hydrogen-impu- simple and quite unexpected. It will force revisions of dopant diffu-
rity and hydrogen-defect complexes in Ge, Si, and many compound sion simulation and modeling of advanced microchips. Diffusion of
semiconductors has been created in recent years. One example of the dopant impurities is controlled by native defects. Most donor and
multiatom center involving platinum binding two hydrogen atoms is acceptor dopants diffuse in Si assisted by Si interstitials, with Sb being
shown in Fig. 5 (23). Molecule formation and dissociation, reaction the notable exception. Any process that significantly changes the
kinetics, and thermodynamic properties, such as the entropy contri- native defect concentration will affect dopant diffusion. Oxidation and
bution of a complex inside the semiconductor, are aspects of this
rapidly expanding subfield of defect science.
Semiconductors with Isotopically Controlled Composition
Pomeranchuk suggested in 1942 that perfect crystal symmetry is
already perturbed when the constituent atoms vary in isotopic atomic
mass and that this isotope disorder should reduce the thermal conduc-
tivity (24). The isotope separation efforts during and after World War
I1 led to sizable quantities of enriched stable isotopes of numerous
elements, among them isotopically pure 74Ge. Geballe and Hull
finally proved the conjecture of Pomeranchuk in 1958 (25). The
enormous expense associated with isotopically enriched materials
(tens of U.S. dollars per milligram) stifled further studies until the end
veiy large donor concentrations increase the Si interstitial concentra- defective GaN layers followed by lateral overgrowth on the mask
tion, leading to an interstitial "wind" moving from the surface toward material has led to vastly improved epitaxial layer q~~ality.
This rapid
the interior. This ~vindcauses transient enhanced dopant diffusion; progress is another example of the ingenuity of the scientists and
one of the most serious problems for modem devices (29). engineers who always find ways to control defects when required.
its neighbor's coordinates. The CC diagram for the DX center de- discovered, too many to describe. Up-to-date accounts of these mul-
scribed by the model of Chadi and Chang is shown in Fig. 7. At low tifaceted defects can be found in the proceediilgs of the biannual
pressures or AlAs mole fractions, the CC diagram to the left applies. Intei~lationalConferences of Defects in Semiconductors (1).
The shallow-donor configuratioi~is stable; but DX coexists in meta-
stable form. Optical excitation can lead to DX formation. At modest Outlook
temperatures, the small energy barrier separating the two defect Defects in semiconductors will continue to attract scientific and
structures is easily overcome, returning the center into its stable form. technical interest. New semiconductors. new hetero-interfaces, and
At pressures 2 2 0 kbar or at AlAs mole fractions 222%: the DX new device structures are the sources of defects with a variety of
configuration is stable. The material is insulating despite the presence electrical, optical, and stmchlral properties. The properties miill have
of dopants. During band edge light illumination free electrons and to be understood so that the defects can either be eliminated or put to
holes are generated: leading to the standard photoconductivity. How- good use. The shrinking dimensions of semiconductor structures will
ever, DX centers are also optically puinped into the shallow-donor require ever more sensitive and selective characterization tools. Has
configuration. If the crystal is kept cold, the shallow-donor configu- defect research reached its plateau? Hardly. Just watch the bustling
ration is trapped by the energy barrier between the two configurations. activities surrounding strained layer structures; nanocrystals, or the
The donors are very shallow and remain ionized, that is, the conduc- group I11 nitrides and their alloys, to name a few.
tivity persists, no longer because of photon illumination but because
of the photon-induced defect configuration change. References and Notes
1. For recent summaries, see Mat. Sci. Forum 258-63 (1997); Proceedings of the Eighth
Although the Chadi and Chang model was broadly accepted; the international Conference on Shallow-Level Centers in Semiconductors, Montpellier,
requirement for DX to be negatively charged was questioned. If true; at France, 27 t o 30 July 1998 [Phys. Status Solidi (Bj, in press].
most half of all the donors (do; dt) could be converted to DX centers: 2d0 2. H. J. Queisser, Mat. Res. Soc. Symp. Proc. in press.
ct d- -t DX-. Wolk et 01. (37) found an elegant way to prove 3. C. Wetzel et a/., Phys. Rev. Lett. 78, 3923 (1997).
4. A. K. Ramdas and S. Rodriguez, Rep. Progr. Phys. 44, 1297 (1981).
experimentally that the DX centers are indeed negatively charged. Com- 5. S. T. Pantelides, Ed., Deep Centers in Semiconductors: A State-of-the-Art Approach
bining large hydrostatic pressure with far-infrared absorption spectrosco- (Gordon & Breach, Lausanne, Switzerland, ed. 2, 1992); A. M. Stoneham, Theory of
py. they showed that the vibrational mode frequencies of the tetrahedral Defects in Solids (Clarendon, Oxford, 1975).
shallow Si donor and the trigonal Si DX center were different and that the 6. W. Shockley, IEEE Trans. Electron. Devices ED-23, 611 (1976).
7. S. Nakamura, Science 281, 956 (1998).
absorption line strength of the shallow donor was at least as large or larger 8. J. Neugebauer and C. Van de Walle, Phys. Rev. B 50, 8067 (1994).
than the DX line strength. Using n-type GaAs samples with different 9. H. R. Huff e t al.,]pn. 1. Appl. Phys. (Part I ) 37, 1210 (1998).
acceptor concents$ions; they showed unambiguously that DX centers are 10, j. P. Hirth and j. Lothe, Theory of Dislocations (Wiley, New York, 1982).
11. H, J. Queisser, Mat. Res. Soc. Symp. Proc. 14, 323 (1983).
stabilized by an extra electron. 12. S. Nakamura and G. Fasol, The Blue Laser Diode (Springer, Heidelberg, 1997).
A second metastable defect is associated with a deep donor (EL2) 13. A. R. Smith, R. M. Feenstra, D. W. Creve, j . Neugebauer, J. E. Northrup, Phys. Rev. Lett.
found in GaAs ciystals with excess As concentrations. The surplus As 79, 3934 (1997).
atoms were found to assume Ga host lattice sites, forming antisites, As,,. 14. K. Graff, Metal impurities in Silicon (Springer, Heidelberg, 1995).
15. C. Obermeier, J. Hage, D. Huber,]. Appl. Phys. 82, 595 (1997).
For many years it was unclear if the isolated As,, antisite or a more 16. For a recent survey, see D. Gilles and A. Ohsawa, in Semiconductor Silicon 7998, H. R.
complicated defect is responsible for forming the EL2 donor level. This Huff, U. Cosele, H. Tsuya, Eds. (Electrochemical Society, Pennington, NJ, 1998), vol.
debate was settled by the theoretical work of Dabrowski and Scheffler 98-1, p. 1047.
17. E. E. Haller and F. S. Goulding, Handbook on Semiconductors, C. Hilsum, Ed. (Elsevier,
(38) and Chadi and Chang (39) in favor of the isolated antisite. New York, ed. 2, 1993), vol. 4, pp. 937-963.
The EL2 donor exhibits fascinating properties that show similar- 18. E. E. Haller, Festkorperprobleme: Advances in Solid State Physics XXVI, P. Crosse, Ed.
ities to those of the DX center. For example; EL2 can be optically (Vieweg, Braunschweig, Germany, 1986), pp. 203-229.
pumped with photons between 1 and 1.3 eV into a metastable state 19. J. T. Walton, R. H. Pehl, Y. K. Wong, C. P. Cork, iEEE Trans. Nucl. Sci. 31 (no. I ) , 331
(1 984).
with an identical charge state but no energy level in the band gap. 20. E. E. Haller, Phys. Rev, Lett. 40, 584 (1978).
From this electrically and optically inaccessible metastable state; only 21. , G. S. Hubbard, W. L. Hansen, IEEE Trans. Nucl. Sci. 24 (no. I ) , 48 (1977).
a return with thermal energy back to EL2 is possible. The barrier 22. See articles in J. Pankove and N. Johnson, Eds., Hydrogen in Semiconductors:
between the two configurations is -0.34 eV. What makes EL2 Semiconductors and Semimetals (Academic Press, Orlando, FL, 1991), vol. 34.
23. S. J. Uftring, M. Stavola, P. M. Williams, G. D. Watkins, Phys. Rev. B 51, 9612 (1995);
important is its ability to fully compensate moderate concentrations of 1.-U. Sachse, E. 0. Sveinbjornsson, W. jost, j. Weber, H. Lemke, ibid. 55, 16176
acceptors in GaAs and to pin the Fermi level near the middle of the (1997).
band gap, yielding the material semi-insulating. Such crystals can be 24. 1. Pomeranchuk,]. Phys. (Moscow) 6, 237 (1942).
used as nonconducting templates for very high-speed GaAs circuitry. 25. T. H. Geballe and G. Hull, Phys. Rev. 110, 773 (1958).
26. E. E. Haller, Appl. Phys. Rev. in 1.Appl. Phys. 77, 2857 (1995).
Over the past two decades other metastable defects have been 27. A. J. Mayur e t a/., Phys. Rev. B 49, 16293 (1994).
28. H. Bracht, E. E. Haller, R. Clark-Phelps, Phys. Rev. Lett., 81, 393 (1998).
29. P. A. Stolk, D. J. Eaglesham, H.-J. Gossmann, J. M. Poate, Appl. Phys. Lett. 66, 1370
(1995).
30. S. P. Murarka, Silicides for VLSI Applications (Academic Press, Orlando, FL, 1983).
31. W. Walukiewicz, Appl. Phys. Lett. 54, 2094 (1989).
32. For reviews, see, P. M. Mooney, Semicond. Sci. Technol. 6, B1 (1991); Appl. Phys. Rev.
in 1. Appl, Phys. 67, R1 (1990).
33. D. V. Lang and R. A. Logan, Phys. Rev. Lett. 39, 635 (1977).
34. M. Mizuta e t al.,]pn. 1.Appl. Phys. 24, L143 (1985).
35. D, j. Chadi and K. J. Chang, Phys. Rev. Lett. 61, 873 (1988).
36. G. D. Watkins, Mat. Sci. Forum 38-41, 39 (1989).
37. J. Wolk e t a/., Phys. Rev. Lett. 66, 774 (1991).
38. J. Dabrowski and M. Scheffler, ibid. 60, 2183 (1988).
39. D. j. Chadi and K. J. Chang, ibid., p. 2187.
40. We gratefully acknowledge suggestions and help from A. R. Smith, R. M. Feenstra, and
D. W. Greve of Carnegie Mellon University for providing us with Fig. 3 before publication;
C. Van de Walle of Xerox, Palo Alto Research Center, for discussions and permission to
reproduce Fig. 2; and J. Weber of the Max-Planck-lnstitut, Stuttgart, Germany, and M.
/ C o n f i g u r a t i o n Coordinate Configuration Coordinate Stavola of Lehigh University for reproducing Fig. 5. W. L. Hansen and W. Walukiewicz at
Lawrence Berkeley National Laboratory (LBNL) have contributed enlightening discus-
1 Fig. 7.
(A) x
C o n f i g u r a t i o n c o o r d i n a t e d i a g r a m s f o r DX c e n t e r s
< 0 . 2 2 (B) x > 0.22.
in AI,Ga,xAs; sions. H,J,Qis grateful for the hospitality extended to him at the University of California
at Berkeley and at LBNL.