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JOURNAL OF APPLIED PHYSICS 106, 071101 2009

APPLIED PHYSICS REVIEWSFOCUSED REVIEW

Defects in ZnO
M. D. McCluskey1,2,a and S. J. Jokela1
1

Department of Physics and Astronomy, Washington State University, Pullman, Washington 99164-2814, USA 2 Institute for Shock Physics, Washington State University, Pullman, Washington 99164-2816, USA

Received 8 May 2009; accepted 8 June 2009; published online 5 October 2009 Zinc oxide ZnO is a wide band gap semiconductor with potential applications in optoelectronics, transparent electronics, and spintronics. The high efciency of UV emission in this material could be harnessed in solid-state white lighting devices. The problem of defects, in particular, acceptor dopants, remains a key challenge. In this review, defects in ZnO are discussed, with an emphasis on the physical properties of point defects in bulk crystals. As grown, ZnO is usually n-type, a property that was historically ascribed to native defects. However, experiments and theory have shown that O vacancies are deep donors, while Zn interstitials are too mobile to be stable at room temperature. Group-III B, Al, Ga, and In and H impurities account for most of the n-type conductivity in ZnO samples. Interstitial H donors have been observed with IR spectroscopy, while substitutional H donors have been predicted from rst-principles calculations but not observed directly. Despite numerous reports, reliable p-type conductivity has not been achieved. Ferromagnetism is complicated by the presence of secondary phases, grain boundaries, and native defects. The famous green luminescence has several possible origins, including Cu impurities and Zn vacancies. The properties of group-I Cu, Li, and Na and group-V N, P, As, and Sb acceptors, and their complexes with H, are discussed. In the future, doping of ZnO nanocrystals will rely on an understanding of these fundamental properties. 2009 American Institute of Physics. doi:10.1063/1.3216464 TABLE OF CONTENTS I. INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . . . II. INTRINSIC PROPERTIES. . . . . . . . . . . . . . . . . . . . III. NATIVE DEFECTS. . . . . . . . . . . . . . . . . . . . . . . . . A. Zinc interstitials. . . . . . . . . . . . . . . . . . . . . . . . B. Oxygen vacancies. . . . . . . . . . . . . . . . . . . . . . . C. Zinc vacancies. . . . . . . . . . . . . . . . . . . . . . . . . D. Damage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV. GROUP-III DONORS. . . . . . . . . . . . . . . . . . . . . . . V. GROUP-IV IMPURITIES. . . . . . . . . . . . . . . . . . . . . VI. GROUP-V ACCEPTORS. . . . . . . . . . . . . . . . . . . . . A. Substitutional nitrogen. . . . . . . . . . . . . . . . . . . B. Nitrogen molecules. . . . . . . . . . . . . . . . . . . . . . C. Phosphorus, arsenic, and antimony. . . . . . . . . D. The p-type controversy. . . . . . . . . . . . . . . . . . VII. GROUP-I ACCEPTORS. . . . . . . . . . . . . . . . . . . . . A. Lithium and sodium. . . . . . . . . . . . . . . . . . . . . B. Copper. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VIII. HYDROGEN. . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Isolated hydrogen. . . . . . . . . . . . . . . . . . . . . . . 1. Diffusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Hydrogen donors. . . . . . . . . . . . . . . . . . . . . 3. Interstitial hydrogen. . . . . . . . . . . . . . . . . . .
a

1 2 2 2 2 3 4 4 5 5 5 5 5 5 6 6 6 7 7 7 7 7

4. Hidden hydrogen. . . . . . . . . . . . . . . . . . . . . 5. Substitutional hydrogen. . . . . . . . . . . . . . . . B. Hydrogen complexes. . . . . . . . . . . . . . . . . . . . 1. Passivation of defects. . . . . . . . . . . . . . . . . 2. Zinc vacancyhydrogen. . . . . . . . . . . . . . . . 3. Nitrogenhydrogen. . . . . . . . . . . . . . . . . . . 4. Copperhydrogen. . . . . . . . . . . . . . . . . . . . . 5. Lithiumhydrogen. . . . . . . . . . . . . . . . . . . . IX. TRANSITION METALS. . . . . . . . . . . . . . . . . . . . . A. Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . B. Ferromagnetism. . . . . . . . . . . . . . . . . . . . . . . . X. EXTENDED DEFECTS. . . . . . . . . . . . . . . . . . . . . . A. Surface conduction. . . . . . . . . . . . . . . . . . . . . . B. Dislocations. . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Stacking faults. . . . . . . . . . . . . . . . . . . . . . . . . D. Grain boundaries. . . . . . . . . . . . . . . . . . . . . . . . XI. CONCLUSIONS. . . . . . . . . . . . . . . . . . . . . . . . . . . .
I. INTRODUCTION

8 8 8 8 8 9 9 9 9 9 9 10 10 10 10 10 10

Electronic mail: mattmcc@wsu.edu.

The past decade has seen dramatic advances in the development of wide band gap semiconductors in devices ranging from blue lasers to solar cells.1,2 Zinc oxide ZnO is an old semiconductor that has attracted resurgent interest as an electronic material for numerous applications.3 With a direct gap of 3.4 eV at room temperature,4 ZnO is a wide band gap semiconductor that emits light in the near-UV region of
2009 American Institute of Physics

0021-8979/2009/106 7 /071101/13/$25.00

106, 071101-1

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M. D. McCluskey and S. J. Jokela

J. Appl. Phys. 106, 071101 2009

the spectrum. The high efciency of the emission5 makes ZnO a strong candidate for solid-state white lighting. ZnO is currently used as a transparent conductor6 in solar cells.7 It is also an UV-absorbing material in sunscreens8 and the active material in varistors.9 ZnO and related alloys are used for transparent transistors, devices that could be incorporated in products such as liquid-crystal displays.10 In addition to optoelectronic and electronic devices, ZnO may become a key material for spintronic applications.1113 In nonvolatile memory systems, ferromagnetism is used to store data for extended periods of time.14 Semiconductors such as ZnO offer the possibility of devices that combine optical and magnetic effects, such as spin light-emitting diodes LEDs ,15 spin-polarized solar cells,16 and magnetooptical switches.17 The development of room-temperature ferromagnetic materials will be essential for the widespread realization of these technologies. Theoretical work predicted ferromagnetism above room temperature for Mn-doped ZnO, given a sufciently high hole concentration.18 Spurred by that prediction, research into ZnO crystals for spintronic applications is an active area of experimental research.19 ZnO has practical benets that make it an attractive material from an industrial point of view. In contrast to GaN, large single crystals can be grown relatively easily.20 The environmental impact and toxicity are lower than most other semiconductorsZnO is actually used as a dietary supplement in animal feed.21 The low cost of Zn as compared to In makes ZnO economically competitive for transparent conductor applications. While ZnO has many inherent advantages, the lack of control over dopants and defects presents an obstacle to the realization of practical devices. This focused review presents a summary of defects in ZnO, with an emphasis on the physical properties of point defects in bulk crystals. The literature in this area is vast, and only a representative sample is presented here. Interested readers are directed to comprehensive review articles on ZnO materials and devices,22 processing,23 and ceramics.24
II. INTRINSIC PROPERTIES

readily.30 While they may play a signicant role as compensating centers, O vacancies and other native point defects are unlikely to be the predominant cause of unintentional n-type conductivity in ZnO.31 As discussed in Secs. III A and III B, the O vacancy is a deep donor, while Zn interstitials are unstable at room temperature. Zn vacancies are present as compensating acceptors in n-type ZnO. Other native defects, such as Zn antisites, O antisites, and O interstitials, have high formation energies. Under normal conditions, they are probably not present in large concentrations, although O interstitials may be important in O self-diffusion.32 Native defects affect the performance of Ohmic and Schottky contacts. Depth-resolved cathodoluminescence CL revealed the formation of point defects at metal-ZnO interfaces, leading to changes in the properties of the Schottky barriers.33 The deposition of metals caused the formation of point defects with CL energies near 2.1, 2.5, and 3 eV. Processing conditions are important; for example, the formation of a AuZn eutectic at 625 C may cause Zn deciency in the adjacent ZnO material.34
A. Zinc interstitials

ZnO has the wurtzite crystal structure, with lattice parameters a = 3.24 and c = 5.21 .25 Its bulk modulus is 142 GPa.26 Bulk ZnO undergoes a transition to the rocksalt phase at a pressure of 9 GPa.27 Room-temperature Raman scattering spectra showed transverse optical phonons at 378 cm1 A1 and 410 cm1 E1 , longitudinal optical LO phonons at 576 cm1 A1 and 588 cm1 E1 , and E2 phonons at 98 cm1 low and 438 cm1 high .28 Due to spin-orbit and crystal-eld splitting, the valence band splits into three levels at the center of the Brillouin zone, resulting in A, B, and C excitons. The A free exciton is the one with the lowest energy. Photoluminescence PL measurements showed that the A free exciton has a binding energy of 60 meV and that the band gap at 10 K is 3.437 eV.29
III. NATIVE DEFECTS

Vlasenko and Watkins35 produced defects in ZnO by electron irradiation at liquid-helium temperatures. Optically detected magnetic resonance ODMR was used to identify O vacancies, Zn interstitials, and Zn vacancyZn interstitial pairs. The Zn interstitials are shallow donors, with a characteristic effective mass EM g-factor of g 1.96.36 They anneal out at a temperature of 170 K. First-principles calculations also show that Zn interstitials are shallow donors. They have high formation energies in n-type ZnO and are fast diffusers with migration barriers as low as 0.57 eV.32 Therefore, Zn interstitials are not stable at room temperature,37 in agreement with the experimental work of Vlasenko and Watkins.35 The possibility that Zn interstitials cause n-type conductivity was further challenged by positron annihilation measurements, which showed that annealing in Zn vapor did not result in a decrease in Zn vacancies.38 If Zn interstitials had diffused into the crystal, then one would have expected the open-volume defects to have been lled. Instead, the authors posited that the Zn vapor caused an increase in O vacancies in the bulk by growing new ZnO on the surface. While there is consensus that Zn interstitials are not stable, it has been proposed that complexes involving N impurities and Zn interstitials could be stable, shallow donors.39
B. Oxygen vacancies

Defects such as O vacancies have low formation enthalpies in p-type ZnO and are therefore predicted to form

First-principles calculations consistently show that the O vacancy is a deep, negative-U donor, where the 1+ charge state is thermodynamically unstable. When the Fermi energy is above the 0 / 2+ level, the defect is in the neutral charge state. When the Fermi energy is below the 0 / 2+ level, the defect has a charge of +2e. The 0 / 2+ level of the O vacancy was calculated to be 0.50.8 eV above the valence-band maximum.4042 Calculations that attempt to correct for the band gap error of the local density approximation LDA estimated the 0 / 2+ level to be 12 eV below the conduction-

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M. D. McCluskey and S. J. Jokela

J. Appl. Phys. 106, 071101 2009 TABLE I. EPR parameters for donors in ZnO, where and refer to directions parallel and perpendicular to the c axis, respectively. The electron 1 spins are S = 2 . Donor Shallow EM donor Zn interstitial 1+ O vacancy 1+ Pb3+ g 1.9570 1.9605 1.9946 2.0133 g 1.9551 1.9595 1.9960 2.0135 Ref. 36 35 35 92

FIG. 1. EPR spectra of electron-irradiated ZnO, taken at 30 K and 9.48 GHz, with the magnetic eld perpendicular to the c axis. a In the dark. b After illumination with 325 nm light. The Zn vacancies are in the 1 charge state and the O vacancies are in the 2+ charge state. Reprinted with permission from L. A. Kappers, O. R. Gilliam, S. M. Evans, L. E. Halliburton and N. C. Giles, Nucl. Instrum. Methods Phys. Res. B, 266, 2953 2008 . Copyright 2008, Elsevier.

an excited-to-ground state transition.53 Annealing in O2 or Zn vapor produces PL lines at 2.35 and 2.53 eV, respectively, and annealing in ZnO powder removes both lines. These observations suggested that the 2.35 eV emission is due to Zn vacancies and the 2.53 eV emission is due to O vacancies.54 It should be noted, however, that numerous defects have been blamed for green luminescence.55 Electron irradiation, which produces O vacancies and other defects, leads to a reduction in green luminescence and an increase in PL bands near 600 and 700 nm.48,51 Also, the congurationcoordinate diagram calculated for the O vacancy does not show any transitions consistent with green emission.56 For these reasons, one should never assume that green PL is due to O vacancies.

band minimum.4346 The calculated migration barrier for the neutral O vacancy is 2 eV.47,32 Theorists disagree on whether O vacancies should be present in n-type ZnO. For example, Lany and Zunger44 predicted concentrations of 1017 cm3 or higher, whereas Janotti and Van de Walle32 claimed that the formation energy is much too high for signicant concentrations to exist at equilibrium. Electron paramagnetic resonance EPR measurements on electron-irradiated ZnO show that neutral O vacancies are converted to the 1+ charge state by illumination at low temperature Fig. 1 . This results in a g-factor of g 1.995 and 1 spin S = 2 Table I .35 The O vacancies are stable up to 48 400 C. From the optical threshold for producing the 1+ charge state, Evans et al.49 estimated that the neutral O vacancy ground state lies 2.1 eV below the conduction-band minimum. An electronic transition results in a broad absorption band near 3.0 eV 409 nm , giving crystals a yellowish or reddish color.50,51 The famous green luminescence band centered around 2.4 eV 510 nm has been attributed to O vacancies,52 due to

C. Zinc vacancies

Zn vacancies are double acceptors. First-principles calculations nd the 0/1 and 1/2 acceptor levels to be 0.1 0.2 and 0.91.2 eV above the valence-band maximum, respectively.31,32,57 Under illumination at low temperatures, Zn vacancies can be transformed to the 1 or neutral charge state, both of which are EPR active Table II . In the 1 1 charge state, the defect has a spin S = 2 and an anisotropic 58,35 A trigonal JahnTeller distortion causes the hole g-tensor. to be localized on one of the neighboring O sites, with nonaxial sites 110 to the c axis being energetically preferred Fig. 1 . In the neutral charge state, two holes are trapped on different nonaxial O sites, resulting in a spin S = 1.58,59 From the wavelength of light required to pump Zn vacancies from the 1 to the neutral charge state, Evans et al.49 estimated that the ground state for the 1 charge state lies 0.9 eV above the valence band.

TABLE II. EPR parameters for acceptors in ZnO. For centers with axial symmetry, and refer to directions parallel and perpendicular to the c axis, respectively. Deep acceptors can have their holes localized on axial or nonaxial O atoms. is the angle between the c and z axes. For Li and the singly ionized Zn vacancy, z points roughly along the ZnO bond direction. For the neutral Zn vacancy, z lies in the basal plane and points from one O atom to an adjacent O atom. Axial Acceptor N neutral N2 1 Li neutral Zn vacancy 1 Zn vacancy neutral S 1/2 1/2 1/2 1/2 1 g 1.9953 2.0036 2.0028 2.0024 g 1.9633 1.9935 2.0253 2.0193 gxx Nonaxial gyy gzz deg Ref. 36 98 136 58 58

2.0223 2.0173 2.0132

2.0254 2.0183 2.0187

2.0040 2.0028 2.0088

113 111 90

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J. Appl. Phys. 106, 071101 2009

Zn vacancies may account for the green luminescence in some ZnO samples. As discussed by Janotti and Van de Walle,32 the transition from a shallow donor level to the 1/2 acceptor level could give rise to PL around 2.5 eV. Also, exposure of ZnO samples to H plasma reduced the intensity of the green luminescence,60 consistent with the passivation of Zn vacancies. However, as noted in Sec. III B, electron irradiation leads to a decrease in green luminescence, even though defects such as Zn vacancies are created. Positron annihilation studies have yielded useful information about vacancies. In bulk ZnO, positrons have a lifetime of 169 ps at room temperature.61 O vacancies do not result in a signicant increase in open volume, due to relaxation of the neighboring Zn atoms.62,63 Therefore, while positron annihilation is sensitive to Zn vacancies, it cannot detect O vacancies. Tuomisto et al.64 showed that Zn vacancies are important deep-level acceptors in as-grown and irradiated ZnO, with trapped positrons having a lifetime of 230 ps. Zn vacancies formed by electron irradiation are annealed at 200 300 C.65,66 As grown, hydrothermal ZnO contains open-volume defects that give rise to a positron lifetime of 182 ps.67,68 It has been suggested that these defects are H-decorated Zn vacancies,67 although this assignment is tentative. In ZnO ceramics, the concentration of vacancy defects decreases steadily with increasing sintering temperature.69
D. Damage

FIG. 2. PL spectrum of ZnO, showing exciton lines 3.33.4 eV , donoracceptor pair transitions DAxP , and their phonon replicas ELO and 2 ELO . The broad green luminescence is centered at 2.45 eV. Reprinted with permission from B. K. Meyer, H. Alves, D. M. Hoffman, W. Kriegseis, D. Forster, F. Bertram, J. Christen, A. Hoffman, M. Strassburg, M. Dworzak, U. Haboeck, and A. V. Rodina, Phys. Status Solidi B, 241, 231 2009 . Copyright 2009, Wiley-VCH Verlag GmbH & Co. KgaA.

Along with electron irradiation, defects produced by ion implantation have been investigated extensively.70 For ZnO implanted with N ions at a uence of 1014 cm2, deep-level transient spectroscopy showed an increase in electron trap states at 0.31 and 0.95 eV below the conduction-band minimum.71 Implantation with 2 MeV O ions produces Zn vacancies for an ion uence of 1015 cm2. At higher uences, vacancy clusters are created.72 Implantation with 220 keV N ions in the 1015 cm2 uence range produces vacancy clusters containing two to four Zn vacancies.73 Even larger vacancy clusters, containing as many as eight Zn vacancies, were reported to form upon implantation with 1015 cm2 Al ions at energies up to 380 keV. After implantation, annealing from 200 to 600 C causes further agglomeration of vacancy clusters to voids.74 In ZnO implanted with protons, the Zn vacancies agglomerated into voids lled with H2.75 At doses of 4 1016 cm2, implantation with Au ions does not make ZnO amorphous. However, similar doses of Si ions do cause ZnO to become amorphous, presumably due to a chemical effect of the Si impurities.76 Irradiation of ZnO with a 193 nm excimer laser causes the formation of defects in a near-surface region 200 nm . The irradiation promotes the diffusion of Zn from the ZnO to the surface, where Zn nanoparticles 1020 nm in diameter are formed.77 Open-volume defects, extending 30 m into the bulk, can also be created by simple mechanical polishing.38
IV. GROUP-III DONORS

As grown, whether by design or by accident, ZnO is usually n-type. For bulk samples with n 1017 cm3, the

room-temperature electron mobility is typically 150 cm2 / V s.22 Electrons from shallow donors, measured by EPR, have a g-factor of g 1.96.7880 From a hydrogenic EM donor model, the calculated electron binding energy is 50 meV.81 Variable-temperature Hall-effect measurements show values consistent with that estimate; for example, Look et al.82 measured a 60 meV donor. Doping levels of n 1020 cm3 are used for transparent conductor applications. Sputtered, polycrystalline thin lms have mobilities as high as 60 cm2 / V s and resistivities as cm.83 The group-III dopants Al and Ga low as 2 104 are preferred donors for transparent ZnO conductors.6 Examples of intentional doping include ZnO:Al grown by photoassisted metalorganic chemical vapor deposition MOCVD ,84 ZnO:Ga grown by chemical vapor deposition CVD ,85 and ZnO:Ga grown on GaN substrates by plasmaassisted molecular beam epitaxy MBE .86 Heavily n-type ZnO:Al shows an increase in the band gap due to the lling of the conduction band.87 As reviewed by Meyer et al.,81 PL spectra provide information about donors in ZnO Fig. 2 . Excitons bound to donors have PL energies slightly below those of free excitons. At liquid-helium temperatures, PL peaks labeled I4 3.3628 eV , I6 3.3608 eV , I8 3.3598 eV , and I9 3.3567 eV arise from excitons bound to H, Al, Ga, and In, respectively Fig. 3 . A donor-acceptor pair transition was observed at 3.217 eV, with phonon replicas at 3.145, 3.073, and 3.001 eV.29 The spacing of the replicas is 72 meV 580 cm1 , which corresponds to the LO phonon frequency.28 As discussed in Sec. III, native defects such as O vacancies and Zn interstitials are unlikely to account for n-type conductivity in ZnO. Instead, impurities play the largest role. Secondary ion mass spectrometry SIMS measurements revealed signicant concentrations of Al in samples of bulk single-crystal ZnO obtained from Cermet Inc., Ga and B in samples from Eagle-Picher, and Si in both.88 H and the group-III elements account for essentially all of the free carriers in bulk, n-type ZnO grown by Eagle-Picher and Cermet.89,88

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J. Appl. Phys. 106, 071101 2009

N2 and O2.112 The oxidation of sputtered Zn3N2 thin lms was reported to yield p-type ZnO,113 as was N implantation of sputtered ZnO thin lms.114 Other studies, however, reported high N concentrations 1019 cm3 but n-type conductivity.115 As discussed in Sec. VI D, the evidence for p-type conductivity in ZnO is not conclusive.
B. Nitrogen molecules

FIG. 3. PL spectrum of donor-bound excitons in ZnO at 4.2 K. Reprinted with permission from B. K. Meyer, H. Alves, D. M. Hoffman, W. Kriegseis, D. Forster, F. Bertram, J. Christen, A. Hoffman, M. Strassburg, M. Dworzak, U. Haboeck, and A. V. Rodina, Phys. Status Solidi B, 241, 231 2009 . Copyright 2009, Wiley-VCH Verlag GmbH & Co. KgaA.

V. GROUP-IV IMPURITIES

Very little is known about group-IV impurities in ZnO. Although C might be expected to be an impurity in ZnO grown by MOCVD or chemical vapor transport CVT with graphite, there is not much evidence that it incorporates in the crystal. Nickel and Fleischer90 did observe a series of Raman lines in the CH bond-stretching region. Si impurities were observed in bulk ZnO from SIMS, but their chemical form is unknown.88 Pb donors were observed using ODMR, with Pb3+ ions having a g-factor of g 2.013.91,92
VI. GROUP-V ACCEPTORS A. Substitutional nitrogen

X-ray photoelectron spectroscopy on sputtered ZnO:N lms showed that N exists in two distinct chemical environments, attributed to N acceptors and N2 molecules on the O site.116,117 The experimental observations are in agreement with rst-principles calculations that predict N2 molecules in O vacancies to be compensating double donors.100,101 It was speculated that such N2 molecules may be removed from ZnO by thermal annealing.118 EPR experiments show evidence for a N2 acceptor.98 N2 impurities in ZnO nanowires give rise to a Raman line at 2306 cm1 at room temperature.119 In the future, Raman spectroscopy performed on bulk ZnO may provide needed microscopic information about N2 defects.
C. Phosphorus, arsenic, and antimony

According to rst-principles calculations, N substitutes for an O and is an acceptor with a hole binding energy of 400 meV.93 PL experiments on n-type ZnO:N showed a more promising hole binding energy of 200 meV,81,94,95 a value that is comparable to that of Mg acceptors in GaN.96 Theory suggests that the binding energy might be lowered by codoping with isovalent Mg or Be.97 Magnetic resonance studies of ZnO identied N acceptors,36,98 and x-ray absorption spectroscopy veried that N occupies the O substitutional site.99 In the absence of laser excitation, the acceptors are negatively ionized due to compensating donors such as group-III impurities.98 N acceptors may also be compensated via the formation of defects such as O vacancies, complexes with Zn interstitials, or N2 molecules.93,100,101 Theory102 and experiment103 have investigated the possibility of using NO or NO2 gas to introduce sufcient concentrations of N acceptors to obtain p-type conductivity. The key challenge is to introduce acceptors without being overwhelmed by compensating donors. Reports of p-type ZnO using NH3 in CVD Ref. 104 and an atomic N source in MBE Ref. 105 were followed by a jkulhlaup of papers that described various means to achieve p-type conductivity. Doping methods included MOCVD with NO,106 N2O,107 diallylamine,108 and NH3 Ref. 109 as N doping sources; metalorganic MBE;110 and plasma-assisted MBE using a NO source111 or a mixture of

First-principles calculations predict that P, As, and Sb are deep acceptors, owing to their large ionic radii as compared to O.93,120 It is therefore surprising that some researchers have reported p-type conductivity using these dopants. ZnO:P lms grown by sputtering121 and MBE Ref. 122 were reported to be p-type. Other groups found that ZnO:P lms grown by pulsed lased deposition PLD were semiinsulating, consistent with P acting as a deep acceptor.123 Device structures using ZnO:P yielded indeterminate Hall voltages.124 Experiments that measured the radioactive decay of implanted arsenic-73 determined that the majority of As atoms reside on the Zn site,125 making it ineffective as an acceptor. Nonetheless, there are reports of p-type ZnO:As Refs. 126 and 127 as well as ZnO:Sb.128
D. The p-type controversy

Reports of p-type ZnO are controversial. Hall-effect measurements on inhomogeneous samples can yield the wrong carrier type.129 As pointed out by Barnes et al.,130 many studies that claimed to have measured hole conduction were based on a small number of samples, and the results were not subsequently reproduced by other groups. Interface and near-surface states131 may be responsible for the apparent p-type conductivity measured by some experiments. Many of the allegedly p-type thin lms were grown on mismatched substrates such as sapphire, silicon, or glass,132 which undoubtedly led to high interface defect densities. The properties of these acceptor-doped samples are often unstable. ZnO:N lms that exhibited p-type conductivity went n-type after a few days, accompanied by a relaxation of the lattice constant to its undoped value.130 ZnO:N sputtered on glass shows p-type conductivity that reverts to n-type after repeated measurements in the dark, only to become p-type again after exposure to sunlight.118

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J. Appl. Phys. 106, 071101 2009

Conduction band
Absorption (arb. units) 5740

Cu2+

T2 E

5760

5780

5800

5820
-1

5840

5860

Wave numbers (cm )

(Cu+,h)

Valence band
FIG. 4. Color online Schematic of Cu energy levels in ZnO see Ref. 148 . Intra-d transitions of Cu2+ result in IR absorption peaks at 10 K, shown in the top spectrum. The transition of a hole from the Cu+ , h state to the T2 state produces a no-phonon emission line at 2.86 eV, shown in the expanded spectrum shifted to the left . Phonon replicas result in the structured green luminescence band centered around 510 nm. Reprinted with permission from R. Dingle, Phys. Rev. Lett. 23, 579 1969 . Copyright 1969, American Physical Society.

Optical emission in ZnO LEDs Ref. 133 may indicate successful p-type doping. However, p-n junctions are not required for a light-emitting deviceit is well known that Schottky diodes can emit light and rectify current.134 A PL band at 3.31 eV was originally attributed a transition from free electrons to group-V acceptors with a hole binding energy of 130 meV.105 Subsequent spatially resolved luminescence experiments showed that the emission is localized at stacking faults, not the bulk of the ZnO.135 Given the doubts raised so far, reports of p-type ZnO should generally be viewed with skepticism.
VII. GROUP-I ACCEPTORS A. Lithium and sodium

hole binding energy near 0.3 eV, in qualitative agreement with rst-principles calculations that show Li and Na should be shallow acceptors.93 However, the acceptors LiZn and NaZn are compensated by the interstitial donors Lii and Nai, respectively.141143 Such compensating defects would need to be eliminated in order to achieve p-type conductivity.
B. Copper

EPR measurements showed that ZnO:Li contains Li acceptors with a hole binding energy of 0.8 eV.136 The Li atoms reside on the substitutional Zn site and cause signicant relaxation of the neighboring O atoms. At low temperatures, exposure to light excites a hole, which becomes trapped on one of the O atoms.137 The hole prefers to sit on the O atom along the c axis axial site , where it has an energy of 15 meV lower than the nonaxial sites. Li Ref. 138 and Na Ref. 139 give rise to PL emission near 570 nm, attributed to the transition from a shallow donor to the deep acceptor state. Recent PL experiments by Meyer et al.140 suggest that Na or Li diffused into bulk ZnO introduce acceptors with a

Cu substitutes for Zn and introduces electronic levels into the band gap.144 The Cu2+ ion is in the 3d9 state. Since there is one unlled d orbital, the hole can undergo intra-d transitions. In a cubic crystal, the lowest-energy transition is from the T2 to the E state. Since ZnO is wurtzite, however, the defect has C3v symmetry and the states split into several components.145 This splitting gives rise to sharp IR absorption peaks at 5782 and 5820 cm1 Fig. 4 . Cu is a common trace impurity in bulk ZnO crystals and should be a candidate for green luminescence in almost any ZnO sample.146 Green emission due to Cu2+ impurities was rst observed by Dingle.147 Under illumination, an electron from a neighboring O atom can be transferred to Cu2+, resulting in Cu+ plus a hole. This state, denoted Cu+ , h , is a transient shallow acceptor.148 The green emission was attributed to the transition from Cu+ , h to the Cu2+ T2 state,149 where the hole is recaptured by the Cu ion core, leading to the emission of a photon. The zero-phonon line for this transition is 2.86 eV 434 nm at low temperatures Fig. 4 . Phonon replicas occur at lower energies, resulting in a struc-

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071101-7

M. D. McCluskey and S. J. Jokela

J. Appl. Phys. 106, 071101 2009

tured band centered at 2.4 eV 510 nm . While green luminescence is enhanced by Cu2+,146,150 the band-edge PL in heavily doped samples is suppressed.151 In semiconductor terminology, the Cu acceptor level is denoted 0/ . When the Fermi level is above the 0/ level, the equilibrium charge state is Cu1+, i.e., a negatively charged acceptor. Electrical measurements on ZnO:Cu indicate that the 0/ level lies 0.2 eV below the conductionband minimum.144,152 The 0/ level is the one labeled T2 in Fig. 4. Garces et al.146 reported that annealing ZnO:Cu in air transformed Cu1+ into Cu2+. The authors proposed that annealing lowered the Fermi level, pushing it below the 0/ level. Yan et al.153 calculated the 0/ levels for Cu, Ag, and Au at 0.7, 0.4, and 0.5 eV above the valence-band maximum, respectively. However, one must take into account the fact that LDA calculations underestimate the band gap. Wardle et al.57 calculated the Cu 0/ level at 1.0 eV above the valence-band maximum, which was only 0.3 eV below the calculated conduction-band minimum.

Zn H O

FIG. 5. Color online Models for interstitial H donors in ZnO. Left: antibonding AB conguration. Right: bond-centered BC conguration. The dashed lines indicate broken ZnO bonds. See Ref. 161.

2. Hydrogen donors

VIII. HYDROGEN A. Isolated hydrogen 1. Diffusion

Studies performed in the 1950s by Mollwo154 and Thomas and Lander155 concerned H diffusion into ZnO crystals. Both studies found that annealing ZnO crystals in a H2 ambient increased their electrical conductivity. However, their conclusions were somewhat different from each other. Mollwo154 considered that the reduction in surface ZnO by H left elemental Zn to diffuse into the crystal and act as interstitial donors. Thomas and Lander155 concluded that H diffuses into the ZnO crystal lattice and is directly responsible for producing donors. From the electrical conductivity measurements, both research groups determined the diffusion rate of H into ZnO crystals at various temperatures. Mollwo154 obtained a diffusion activation energy of 1.12 eV while Thomas and Lander155 determined the value to be 0.91 eV. However, recent experiments that exposed ZnO to H plasmas yielded an activation energy for diffusion of only 0.17 eV.156 This low activation energy seemed to support calculations that obtained a low migration barrier 0.40.5 eV for interstitial H.157,158 The discrepancy between the experimental activation energies was resolved by Nickel,159 who measured H and D depth proles as a function of passivation temperature for polycrystalline and single-crystal ZnO. The low activation energies measured in H plasma experiments were ascribed to large effects from the H chemical potential. The migration barrier was found to be 1.0 eV, in agreement with the earlier work. It was proposed that the migration was limited by H traps. Experiments on D-implanted ZnO conrmed that diffusion is described by a trap-limited model, with an activation energy of 0.85 0.19 eV.160

Theoretical work by Van de Walle161 showed that H is a shallow donor in ZnO, stimulating new research into the electrical and structural properties of H donors. The low energy of the conduction-band minimum relative to the vacuum results in the H + / level being in the band.162,163 Experimental results on muonium164,165 implanted into ZnO and electron-nuclear resonance measurements89 on lightly doped, n-type ZnO provided evidence that, as predicted, H is a shallow donor. In order to determine the microscopic structure of H donors, IR spectroscopy was used to measure OH vibrational modes arising from these complexes.166168 Thin lms grown by MOCVD experience a factor-of-3 increase in free-electron concentration after exposure to a H plasma.169 ZnO ceramics implanted with H also show an increase in conductivity.170 Films grown by PLD in a H2 or D2 ambient have carrier concentrations three orders of magnitude greater than lms grown in an O2 ambient.171 Growing in H2 or D2 appeared to form a shallow donor a few meV that could not be produced via postgrowth annealing in H2 gas.172

3. Interstitial hydrogen

In Fig. 5, two proposed models161 for interstitial H donors are shown. In one model, H is in the antibonding AB orientation, attached to a host O atom and pointing away from the ZnO bond. Another model is the bond-centered BC conguration, where H sits between the hosts Zn and O. By measuring the pressure and polarization dependence of the OH vibrational mode, and comparing it to the predictions of rst-principles calculations,173,174 Jokela and McCluskey175 attributed an IR peak at 3326 cm1 10 K to H donors in the AB conguration Table III . There were problems with this assignment, however. and ab initio Muon-implantation experiments176 168 calculations indicated that H donors should reside in the BC conguration, not the AB conguration. Experiments by Lavrov et al.168 on CVT-grown ZnO samples revealed a peak at 3611 cm1 10 K , attributed to H in the BC conguration. Seager and Myers177 observed a similar peak, although shifted and broadened, at room temperatures. The work by Shi et al.178 showed that samples annealed in H generally show the 3611 and 3326 cm1 peaks, but in different ratios depending on the type of sample. For example, Eagle-Picher samples show a strong 3611 cm1 peak whereas Cermet samples show a strong 3326 cm1 peak Fig. 6 . This sample-dependent variation suggests that one

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071101-8

M. D. McCluskey and S. J. Jokela

J. Appl. Phys. 106, 071101 2009

TABLE III. Local vibrational modes of H complexes in ZnO, determined by IR spectroscopy at liquid-helium temperatures. Frequencies correspond to OH or NH bond-stretching vibrations. Frequency cm1 2783 3151 3192 3312 3349 3326 3347 3374 3577 3611

Assignment NiH NH CuH Zn vacancy2H H donor AB CaH donor? Cu2H LiH H donor BC

Ref. 208 191 196 168 166, 175, and 178 88 and 179 199 200 and 202 168 and 178

weeks.175 They form a species of hidden hydrogen that remains in the crystal. Shi et al.180 proposed that the H donors combine to form H2 molecules, which are electrically neutral and nearly invisible to IR. When the crystal is reheated, the H2 molecules dissociate and form H donors again. Experimental verication for H2 molecules in ZnO was achieved using low-temperature Raman spectroscopy.181 Theoretical work by Karazhanov and Ulyashin182 suggests that two interstitial H atoms can form a H2 defect, where one H attaches to an O while the other attaches to a Zn. Unlike H2 molecules, however, the H2 defect should have clear IR signatures. To our knowledge, H2 has not been observed experimentally in ZnO.
5. Substitutional hydrogen

of the peaks actually arises from H paired with another impurity.158 Subsequent SIMS analysis showed that Cermet samples contained Ca impurities at concentrations of 4 1016 cm3, whereas Eagle-Picher samples contained 1015 cm3.88 This difference led us to propose that the 3326 cm1 line is due to CaH complexes. First-principles calculations support this idea.179 They show that the electropositive Ca atom donates extra electric charge to the neighboring O atoms, one of which traps a H atom. The H atom resides in an AB conguration and acts as a shallow donor, in agreement with experiment. As of this writing, however, there is no direct conrmation of the CaH model.
4. Hidden hydrogen

First-principles calculations by Janotti and Van de Walle45 showed that H can occupy an O substitutional site and act as a shallow donor. One can think of substitutional H as an O vacancy with a single H atom near the center. The predicted vibrational frequency is 800 cm1. The mode has not been seen, perhaps because free-carrier and two-photon absorptions are too strong in that region of the IR spectrum. Unlike interstitial H, substitutional H is stable, with a calculated migration energy of 1.7 eV.157 This makes it a strong candidate for H-related donors in as-grown ZnO.89 The H-related I4 3.363 eV line183,184 may be due to substitutional H. The calculated electron density suggests that H bonds equally with its four Zn neighbors.45 However, Takenaka and Singh62 claimed that substitutional H is ionic H and does not form ZnH bonds.
B. Hydrogen complexes 1. Passivation of defects

The IR peaks at 3326 and 3611 cm1 are unstable, decaying at room temperature with a time constant of several

The efciency of band-edge emission was found to increase after exposure to a H plasma,185 presumably due to passivation of deep-level states.60,186 Implantation of H, however, causes damage that reduces the emission intensity.187 Raman spectra also show changes after hydrogenation. A Raman line at 582 cm1, which is correlated with defects in ZnO powders and thin lms,188 diminishes after exposure to H2 at 400 C.189
2. Zinc vacancyhydrogen

FIG. 6. IR absorption spectra 4.2 K of OH complexes in three different ZnO samples. The Eagle-Picher and Cermet samples were c-cut crystals tilted at 45 to the IR beam inset . The Erlangen sample was a-cut and was perpendicular to the IR beam. All samples contained the 3326 and 3611 cm1 peaks, but the intensities of the peaks varied from sample to sample. Reprinted with permission from G. Alvin Shi, M. Stavola, S. J. Pearton, M. Thieme, E. V. Lavrov, and J. Weber, Phys. Rev. B, 72, 195211 2008 . Copyright 2005, American Physical Society.

As noted in Sec. III C, the green luminescence intensity in ZnO decreases after exposure to a H plasma. This observation suggests that 1 Zn vacancies are responsible for green luminescence and 2 H passivates Zn vacancies.60 Evidence for passivation was provided by Lavrov et al.,168 who observed OH modes at 3312 and 3350 cm1 10 K after exposure of CVT-grown ZnO to H plasma. The frequencies of these modes agreed with rst-principles calculations for a Zn vacancy with two H atoms. This fully passivated vacancy has no electronic levels in the gap. EPR experiments on electron-irradiated samples provided evidence for a Zn vacancy with a single H atom.49 It has been suggested that the 3326 cm1 line Sec. VIII A 3 might actually be due to such a complex.190

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071101-9

M. D. McCluskey and S. J. Jokela

J. Appl. Phys. 106, 071101 2009

14

N-H

15

N-H

only at temperatures above 1100 C.201 The OD line at 2645 cm1 showed isotopic splitting due to 6Li and 7Li. That result, combined with rst-principles calculations, provided evidence that H is in a bond-centered location, between Li and O, parallel to the c axis.202 The temperature dependence of the OH and OD modes was explained by coupling to host phonons.203

Absorbance

IX. TRANSITION METALS


3130 3140 3150 3160 3170 -1 Wave numbers (cm ) 3180

A. Spectroscopy

FIG. 7. Color online IR spectrum 10 K of ZnO grown in a mixture of 14 NH3 90% and 15NH3 10% ; see Ref. 191. Absorption peaks from NH bond-stretching vibrational modes are indicated by the arrows. The ball-andstick model is from rst-principles calculations Ref. 193 .

3. Nitrogenhydrogen

A possible route toward p-type conductivity involves the incorporation of neutral NH complexes, followed by annealing to drive out the H atoms. Jokela and McCluskey191 reported NH complexes in ZnO grown by CVT in a NH3 ambient. The NH bond-stretching mode gives rise to an IR absorption peak at 3151 cm1 Fig. 7 . Isotopic substitutions of D for H and 15N for 14N resulted in the appropriate frequency shifts. The NH complexes were stable up to 700 C. The NH mode was also observed by Raman spectroscopy in ZnO:N lms grown by MOCVD.192 Firstprinciples calculations predicted that H attaches to a N atom, nearly perpendicular to the c axis.193 The vibrational modes predicted by the calculations were in good agreement with the experimental observations. Calculations show that the NH bond is more stable than the OH bond for interstitial H, also in agreement with experiment.194 Other researchers reported that NH modes resulted in vibrations at 2400,195 3000,193 and 3100 cm1.90 Since none of those studies used isotopic substitution to verify the assignments, we believe that the reported modes came from CH or OH bonds. It is possible, however, that there may be more than one possible complex involving N and H.
4. Copperhydrogen

Transition-metal dopants occupy the substitutional Zn site and are normally in the 2+ or 3+ oxidation state.57,204 ZnO:Co exhibits low-temperature absorption205 and luminescence206 peaks at 3611 and 3616 cm1, which were attributed to Co2+ 3d7 transitions between the A2 and T2 levels. ZnO:Ni showed similar peaks at 6091 and 6096 cm1, which Schulz and Thiede206 attributed to the same transitions in Ni3+ 3d7 . The Ni2+ 3d8 oxidation state gives rise to intra-d absorption peaks near 4200 cm1.207,208 Luminescence features near 6880 cm1 were attributed to T2 A2 transitions of V3+ 3d2 .209 Transition metals also affect the visible luminescence properties. In ZnO:Ni, Shulz and Thiede206 claimed that intra-d transitions caused the red PL emission near 661 nm. Electron irradiation transformed Fe impurities from the 2+ state to the 3+ state,49 resulting in an EPR-active Fe3+ center with spin S = 5 / 2.210 The structured luminescence around 690 nm was attributed to the T1 A1 transitions of Fe3+ 3d5 .211 Mn2+ dopants suppress green luminescence212 and electrical conductivity213 in ZnO, perhaps because they ll Zn vacancies or other defects.

B. Ferromagnetism

The CuH complex gives rise to an OH bond-stretching mode at 3192 cm1 Ref. 196 and is stable up to 650 C.168 First-principles calculations show that H attaches to an O atom and resides in a bond-centered location, nearly perpendicular to the c axis.57 Stress-induced dichroism experiments performed at various temperatures determined a reorientation activation barrier for H of 0.5 eV,197,190 in reasonable agreement with theory.198 The CuH complex can bind an additional H atom, resulting in Cu2H. This complex consists of a substitutional Cu atom and two adjacent bond-centered H atoms, giving rise to OH modes at 3347 and 3374 cm1.199
5. Lithiumhydrogen

H-related defects in hydrothermal ZnO exhibit an OH bond-stretching vibration at 3577 cm1 12 K due to a LiH complex.200 The complex is highly stable,143 annealing out

The possibility of room-temperature dilute magnetic semiconductors stimulated a great deal of research into ferromagnetic doping of ZnO. Reviews of dilute magnetic semiconductor oxides include Refs. 214219. There are numerous reports of ferromagnetism, cited in these reviews. For example, ZnO:Co lms were reported to exhibit ferromagnetism with a Curie temperature higher than 300 K.220 After the initial reports, subsequent studies cast doubt on the idea that room-temperature ferromagnetism arises from the bulk of the ZnO material. Polycrystalline ZnO doped with Co and Mn showed no ferromagnetism.221223 Highquality thin lms of n-type ZnO:Co deposited by PLD were also not ferromagnetic.224 ZnO:Co thin lms only showed room-temperature ferromagnetism for high Co doping levels, and those samples had Co clusters.225 Correct identication of phases in the material is essential to determine whether the ferromagnetism actually comes from the ZnO.226 In ZnO:Co thin lms, x-ray photoelectron spectroscopy clearly showed that CoZn secondary phases were responsible for the ferromagnetism of the sample.227 Grain boundaries and intrinsic defects such as oxygen vacancies may also enhance ferromagnetism.228

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071101-10

M. D. McCluskey and S. J. Jokela

J. Appl. Phys. 106, 071101 2009

X. EXTENDED DEFECTS A. Surface conduction

Bulk ZnO samples often contain a surface conduction layer, with a free-electron concentration of 1 3 1012 cm2.229,230 Since the conduction band of ZnO has a low energy relative to vacuum,162 the Fermi level at the surface is probably pinned above the conduction-band minimum. This leads to a surface accumulation of electrons, similar to the situation in InN.231,232 Exposure to air229 or an O2 plasma230 reduces the conductivity of the layer, presumably due to adsorption of O2 and/or changes in the surface reconstruction. The surface conduction electrons do not freeze out and they contribute to the overall conductivity of an n-type sample. Hall-effect measurements can be interpreted with a two-layer model, where one layer is the surface conducting channel and the second layer is the underlying bulk.233
B. Dislocations

comprised of conductive grains surrounded by additive cations e.g., Bi or Pr that segregate to the grain boundary. Grain sizes are typically around 10 m and the typical grain resistivity is 1 cm. A depletion region is believed to form at each grain boundary, where the depletion is wholly within the ZnO grain,246 resulting in a breakdown voltage of 3 V/grain. First-principles calculations showed that Bi may substitute for Zn atoms at the grain boundary, resulting in a localized acceptor state.247 Such a state could create a p-n junction between the grain boundary and the n-type ZnO grain.
XI. CONCLUSIONS

Heteroepitaxial layers of ZnO typically contain threading dislocation densities of 109 cm2. Threading dislocations generally run along the c axis, although ZnO grown under Zn-rich conditions showed some dislocations 2030 from the c axis.234 Transmission electron holography indicates that the dislocations are negatively charged,235 perhaps due to the accumulation of Zn vacancies near the dislocation core. The activation energy for dislocation motion was estimated to be 0.71.2 eV in the range 650 850 C.236 Dislocations created by plastic deformation actually seem to increase the excitonic emission intensity.237 ZnO grown on r-cut sapphire is single crystal, but the interface contains a high density of mist dislocations.238
C. Stacking faults

While the intrinsic properties of ZnO provide signicant advantages for device applications, the overarching goal of reliable p-type conductivity has not been met. The evidence suggests that ferromagnetic ZnO, which probably requires high hole concentrations, has not been achieved either. Despite these roadblocks, researchers have made great strides in understanding the fundamental properties of defects and dopants in this material. N-type conductivity, historically blamed on native defects, is likely due to impurities such as group-III elements and H. Experimental and theoretical investigations have provided insight into the microscopic structure of Li, Cu, and N acceptors, and their complexes with H. We hope, of course, that these fundamental insights will result in transformative technological breakthroughs. While this review focused on bulk ZnO, the topic of defects in ZnO nanocrystals is an emerging eld that will impact many areas of science and technology. The relative ease and reproducibility of nanoparticle synthesis makes ZnO a natural system for such investigations. Applications involving nanoscale ZnO will require a fundamental understanding of defect phenomena across different length scales.
ACKNOWLEDGMENTS

Samples grown by MBE on r-cut sapphire showed a basal-plane stacking fault density of 105 cm1 and partial dislocation density in the mid-1010 cm2 range.239 Calculations showed that basal-plane stacking faults have low formation energies but do not introduce electronic states into the gap.240 However, spatially resolved CL measurements showed that basal-plane stacking faults contain localized acceptors with a hole binding energy of 130 meV.135 The recombination of free electrons with acceptor-bound holes leads to an emission at 3.31 eV. An emission at 3.333 eV was attributed to excitons bound to structural defects.81
D. Grain boundaries

We gratefully acknowledge the authors who gave permission to reprint their gures. We beneted from discussions with L. E. Halliburton, E. E. Haller, A. Janotti, S. Limpijumnong, N. H. Nickel, W. M. Hlaing Oo, M. Stavola, M. C. Tarun, S. Teklemichael, C. G. Van de Walle, S. B. Zhang, and many others. The research at WSU was supported primarily by the National Science Foundation Grant No. DMR-0704163, LaVerne Hess and Charles Ying and the Department of Energy Grant No. DE-FG02-07ER46386, Rek Kortan .
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Thin lms sputtered on c-cut sapphire show columnar growth, not unlike GaN, with low-energy grain boundaries.241 At the grain boundaries, some atoms have threefold or vefold coordination.242 In ZnO grown on silica, several types of 0001 -tilt grain boundaries were observed.243 Defects at grain boundaries play an important role in ZnO varistors,244 and ceramic semiconductor devices with highly nonlinear current-voltage characteristics.245 Varistors are insulating up to a well-dened breakdown eld. They are

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M. D. McCluskey and S. J. Jokela

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