Materials Science and Engineering B80 (2001) 383 387 www.elsevier.

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Recent advances in ZnO materials and devices

D.C. Look *
Semiconductor Research Center, Wright State Uni6ersity, Dayton, OH 45435, USA

Abstract Wurtzitic ZnO is a wide-bandgap (3.437 eV at 2 K) semiconductor which has many applications, such as piezoelectric transducers, varistors, phosphors, and transparent conducting lms. Most of these applications require only polycrystalline material; however, recent successes in producing large-area single crystals have opened up the possibility of producing blue and UV light emitters, and high-temperature, high-power transistors. The main advantages of ZnO as a light emitter are its large exciton binding energy (60 meV), and the existence of well-developed bulk and epitaxial growth processes; for electronic applications, its attractiveness lies in having high breakdown strength and high saturation velocity. Optical UV lasing, at both low and high temperatures, has already been demonstrated, although efcient electrical lasing must await the further development of good, p-type material. ZnO is also much more resistant to radiation damage than are other common semiconductor materials, such as Si, GaAs, CdS, and even GaN; thus, it should be useful for space applications. 2001 Elsevier Science B.V. All rights reserved.
Keywords: ZnO; UV lasing; Epitaxial growth

1. Introduction Wide-bandgap semiconductors, such as 6H-SiC (3.0 eV, at 2 K) and GaN (3.5 eV), have come to the forefront in the past decade because of an increasing need for short-wavelength photonic devices and highpower, high-frequency electronic devices, and because of breakthroughs in high-quality growths of these materials. On the other hand, another wide-bandgap semiconductor, ZnO (3.4 eV), has not received the same attention, probably because this material has been perceived as being useful only in its polycrystalline form. Indeed, polycrystalline ZnO has found numerous applications in such diverse areas as facial powders, piezoelectric transducers, varistors, phosphors, and transparent conducting lms. Recently, however, largearea bulk growth has been achieved [1], and, furthermore, several epitaxial methods have produced excellent material [2 10]. Also, quantum wells have been successfully grown, by alloying with Mg or Cd [11]. Thus, ZnO is now being proposed for the same applications as those listed above for GaN and SiC. In fact, ZnO has several fundamental advantages over its
* Tel.: + 1-937-2551725; fax: + 1-937-2553374. E -mail address: david.look@wpafb.af.mil (D.C. Look).

chief competitor, GaN: (1) its free exciton is bound with 60 meV, much higher than that of GaN (21 25 meV); (2) it has a native substrate; (3) wet chemical processing is possible; and (4) it is more resistant to radiation damage (although both are much better than Si or GaAs). The new interest in ZnO has recently culminated in the First International Workshop on ZnO, held in Dayton, OH, 78 October, 1999. In this paper, we will discuss the progress in the growth and applications of ZnO, and the challenges remaining.

2. Growth and structural properties Large-area single-crystal growth, by a seeded vaporphase (SVP) method, has been successfully developed in the past few years [1], and commercial 2-in. wafers are now available [12]. (In contrast, no bulk wafers of GaN are available.) These SVP ZnO wafers have dislocation densities in the 104 105 cm 2 range, and X-ray rocking-curve (004) linewidths as low as 36 arcsec. Impurity concentrations, as measured by glow-discharge mass spectroscopy, are very low: only N at 8 1016 and Si at 1.5 1016 cm 3 are detected at all, and everything else is at a level below 1 1016 cm 3. Also, excellent ZnO crystals can now be grown by the hydrothermal [13]

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and melt methods [14], which, in the past, have not been nearly as competitive. Finally, good epitaxial layers have been grown by all of the common techniques: molecular beam epitaxy (MBE) [2,3]; pulsed laser deposition (PLD) [4,5], or laser MBE [6]; metal-organic chemical vapor deposition (MOCVD) [7,8]; and hydride or chloride vapor phase deposition (HVPE) [9,10]. Although homoepitaxy is now possible, most of the growth up to now has been heteroepitaxy, usually on sapphire (Al2O3). In comparison with GaN/Al2O3, ZnO/Al2O3 has roughly equivalent X-ray linewidths and photoluminescence (PL) linewidths, and even lower dislocation densities [5]. Also, ZnO has been grown on many other substrates, such as CaF2, Si, GaAs, MgAl2O4, and ScAlMgO4, as well as on GaN itself [15]. The latter system, n-ZnO/p-GaN, has produced blue light emitting diodes.

3. Electrical properties In general, the electrical properties of bulk ZnO are excellent, as might have been expected from the low background impurity concentrations, mentioned above. However, good electrical properties also demand low point-defect and dislocation concentrations, and bulk ZnO also excels in these aspects. In Figs. 1 and 2, we show carrier concentration and mobility data, respectively, for three different bulk ZnO samples, which are representative of all the samples that we have looked at, and also those in the literature. Sample A was grown by the SVP method [1], and the data in Fig. 1 were tted by temperature-dependent Hall (TDH) measurements to give: ND1 = 9 1015 cm 3, ED1 = 31 meV; ND2 = 1 1017 cm 3, ED2 = 61 meV; and NA = 2 1015 cm 3. (Here, ND and NA denote donor and acceptor concentrations, respectively, and ED denotes the donor energy.) Sample B was also grown by the SVP method, but was annealed at 950C for 4 h, in an atmosphere of He bubbled through H2O held at 50C. The anneal seemed to get rid of most of the shallowest center, or at least it caused the Fermi level to drop below the energy of this center. For sample B, the TDH results were: ND2 = 4 1016 cm 3, ED2 = 63 meV; and NA = 1 1016 cm 3. Finally, sample C was grown by the hydrothermal method [13], and gave: ND3 = 7 1015 cm 3, ED3 = 340 meV; and NA = 1 1015 cm 3. We rst note that all of the samples have relatively low donor and acceptor concentrations, certainly in comparison with those of GaN, and thus they also must have low impurity, point defect, and dislocation concentrations, since all of these species are known to produce electrically-active centers, at least in most semiconductors. Secondly, there appear to be three dominant donors in ZnO, with approximate energies 30, 60, and 340 meV. The 30-meV level has been reported often in the literature [16], and is usually assigned to either the oxygen vacancy, VO [17], or the zinc interstitial, ZnI [18]. In fact, from electron-irradiation experiments, we have recently shown that ZnI is the best candidate [18]. However, even more recently, rst-principles theoretical calculations have suggested that V (sub) O is a deep donar, not a shallow donar, and that impurity H is a better candidate for the dominant shallow donar [19]. Thus, this situation is unresolved. The 60-meV donor is what is expected from effectivemass theory; i.e., Eem = 13.6m*/m 2 = 65 meV. Thus, simple substitutional donors, such as AlZn or ClO, might be expected to have energies near 65 meV. The 340-meV donor, on the other hand, could be an antisite such as OZn, or some other defect or impurity. Whatever the identities of the various donors, it is clear that the compensation ratio is often quite low; i.e., for sample A, the ratio NA/ND is only 0.02, very low for semiconductor materials.

Fig. 1. Temperature-dependent carrier concentration data for three samples of different resistivities. The solid line through sample A is a theoretical t, while the lines through B and C are simply a joining of experimental points. However, all of the listed donor energies result from theoretical ts. Impurity conduction is clearly indicated at low temperatures in sample B.

Fig. 2. Mobility data for samples A, B, and C. The solid line through sample A is a theoretical t.

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4. Optical properties Low-temperature (LT) PL measurements reveal a group of donor-bound excitons (DBEs) around 3.36 eV, as shown in Fig. 3 [21]. The free exciton (not shown) appears at about 3.372 eV, and since the LT bandgap is about 3.437 eV, the free-exciton binding energy is approx. 65 meV, as stated earlier. The linewidths of these DBEs are always less than 1 meV, and sometimes are about 0.1 meV, much narrower than those seen in most GaN samples. Of course, for heteroepitaxial ZnO, such as ZnO/Al2O3, the linewidths are larger, the best being about 13 meV, the same as those found in the best GaN/Al2O3 layers. Other features, such as acceptor-bound excitons, donor acceptor-pair lines, and deep free-to-bound or bound-to-bound transitions, are also seen, but are not discussed here. We dwell on the DBE spectra because of a very interesting annealing effect, namely, that when annealed in Ar or air at 800C or above, all of the DBE lines seem to merge into one line, at 3.357 eV [21]. We believe that the DBE lines represent impurity or defect pairs, of different separations or orientations; then, upon annealing, only one line survives, and this line perhaps represents the isolated impurity or defect. We are now attempting to anneal in other atmospheres, such as H and O, to see if the pairs can be restored. Whatever the identity of the DBE lines, they constitute a very strong UV emission, much stronger than any seen in GaN. In fact, several groups have seen stimulated emission in ZnO, even at room temperature [22,23].

Fig. 3. Low-temperature photoluminescence spectra of closely-spaced donor-bound-exciton lines in sample A. Note that an 800C, 10-min anneal nearly eliminates all of the PL lines except one.

Fig. 4. Normalized acceptor density, as a function of electron-irradiation energy, for ZnO sample A, and also for GaN and GaAs samples which had about the same initial carrier concentration. Each point represents a uence of 4 1016 cm 2, at the given energy.

5. Radiation damage Fig. 4 shows the effects of high-energy electrons on ZnO (sample A), GaN, and GaAs. For each energy, the dose is 4 1016 cm 2. Here we are plotting the acceptor concentration, which always increases with irradiation. The donor behavior, on the other hand, is more complex, with the 30-meV donor increasing, and the 60-meV donor, decreasing. (The latter behavior probably involves a replacement reaction.) We note that the damage threshold is about 1.5 MeV in this sample, and a number this high cannot be explained by the creation of simple vacancy-interstitial (Frenkel) pairs, but must involve chains of defects [18]. That is, instead of, say, VZn ZnI defects, we must have things like VZn ZnO OZn ZnI. For Zn-face irradiation, annealing of these defects occurs in a sharp stage at about 325C, and follows rst-order kinetics, with an activation energy EA of 1.73 eV [24]. For O-face irradiation, on the other hand, EA varies from about 1.68 2.03 eV with annealing temperature, implying that more than one defect is involved. Also shown in Fig. 4 are irradiation data for

We next look at the mobility (Fig. 2). For sample C, the mobility data are rather inaccurate at the lower temperatures because of carrier freezeout. In this case, the value of NA = 1 1015 cm 3 comes from a t of n versus T, not v versus T, so the value is not as accurate. Overall, the mobility of ZnO is lower than that of GaN, because the effective mass is higher, and the optical phonon scattering parameter is larger. However, it is interesting that the theoretical saturation velocity 6s in ZnO is higher than it is in GaN [20], and 6s is more important for high-speed devices than is v. Comparing samples A and B, the anneal performed on sample B denitely added acceptors, since both the electron concentration and the mobility have decreased. Possibly the water bubbling process added interstitial oxygen, which is an acceptor, according to theory [19]. It is hoped that analytical measurements will help to answer these questions.

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GaN and GaAs. Clearly, GaAs is the poorest of the three, and Si (not shown) is even worse. Thus, relative to Si, GaAs, and GaN, ZnO is more resistant to particle irradiation. However, we should mention here that other ZnO samples are more susceptible to irradiation than is sample A, and some are less. For example, sample B at 1 MeV is affected more than sample A, but still less than GaN or GaAs. Perhaps there is a stabilizing effect in sample A that we dont understand yet. 6. Present devices and challenges for the future

Acknowledgements Support was received under US Air Force Contract F33615-95-C-1619, and some of the work was performed at the Air Force Research Laboratory, Wright Patterson Air Force Base, OH. Also, partial support was received from the Air Force Ofce of Scientic Research.

References Although ZnO-based photonic and electronic devices show great promise for the future, still there are some severe problems which must be overcome before the most attractive devices can be produced. One problem is that Schottky barriers are not easy to fabricate, although some groups have been successful [7]. Another, more serious problem, is that usable, reproducible p-type ZnO has not yet been reported, even though several laboratories, including ours, have measured weak p-type conduction in acceptor-doped materials [25,26]. Indeed, diode-like behavior and light emission have been measured, but the mechanism is not clear [27]. One device, which does not require p-type material, is a photoconductive detector. Liu et al. have fabricated a ZnO MSM detector with a low-frequency responsivity of 400 A/W at 5 V bias, and a response time of about 1 ms [7]. The cutoff is quite sharp, at 373 nm, although a small tail does exist, probably due to gap states. These characteristics are better than those of GaN detectors, so that ZnO stands a good chance of being a material of choice for UV detectors in the future. However, other devices, such as blue and UV LEDs and lasers, will require much more development. Although some might argue that ZnO stands where GaN did ten years ago, the learning curve will be much faster, primarily because of what we have learned in the GaN eld. 7. Summary Bulk ZnO crystals of very high optical and electrical quality can be grown by several different methods. Furthermore, epitaxial ZnO layers have been grown by PLD, MBE, MOCVD, and HVPE on many different types of substrate material, including Al2O3 and GaN, and devices such as blue light emitters and UV MSM photodetectors have been successfully fabricated. Electron-irradiation damage is less severe than that found in other common semiconductor materials, which suggests the possibility of ZnO space applications. However, the greatest challenge is the development of good p-type ZnO, which will be necessary for the most efcient light-emitting devices.
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