S.J. Jokela

Defects in ZnO

Zinc oxide (ZnO) is a wide band gap semiconductor with potential applications in optoelectronics, transparent electronics, and spintronics. The high efficiency 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 first-principles calculations but not observed directly. Despite numerous reports, reliable p-t...

Infrared spectroscopy of hydrogen in ZnO

Zinc oxide (ZnO) is a wide-band gap semiconductor that has attracted tremendous interest for optical, electronic, and mechanical applications. First-principles calculations by [C. G. Van de Walle, Phys. Rev. Lett. 85, 1012 (2000)] have predicted that hydrogen impurities in ZnO are shallow donors. In order to determine the microscopic structure of hydrogen donors, we have used IR spectroscopy to measure local vibrational modes in ZnO annealed in hydrogen gas. An oxygen–hydrogen stretch mode is observed at 3326.3 cm−1 at a temperature of 8 K, in good agreement with the theoretical predictions for hydrogen in an antibonding configuration. The results of this study suggest that hydrogen annealing may be a practical method for controlled n-type doping of ZnO.

Pressure response of the ultraviolet photoluminescence of ZnO and MgZnO nanocrystallites

The pressure response of the ultraviolet photoluminescence of ZnO nanocrystallites and MgZnO nanoalloy of composition 15% Mg:85% Zn of the wurtzite structure was studied. The authors found that up to 7GPa the pressure coefficients of ZnO and MgZnO are 23.6 and 27.1meV∕GPa, respectively. The pressure coefficient of the ZnO nanocrystallites is similar to that reported elsewhere for bulk ZnO material. The higher value found for MgZnO is discussed in terms of the d orbitals of the alloy constituents and their compliance to stress. Additionally, the volume deformation potential was derived from the experimental results.

Structure and stability of N–H complexes in single-crystal ZnO

Zinc oxide (ZnO) is semiconductor with a wide band gap of 3.4 eV. It continues to gain more attention not only for its versatile use in industry but also its potential for further application in electronics, optics, spintronics, and transparent circuits. Many of these applications require p-type ZnO. Nitrogen substituting for oxygen is a possible acceptor for such applications. In this paper, we report a study of nitrogen-hydrogen (N–H) complexes grown into single-crystal ZnO, using seeded chemical vapor transport in an ammonia ambient. An infrared (IR) absorption peak arising from N–H complexes was observed at 3150.6 cm−1 at liquid-helium temperatures. The assignment of this peak was confirmed by nitrogen and hydrogen isotope substitution. Polarized IR spectroscopy shows that the N–H dipole is oriented at an angle ∼114° to the c axis, in agreement with previous first-principles calculations. To probe the stability of the N–H complexes, samples were annealed in air, oxygen, and argon. Samples annealed in ...

Hydrogen donors in zinc oxide

Zinc oxide (ZnO) has emerged as a leading material for micro- and optoelectronic applications. Although the fabrication of ZnO, from nanocrystals to bulk single crystals, is well established, a major roadblock for fabricating optoelectronic devices is the lack of reliable p-type doping. The presence of compensating donors inhibits the growth of p-type ZnO. In this paper, studies pertaining to the microscopic structure and doping properties of hydrogen in ZnO are described. Results from infrared (IR) spectroscopy are consistent with a model where the hydrogen attaches to a host oxygen atom, in an anti-bonding orientation, which is not aligned along the c axis. These hydrogen complexes are unstable, however, perhaps due to the formation of H2 molecules.

Hydrogen Donors in ZnO

Zinc oxide (ZnO) has shown great promise as a wide-bandgap semiconductor with a range of optical, electronic, and mechanical applications. The presence of compensating donors, however, is a major roadblock to achieving p-type conductivity. Recent first-principles calculations and experimental studies have shown that hydrogen acts as a shallow donor in ZnO, in contrast to hydrogen’s usual role as a passivating impurity. Given the omnipresence of hydrogen during growth and processing, it is important to determine the structure and stability of hydrogen donors in ZnO. To address these issues, we performed vibrational spectroscopy on bulk, single-crystal ZnO samples annealed in hydrogen (H2) or deuterium (D2) gas. Using infrared (IR) spectroscopy, we observed O-H and O-D stretch modes at 3326.3 cm -1 and 2470.3 cm -1 respectively, at a sample temperature of 10 K. These frequencies indicate that hydrogen forms a bond with a host oxygen atom, consistent with either an antibonding or bond-centered model. In the antibonding configuration, hydrogen attaches to a host oxygen and points away from the Zn-O bond. In the bond-centered configuration, hydrogen sits between the Zn and O. To discriminate between these two models, we measured the shift of the stretch-mode frequency as a function of hydrostatic pressure. By comparing with first-principles calculations, we conclude that the antibonding model is the correct one. Surprisingly, we found that the O-H complex is unstable at room temperature. After a few weeks, the peak intensity decreases substantially. It is possible that the hydrogen forms H2 molecules, which have essentially no IR signature. Electrical measurements show a corresponding decrease in electron concentration, which is consistent with the formation of neutral H2 molecules. The correlation between the electrical and spectroscopic measurements, however, is not perfect. We therefore speculate that there may be a second “hidden” hydrogen donor. One candidate for such a donor is a hydrogen-decorated oxygen vacancy. Table I. Band gaps of several important wide-band-gap semiconductors. Energies are given in eV (nm). The cubic structure for GaN and AlN is zincblende. The hexagonal structure for GaN, AlN, and ZnO is wurtzite. 4H, 6H, and 2H denote the hexagonal polytypes of SiC.

Using persistent photoconductivity to write a low-resistance path in SrTiO 3

Materials with persistent photoconductivity (PPC) experience an increase in conductivity upon exposure to light that persists after the light is turned off. Although researchers have shown that this phenomenon could be exploited for novel memory storage devices, low temperatures (below 180 K) were required. In the present work, two-point resistance measurements were performed on annealed strontium titanate (SrTiO3, or STO) single crystals at room temperature. After illumination with sub-gap light, the resistance decreased by three orders of magnitude. This markedly enhanced conductivity persisted for several days in the dark. Results from IR spectroscopy, electrical measurements, and exposure to a 405 nm laser suggest that contact resistance plays an important role. The laser was then used as an “optical pen” to write a low-resistance path between two contacts, demonstrating the feasibility of optically defined, transparent electronics.

Hydrogen-related defects in bulk ZnO

Zinc oxide (ZnO) has attracted resurgent interest as an active material for energy-efficient lighting applications. An optically transparent crystal, ZnO emits light in the blue-to-UV region of the spectrum. The efficiency of the emission is higher than more “conventional” materials such as GaN, making ZnO a strong candidate for solid-state white lighting. Despite its advantages, however, ZnO suffers from a major drawback: as grown, it contains a relatively high level of donors. These unwanted defects compensate acceptors or donate free electrons to the conduction band, thereby keeping the Fermi level in the upper half of the band gap. This paper reviews recent work on hydrogen donors and nitrogen-hydrogen complexes in ZnO.

Infrared Spectroscopy of Hydrogen in ZnO

Zinc oxide (ZnO) has shown great promise as a wide band gap semiconductor with optical, electronic, and mechanical applications. Recent first-principles calculations and experimental studies have shown that hydrogen acts as a shallow donor in ZnO, in contrast to hydrogen’s usual role as a passivating impurity. The structures of such hydrogen complexes, however, have not been determined. To address this question, we performed vibrational spectroscopy on bulk, single-crystal ZnO samples annealed in hydrogen (H2) or deuterium (D2) gas. Using infrared (IR) spectroscopy, we have observed O-H and O-D stretch modes at 3326.3 cm -1 and 2470.3 cm -1 respectively, at a sample temperature of 14 K. These frequencies are in good agreement with the theoretical predictions for hydrogen and deuterium in an antibonding configuration, although the bond-centered configuration cannot be ruled out. The IR-active hydrogen complexes are unstable, however, with a dissocation barrier on the order of 1 eV.