L. E. Halliburton

Role of copper in the green luminescence from ZnO crystals

Electron paramagnetic resonance (EPR), photoluminescence, and infrared optical absorption have been used to investigate a ZnO crystal before and after a thermal anneal for 1 h in air at 900 °C. The sample was an undoped high quality crystal grown by the chemical vapor transport method. In addition to shallow donor impurities, the crystal contained trace amounts of copper ions. Prior to the thermal anneal, these ions were all in the Cu+ (3d10) state and the observed luminescence at 5 K, produced by 364 nm light, consisted of a broad structureless band peaking at 500 nm. After the high-temperature anneal, the Cu2+ (3d9) EPR spectrum was observed and the luminescence had changed significantly. The emission then peaked near 510 nm and showed structure identical to that reported by Dingle [Phys. Rev. Lett. 23, 579 (1969)]. Our data reaffirm that the structured green emission in ZnO is associated with Cu2+ ions. We suggest that the unstructured green emission (observed before the high-temperature anneal) is don...

Production of Nitrogen Acceptors in ZnO by Thermal Annealing

Nitrogen acceptors are formed when undoped single crystals of zinc oxide (ZnO) grown by the chemical-vapor transport method are annealed in air or nitrogen atmosphere at temperatures between 600 and 900 °C. After an anneal, an induced near-edge absorption band causes the crystals to appear yellow. Also, the concentration of neutral shallow donors, as monitored by electron paramagnetic resonance (EPR), is significantly reduced. A photoinduced EPR signal due to neutral nitrogen acceptors is observed when the annealed crystals are exposed to laser light (e.g., 364, 442, 458, or 514 nm) at low temperature. The nitrogens are initially in the nonparamagnetic singly ionized state (N−) in an annealed crystal, because of the large number of shallow donors, and the light converts a portion of them to the paramagnetic neutral acceptor state (N0).

Remote hydrogen plasma doping of single crystal ZnO

We demonstrate that remote plasma hydrogenation can increase electron concentrations in ZnO single crystals by more than an order of magnitude. We investigated the effects of this treatment on Hall concentration and mobility as well as on the bound exciton emission peak I4 for a variety of ZnO single crystals–bulk air annealed, Li doped, and epitaxially grown on sapphire. Hydrogen increases I4 intensity in conducting samples annealed at 500 and 600 °C and partially restores emission in the I4 range for Li-diffused ZnO. Hydrogenation increases carrier concentration significantly for the semi-insulating Li doped and epitaxial thin film samples. These results indicate a strong link between the incorporation of hydrogen, increased donor-bound exciton PL emission, and increased n-type conductivity.

Production of native donors in ZnO by annealing at high temperature in Zn vapor

Zinc oxide crystals grown by the seeded chemical vapor transport method have been annealed in zinc vapor at 1100 °C for 30 min. These thermochemical reduction treatments produce a deep red coloration in the crystals and increase their n-type electrical conductivity. Electron paramagnetic resonance (EPR), optical absorption, and Hall measurements were used to monitor changes in the crystals. After an anneal, an intense optical absorption band is present that extends from the band edge out to approximately 550 nm, and the EPR signal near g=1.96 (due to shallow donors and/or conduction-band electrons), the free-carrier absorption, and the Hall electron concentration are all larger. Hydrogen was not present during these anneals, thus leaving oxygen vacancies and zinc interstitials as candidates for the added donors. Neutral oxygen vacancies are produced at high temperature by the additive-coloration mechanism, and are responsible for the broad near-edge absorption band. The observed increase in the number of ...

Further characterization of oxygen vacancies and zinc vacancies in electron-irradiated ZnO

Electron paramagnetic resonance (EPR) has been used to monitor oxygen vacancies and zinc vacancies in a ZnO crystal irradiated near room temperature with 1.5MeV electrons. Out-of-phase detection at 30K greatly enhances the EPR signals from these vacancies. Following the electron irradiation, but before illumination, Fe3+ ions and nonaxial singly ionized zinc vacancies are observed. Illumination with 325nm laser light at low temperature eliminates the Fe3+ signal while producing spectra from singly ionized oxygen vacancies, neutral zinc vacancies, and axial singly ionized zinc vacancies. This light also produces EPR spectra from zinc vacancies having a OH− ion at an adjacent oxygen site. The low-temperature response of the irradiated crystal to illumination wavelengths between 350 and 750nm is described. Wavelengths shorter than 600nm convert Fe3+ ions to Fe2+ ions and convert neutral oxygen vacancies to singly ionized oxygen vacancies. Neutral zinc vacancies are formed by wavelengths shorter than 500nm as...

Infrared absorption from OH− ions adjacent to lithium acceptors in hydrothermally grown ZnO

An intense infrared absorption band has been observed in a hydrothermally grown ZnO crystal. At 12K, the band peaks near 3577.3cm−1 and has a half width of 0.40cm−1, and at 300K, the band peaks at 3547cm−1 and has a half width of 41.3cm−1. This absorption band is highly polarized, with its maximum intensity occurring when the electric field of the measuring light is parallel to the c axis of the crystal. Photoinduced electron-paramagnetic-resonance experiments show that the crystal contains lithium acceptors (i.e., lithium ions occupying zinc sites). Lithium and OH− ions are present in the crystal because lithium carbonate, sodium hydroxide, and potassium hydroxide are used as solvents during the hydrothermal growth. In the as-grown crystal, some of the lithium acceptors will have an OH− ion located at an adjacent axial oxygen site (to serve as a passivator), and we assign the 3577.3-cm−1 band observed at 12K to these neutral complexes. Our results illustrate the role of hydrogen as a charge compensator f...

Molecular nitrogen (N2−) acceptors and isolated nitrogen (N−) acceptors in ZnO crystals

Electron paramagnetic resonance (EPR) has been used to investigate molecular nitrogen and isolated nitrogen acceptors in single crystals of ZnO. These samples were grown by the seeded chemical vapor transport method with N2 added to the gas stream. A five-line EPR spectrum is observed at low temperature in the as-grown bulk crystals and is assigned to N2− molecules substituting for oxygen. This structure arises from nearly equal hyperfine interactions with two nitrogen nuclei (14N, 99.63% abundant, I=1). The spin Hamiltonian parameters for the N2− center are g∥=2.0036, g⊥=1.9935, A∥=9.8 MHz, and A⊥=20.1 MHz, with the unique directions parallel to the c axis. Laser excitation at 9 K, with 325 or 442 nm light, eliminates the N2− spectrum (when the N2− convert to N20) and independently introduces the EPR spectrum due to isolated nitrogen acceptors (when N− acceptors convert to N0). Removing the laser light and warming to approximately 100 K restores the crystal to its preilluminated state. In separate experi...

Defects responsible for gray tracks in flux‐grown KTiOPO4

Electron paramagnetic resonance (EPR) has been used to identify the primary electron and hole traps responsible for ‘‘gray tracks’’ in flux‐grown KTiOPO4(KTP). Ionizing radiation (x rays) was used to produce the gray‐track effect. During an irradiation at 0 °C, a broad absorption band peaking near 500 nm is introduced, the EPR spectra from a series of Ti3+ centers appear, and the dominant EPR spectrum associated with Fe3+ ions decreases significantly. Following the irradiation, the decay of the optical absorption and the Ti3+ centers, along with the growth of Fe3+ centers, were monitored over a period of 20 h at room temperature. Changes in the EPR spectra of the Ti3+ and Fe3+ centers during the anneal correlated with the decay of the induced optical absorption (i.e., gray track). These results demonstrate that Fe3+ centers are the primary hole trap and Ti4+‐VO complexes are the primary electron trap responsible for gray track formation in flux‐grown KTP crystals.

Photoinduced electron paramagnetic resonance study of electron traps in TiO2 crystals: Oxygen vacancies and Ti3+ ions

Electron paramagnetic resonance (EPR) is used to identify photoinduced titanium-associated electron traps in TiO2 crystals (rutile). Defect production occurs at low temperature with 442 nm laser light. Spectra with S=1/2 and S=1 are assigned to singly ionized and neutral oxygen vacancies, respectively. These oxygen vacancies have their unpaired spins localized on the two neighboring titanium ions aligned along the c axis. A Ti3+ ion next to a Si4+ ion, a Ti3+ self-trapped electron, and a self-trapped hole shared by two adjacent oxygen ions are also observed. Isolated substitutional Fe3+ and Cr3+ ions serve as hole traps.

Effect of crystal growth on Ti3+ centers in KTiOPO4

A series of Ti3+ centers have been formed in hydrothermally grown and flux‐grown potassium titanyl phosphate (KTiOPO4 or KTP). These 3d1 defects (S=1/2) were created with 60 kV x rays at 77 K, and electron paramagnetic resonance and electron‐nuclear double‐resonance (ENDOR) data were taken below 30 K. The ENDOR spectra show that the two Ti3+ centers having the largest concentrations in hydrothermally grown KTP have a neighboring proton, presumably in the form of an adjacent OH− ion. In contrast, ENDOR spectra show that neither of the two Ti3+ centers having the largest concentrations in flux‐grown KTP have a neighboring proton. These significant differences in the local environment of the Ti3+ centers may help explain why KTP crystals have shown differing susceptibilities to gray tracking.