Polarity Determination of Polarity-Controlled ZnO Films Using Photoresponse Characteristics

We report on the use of the photoresponse characteristics of polarity- controlled ZnO films for determining ZnO polarity. ZnO films were grown on CrN and Cr₂O₃ buffer layers in order to produce Zn- and O-polar films, respectively, and Ti/Au metal contacts were formed. All samples showed Ohmic behavior, but the Zn-polar ZnO film showed lower contact resistance than the O-polar ZnO film. The O-polar ZnO film showed higher photocurrent and longer decay time than the Zn-polar film by photoresponse measurement. These phenomena can be explained by the expansion of the depletion layer into the bulk ZnO surface. Compared with current methods, this method of determination of the polarity of ZnO films through the measurement of photoresponse characteristics is very easy and simple to implement.     

ZnO and related materials: Plasma-Assisted molecular beam epitaxial growth, characterization and application

This paper will address features of plasma-assisted molecular beam epitaxial growth of ZnO and related materials and their characteristics. Two-dimensional, layer-by-layer growth is achieved both on c-plane sampphire by employing MgO buffer layer growth and on (0001) GaN/Al₂O₃ template by predepositing a low-temperature buffer layer followed by high-temperature annealing. Such two-dimensional growth results in the growth of high-quality heteroepitaxial ZnO epilayers. Biexciton emission is obtained from such high quality epilayers The polarity of heteroepitaxial ZnO epilayers is controlled by engineering the heterointerfaces. We achieved selective growth of Zn-polar and O-polar ZnO heteroepitaxial layers. The origin of different polarities can be successfully explained by an interface bonding sequence model. N-type conductivity in Gadoped ZnO epilayers is successfully controlled. High conductivity, enough to be applicable to devices, is achieved. Mg_xZn_1-xO/ZnO heterostructures are grown and emission from a ZnO quantum well is observed. Mg incorporation in a MgZnO alloy is determined by in-situ reflection high-energy electron diffraction intensity oscillations, which enables precise control of the composition. Homoepitaxy on commericial ZnO substrates has been examined. Reflection high-energy electron diffraction intensity oscillations during homoepitaxy growth are observed.     

Optical properties of InAs<Subscript>1−x</Subscript>N<Subscript>x</Subscript>/In<Subscript>0.53</Subscript>Ga<Subscript>0.47</Subscript>As single quantum wells grown by gas source molecular beam epitaxy

Optical properties of InAs_1−xN_x/In_0.53Ga_0.47As (hereafter, abbreviated as InAsN/InGaAs) single quantum wells (SQWs) grown on InP substrates by gas source molecular-beam epitaxy are studied using photoluminescence (PL) measurements. By comparing the low-temperature PL spectra of InAs/InGaAs and InAsN/InGaAs SQWs, InAs and InAsN phases are found to coexist in the InAsN layer. Such serious alloy inhomogeneities result in obvious exciton localization by potential irregularities. The blue shift of the PL peak after rapid thermal annealing (RTA) is found to originate mainly from As-N interdiffusion inside the well layer. According to the temperature-dependent PL results, uniformity of the InAsN layer can be effectively improved by RTA, and the exciton localization is, thus, relieved. Comparison of luminescence quenching and excitation-power-dependent PL behavior between the QWs with and without nitrogen content suggests that the quality of the QW is degraded by the introduction of nitrogen, and the degradation can only be partially recovered by post-growth RTA.     

Cathodoluminescence of ZnO/GaN/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> heteroepitaxial structures grown by chemical vapor deposition

The cathodoluminescent properties of ZnO films in ZnO/GaN/α-Al₂O₃ and ZnO/α-Al₂O₃ heteroepitaxial structures grown by chemical vapor deposition in a low-pressure flowing-gas reactor were studied and compared. A superlinear dependence of the excitonic-band intensity in the cathodoluminescence spectrum of the ZnO/GaN/α-Al₂O₃ structures on the electron-beam current is ascertained, which indicates that the emission is stimulated for relatively low thresholds of the excitation intensity. It is shown that the ZnO films grown on the GaN substrates exhibit a much more effective cathodoluminescence compared to the cathodoluminescence in the films grown on α-Al₂O₃. It was observed that the luminescent properties of ZnO layers in the ZnO/GaN/α-Al₂O₃ structures subjected to long-term heat treatment at 750°C in an oxygen atmosphere exhibit a high thermal stability.     

Structural and optical properties of Zn<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>O thin films synthesized with metal organic chemical vapor deposition

We present the structural and optical properties of Zn_1?xMg_xO thin films studied using x-ray diffraction (XRD), extended x-ray absorption fine structure (EXAFS), and photoluminescence (PL) measurements. The Zn_1?xMg_xO films on sapphire [0001] substrates were fabricated with metal organic chemical vapor deposition (MOCVD). The XRD measurements showed that the Zn_1?xMg_xO films (x≤0.05) had a wurtzite structure without any MgO phase and were epitaxially grown along the c-axis of the Al₂O₃ substrate. The lattice constant of the Zn_0.95Mg_0.05O film shrank by 0.023 Å, compared with that of ZnO crystals. From the EXAFS measurements on the Zn_1?xMg_xO films at Zn K-edge, we found a substantial amount of distortion in the bond length of Zn-Zn pairs with a small amount of Mg substitution on the Zn site. The PL measurements showed a gradual increment of the main exciton transitions from 3.36 eV (x=0.0) to 3.57 eV (x=0.05) at 10 K. We also observed a strong deep-level emission near 2.3 eV from the specimen with x=0.05.     

Microstructure and Characteristics of Thin-Film La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>Co<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>O<Subscript>3</Subscript>/ZnO:Al Heterocontact CO Sensors Prepared by RF Magnetron Sputtering

Highly sensitive CO gas sensors based on heterocontacts of ZnO:Al on La_0.8Sr_0.2Co_0.5Ni_0.5O₃ (LSCNO) were fabricated successfully. La_0.8Sr_0.2Co_0.5Ni_0.5O₃ thin films were coated on (100) silicon wafers by a sol-gel method including the Pechini process followed by a spin-coating procedure. Then, ZnO:Al films prepared by radiofrequency (RF) magnetron sputtering at various oxygen partial pressures and deposited on as-deposited La_0.8Sr_0.2Co_0.5Ni_0.5O₃ films were investigated. The results revealed that the CO sensing ability of the film prepared with the ratio of O₂/Ar = 5/5 (ratio of volume flow rate) was the worst, owing to the highest (002) plane orientation in the ZnO:Al film. In contrast, the ZnO:Al film prepared with O₂/Ar = 3/7 exhibited better CO sensitivity. Furthermore, all two-layer samples showed higher CO sensitivities than single-layer samples. The CO sensitivity of ZnO:Al/La_0.8Sr_0.2Co_0.5Ni_0.5O₃ thin film was 45% for 500 ppm CO at a sensing temperature of 200°C.     

Fabrication and Characterization of Pb(Zr<Subscript>0.53</Subscript>,Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript>-Pb(Nb<Subscript>1/3</Subscript>,Zn<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> Thin Films on Cantilever Stacks

0.9Pb(Zr_0.53,Ti_0.47)O₃-0.1Pb(Zn_1/3,Nb_2/3)O₃ (PZT–PZN) thin films and integrated cantilevers have been fabricated. The PZT–PZN films were deposited on SiO₂/Si or SiO₂/Si₃N₄/SiO₂/poly-Si/Si membranes capped with a sol–gel-derived ZrO₂ buffer layer. It is found that the membrane layer stack, lead content, existence of a template layer of PbTiO₃ (PT), and ramp rate during film crystallization are critical for obtaining large-grained, single-phase PZT–PZN films on the ZrO₂ surface. By controlling these parameters, the electrical properties of the PZT–PZN films, their microstructure, and phase purity were significantly improved. PZT–PZN films with a dielectric constant of 700 to 920 were obtained, depending on the underlying stack structure.     

Charge transport in thin layers of ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The mechanism responsible for the charge transport in thin ferroelectric Hf_0.5Zr_0.5O₂ films has been studied. It is shown that in these films the transport mechanism is phonon-assisted tunneling between the traps. The optimal thickness of dielectric film for TiN/Hf_0.5Zr_0.5O₂/Pt structures is determined. As a result of comparing the experimental current–voltage (I–V) characteristics of TiN/Hf_0.5Zr_0.5O₂/Pt structures with the calculated ones, the thermal and optical energies of the traps are determined and the concentration of the traps is estimated. A comparison between the transport properties of ferroelectric and amorphous Hf_0.5Zr_0.5O₂ films is carried out. It is shown that the charge transport mechanism in this dielectric does not depend on its crystalline phase. A method for decreasing leakage currents in Hf_0.5Zr_0.5O₂ is proposed. A study of the resource of repolarization cycles for TiN/Hf_0.5Zr_0.5O₂/TiN metal-dielectric-metal (MDM) structures fully grown by atomic layer deposition (ALD) has been carried out.     

Epitaxial growth and properties of Mg<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>O films produced by pulsed laser deposition

The Mg _x Zn_1-x O thin films with a Mg content corresponding to x = 0–0.45 are grown by pulsed laser deposition on ablation of ceramic targets. The conditions for epitaxial growth of the films on the single-crystal Al₂O₃ (00.1) substrates are established. The record limit of solubility of Mg in hexagonal ZnO, x = 35 is attained. In this case, the lattice mismatch for the parameter a of the ZnO and Mg_0.35Zn_0.65O films does not exceed 1%, whereas the band gaps of the films differ by 0.78 eV. The surface roughness of the films corresponds to 0.8–1.5 nm in the range of x = 0–0.27.     

Correlation of in-situ reflectance spectra and resistivity of GaN/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> interfacial layer in metalorganic chemical vapor deposition

The correlation between the resistivity of an undoped GaN/Al₂O₃ interfacial layer and in-situ reflectance spectrum in metalorganic chemical vapor deposition and the mechanism of this correlation were investigated. The first minimum reflectance during the initial high-temperature GaN growth was found to be a good indicator of the resistivity of the GaN buffer. The background electron concentration and mobility were both higher in the samples with higher indicative reflectance at that point. The resistivity of the GaN buffer layer was predominantly determined by an ∼0.25-μm-thick layer near the GaN/Al₂O₃ interface. Atomic force microscope (AFM) and high-resolution x-ray diffraction (HRXRD) results showed that the samples with higher indicative reflectance had smaller sized but higher density nuclei before the high-temperature GaN growth and lower screw threading dislocation (TD) density in the initially grown GaN. The difference in the background electron concentration and mobility of the interfacial layer was related to the relatively higher concentration of the O and Al diffused from Al₂O₃, which is also dependent on the size and density of the nuclei. These differences were found not to affect the structural and electrical properties or the surface morphology of AlGaN/GaN high electron-mobility transistors (HEMTs, except for the buffer conduction) when the GaN buffer is thick enough (e.g., ∼2.5 μm).     

Growth of Epitaxial (110) 0.7Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-0.3PbTiO<Subscript>3</Subscript> Thin Films on r-Plane Sapphire Substrates by RF Magnetron Sputtering

The role of substrate temperature and substrate surface geometry in determining the crystal structure and crystallinity of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) thin films grown on r-plane sapphire substrates is examined. A 30-nm-thick amorphous PMN-PT seed layer deposited at 250°C and subjected to rapid thermal annealing at 850°C results in the formation of an epitaxial (110) perovskite PMN-PT growth template that can be used for subsequent growth of single-crystal (110) perovskite PMN-PT films at elevated temperature. The data show that single-crystal perovskite is promoted when the films nucleate with the \( \langle \overline{1} 11 \rangle \) PMN-PT direction parallel to the \( \langle 0\bar{2}21 \rangle \) Al₂O₃ direction.     

Room-temperature photoluminescence of Ga<Subscript>0.96</Subscript>In<Subscript>0.04</Subscript>As<Subscript>0.11</Subscript>Sb<Subscript>0.89</Subscript> lattice matched to InAs

Photoluminescence (PL) has been observed at room temperature from a Ga_0.96In_0.04As_0.11Sb_0.89 quaternary solid solution for the first time. High-quality epitaxial layers of n-type (Te-doped) Ga_0.96In_0.04As_0.11Sb_0.89 with low In content were grown by liquid phase epitaxy (LPE) lattice-matched to InAs(100) substrates from a Ga-rich melt. The PL properties of the material were investigated over a wide temperature range, and the principal radiative transitions were identified. In the temperature range <150 K, donor-acceptor recombination involving the first and second ionization state of native antisite defects was the dominant radiative-recombination process, whereas interband recombination was found to dominate at room temperature.     

Self-limiting growth of ZrO<Subscript>2</Subscript> films on a Si(100) substrate using ZrCl<Subscript>4</Subscript> and O<Subscript>2</Subscript> under atmospheric pressure

The ZrO₂ films were deposited onto a Si(100) substrate using an alternate reaction of ZrCl₄ and O₂ under atmospheric pressure. It is found that the growth rate of ZrO₂ film depends on the growth conditions, such as growth temperature, partial pressure of the sources being supplied, and exposure time of the substrate to the gaseous sources. Self-limiting growth of the ZrO₂ was achieved in the range of the growth temperature of 673–923 K. The x-ray diffractogram of the ZrO₂ films showed a typical diffraction pattern assigned to the tetragonal polycrystalline phase. The obtained ZrO₂ films were of smooth and uniform surface. It was found that the [O]/[Zr] ratio of the ZrO₂ films are similar to that of the ZrO₂ bulk.     

Polarity control of GaN epilayers grown on ZnO templates

We report the successful growth of Ga-polar GaN epilayers on O-polar ZnO templates pre-deposited on c-sapphire. Prior to GaN growth, NH₃ is exposed onto the ZnO template. The polarity of the GaN layers is confirmed by etching of the surface and by conversion beam electron diffraction (CBED), while the O-polar ZnO is confirmed by CBED. It is suggested that the NH₃ pre-exposure helps form a Zn₃N₂ layer, which possesses inversion symmetry and inverts the crystal from anion polar to cation polar.     

Low Fatigue in Epitaxial Pb(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> on Si Substrates with LaNiO<Subscript>3</Subscript> Electrodes by RF Sputtering

Epitaxial PZT (001) thin films with a LaNiO₃ bottom electrode were deposited by radio-frequency (RF) sputtering onto Si(001) single-crystal substrates with SrTiO₃/TiN buffer layers. Pb(Zr_0.2Ti_0.8)O₃ (PZT) samples were shown to consist of a single perovskite phase and to have an (001) orientation. The orientation relationship was determined to be PZT(001)[110]∥LaNiO₃(001)[110]∥SrTiO₃ (001)[110]∥TiN(001)[110]∥Si(001)[110]. Atomic force microscope (AFM) measurements showed the PZT films to have smooth surfaces with a roughness of 1.15 nm. The microstructure of the multilayer was studied using transmission electron microscopy (TEM). Electrical measurements were conducted using both Pt and LaNiO₃ as top electrodes. The measured remanent polarization P _r and coercive field E _c of the PZT thin film with Pt top electrodes were 23 μC/cm² and 75 kV/cm, and were 25 μC/cm² and 60 kV/cm for the PZT film with LaNiO₃ top electrodes. No obvious fatigue after 10¹⁰ switching cycles indicated good electrical endurance of the PZT films using LaNiO₃ electrodes, compared with the PZT film with Pt top electrodes showing a significant polarization loss after 10⁸ cycles. These PZT films with LaNiO₃ electrodes could be potential recording media for probe-based high-density data storage.     

Formation of Cu<Subscript>2</Subscript>O and ZnO Crystal Layers by Magnetron Assisted Sputtering and Their Optical Characterization

Copper (I) oxide and zinc oxide films are formed on silicon and glassy quartz substrates by magnetron assisted sputtering. The thickness of the films is tens and hundreds of nanometers. The films are grown at different substrate temperatures and different oxygen pressures in the working chamber. The film samples are studied by the X-ray diffraction technique, scanning electron microscopy, and optical methods. It is established that an increase in the substrate temperature yields a change in the surface morphology of copper (I) oxide films towards the formation of well-pronounced crystallites. The reflectance and Raman spectra suggest that the quality of such films is close to that of bulk Cu₂O crystals produced by the oxidation of copper. As concerns ZnO films, an increase in the substrate temperature and an increase in the partial oxygen pressure make it possible to produce films, for which a sharp exciton structure is observed in the reflectance spectra and the emission of excitons bound at donors is observed in the luminescence spectra.     

Influences of ZnO buffer layers on the quality of ZnO films synthesized by the metal-organic chemical vapor deposition process

High-quality ZnO thin films were prepared by metal-organic chemical vapor deposition (MOCVD) on a sapphire (a-Al₂O₃) substrate. The synthesis of ZnO films was performed over a substrate temperature of 400–700°C and at chamber pressures of 0.1–10 torr. The structural and optical properties of ZnO films were investigated in terms of deposition conditions, such as substrate temperature, working pressure, and the ratio of Zn precursor (Diethylzinc (DEZn)) to oxygen. The ZnO films, preferentially oriented to 34.42° diffraction because of the (002) plane, were obtained under processing conditions of 700°C and 3 torr. This film shows a full-width at half-maximum (FWHM) of 0.4–0.6°. The results of photoluminescence (PL) spectroscopy also show a strong near band-edge emission at 3.36 eV at 10 K as well as a very weak emission at deep levels around 2.5 eV at room temperature. In addition, we are interested in the introduction of ZnO buffer-layer growth by the sputtering process to reduce lattice mismatch stress. This paper addresses how to advance the crystalline and optical properties of film. The ZnO film grown with the aid of a buffer layer shows a FWHM of 0.06–0.1° in the x-ray diffraction (XRD) pattern. This result indicates that crystalline properties were highly improved by the ZnO buffer layers. The PL spectroscopy data of ZnO film also shows a strong near band-edge emission and very weak deep-level emission similar to films synthesized without a buffer layer. Accordingly, synthesized ZnO films with buffer layers indicate fairly good optical properties and low defect density as well as excellent crystallinity.     

Terahertz radiation in In<Subscript>0.38</Subscript>Ga<Subscript>0.62</Subscript>As grown on a GaAs wafer with a metamorphic buffer layer under femtosecond laser excitation

The results of time-domain spectroscopy of the terahertz (THz) generation in a structure with an In_0.38Ga_0.62As photoconductive layer are presented. This structure grown by molecular-beam epitaxy on a GaAs substrate using a metamorphic buffer layer allows THz generation with a wide frequency spectrum (to 6 THz). This is due to the additional contribution of the photo-Dember effect to THz generation. The measured optical-to-terahertz conversion efficiency in this structure is 10^–5 at a rather low optical fluence of ~40 μJ/cm², which is higher than that in low-temperature grown GaAs by almost two orders of magnitude.     

Free-Standing PEDOT-PSS/Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> Composite Films as Novel Thermoelectric Materials

Free-standing poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT- PSS)/Ca₃Co₄O₉ composite films have been successfully prepared by mechanically blending Ca₃Co₄O₉ powder and PEDOT-PSS solution (Baytron P) and casting the mixed solution on polypropylene (PP) film substrates. X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterization indicated that the Ca₃Co₄O₉ particles were in the shape of sheets and composited well together with PEDOT-PSS. Thermoelectric (TE) measurements revealed that the Seebeck coefficient can be improved by increasing the Ca₃Co₄O₉ content in the composite films, with the largest enhancement being 24.8% compared with a free-standing PEDOT-PSS film. However, it is also shown that the power factor of the composite films decreases with increasing Ca₃Co₄O₉ content, mainly due to the decline of electrical conductivity and the limited improvement of the Seebeck coefficient.     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).