Thermal stability of sputter-deposited ZnO thin films

This paper describes our investigation on the thermal stability of sputterdeposited, piezoelectric, ZnO thin films, using x-ray photoelectron spectroscopy (XPS), capacitance-voltage (C-V) measurements of metal-insulator-semiconductor structures, and electron microprobe. We focus on out-diffusion of Zn from ZnO thin films at a high temperature (450°C) and the composition change of zinc and oxygen after high temperature annealing (up to 700°C), since these factors are related to reliability and integrated circuits-process-compatibility of the ZnO films which are being used increasingly more in microtransducers and acoustic devices. Our experiments with electron microprobe show that ZnO thin films sputter-deposited from a ZnO target in a reactive environment (i.e., with O₂) are thermally stable (up to 700°C). Additionally, the out-diffusion of zinc atoms from the ZnO films at a high temperature (450°C) is verified to be negligible using the XPS and C-V measurement techniques. The usage of a compound ZnO target, reactive environment with O₂ and optimized deposition parameters (including gas ratio and pressure, substrate temperature, target-substrate distance and rf power, etc.) is critical to deposit thermally stable, high quality ZnO films.     

Nanostructured thin films of the La0.7Sr0.3MnO3 manganite obtained using the extraction pyrolytic method

The extraction pyrolytic method is used to fabricate thin (100–300 nm) films of the lanthanum manganites La_0.7Sr_0.3MnO₃ on fused silica substrates. The films are deposited on the substrate using the alternate sessions of the centrifuging of solution and pyrolysis. The annealing of thin films at temperatures of greater than 650°C yields the single-phase La_0.7Sr_0.3MnO₃ material. It is demonstrated that the annealing temperature substantially affects the magnetic properties of the resulting films: the films exhibit the properties of spin glasses and ferromagnetic properties at temperatures of less than 700°C and greater than 700°C, respectively.     

Investigation of optical and electronic properties in Al–Sn co-doped ZnO thin films

Al-Sn co-doped ZnO thin films were deposited onto quartz substrates by sol-gel processing. The surface morphology and electrical and optical properties were investigated at different annealing temperatures. The surface morphology showed a closely packed arrangement of crystallites in all the doped films. As prepared co-doped films show a preferred orientation along an (0 0 2) plane. This preferred orientation was enhanced by increasing the annealing temperature to between 400 °C and 500 °C, but there was a shift to the (1 0 1) plane when the annealing temperature rose above 500 °C. These samples show, on average, 91.2% optical transmittance in the visible range. In this study, the optical band gap of all the doped films was broadened compared with pure ZnO, regardless of the different annealing temperature. The carrier concentration and carrier mobility of the thin films were also investigated.     

Influence of flexible substrates on inverted organic solar cells using sputtered ZnO as cathode interfacial layer

Zinc oxide (ZnO) has recently shown to be of considerable interest for the development of interfacial buffer layers in inverted organic solar cells (OSCs). High quality ZnO thin films can indeed be prepared on large-area ITO-coated flexible substrates, using low temperature deposition techniques such as sputtering, a compatible technique with roll-to-roll process. However, further studies are still needed for a better understanding of the influence of the flexible substrate properties on the photovoltaic performances of those devices. In this work, ZnO films have been sputtered on ITO-coated flexible (PEN) substrates and annealed at different temperatures. The role of the surface morphology and the crystalline quality of ZnO films has been investigated. In the window of flexible compatible process, we found that moderate annealing temperatures of ZnO (?180 °C) lead to improved structural properties and performances. Interestingly, we achieve optimal performances for an annealing temperature of 160 °C, resulting in power conversion efficiency (PCE) equivalent to the highest performances usually achieved on rigid cells.     

Tuning the Properties of CZTS Films by Controlling the Process Parameters in Cost-Effective Non-vacuum Technique

Highly dispersive Cu₂ZnSnS₄ (CZTS) nanoparticles were successfully synthesized by a simple solvothermal route. A low cost, non-vacuum method was used to deposit CZTS nanoparticle ink on glass substrates by a doctor blade process followed by selenization in a tube furnace to form Cu₂ZnSn (S,Se)₄ (CZTSSe) layers. Different selenization conditions and particle concentrations were considered in order to improve the crystallinity and surface morphology; the annealing temperature was varied between 400°C and 550°C and the annealing time was varied between 5 min and 20 min in a selenium-nitrogen atmosphere. The influence of annealing conditions on structural, compositional, optical and electrical properties of CZTSSe thin films was studied. An improvement in the structural and surface morphology was observed with increasing of annealing temperature (up to 500°C). An enhancement in the crystallinity and surface morphology were observed for thin films annealed for 10–15 min. Absorption study revealed that the band gap energy of as-deposited CZTS thin film was approximately 1.43 eV, while for CZTSSe thin films it ranged from 1.15 eV to 1.34 eV at different annealing temperatures, and from 1.33 eV to 1.38 eV for different annealing times.     

The Effect of Substrate Material and Postannealing on the Photoluminescence and Piezo Properties of DC-Sputtered ZnO

Abstact Zinc oxide (ZnO) thin films were deposited on various substrates by DC sputtering deposition. Thermal annealing was performed at up to 1,200°C in N₂ for 30 min. The effect was investigated using x-ray diffraction (XRD), photoluminescence (PL) spectra, scanning electron microscopy (SEM), and piezoresponse force microscopy (PFM). The influence on PL response depends both on substrate material and annealing temperature. The PFM images reveal that the ZnO films have inversion domains. While annealing improves the piezoresponse, the inversion domains still persist. The cross-sectional analysis of the inversion domains shows domain boundary widths of approximately 1.5 nm. (Received ...; accepted ...)     

Microstructure evolution of amorphous silicon thin films upon annealing studied by positron annihilation

Amorphous silicon (a-Si) thin films were prepared on glass substrates by plasma enhanced chemical vapor deposition (PECVD). Influence of annealing temperature on the microstructure, surface morphology, and defects evolution of the films were studied by X-ray diffraction (XRD), atomic force microscope (AFM) and positron annihilation Doppler broadening spectroscopy (DBS) based on a slow positron beam, respectively. The S parameter of the as-deposited a-Si thin film is high, indicative of amorphous state of Si film with many defects. The a-Si gradually grows into polycrystalline silicon with increasing temperature to 650 °C. For the films annealed below ~450 °C, positron diffusion lengths are rather small because most positrons are trapped in the defects of the a-Si films and annihilated there. With further rising the temperature to 600 °C, the diffusion length of positrons increases significantly due to the removal of vacancy-type defects upon annealing at a high temperature. The results indicate that the coalescence of small vacancy-type defects in a-Si thin film and the crystallization of a-Si occur around 450 °C and 650 °C, respectively.     

Influence of Substrate Temperature and Post-Deposition Annealing on Material Properties of Ga-Doped ZnO Prepared by Pulsed Laser Deposition

Ga-doped ZnO films were prepared at 10 mTorr of oxygen over a broad temperature range using pulsed laser deposition. The carrier concentration of as-deposited films decreased monotonically with deposition temperature over a temperature range of 25°C to 450°C. Post-deposition annealing of as-deposited films in forming gas (5% H₂ in argon) or vacuum resulted in a substantial increase in both carrier concentration and electron mobility. The figure of merit was highest for films deposited at 250°C then annealed in forming gas at 400°C. The optical transmittance was near 90% throughout the visible and near-infrared spectral regions. These results indicate that Ga-doped ZnO is a viable alternative to transparent indium-based conductive oxides.     

Effect of annealing on the morphology and optoelectrical characteristics of ZnO thin films grown by plasma-assisted molecular beam epitaxy

The dependence of characteristics of plasma-assisted molecular beam epitaxy-grown ZnO thin films on different postgrowth annealing conditions was investigated. It was found that, under oxygen atmosphere, annealing temperature can profoundly affect the morphological, electrical, and optical properties of ZnO thin films. In particular, the surface morphology changed from a relatively smooth surface before annealing to various island morphologies after annealing above 800°C for samples grown directly on sapphire without a buffer layer. It is speculated that intrinsic stress due to lattice mismatch drives the island formation and the high temperature provides the energy needed for this surface rearrangement. Single-field Hall-effect measurement showed that the carrier concentration improved by an order of magnitude and the mobility increased from about 30 cm²/Vs to ∼70 cm²/Vs by annealing at 750°C. Variable-field Hall effect shows that a model with two carriers, one a degenerate low-mobility electron and the other a higher mobility non-degenerate electron, is needed to explain the transport properties of the thin film. Analysis indicates that annealing at 750°C decreased the carrier concentration and increased the mobility for the high-mobility carrier. Annealing also led to a significant improvement in photoluminescence, with temperatures of ∼750–850°C yielding the best results.     

Effects of post-annealing by the rapid thermal process on the characteristics of MOCVD-Cu/TiN/Si structures

Effects of rapid thermal annealing on the characteristics of Cu films deposited from the (hfac)Cu(VTMS) precursor and on the barrier properties of TiN layers were studied. By the post-annealing, the electrical characteristics of Cu/TiN and the microstructures of Cu films were significantly changed. The properties of Cu films were more sensitive to the annealing temperature than the annealing time. Sheet resistances were decreased in 400–450°C ranges, and abrupt increases were observed above 750°C. It was also found that the copper films showed pronounced grain growth with the (111) preferred orientation. The grain growth and condensation of copper were observed below 500°C without formation of the CuO and Cu₂O phase resulting in surface degradation. Above 500°C, the oxide compound of copper was partially formed on the surface and the inter-reaction on the Cu-TiN interface was started. The inter-reaction of Cu-Ti and Cu-Si interface vigorously occurred and the surface roughness was continuously deteriorated above 650°C. It revealed that the optimum annealing conditions for MOCVD-Cu/PVD-TiN structures to enhance the electrical characteristics without degradation of TiN barriers were in the range of 400°C.     

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).     

Spontaneous growth by sol-gel process of low temperature ZnO as cathode buffer layer in flexible inverted organic solar cells

In this study, the sol–gel method was employed to prepare zinc oxide (ZnO) thin films as cathode buffer layers for inverted organic solar cells (IOSCs). We used a low temperature sol-gel process for the synthesis of ZnO thin films, in which the molar ratio of zinc acetate dihydrate (ZAD) to ethanolamine (MEA) was varied; subsequently, using the thin films, we successfully fabricated inverted solar cells on flexible plastic substrates. A ZnO sol–gel was first prepared by dissolving ZAD and MEA in ethylene glycol monomethyl ether (EGME). The molar ratios of ZAD to MEA were set as 1:1.2, 1:1, and 1:0.8, and we investigated the characteristics of the resulting ZnO thin films. We investigated the optical transmittance, surface roughness, and surface morphology of the films. Then, we discussed the reasons about the improvement of the device efficiency. The devices were fabricated using the ZnO thin films as cathode buffer layers. The results indicated that the morphology of the thin films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 changed to a rippled nanostructure after two-step annealing. The PCE was enhanced because of the higher light absorption in the active layer caused by the nanostructure. The structure of the inverted device was ITO/ZnO/P3HT:PC₆₁BM/MoO₃/Ag. The short-circuit current densities (8.59 mA/cm² and 8.34 mA/cm²) of the devices with films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 ratios, respectively, and annealed at 125 °C were higher than that of the device containing the ZnO thin film that was annealed at 150 °C. Inverted solar cells with ZnO films that were prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 and annealed at 125 °C exhibited PCEs of 3.38% and 3.30%, respectively. More than that, PCEs of the flexible device can reach up to 1.53%.     

Optical and electrical properties of nickel oxide thin films synthesized by sol–gel spin coating

Nickel oxide thin films were prepared by the sol–gel technique combined with spin coating onto glass substrates. The as-deposited films were pre-heated at 275 °C for 15 min and then annealed in air at different temperatures. The effects of the annealing temperature on the structural and optical properties of the films are studied. The results show that 600 °C is the optimum annealing temperature for preparation of NiO films with p-type conductivity and high optical transparency. Then, by using these optimized deposition parameters, NiO thin films of various thicknesses were deposited at the same experimental conditions and annealed under different atmospheres. Surface morphology of the films was investigated by atomic force microscopy. The surface morphology of the films varies with the annealing atmosphere. Optical transmission was studied by UV–vis spectrophotometer. The transmittance of films decreased as the thickness of films increased. The electrical resistivity, obtained by four-point probe measurements, was improved when NiO layers were annealed in N₂ atmosphere at 600 °C.     

Effect of annealing on electrical properties of radio-frequency-sputtered ZnO films

We report on the electrical properties of ZnO films and devices grown on different substrates by radio-frequency magnetron sputtering. The films grown on c-plane sapphire were annealed in the range 800–1,000°C. The electron concentration increased with annealing temperature reaching 1.4×10¹⁹ cm^?3 for 1,000°C. Mobility also increased, however, reaching its maximum value 64.4 cm²/V · sec for 950°C anneal. High-performance Schottky diodes were fabricated on ZnO films grown on n-type 6H-SiC by depositing Au/Ni(300/300 Å). After annealing at 900°C, the leakage current (at ?5 V reverse bias) decreased from 2.2 × 10^?7 A to ～5.0 × 10^?8 A after annealing at 900°C, the forward current increased by a factor of 2, and the ideality factor decreased from 1.5 to 1.03. The ZnO films were also grown on p-type 6H-SiC, and n-ZnO/p-SiC heterostructure diodes were fabricated. The p-n diode performance increased dramatically after annealing at 950°C. The leakage current decreased from 2.0×10^?4 A to 3.0×10^?7 A at ?10 V reverse bias, and the forward current increased slightly from 2.7 mA to 3.9 mA at 7 V forward bias; the ideality factor of the annealed diode was estimated as 2.2, while that for the as-grown sample was considerably higher.     

热氧化磁控溅射金属锌膜制备ZnO纳米棒

利用射频磁控溅射技术在Si(111)衬底上制备金属锌膜 ,在空气中退火热氧化合成了一维ZnO纳米棒。用X射线衍射 (XRD) ,扫描电子显微镜 (SEM) ,透射电子显微镜 (TEM)和光致发光谱 (PL)对样品进行了结构、形貌及光学特性分析。结果表明 :ZnO纳米棒为六方纤锌矿结构单晶相 ,直径在 30～ 6 0nm左右 ,其长度可达5～ 8μm左右。在 2 80nm波长光激发下 ,有很强的 372nm带边紫外光发射和较微弱的 5 16nm深能级绿光发射 ,说明合成的单晶ZnO纳米棒的质量较高     

Effects of excess Bi concentration, buffered Bi2O3 layer, and Ta doping on the orientation and ferroelectricity of chemical-solution-deposited Bi3.25La0.75Ti3O12 films

Effects of excess Bi concentration, buffered Bi₂O₃ layer, and Ta doping on the orientation and ferroelectricity of chemical-solution-deposited (CSD) Bi_3.25La_0.75Ti₃O₁₂ (BLT) films on Pt/SiO₂/Si(100) were studied. The optimum concentration of excess Bi added to the BLT films to achieve a larger remanent polarization (2Pr) was 10 mol.%. The buffered Bi₂O₃ layers could reduce the temperature for c-axis-oriented growth of BLT films from 850°C to 700°C. However, two-step annealing, i.e., first annealed at 650°C and then annealed at a temperature of 700–850°C, could effectively suppress the c-axis-oriented growth and thus improve the 2Pr of BLT films. The improvement of the 2Pr of BLT films can be explained in terms of the large polarization along the a-axis orientation and buffered Bi₂O₃ layers, which compensate the BLT films for Bi evaporation during annealing. The Ta doping can induce two contrary effects on the 2Pr of BLT films. For the (Bi_3.25La_0.75)(Ti_3−xTa_x)O₁₂ (BLTTx) films with x=0.005, the effect of a decrease of oxygen vacancies would be dominant, resulting in the improvement of 2Pr. Because the Ta concentration (x) in the BLTTx films exceeds 0.01, the effect of a decrease of grain size would become dominant, resulting in the degradation of 2Pr.     

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.     

Effects of Growth Temperature on Properties of Nonpolar <Emphasis Type="Italic">a</Emphasis>-Plane ZnO Films on GaN Templates by Pulsed Laser Deposition

In this work, a-plane GaN/r-sapphire templates have been used to grow nonpolar a-plane ZnO films by pulsed laser deposition. The ZnO film growth temperature was varied in the range of 400°C to 600°C, and the effect of growth temperature on the properties of the ZnO thin films was investigated using x-ray diffraction, atomic force microscopy, photoluminescence (PL) spectroscopy, and Raman measurements. The results show that the crystal quality, surface morphology, strain states, and optical properties of a-plane ZnO films are strongly correlated with the deposition temperature. It is found that the crystallinity of the ZnO films gets better and the surface roughness decreases with increasing growth temperature. At a growth temperature of 600°C, the a-ZnO films display the best crystal quality with x-ray (11[`2]0) (11\bar{2}0) omega scan full-width at half-maximum values of 0.28° and 0.41° on axis (11[`2]0) (11\bar{2}0) at azimuth 0° and 90°, respectively. Furthermore, the PL spectrum measured at 83 K is dominated by neutral donor-bound excitons and free-electron-to-bound (e-A ₀) emission, and relatively intense LO-phonon replicas of (e-A ₀) have also been observed in the a-plane ZnO. The dominance of the free exciton and the appearance of its replicas strongly indicate the high quality of the film.     

Preparation of PbTiO3 thin films by plasma enhanced MOCVD and the effect of rapid thermal annealing

Dielectric PbTiO₃-thin films were prepared on p-Si(100) substrate by plasma enhanced metalorganic chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄, Pb(tmhd)₂, and oxygen. As-deposited films were post-treated by rapid thermal annealing method, and the effect of annealing was examined under various conditions. The deposition process was controlled by mixed-control scheme at temperatures lower than 350°C, but controlled by heterogeneous surface reaction at temperatures greater than 350°C. The as-deposited films showed PbO structure at 350∼400°C, but (100) and (101) PbTiO₃ orientations started to appear at 450°C. The deposition rate was increased with rf power due to the enhanced dissociation of Ti and Pb precursors. It was found that the concentration of oxygen plays an important role in crystallization of PbTiO₃ during the rapid thermal annealing. A linear relationship was obtained between the dielectric constant of PbTiO₃ films and the annealing temperature. However, the surface roughness and leakage current density increased mainly due to the defects caused by volatilization of lead and the interface layer formed during the high temperature annealing.     

InxGa1-xAs ohmic contacts to n-type GaAs prepared by sputter deposition

Thermally stable, low contact resistance InAs/Ni/W contacts were previously prepared by sputter depositing InAs, Ni, and W targets in our laboratory. However, the optimum annealing temperature to provide low contact resistance (R_c) was high, resulting in rough contact surface. In the present experiment, the effects of the In concentrations of In_xGa_1-x As targets on the optimum annealing temperature to prepare low R_cand the surface morphology of the_xGa_1-x/ W contacts were studied. In addition, the electrical properties and the interfacial microstructure were correlated to search the optimum In concentration to provide the minimum R_c, where the interfacial microstructure was analyzed by x-ray diffraction and transmission electron microscopy and the contact resistances (R_cc) were measured by the transmission line method. The optimum annealing temperature to provide minimum R_c was reduced by 150°C by using the In_0.7Ga_0.3As targets instead of the previous targets. The contact resistance of 0.4 Ω-mm was obtained for the In_0.7Ga_0.3As/Ni/W contacts after annealing at temperatures of around 600°C. The R_c values did not deteriorate after annealing at 400°C for 2 h. Also, the surface of this contact was smooth and no evidence of In outdiffusion on the contact surface was seen. Finally, the effect of the In concentrations at the metal/GaAs interfaces on the electrical properties will be discussed.