原子层沉积低温制备AZO薄膜

采用原子层沉积技术与改进的Al掺杂模式在石英玻璃基体上低温制备AZO薄膜,利用椭圆偏振仪、原子力显微镜、X射线衍射仪、X射线光电子能谱仪、Hall效应测试仪系统地对样品的生长速率、表面形貌、晶体结构、薄膜成分与电学性能进行了表征和分析。结果表明,采用原子层沉积在150℃下制备AZO薄膜,其为六方纤锌矿结构,Al掺杂对Zn O的(002)有明显的抑制作用,Al在基体中弥散分布,其部分替换Zn O晶格中的Zn,以Al—O的形式存在于晶体中,晶体中存在大量的氧空位,最佳铝锌循环比为1∶19,此条件下AZO薄膜电阻率为4.61×10-4Ω·cm。     

Self-limiting low-temperature growth of crystalline AlN thin films by plasma-enhanced atomic layer deposition

We report on the self-limiting growth and characterization of aluminum nitride (AlN) thin films. AlN films were deposited by plasma-enhanced atomic layer deposition on various substrates using trimethylaluminum (TMA) and ammonia (NH₃). At 185 °C, deposition rate saturated for TMA and NH₃ doses starting from 0.05 and 40 s, respectively. Saturative surface reactions between TMA and NH₃ resulted in a constant growth rate of ~ 0.86 Å/cycle from 100 to 200 °C. Within this temperature range, film thickness increased linearly with the number of deposition cycles. At higher temperatures (≥ 225 °C) deposition rate increased with temperature. Chemical composition and bonding states of the films deposited at 185 °C were investigated by X-ray photoelectron spectroscopy. High resolution Al 2p and N 1s spectra confirmed the presence of AlN with peaks located at 73.02 and 396.07 eV, respectively. Films deposited at 185 °C were polycrystalline with a hexagonal wurtzite structure regardless of the substrate selection as determined by grazing incidence X-ray diffraction. High-resolution transmission electron microscopy images of the AlN thin films deposited on Si (100) and glass substrates revealed a microstructure consisting of nanometer sized crystallites. Films exhibited an optical band edge at ~ 5.8 eV and an optical transmittance of > 95% in the visible region of the spectrum.     

ZnO thin films prepared by atomic layer deposition and rf sputtering as an active layer for thin film transistor

Recently, the application of ZnO thin films as an active channel layer of transparent thin film transistor (TFT) has become of great interest. In this study, we deposited ZnO thin films by atomic layer deposition (ALD) from diethyl Zn (DEZ) as a metal precursor and water as a reactant at growth temperatures between 100 and 250 °C. At typical growth conditions, pure ZnO thin films were obtained without any detectable carbon contamination. For comparison of key film properties including microstructure and chemical and electrical properties, ZnO films were also prepared by rf sputtering at room temperature. The microstructure analyses by X-ray diffraction have shown that both of the ALD and sputtered ZnO thin films have (002) preferred orientation. At low growth temperature T_s ≤ 125 °C, ALD ZnO films have high resistivity (> 10 Ω cm) with small mobility (< 3 cm²/V s), while the ones prepared at higher temperature have lower resistivity (< 0.02 Ω cm) with higher mobility (> 15 cm²/V s). Meanwhile, sputtered ZnO films have much higher resistivity than ALD ZnO at most of the growth conditions studied. Based upon the experimental results, the electrical properties of ZnO thin films depending on the growth conditions for application as an active channel layer of TFT were discussed focusing on the comparisons between ALD and sputtering.     

Characterizations of NbAlO thin films grown by atomic layer deposition

Niobium-aluminate (NbAlO) thin films have been prepared on silicon (100) with different Nb₂O₅:Al₂O₃ growth cycle ratio by atomic layer deposition (ALD) technology. The structural, chemical and optical properties of NbAlO thin films are investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and spectroscopic ellipsometry (SE). The results show that all the obtained NbAlO films are amorphous and fully oxidized. It is also found that the proportion of components in the NbAlO film can be well-controlled by varying the ALD growth cycles of the independent oxides. Furthermore, the refraction index of the prepared films is observed to increase with an increase of the concentration of Nb in the mixtures.     

Low-temperature atomic layer deposition of ZnO thin films: Control of crystallinity and orientation

Low-temperature atomic layer deposition (ALD) processes are intensely looked for to extend the usability of the technique to applications where sensitive substrates such as polymers or biological materials need to be coated by high-quality thin films. A preferred film orientation, on the other hand, is often required to enhance the desired film properties. Here we demonstrate that smooth, crystalline ZnO thin films can be deposited from diethylzinc and water by ALD even at room temperature. The depositions were carried out on Si(100) substrates in the temperature range from 23 to 140 °C. Highly c-axis-oriented films were realized at temperatures below ~ 80 °C. The film crystallinity could be further enhanced by post-deposition annealing under O₂ or N₂ atmosphere at 400-600 °C while keeping the original film orientation intact.     

Luminescence from single CdSe nanocrystals embedded in ZnO thin films using atomic layer deposition

We report the embedding of CdSe/ZnS core-shell nanocrystals into thin films of ZnO grown by atomic layer deposition. Fluorescence from ensembles and that from individual nanocrystals show that the nanocrystal luminescence intensity and stability are preserved through the embedding process. These results are encouraging for the fabrication of optoelectronic nanodevices based on colloidal nanoparticles.     

Properties of tantalum oxide thin films grown by atomic layer deposition

Thin tantalum oxide films were deposited using atomic layer deposition from TaCl₅ and H₂O at temperatures in the range 80–500 °C. The films deposited at temperatures below 300 °C were predominantly amorphous, whereas those grown at higher temperatures were polycrystalline containing the phases TaO₂ and Ta₂O₅. The oxygen to tantalum mass concentration ratio corresponded to that of TaO₂ at all growth temperatures. The optical band gap was close to 4.2 eV for amorphous films and ranged from 3.9 to 4.5 eV for polycrystalline films. The refractive index measured at λ = 550 nm increased from 1.97 to 2.20 with an increase in growth temperature from 80 to 300 °C. The films deposited at 80 °C showed low absorption with absorption coefficients of less than 100 cm⁻¹ in the visible region.     

Low temperature atomic layer deposition of titania thin films

This paper presents a comprehensive study of atomic layer deposition of TiO₂ films on silicon and polycarbonate substrates using TiCl₄ and H₂O as precursors at temperatures in the range 80-120 °C. An in-situ quartz crystal microbalance was used to monitor different processing conditions and the resultant films were characterised ex-situ using a suite of surface analytical tools. In addition, the contact angle and wettability of as-deposited and UV irradiated films were assessed. The latter was found to reduce the contact angle from ≥ 80° to < 10°. Finally, the effect of surface pre-treatment on film toughness and adhesion was investigated and the results show a significant improvement for the pre-treated films.     

Spatial atomic layer deposition of zinc oxide thin films

Zinc oxide thin films have been deposited at high growth rates (up to ~1 nm/s) by spatial atomic layer deposition technique at atmospheric pressure. Water has been used as oxidant for diethylzinc (DEZ) at deposition temperatures between 75 and 250 °C. The electrical, structural (crystallinity and morphology), and optical properties of the films have been analyzed by using Hall, four-point probe, X-ray diffraction, scanning electron microscopy, spectrophotometry, and photoluminescence, respectively. All the films have c-axis (100) preferential orientation, good crystalline quality and high transparency (～ 85%) in the visible range. By varying the DEZ partial pressure, the electrical properties of ZnO can be controlled, ranging from heavily n-type conductive (with 4 mOhm.cm resistivity for 250 nm thickness) to insulating. Combining the high deposition rates with a precise control of functional properties (i.e., conductivity and transparency) of the films, the industrially scalable spatial ALD technique can become a disruptive manufacturing method for the ZnO-based industry.     

Monocrystalline thin films of ZnSe and ZnO grown by atomic layer epitaxy

We report on the growth of monocrystalline thin films of ZnSe and ZnO by atomic layer epitaxy by simple reaction between elemental precursors. Structural and optical properties of these films are discussed with reference to the investigations performed with atomic force microscopy, scanning electron microscopy, cathodoluminescence and photoluminescence.     

Electrical properties of quaternary HfAlTiO thin films grown by atomic layer deposition

Quaternary alloyed HfAlTiO thin (~ 4-5 nm) films in the wide range of Ti content have been grown on Si substrates by Atomic Layer Deposition technique, and the effect of both the film composition and the interfacial reactions on the electrical properties of HfAlTiO films is investigated. It is shown that depending on the Ti content, the permittivity and the leakage current density I_leak in HfAlTiO films vary in the range k = 18 ÷ 28 and 0.01-2.4 A cm^− 2, respectively. The incorporation of ultra thin SiN interlayer in Al/HfAlTiO/SiN/Si stack gives rise to the sharp (× 10³) decrease of the I_leak ~ 6 · 10^− 5 A/cm² at the expense of the rather low capacitance equivalent thickness ~ 0.9 nm.     

Growth of aluminum nitride thin films prepared by plasma-enhanced atomic layer deposition

Aluminum nitride (AlN) thin films were deposited by atomic layer deposition from aluminum chloride (AlCl₃) and an ammonia/hydrogen plasma. The most important role of the ammonia/hydrogen plasma was to act as a reducing agent to extract Cl from AlCl₃, and to form AlN subsequently. The growth rate was saturated at ∼0.042 nm/cycle, and the thickness was proportional to the number of reaction cycles. Repeating this reaction cycle led to precisely controlled growth. The film properties were analyzed using Auger electron spectroscopy, X-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy and time-of-flight elastic recoil detection analysis. The concentration of chlorine and hydrogen impurities was 0.23 and 2.01 at.%, respectively. AlN films showed good anti-oxidation properties when O₂ was annealed at 650 °C for 30 min.     

Characteristics of ZnO films prepared by atomic layer deposition for transparent electronic devices

Recently, nanostructured zinc oxide (ZnO) for many different applications in micro- and opto-electronic devices has been studied intensively. However, its structural and electrical properties still require improvements for ZnO-based transparent electronics. In this study, we fabricated ZnO films (thicknesses from 30 to 70 nm) on glass substrates using atomic layer deposition (ALD) and investigated the film properties in relation with substrate temperatures. The processing window (thermal ALD window) of self-limiting growth was observed at 110-190 degrees C. In our thermal ALD window, the average growth rate of ZnO films was 0.26 nm/cycle, and the (002) orientation became dominant with increasing substrate temperatures. For all growth temperatures, ZnO films have shown n-type conductivity. At 170 degrees C, ZnO with good electrical properties of carrier concentration (1.3 x 10(19) cm(-3)), mobility (18 cm2/Vs), and resistivity (2.7 x 10(-2) omegacm) was successfully obtained.     

Enhancement of crystallinity and optical properties of bilayer TiO2/ZnO thin films prepared by atomic layer deposition

Bilayer and multilayer thin films are becoming increasingly important in the development of faster, smaller and more efficient electronic and optoelectronic devices. One of the motivations of applying bilayer or multilayer structures is to modify the optical properties of materials. Atomic layer deposition (ALD) is a variant of Chemical Vapour Deposition that can produce uniform and conformal thin films with well controlled nanostructures. In this study, we have demonstrated new findings of the use of ALD fabricated bilayer TiO2/ZnO thin films with enhanced crystallinity and optical properties. TiO2 films have been deposited at 300 degrees C for 1000 (51 nm in thickness) or 3000 (161 nm in thickness) deposition cycles onto glass and Si substrates. ZnO films are subsequently deposited on the TiO2 layers at 280 degrees C for 500 deposition cycles (55 nm). The crystallinity and optical properties of the TiO2/ZnO thin films have been analysed by X-ray diffraction, photoluminescence, UV-Vis spectroscopy, Atomic Force Microscopy and Scanning Electron Microscopy. XRD diffraction pattern confirmed the presence of ZnO with wutrtize crystal structure and TiO2 with anatase structure. It shows that the crystallinity of the TiO2 films has been improved with the deposition of ZnO. The intensity of UV luminescence has increased by almost 30% for TiO2/ZnO bilayer as compared to the single layer TiO2. The possible mechanism for the enhancement of the optical properties of bilayer TiO2/ZnO thin films will be discussed.     

Electrical resistivity of Ti-Zn mixed oxide thin films deposited by atomic layer deposition

Ti-Zn mixed oxide thin films, with thickness less than 50 nm, were grown with atomic layer deposition (ALD) technique at low temperature (90 °C) varying the composition. ALD is a powerful chemical technique to deposit thin films with thickness of few atomic layers. ALD oxide material growth is achieved by dosing sequentially the metal precursor and the oxidizing agent. Thanks to ALD nature of layer by layer growth it was possible to realize mixed metal, Ti and Zn, oxide thin films with controlled composition, simply by changing the number of cycles of each metal oxide layer. Structural and electrical properties of the prepared thin films were studied as a function of their composition. Synchrotron radiation X-ray diffraction technique was used to follow thin film crystallization during sample annealing, performed in situ. It was observed that the onset temperature of crystallization raises with Ti content, and sample structure was Zn₂TiO4 phase. Electrical resistivity measurements were performed on crystalline samples, annealed at 600 °C, revealing an increase in resistivity with Ti content.     

Nitrogen-doped ZnO thin films grown on glass substrates by atomic layer deposition using NH3 as a doping source

Nitrogen-doped ZnO (ZnO:N) films were successfully grown on glass substrates by atomic layer deposition (ALD). NH3 was used as a doping source, and the substrate temperature was relatively low (90 approximately 210 degrees C). The main focus of the study was to report on the effect of the temperature on the electrical properties (e.g., carrier concentration, mobility, etc.) of the grown ZnO:N films. At all temperatures, the carrier was found to be n-type, and its electron concentration did not show much variation within the values between 3 x 10(16) and 6 x 10(16) cm-3; the mobility increased with the temperature (1 cm2/Vs at 110 degrees C, 5 cm2/Vs at 190 degrees C); and the resistivity decreased with the temperature (203 omegacm at 110 degrees C, 21 omegacm at 190 degrees C). The electrical properties are discussed in relation with the nitrogen concentration, crystallinity, crystal orientation, grain size, and surface morphology. The nitrogen concentration in the ZnO:N films was constant at all temperatures (approximately 2.5 atomic percent); the crystallinity and crystal orientation improved with the temperature; and the mean grain size increased with the temperature (13.2 nm at 110 degrees C, 35.3 nm at 190 degrees C). The results for the ZnO:N films were also compared with the results for the undoped ZnO films.     

Epitaxial growth of non-polar m-plane ZnO thin films by pulsed laser deposition

Non-polar ZnO thin films were deposited on m-plane sapphire substrates by pulsed laser deposition at various temperatures from 300 to 700 °C. The effects of growth temperature on surface morphology, structural, electrical, and optical properties of the films were investigated. All the films exhibited unique m-plane orientation indicated by X-ray diffraction and transmission electron microscopy. Based on the scanning electron microscopy and atomic force microscopy, the obtained films had smooth and highly anisotropic surface, and the root mean square roughness was less than 10 nm above 500 °C. The maximum electron mobility was ～18 cm²/V s, with resistivity of ～0.26 Ω cm for the film grown at 700 °C. Room temperature photoluminescence of the m-plane films was also investigated.     

ZnO thin films prepared by pulsed laser deposition

Zinc oxide (ZnO) thin films were deposited on soda lime glass substrates by pulsed laser deposition (PLD) in an oxygen-reactive atmosphere. The structural, optical, and electrical properties of the as-prepared thin films were studied in dependence of substrate temperature and oxygen pressure. High quality polycrystalline ZnO films with hexagonal wurtzite structure were deposited at substrate temperatures of 100 and 300 °C. The RMS roughness of the deposited oxide films was found to be in the range 2-9 nm and was only slightly dependent on substrate temperature and oxygen pressure. Electrical measurements indicated a decrease of film resistivity with the increase of substrate temperature and the decrease of oxygen pressure. The ZnO films exhibited high transmittance of 90% and their energy band gap and thickness were in the range 3.26-3.30 eV and 256-627 nm, respectively.