Characteristics and properties of metal aluminum thin films prepared by electron cyclotron resonance plasma-assisted atomic layer deposition technology

Metal aluminum (Al) thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for the thin-film preparation and annealing of the as-deposited films relative to the surface square resistivity. The square resistivity of as-deposited Al films is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structural analysis, we conclude that the square resistivity is determined by neither the contaminant concentration nor the surface morphology, but by both the crystallinity and crystal size in this process.     

Effect of Al doping on structural,optical and electrical properties of SnO2 thin films synthesized by pulsed laser deposition

Aluminium-doped (Al = 0–5?wt.%) SnO₂ thin films with low-electrical resistivity and high optical transparency have been successfully synthesized by pulsed laser deposition technique at 500 °C. Structural, optical and electrical properties of the as-deposited and post-annealed thin films were investigated. X-ray diffraction patterns suggest that the films transform from crystalline to amorphous state with increasing aluminium content. The root mean square (R_q) surface roughness parameter, determined by atomic force microscopy decreases upon annealing of the as-deposited film. While resistivity of the film is the lowest (9.49 × 10^?4 Ω-cm) at a critical doping level of 1?wt.% Al, optical transparency is the highest (nearly 90%) in the as-deposited condition. Temperature dependence of the electrical resistivity suggests that the Mott’s variable range hopping process is the dominant carrier transport mechanism in the lower temperature range (40–135 K) for all the films whereas, thermally activated band conduction mechanism seems to account for conduction in the higher temperature region (200–300 K).     

Annealing effect on microstructure and mechanical properties of amorphous Al-C-N films

Al-C-N thin films with different Al contents were deposited on Si (1 0 0) substrates by closed-field unbalanced reactive magnetron sputtering in the mixture of argon and nitrogen gases. These films were subsequently vacuum-annealed at 700 °C and 1000 °C, respectively. The microstructures of as-deposited and annealed films were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM); while the hardness and elastic modulus values were measured by nano-indention method. The results indicated that the microstructure of both as-deposited and annealed Al-C-N films strongly depended on Al content. For thin films at low Al content, film delamination rather than crystallization occurred after the sample was annealed at 1000 °C. For thin films at high Al content, annealing led to the formation of AlN nanocrystallites, which produced nanocomposites of AlN embedded into amorphous matrices. Both the density and size of AlN nanocrystallites were found to decrease with increasing depth from the film surface. With increasing of annealing temperature, both hardness and elastic modulus values were decreased; this trend was decreased at high Al content. Annealing did not change elastic recovery property of Al-C-N thin films.     

Electrical and magnetic properties of CoFeAlO thin films

Influences of oxygen-partial pressure and annealing on the electrical and magnetic properties of CoFeAlO thin films were systematically investigated by means of resistivity, permeability, magnetization and ferromagnetic resonance (FMR) measurements. It was found that, with increasing oxygen-partial pressure or under annealing, the electrical resistivity of the film increased and the magnetic softness decreased, which is attributed to the microstructural change of the film. Interestingly, an as-deposited Co_45.30Fe_20.65Al_19.34O_14.71 film was found to exhibit an inverted hysteresis loop with negative coercivity, and this peculiar phenomenon disappeared upon effects of oxygen-partial pressure and annealing. It was also found that the as-deposited films owned a narrow FMR line width that increased with increasing oxygen-partial pressure or under annealing.     

Study of titania nanorod films deposited by matrix-assisted pulsed laser evaporation as a function of laser fluence

The effects of annealing at 300 °C on gold nanostructures sputtered onto glass substrate were studied using XRD, SAXSees, the Van der Pauw method and ellipsometry. As-sputtered and annealed samples exhibit a different dependence of the gold lattice parameter on the sputtering time. With increasing sputtering time the average thickness of the layer and the size of gold crystallites increased. Another rapid enlargement of the crystallites is observed after annealing. The volume resistivity decreases rapidly with the increasing sputtering time for both, as-deposited and annealed structures. With increasing sputtering time initially discontinuous gold coverage changes gradually in a continuous one. Electrically continuous gold coverage on the as-sputtered and annealed samples exhibits the same concentration of free charge carriers and Hall mobility. Optical constants of as-deposited and annealed gold films determined by ellipsometry support resistivity measurements and clearly manifest the presence of plasmons in discontinuous films.     

Effect of annealing on the optical and electrical properties of ZnO:Er films

The effect of dopant concentration and annealing in the oxidizing atmosphere on the structural, optical, and electrical properties of ZnO:Er films deposited on sapphire substrates by the electron-beam evaporation method is investigated. The optical and electrical properties of these films were studied by UV-VIS-IR absorption and reflection spectroscopy, photoluminescence, and resistivity measurements. Experimental results reveal that as-deposited ZnO:Er films have both high transmittance in the visible range and low electrical resistivity and can be used as efficient transparent conducting oxides (TCOs). These films annealed in the oxidizing atmosphere have a visible emission band which can be used to fabricate light-emitting diodes.     

Characteristics of electron beam evaporated nanocrystalline SnO2 thin films annealed in air

Tin oxide (SnO₂) thin films (about 200 nm thick) have been deposited by electron beam evaporation followed by annealing in air at 350-550 °C for two hours. Optical, electrical and structural properties were studied as a function of annealing temperature. The as-deposited film is amorphous, while all other annealed films are crystalline (having tetragonal structure). XRD suggest that the films are composed of nanoparticles of 5-10 nm. Raman analysis and optical measurements suggest quantum confinement effects that are enhanced with annealing temperature. For instance, Raman peaks of the as-deposited films are blue-shifted as compared to those for bulk SnO₂. Blue shift becomes more pronounced with annealing temperature. Optical band gap energy of amorphous SnO₂ film is 3.61 eV, which increases to about 4.22 eV after crystallization. Two orders of magnitude decrease in resistivity is observed after annealing at 350-400 °C due to structural ordering and crystallization. The resistivity, however, increases slightly with annealing temperature above 400 °C, possibly due to improvement in stoichiometry and associated decrease in charge carrier density.     

Annealing induced refinement on optical transmission and electrical resistivity of indium tin oxide

The effect of annealing condition on sputtered indium tin oxide （ITO） films on quartz with the thickness of 200 nm is characterized to show enhanced optical transparency and optimized electrical contact resistivity. The as-deposited grown ITO film exhibits only 65% and 80% transmittance at 532 and 632.8 nm, respectively. After annealing at 475 ℃ for 15 min, the ITO film is refined to show improved transmittance at shorter wavelength region. The transmittances of 88.1% at 532 nm and 90.4% at 632.8 nm can be obtained. The 325-nm transmittance of the post-annealed ITO film is greatly increased from 12.7% to 41.9%. Optimized electrical property can be obtained when annealing below 450 ℃, leading to a minimum sheet resistance of 26 Ω/square. Such an ITO film with enhanced ultraviolet （UV） transmittance has become an alternative candidate for applications in current UV photonic devices. The morphology and conductance of the as-deposited and annealed ITO films are determined by using an atomic force microscopy （AFM）, showing a great change on the uniformity distribution with finite improvement on the surface conductance of the ITO film after annealing.     

Influence of films thickness and structure on the photo-response of ZnO films

ZnO thin films were grown using Successive Ionic Layer Adsorption and Reaction (SILAR) method on glass substrates at room temperature. Annealing temperatures and film thickness effect on the structural, morphological, optical and electrical properties of the films were studied. For this as-deposited films were annealed at 200, 300, 400 and 500 °C for 30 min in oxygen atmosphere. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies showed that the films are covered well with glass substrates and have good polycrystalline structure and crystalline levels. The film thickness effect on band gap values was investigated and band gap values were found to be within the range of 3.49-3.19 eV. The annealing temperature and light effect on electrical properties of the films were investigated and it was found that the current increased with increasing light intensity. The resistivity values were found as 10⁵ Ω-cm for as-deposited films from electrical measurements. The resistivity decreased decuple with annealing temperature and decreased centuple with light emission for annealed films.     

硅衬底GaN基LED N极性n型欧姆接触研究

在Si衬底GaN基垂直结构LED的N极性n型面上,利用电子束蒸发的方法制作了Ti/Al电极,通过了I-V曲线研究了有无AlN缓冲层对这种芯片欧姆接触的影响.结果显示,去除AlN缓冲层后的N极性n型面与Ti/Al电极在500到600 ℃范围内退火才能形成欧姆接触.而保留AlN缓冲层的N极性n型面与Ti/Al电极未退火时就表现为较好的欧姆接触,比接触电阻率为2×10^-5 Ω·cm²,即使退火温度升高至600 ℃,也始终保持着欧姆接触特性.因此,AlN缓冲层的存在是Si衬底GaN基垂直结构LED获得高热稳定性n型欧姆接触的关键. 关键词： 硅衬底 N极性 AlN缓冲层 欧姆接触     

Effect of annealing on structural, optical and electrical properties of nanostructured Ge thin films

Ge thin films with a thickness of about 110 nm have been deposited by electron beam evaporation of 99.999% pure Ge powder and annealed in air at 100-500 °C for 2 h. Their optical, electrical and structural properties were studied as a function of annealing temperature. The films are amorphous below an annealing temperature of 400 °C as confirmed by XRD, FESEM and AFM. The films annealed at 400 and 450 °C exhibit X-ray diffraction pattern of Ge with cubic-F structure. The Raman spectrum of the as-deposited film exhibits peak at 298 cm⁻¹, which is left-shifted as compared to that for bulk Ge (i.e. 302 cm⁻¹), indicating nanostructure and quantum confinement in the as-deposited film. The Raman peak shifts further towards lower wavenumbers with annealing temperature. Optical band gap energy of amorphous Ge films changes from 1.1 eV with a substantial increase to ∼1.35 eV on crystallization at 400 and 450 °C and with an abrupt rise to 4.14 eV due to oxidation. The oxidation of Ge has been confirmed by FTIR analysis. The quantum confinement effects cause tailoring of optical band gap energy of Ge thin films making them better absorber of photons for their applications in photo-detectors and solar cells. XRD, FESEM and AFM suggest that the deposited Ge films are composed of nanoparticles in the range of 8-20 nm. The initial surface RMS roughness measured with AFM is 9.56 nm which rises to 12.25 nm with the increase of annealing temperature in the amorphous phase, but reduces to 6.57 nm due to orderedness of the atoms at the surface when crystallization takes place. Electrical resistivity measured as a function of annealing temperature is found to reduce from 460 to 240 Ω-cm in the amorphous phase but drops suddenly to 250 Ω-cm with crystallization at 450 °C. The film shows a steep rise in resistivity to about 22.7 KΩ-cm at 500 °C due to oxidation. RMS roughness and resistivity show almost opposite trends with annealing in the amorphous phase.     

Effect of process parameters and post-deposition annealing on the microwave dielectric and optical properties of pulsed laser deposited Bi<Subscript>1.5</Subscript>Zn<Subscript>1.0</Subscript>Nb<Subscript>1.5</Subscript>O<Subscript>7</Subscript> thin films

Bismuth Zinc niobate (Bi_1.5Zn_1.0Nb_1.5O₇) thin films were deposited by pulsed laser deposition (PLD) method on fused silica substrates at different oxygen pressures. The structural, microwave dielectric and optical properties of these thin films were systematically studied for both the as-deposited and the annealed films at 600°C. The as-deposited films were all amorphous in nature but crystallized on annealing at 600°C in air. The surface morphology as studied by atomic force microscopy (AFM) reveals ultra-fine grains in the case of as-deposited thin films and cluster grain morphology on annealing. The as-deposited films exhibit refractive index in the range of 2.36–2.53 (at a wavelength of 750 nm) with an optical absorption edge value of 3.30–3.52 eV and a maximum dielectric constant of 11 at 12.15 GHz. On annealing the films at 600°C they crystallize to the cubic pyrochlore structure accompanied by an increase in band gap, refractive index and microwave dielectric constant.     

不同衬底和CdCl2退火对磁控溅射CdS薄膜性能的影响

在科宁7059玻璃, FTO, ITO, AZO四种衬底上磁控溅射CdS薄膜, 并在CdCl₂+干燥空气380 ℃退火, 分别研究了不同衬底和退火工艺对CdS薄膜形貌、结构和光学性能的影响. 扫描电子显微镜形貌表明: 不同衬底原位溅射CdS薄膜的形貌不同, 退火后相应CdS薄膜的晶粒度和表面粗糙度明显增大. XRD衍射图谱表明: 不同衬底原位溅射和退火CdS薄膜均为六角相和立方相的混相结构, 退火前后科宁7059玻璃, FTO, AZO衬底上CdS薄膜有 H(002)/C(111) 最强衍射峰, ITO衬底原位溅射CdS薄膜没有明显的最强衍射峰, 退火后出现 H(002)/(111) 最强衍射峰. 紫外-可见分光光度计分析表明: AZO, FTO, ITO, 科宁7059玻璃衬底CdS薄膜的可见光平均透过率依次减小, 退火后相应衬底CdS薄膜的可见光平均透过率增大, 光学吸收系数降低; 退火显著增大了不同衬底CdS薄膜的光学带隙. 分析得出: 上述结果是由于不同衬底类型和退火工艺对CdS多晶薄膜的形貌、结构和带尾态掺杂浓度改变的结果. 关键词： CdS薄膜 磁控溅射 退火再结晶 带尾态     

Formation of CdO films from chemically deposited Cd(OH)2 films as a precursor

Formation of cadmium hydroxide at room temperature onto glass substrates from an aqueous alkaline cadmium nitrate solution using a simple soft chemical method and its conversion to cadmium oxide (CdO) by thermal annealing treatment has been studied in this paper. The as-deposited film was given thermal annealing treatment in oxygen atmosphere at 450 °C for 2 h for conversion into cadmium oxide. The structural, surface morphological and optical studies were performed for as-deposited and the annealed films. The structural analyses revealed that as-deposited films consists of mixture of Cd(OH)₂ and CdO, while annealed films exhibited crystalline CdO. From surface morphological studies, conversion of clusters to grains after annealing was observed. The band gap energy was changed from 3.21 to 2.58 eV after annealing treatment. The determination of elementals on surface composition of the core-shell nanoparticles of annealed films was carried out using X-ray photoelectron spectroscopy (XPS).     

Comparable study on the effect of diluted NH4Cl solution on the postdeposition surface texture of as-deposited aluminum-doped zinc oxide films by direct current pulse and direct current reactive magnetron sputtering

Effect of 5.0% diluted NH₄Cl aqueous solution was comparably investigated on the postdeposition surface texture of the as-deposited smooth aluminum-doped zinc oxide (AZO) films by direct current pulse reactive magnetron sputtering (DCP-sputtering) and direct current reactive magnetron sputtering (DC-sputtering). The as-deposited AZO films by DCP-sputtering showed an effective surface texture for light trapping upon the etching of 5.0% diluted NH₄Cl solution, while the as-deposited AZO films by DC-sputtering demonstrated an obscure surface texture upon the same etching treatment. The different result might be attributable to a big difference in film strain and film compactness. The formation of interstitial Zn, interstitial Al and grain boundary is the key to realize effective surface texture for the as-deposited AZO films.     

Effect of N2 ambient annealing on the field emission properties of HfNxOy thin films

HfN_xO_y thin films were deposited on Si substrates by direct-current sputtering. The influence of N₂ ambient annealing on the morphology, structure and field emission properties of the HfN_xO_y thin films was studied systematically. Scanning electron microscopy indicates that both the as-deposited and the annealed films are composed of nanoparticles, and the particle sizes of these films do not change much before and after annealing. Atomic force microscopy shows that the surface of the as-deposited films is smooth while that of the annealed films becomes rough, with many protrusions. X-ray diffraction patterns demonstrate that the as-deposited films are amorphous while the samples annealed at over 500 °C are polycrystalline. It is found that the field electron emission properties of the annealed films are better than those of the as-deposited films. The film annealed at 800 °C shows the best field emission properties. The mechanism for the improvement of the field electron emission property of the annealed thin films is also discussed. PACS 73.61.-r; 79.70.+q; 81.05.-t     

温度对AZO薄膜红外辐射性能的影响

随着全球资源的减少和环境的恶化,节能减排已成为人们关注的焦点,具有保温隔热功能的低辐射玻璃成为研究的热点。提高玻璃保温隔热性能最有效的方法就是在其表面涂覆低辐射率层。原材料丰富、导电性能好、可见光透过率高等优势使得Al掺杂ZnO (AZO)薄膜成为最具潜力的低辐射率层。系统研究了温度对AZO薄膜红外辐射性能的影响,分析了变化机理。首先研究了在一定的温度下持续一段时间后,AZO薄膜的红外比辐射率的变化情况。然后研究了在变温环境中红外比辐射率的变化情况。采用直流磁控溅射法在室温下玻璃基片上沉积500 nm厚的AZO薄膜,将薄膜放到马弗炉中进行热处理,在100～400 ℃空气气氛下保温1 h,随炉冷却。采用X射线衍射仪对AZO薄膜进行物相分析,采用扫描电子显微镜观察薄膜表面形貌变化。利用四探针测试法测量AZO薄膜的电阻率,采用红外比辐射率测试仪测试薄膜红外比辐射率, 可见分光光度计测量可见光谱。测试的结果表明,薄膜热处理前后均为六角纤锌矿结构,(002)择优取向。300 ℃及以下热处理1 h后,(002)衍射峰增强,半高宽变窄,晶粒尺寸长大。随着热处理温度的升高,薄膜的电阻率先减小后增大,200 ℃热处理后的薄膜具有最小的电阻率(0.9×10-3 Ω·cm)。热处理温度升高,晶粒长大使得薄膜电阻率降低。热处理温度过高,薄膜会从空气中吸收氧,电阻率下降。薄膜的红外比辐射率变化趋势和电阻率的一致,在200 ℃热处理后获得最小值(0.48)。自由电子对红外光子有较强的反射作用,当电阻率低,自由电子浓度高的时候,更多的红外光子被反射,红外辐射作用弱,红外比辐射率小。薄膜的可见光透过率随着热处理温度的升高先减小后增大,200 ℃热处理后的薄膜的可见光透过率最小,但仍高达82%。这种变化是由于自由电子浓度变化引起的,自由电子对可见光有很强的反射作用。选取未热处理和200 ℃热处理后的样品进行变温红外比辐射率的测量,将样品放在可加热的样品台上,位置固定,在室温到350 ℃的升温和降温过程中每隔25 ℃测量一次红外比辐射率,结果表明,在室温到350 ℃的温度范围内,AZO薄膜的红外比辐射率在升温过程中随着温度的上升而增大,在降温过程中减小,经过整个升、降温过程后,薄膜的红外比辐射率增大。     

Influences of annealing on structural and compositional properties of Al_2O_3 thin films grown on 4H–SiC by atomic layer deposition

Annealing effects on structural and compositional performances of Al_2O_3 thin films on 4H–Si C substrates are studied comprehensively. The Al_2O_3 films are grown by atomic layer deposition through using trimethylaluminum and H_2 O as precursors at 300?C, and annealed at various temperatures in ambient N_2 for 1 min. The Al_2O_3 film transits from amorphous phase to crystalline phase as annealing temperature increases from 750?C to 768?C. The refractive index increases with annealing temperature rising, which indicates that densification occurs during annealing. The densification and grain formation of the film upon annealing are due to crystallization which is relative with second-nearest-neighbor coordination variation according to the x-ray photoelectron spectroscopy(XPS). Although the binding energies of Al 2p and O 1s increase together during crystallization, separations between Al 2p and O 1s are identical between as-deposited and annealed sample, which suggests that the nearest-neighbour coordination is similar.     

Initial study on the structure and photoluminescence properties of SiC films doped with Al

SiC films doped with aluminum (Al) were prepared by the rf-magnetron sputtering technique on p-Si substrates with a composite target of a single crystalline SiC containing several Al pieces on the surface. The as-deposited films were annealed in the temperature range of 400-800 °C under nitrogen ambient. The thin films have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results show that the introduction of Al into films hinders crystalline formation process. And with the increase of annealing temperature, more Si particles are formed in the films, which strongly affect the optical absorption properties. The photoluminescence (PL) spectra of the samples show two peaks at 370 nm and 412 nm. The intensities of the PL peaks are evidently improved after Al doped. We attribute the origin of the two PL peaks to a kind of Si-related defect centres. The obtained results are expected to have important applications in modern optoelectronic devices.     

A non-thermal chemical synthesis of hydrophilic and amorphous cobalt oxide films for supercapacitor application

Present work explored a room temperature, simple and low cost chemical route for the preparation of hydrophilic cobalt oxide films from alkaline cobalt chloride (CoCl₂:6H₂O) and double distilled water precursor solutions. As-deposited cobalt oxide films showed amorphous nature, which is one of the prime requirements for supercapacitor, as confirmed from X-ray diffraction studies. Changes in direct band gap energy and electrical resistivity of as-deposited cobalt oxide films were confirmed after annealing. Spherical grains of about 40-50 nm diameters were uniformly distributed over the substrate surface. Surface wettability studied in contact with liquid interface, showed hydrophilic nature as water contact angle was <90°. Finally, presence of cobalt-oxygen covalent bond was observed from Raman shift experiment.