Atomic layer deposition of HfO2 thin films and nanolayered HfO2–Al2O3–Nb2O5 dielectrics

Smooth, 4–6-nm thick hafnium oxide films were grown by atomic layer deposition from HfI₄ or HfCl₄ and H₂O on SiO₂/Si(1 0 0) substrates at 300 °C. Non-uniform films were obtained on hydrogen-terminated Si(1 0 0). The stoichiometry of the films corresponded to that of HfO₂. The films contained small amounts of residual chlorine and iodine. The films deposited on SiO₂/Si(1 0 0) were amorphous, but crystallized upon annealing at 1000 °C. In order to decrease the conductivity, the HfO₂ films were mixed with Al₂O₃, and to increase the capacitance, the films were mixed with Nb₂O₅. The capacitance–voltage curves of the Hf–Al–O mixture films showed hysteresis. The capacitance–voltage curves of HfO₂ films and mixtures of Hf–Al–Nb–O were hysteresis free.     

Atomic layer deposition of SiO2 thin films using tetrakis(ethylamino)silane and ozone

We examined the atomic layer deposition (ALD) of silicon dioxide thin films on a silicon wafer by alternating exposures to tetrakis(ethylamino)silane [Si(NHC2H5)4] and O3. The growth kinetics of silicon oxide films was examined at substrate temperatures ranging from 325 to 514 degrees C. The deposition was governed by a self-limiting surface reaction, and the growth rate at 478 degrees C was saturated at 0.17 nm/cycle for Si(NHC2H5)4 exposures of 2 x 10(6) L (1 L = 10(-6) Torr x s). The films deposited at 365-404 degrees C exhibited a higher deposition rate of 0.20-0.21 nm/cycle. However, they contained impurities, such as carbon and nitrogen, and showed poor film qualities. The concentration of impurities decreased with increasing substrate temperature. It was found that the films deposited in the high-temperature regime (478-514 degrees C) showed excellent physical and electrical properties equivalent to those of LPCVD films.     

Atomic layer deposition of BN thin films

Boron nitride has for the first time been deposited from gaseous BBr₃ and NH₃ by means of atomic layer deposition. The deposition temperatures were 400 and 750 °C, and the total pressure was 10 torr. The BN films, deposited on silica substrates, showed a turbostratic structure with a c-axis of 0.70 nm at a deposition temperature of 750 °C as determined by X-ray diffraction. The films deposited at 400 °C were significantly less ordered. The film density was obtained by means of X-ray reflectivity, and it was found to be 1.65–1.70 and 1.90–1.95 g cm⁻³ for the films deposited at 400 and 750 °C, respectively. Furthermore, the films were, regardless of deposition temperature, fully transparent and very smooth. The surface roughness was 0.3–0.5 nm as measured by optical interferometry.     

Atomic layer deposition of Ru thin film using N2/H2 plasma as a reactant

Ruthenium (Ru) thin films were grown by atomic layer deposition using IMBCHRu [(η6-1-Isopropyl-4-MethylBenzene)(η4-CycloHexa-1,3-diene)Ruthenium(0)] as a precursor and a nitrogen-hydrogen mixture (N₂/H₂) plasma as a reactant, at the substrate temperature of 270 °C. In the wide range of the ratios of N₂ and total gas flow rates (fN₂/N₂ + H₂) from 0.12 to 0.70, pure Ru films with negligible nitrogen incorporation of 0.5 at.% were obtained, with resistivities ranging from ~ 20 to ~ 30 μΩ cm. A growth rate of 0.057 nm/cycle and negligible incubation cycle for the growth on SiO₂ was observed, indicating the fast nucleation of Ru. The Ru films formed polycrystalline and columnar grain structures with a hexagonal-close-packed phase. Its resistivity was dependent on the crystallinity, which could be controlled by varying the deposition parameters such as plasma power and pulsing time. Cu was electroplated on a 10-nm-thick Ru film. Interestingly, it was found that the nitrogen could be incorporated into Ru at a higher reactant gas ratio of 0.86. The N-incorporated Ru film (~ 20 at.% of N) formed a nanocrystalline and non-columnar grain structure with the resistivity of ~ 340 μΩ cm.     

Atomic layer deposition of TiO(2) nanostructures for self-cleaning applications

Nanostructured titanium dioxide (TiO(2)) porous films and nanotube arrays were prepared by atomic layer deposition (ALD) on porous anodic alumina (PAA) templates. The nanostructures were characterized by FESEM and XRD to investigate the structural and crystallographic characteristics. They were then evaluated as self-cleaning surfaces by comparing their photocatalytic activities and photoinduced hydrophilic property under 365?nm illumination. The?nanostructures showed photocatalytic activities and photoinduced hydrophilicity, with nanostructures showing enhanced photoactivity when compared to planar structures. Both photocatalytic and photoinduced hydrophilic properties were strongly affected by the dimension and morphology of the nanostructures. The prepared nanostructures could have potential application as self-cleaning surfaces.     

Preparation of taN thin film by H2 plasma assisted atomic layer deposition using tert-butylimino-tris-ethylmethylamino tantalum

The plasma assisted atomic layer deposition (ALD) of tantalum nitride (TaN) thin films were conducted using tert-butylimino-tris-ethylmethylamino tantalum (TBTEMAT) and hydrogen plasma at 250 degrees C. The effects of H2-plasma pulse time and RF power on the film properties, such as resistivity, surface roughness, step coverage and stability in air, were examined. The film growth rate (thickness/cycle) was in the range of 0.05-0.08 nm/cycle and the resistivity of the films varied from 490 to 70,000 microomega cm, depending on the plasma conditions. Longer plasma pulse times and increasing RF power yielded films of lower resistivity along with improving the stability. The films were smooth and the conformality of the films deposited in 0.28 microm holes with an aspect ratio of 7:1 was 100%.     

Bi2Te3热电薄膜的电化学原子层外延制备

采用电化学原子层外延法(ECALE)在Au电极上成功地制备了Bi2Te3化合物热电薄膜.通过循环伏安扫描研究Te和Bi在Au衬底上的电化学特性,使用自动沉积系统交替欠电位沉积Te、Bi原子层200个循环获得沉积物.XRD、EDX和FESEM测试结果表明循环沉积200层后得到的沉积物Bi和Te的化学计量比为2:3,且是Bi2Te3薄膜化合物,而非单质Bi和Te的简单混合;薄膜均匀、致密、平整且可重复性好,以(015)为最优取向外延生长的.     

Atomic layer deposition and characterization of biocompatible hydroxyapatite thin films

Atomic layer deposition (ALD) was used to produce hydroxyapatite from Ca(thd)₂ (thd = 2,2,6,6-tetramethyl-3,5-heptanedionato) and (CH₃O)₃PO onto Si(100) and Corning (0211). Film crystallinity, stoichiometry, possible impurities and surface morphology were determined. The as-deposited films contained significant amounts of carbonate impurities however, annealing at moist N₂ flow reduced the carbonate content even at 400 °C. The as-deposited Ca-P-O films were amorphous but rapid thermal annealing promoted the formation of the hydroxyapatite phase. Mouse MC 3T3-E1 cells were used for the cell culture experiments. According to the bioactivity studies cell proliferation was enhanced on as-deposited ALD-grown Ca-P-O films and greatly enhanced on films annealed at 500 °C in comparison with reference cells on borosilicate glass or cell culture polystyrene.     

Atomic layer deposition of MnO using Bis(ethylcyclopentadienyl)manganese and H2O

Manganese oxide (MnO) atomic layer deposition (ALD) was accomplished using sequential exposures of bis(ethylcyclopentadienyl)manganese (Mn(CpEt)₂) and H₂O. Rutherford backscattering analysis revealed a nearly 1:1 atomic ratio for Mn:O in the MnO ALD films. X-ray diffraction determined that the films were crystalline and consistent with the cubic phase of MnO. Quartz crystal microbalance (QCM) measurements monitored the mass deposition rate during MnO ALD and verified self-limiting reactions for each reactant. Extremely efficient reactions were observed that required reactant exposures of only 3 × 10⁴ L (1 L = 1.33 × 10^− 4 Pa s). X-ray reflectivity (XRR) studies were used to confirm the QCM measurements and determine the film density and film thicknesses. The MnO ALD film density was 5.23 g/cm³. The growth per cycle was investigated from 100-300 °C. The largest MnO ALD growth per cycle was 1.2 Å/cycle at 100 °C and the growth per cycle decreased at higher temperatures. Transmission electron microscopy images observed the conformality of MnO films on ZrO₂ nanoparticles and confirmed the growth per cycle observed by the XRR studies. Fourier transform infrared spectroscopy was used to study the -CpEt? and -OH? surface species during MnO ALD and also monitored the bulk vibrational modes of the growing MnO films. The results allowed a growth mechanism to be established for MnO ALD using Mn(CpEt)₂ and H₂O. Only 54% of the Mn sites are observed to retain the -CpEt? surface species after the Mn(CpEt)₂ exposure. Efficient MnO ALD using Mn(CpEt)₂ and H₂O should be useful for a variety of applications where metal oxides are required that can easily change their oxidation states.     

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.     

Boron thin film deposition by using Thermionic Vacuum Arc (TVA) technology

In this paper a new technology for boron thin film deposition is presented. The film in high vacuum conditions is condensing on the sample from the plasma state of the vapor phase of the anode material, generated by a Thermionic Vacuum Arc (TVA). Boron coating is one of the technologies recently considered to be of special interest due to the qualities of boron. The aim of this paper is to present the use of TVA technology for boron coating.     

Atomic layer deposition of ferromagnetic cobalt doped titanium oxide thin films

TiO₂ thin films doped or mixed with cobalt oxide were grown by atomic layer deposition using titanium tetramethoxide and cobalt(III)acetylacetonate as metal precursors. The films could be deposited using both O₃ and H₂O as oxygen precursors. The films grown using water exhibited considerably smoother surface than those grown with ozone. The TiO₂:Co films with Co/(Co + Ti) cation ratio ranging from 0.01 to 0.30 were crystallized by annealing at 650 °C, possessing mixed phase composition comprising rutile and anatase and, additionally, CoTiO₃ or CoTi₂O₅. The annealed films demonstrated magnetic response expressed by magnetization curves with certain hysteresis and coercive fields.     

(111)-Oriented Pb(Zr0.52Ti0.48)O3 thin film on Pt(111)/Si substrate using CoFe2O4 nano-seed layer by pulsed laser deposition

Perovskite Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film with perfect (111)-orientation was achieved on CoFe₂O₄ seeded-Pt(111)/Ti/SiO₂/Si substrate by pulsed laser deposition technique using target with limited excess Pb. Pyrochlore phase formation was suppressed on Pt by CoFe₂O₄ nano-seed layer (~7 nm), and perovskite PZT was achieved at temperature as low as 550 °C. CoFe₂O₄ seed layer that has perfect (111)-orientation acts as a promoter for perfectly (111)-orientated growth of PZT. PZT film grown at 600 °C has higher degree of crystalline orientation, lower surface roughness, and compacted microstructure in comparison to the film grown at 550 °C. The PZT film has a nano-size grain-feature structure with grain size of about 40–60 nm. Perovskite formation was also confirmed by ferroelectric measurement. The ferroelectric properties of PZT film grown at 600 °C is higher than that grown at 550 °C which could be attributed to the enhancement of the crystalline orientation, crystallinity, and microstructure of the film.     

Atomic layer deposition of TiO2 thin films on glass fibers for enhanced photocatalytic activity

Photocatalytic wastewater treatment is expected to become a sustainable way of eliminating toxic chemicals. Due to the surface-driven mechanism of the photocatalysis, surface area of the catalyst material plays a crucial role in the efficiency of the process, which is usually achieved by nanoparticles. However, using powder materials introduces a new problem: removing the catalyst materials out of clean water. As an alternative, atomic layer deposition (ALD) can form conformal thin films on high surface area substrates providing an immobilization route with high photocatalytic activity. Textile materials are inexpensive and accessible therefore good candidates for the substrate materials. Here, we deposit thin films on TiO₂ on fiberglass fabrics and investigate the photocatalytic activity. Since the as-deposited ALD TiO₂ films are amorphous, they have very limited photocatalytic activity. Upon thermal treatment of the films after deposition, photocatalytic activity is achieved. After four hours of exposure to the solar simulator and UV lamp, TiO₂-coated fibers demonstrated much higher photocatalytic activity than films on planar substrates previously described in the literature. The photocatalytic activity and structure of the coated fibers were investigated using XRD, XPS, UV–Vis, and PL analyses.

     

Direct liquid injection metal-organic chemical vapor deposition of HfO2 thin films using Hf(dimethylaminoethoxide)4

Hf(OCH₂CH₂NMe₂)₄, [Hf(dmae)₄] (dmae=dimethylaminoethoxide) was synthesized and used as a chemical vapor deposition precursor for depositing Hf oxide (HfO₂). Hf(dmae)₄ is a liquid at room temperature and has a moderate vapor pressure (4.5 Torr at 80 °C). It was found that HfO₂ film could be deposited as low as 150 °C with carbon level not detected by X-ray photoelectron spectroscopy. As deposited film was amorphous but when the deposition temperature was raised to 400 °C, X-ray diffraction pattern showed that the film was polycrystalline with weak peak of monoclinic (020). Scanning electron microscope analysis indicated that the grain size was not significantly changed with the increase of the annealing temperature. Capacitance–voltage measurement showed that with the increase of annealing temperature, the effective dielectric constant was increased, but above 900 °C, the effective dielectric constant was decreased due to the formation of interface oxide. For 500 Å thin film, the dielectric constant of HfO₂ film annealed at 800 °C was 20.1 and the current–voltage measurements showed that the leakage current density of the HfO₂ thin film annealed at 800 °C was 2.2×10⁻⁶ A/cm² at 5 V.     

Atomic layer deposition process with TiF4 as a precursor for depositing metal fluoride thin films

A novel atomic layer deposition process for the preparation of fluoride thin films in a temperature range of 225 degrees C-400 degrees C is introduced. The crystallinity, morphology, composition, thicknesses, refractive indices, and transmittance of the films are analyzed. Low impurity levels are obtained at 350 degrees C-400 degrees C with good stoichiometry. Refractive indices of 1.34-1.42 for MgF(2), 1.43 for CaF(2), and 1.57-1.61 for LaF(3) films are obtained.     

Molecular layer deposition of ZrO2-based organic-inorganic nanohybrid thin films for organic thin film transistors

Molecular layer deposition (MLD) technique can be used for preparation of various organic-inorganic nanohybrid superlattices at a gas-phase. The MLD method is a self-controlled layer-by-layer growth process under vacuum conditions, and is perfectly compatible with the atomic layer deposition (ALD) method. In this paper, we fabricated a new type organic-inorganic nanohybrid thin film using MLD method combined with ALD. A self-assembled organic layer (SAOL) was formed at 170 °C using MLD with repeated sequential adsorptions of CC terminated alkylsilane and zirconium hydroxyl with ozone activation. A ZrO₂ inorganic nanolayer was deposited at the same temperature using ALD with alternating surface-saturating reactions of Zr(OC(CH₃)₃)₄ and H₂O. The prepared SAOL-ZrO₂ organic-inorganic nanohybrid films exhibited good mechanical stability, excellent insulating properties, and relatively high dielectric constant k (~ 16). They were then used as a 23 nm-thick dielectric for low voltage pentacene-based thin film transistors, which showed a maximum field effect mobility of 0.63 cm²/V s, operating at − 1 V with an on/off current ratio of ~ 10³.     

Physical/chemical properties of tin oxide thin film transistors prepared using plasma-enhanced atomic layer deposition

Thin film transistors (TFTs) with tin oxide films as the channel layer were fabricated by means of plasma enhanced atomic layer deposition (PE-ALD). The as-deposited tin oxide films show n-type conductivity and a nano-crystalline structure of SnO₂. Notwithstanding the relatively low deposition temperatures of 70, 100, and 130 °C, the bottom gate tin oxide TFTs show an on/off drain current ratio of 10⁶ while the device mobility values were increased from 2.31 cm²/V s to 6.24 cm²/V s upon increasing the deposition temperature of the tin oxide films.     

Study of n-ZnO/p-Si (100) thin film heterojunctions by pulsed laser deposition without buffer layer

ZnO/Si heterojunctions were fabricated by growing ZnO thin films on p-type Si (100) substrate by pulsed laser deposition without buffer layers. The crystallinity of the heterojunction was analyzed by high resolution X-ray diffraction and atomic force microscopy. The optical quality of the film was analyzed by room temperature (RT) photoluminescence measurements. The high intense band to band emission confirmed the high quality of the ZnO thin films on Si. The electrical properties of the junction were studied by temperature dependent current-voltage measurements and RT capacitance-voltage (C-V) analysis. The charge carrier concentration and the barrier height (BH) were calculated, to be 5.6 × 10¹⁹ cm^− 3 and 0.6 eV respectively from the C-V plot. The BH and ideality factor, calculated using the thermionic emission (TE) model, were found to be highly temperature dependent. We observed a much lower value in Richardson constant, 5.19 × 10^− 7 A/cm² K² than the theoretical value (32 A/cm² K²) for ZnO. This analysis revealed the existence of a Gaussian distribution (GD) with a standard deviation of σ² = 0.035 V. By implementing the GD to the TE, the values of BH and Richardson constant were obtained as 1.3 eV and 39.97 A/cm² K² respectively from the modified Richardson plot. The obtained Richardson constant value is close to the theoretical value for n-ZnO. These high quality heterojunctions can be used for solar cell applications.     

Fabrication of an a-IGZO thin film transistor using selective deposition of cobalt by the self-assembly monolayer (SAM) process

Interest in transparent oxide thin film transistors utilizing ZnO material has been on the rise for many years. Recently, however, IGZO has begun to draw more attention due to its higher stability and superior electric field mobility when compared to ZnO. In this work, we address an improved method for patterning an a-IGZO film using the SAM process, which employs a cost-efficient micro-contact printing method instead of the conventional lithography process. After a-IGZO film deposition on the surface of a SiO2-layered Si wafer, the wafer was illuminated with UV light; sources and drains were then patterned using n-octadecyltrichlorosilane (OTS) molecules by a printing method. Due to the low surface energy of OTS, cobalt was selectively deposited on the OTS-free a-IGZO surface. The selective deposition of cobalt electrodes was successful, as confirmed by an optical microscope. The a-IZGO TFT fabricated using the SAM process exhibited good transistor performance: electric field mobility (micro(FE)), threshold voltage (V(th)), subthreshold slope (SS) and on/off ratio were 2.1 cm2/Vs, 2.4 V, 0.35 V/dec and 2.9 x 10(6), respectively.