Passivation of pigment-grade TiO(2) particles by nanothick atomic layer deposited SiO(2) films

Pigment-grade TiO(2) particles were passivated using nanothick insulating films fabricated by atomic layer deposition (ALD). Conformal SiO(2) and Al(2)O(3) layers were coated onto anatase and rutile powders in a fluidized bed reactor. SiO(2) films were deposited using tris-dimethylaminosilane (TDMAS) and H(2)O(2) at 500?°C. Trimethylaluminum and water were used as precursors for Al(2)O(3) ALD at 177?°C. The photocatalytic activity of anatase pigment-grade TiO(2) was decreased by 98% after the deposition of 2?nm SiO(2) films. H(2)SO(4) digest tests were performed to exhibit the pinhole-free nature of the coatings and the TiO(2) digest rate was 40 times faster for uncoated TiO(2) than SiO(2) coated over a 24?h period. Mass spectrometry was used to monitor reaction progress and allowed for dosing time optimization. These results demonstrate that the TDMAS-H(2)O(2) chemistry can deposit high quality, fully dense SiO(2) films on high radius of curvature substrates. Particle ALD is a viable passivation method for pigment-grade TiO(2) particles.     

Laser damage properties of TiO2/Al2O3 thin films grown by atomic layer deposition

Research on thin film deposited by atomic layer deposition (ALD) for laser damage resistance is rare. In this paper, it has been used to deposit TiO(2)/Al(2)O(3) films at 110 °C and 280 °C on fused silica and BK7 substrates. Microstructure of the thin films was investigated by x-ray diffraction. The laser-induced damage threshold (LIDT) of samples was measured by a damage test system. Damage morphology was studied under a Nomarski differential interference contrast microscope and further checked under an atomic force microscope. Multilayers deposited at different temperatures were compared. The results show that the films deposited by ALD had better uniformity and transmission; in this paper, the uniformity is better than 99% over 100 mm Φ samples, and the transmission is more than 99.8% at 1064 nm. Deposition temperature affects the deposition rate and the thin film microstructure and further influences the LIDT of the thin films. As to the TiO(2)/Al(2)O(3) films, the LIDTs were 6.73±0.47 J/cm(2) and 6.5±0.46 J/cm(2) at 110 °C on fused silica and BK7 substrates, respectively. The LIDTs at 11 °C are notably better than 280 °C.     

Charge-trapping characteristics of Al2O3/Cu/Al2O3 nanolaminate structures prepared through atomic layer deposition

The nanolaminate Al2O3/Cu/Al2O3 structures were constructed on p-type Si (001) substrates using atomic layer deposition (ALD) process with the aim to fabricating nonvolatile charge-trap memories. Low temperature Cu thin layers were deposited through plasma-enhanced atomic layre depositon of Cu aminoalkoxide (Cu(dmamb)2) combined with hydrogen plasma and Al2O3 layers were prepared by thermal atomic layer deposition of trimethylaluminum (TMA) combined with H2O. Nonvolatile features were confirmed using capacitance-voltage (C-V) measurements. The copper film functions as a charge-trapping layer and the Al2O3 thin layers were employed as tunneling and control oxide layers. Line shapes and binding energies of Cu metal and the thin layer of 6 nm Cu in nanolaminate structures were observed in the X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (TEM) image. The V(FB) shift width of the Al2O3 (28 nm)/Cu (6 nm)/Al2O3 (4.2 nm)/Si laminate structure is found to be 4.75 V in voltage sweeping between -10 and +10 V, leading to the trap density of 1.68 x 10(18) cm(-3).     

Electromechanical Behavior of Al/Al2O3 Multilayers on Flexible Substrates: Insights from In Situ Film Stress and Resistance Measurements

A series of Al and Al/Al₂O₃ thin-film multilayer structures on flexible polymer substrates are fabricated with a unique deposition chamber combining magnetron sputtering (Al) and atomic layer deposition (ALD, Al₂O₃, nominal thickness 2.4–9.4 nm) without breaking vacuum and thoroughly characterized using transmission electron microscopy (TEM). The electromechanical behavior of the multilayers and Al reference films is investigated in tension with in situ X-ray diffraction (XRD) and four-point probe resistance measurements. All films exhibit excellent interfacial adhesion, with no delamination in the investigated strain range (12%). For the first time, an adhesion-promoting naturally forming amorphous interlayer is confirmed for thin films sputter deposited onto polymers under laboratory conditions. The evolution of Al film stresses and electrical resistance reveal changes in the deformation behavior as a function of oxide thickness. Strengthening of Al is observed with increasing oxide thickness. Significant embrittlement can be avoided for oxide layer thicknesses ≤2.4 nm.     

Characteristics of nanocomposite ZrO2/Al2O3 films deposited by plasma-enhanced atomic layer deposition

Nanocomposite ZrO2/Al2O3 (ZAO) films were deposited on Si by plasma-enhanced atomic layer deposition and the film characteristics including interfacial oxide formation, dielectric constant (k), and electrical breakdown strength were investigated without post-annealing process. In both the mixed and nano-laminated ZAO films, the thickness of the interfacial oxide layer (T(IL)) was considerably reduced compared to ZrO2 and Al2O3 films. The T(IL) was 0.8 nm in nano-composite films prepared at a mixing ratio (ZrO2:Al2O3) of 1:1. The breakdown strength and the leakage current level were greatly improved by adding Al2O3 as little as 7.9% compared to that of ZrO2 and were enhanced more with increasing content of Al2O3. The k of ZrO2 and mixed ZAO (Al2O3 7.9%) films were 20.0 and 16.5, respectively. These results indicate that the addition of Al2O3 to ZrO2 greatly improves the electrical properties with less cost of k compared to the addition of SiO2.     

Effect of SiO2 passivation overlayers on hillock formation in Al thin films

Hillock formation in Al thin films with varying thicknesses of SiO₂ as a passivation layer was investigated during thermal cycling. Based on the stress measurements and the number of hillocks, 250 nm thick SiO₂ was thick enough to suppress the hillock formation and the suppression of hillock at 250 nm passivation and the lack of suppression at thinner passivation is related to the presence/absence of protection against the diffusive flow of atoms from the surrounding area to the surface due to the biaxial compressive stresses present in the film through the weak spots in the passivation layer. The stress state of Al films measured during annealing (the driving force for hillock formation) did not vary much with SiO₂ thickness. A small number of hillocks formed during the plasma enhanced chemical vapor deposition of SiO₂ overlayers at 300 °C.     

Characteristics of Al-doped ZnO films grown by atomic layer deposition for silicon nanowire photovoltaic device

We report the structural, electrical, and optical characteristics of Al-doped ZnO (ZnO:Al) films deposited on glass by atomic layer deposition (ALD) with various Al2O3 film contents for use as transparent electrodes. Unlike films fabricated by a sputtering method, the diffraction peak position of the films deposited by ALD progressively moved to a higher angle with increasing Al2O3 film content. This indicates that Zn sites were effectively replaced by Al, due to layer-by-layer growth mechanism of ALD process which is based on alternate self-limiting surface chemical reactions. By adjusting the Al2O3 film content, a ZnO:Al film with low electrical resistivity (9.84 x 10(-4) Omega cm) was obtained at an Al2O3 film content of 3.17%, where the Al concentration, carrier mobility, optical transmittance, and bandgap energy were 2.8 wt%, 11.20 cm2 V(-1) s(-1), 94.23%, and 3.6 eV, respectively. Moreover, the estimated figure of merit value of our best sample was 8.2 m7Omega(-1). These results suggest that ZnO:Al films deposited by ALD could be useful for electronic devices in which especially require 3-dimensional conformal deposition of the transparent electrode and surface passivation.     

Fabrication of TiO2/Tin-doped indium oxide-based photoelectrode coated with overlayer materials and its photoelectrochemical behavior

The photoelectrochemical properties of TiO2-based photoelectrodes with metal oxide overlayers (e.g., ZnO, ZrO2, MgO, and Al2O3) were investigated. The metal oxides were deposited on TiO2/tin-doped indium oxide (ITO) films by spin-coating metal-alkoxide precursors. The formation of the overlayers was confirmed by energy dispersive X-ray spectroscopy (EDS) and high resolution transmission electron microscopy (HRTEM). Each overlayers were well-coated on the TiO2-based films and have approximately 2 nm thickness. The prepared films were used as photoanodes in a photoelectrochemical system with a Pt counter electrode to evaluate hydrogen production performance. Comparing with other overlayers, the ZnO-coated photoelectrode exhibits the highest rate of hydrogen evolution and which is better than the uncoated one. From the photoelectrochemical and spectroscopic study, the superior hydrogen production property of the ZnO-coated TiO2 photoelectrode was attributed to both the higher light absorbance of ZnO compared to TiO2 and the formation of hydroxyl groups at the ZnO surface.     

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.     

Controlling the crystallinity and roughness of atomic layer deposited titanium dioxide films

The surface roughness of thin films is an important parameter related to the sticking behaviour of surfaces in the manufacturing of microelectomechanical systems (MEMS). In this work, TiO2 films made by atomic layer deposition (ALD) with the TiCl4-H2O process were characterized for their growth, roughness and crystallinity as function of deposition temperature (110-300 degrees C), film thickness (up to approximately 100 nm) and substrate (thermal SiO2, RCA-cleaned Si, Al2O3). TiO2 films got rougher with increasing film thickness and to some extent with increasing deposition temperature. The substrate drastically influenced the crystallization behaviour of the film: for films of about 20 nm thickness, on thermal SiO2 and RCA-cleaned Si, anatase TiO2 crystal diameter was about 40 nm, while on Al2O3 surface the diameter was about a micrometer. The roughness could be controlled from 0.2 nm up to several nanometers, which makes the TiO2 films candidates for adhesion engineering in MEMS.     

Al2O3 and TiO2 atomic layer deposition on copper for water corrosion resistance

Al(2)O(3) and TiO(2) atomic layer deposition (ALD) were employed to develop an ultrathin barrier film on copper to prevent water corrosion. The strategy was to utilize Al(2)O(3) ALD as a pinhole-free barrier and to protect the Al(2)O(3) ALD using TiO(2) ALD. An initial set of experiments was performed at 177 °C to establish that Al(2)O(3) ALD could nucleate on copper and produce a high-quality Al(2)O(3) film. In situ quartz crystal microbalance (QCM) measurements verified that Al(2)O(3) ALD nucleated and grew efficiently on copper-plated quartz crystals at 177 °C using trimethylaluminum (TMA) and water as the reactants. An electroplating technique also established that the Al(2)O(3) ALD films had a low defect density. A second set of experiments was performed for ALD at 120 °C to study the ability of ALD films to prevent copper corrosion. These experiments revealed that an Al(2)O(3) ALD film alone was insufficient to prevent copper corrosion because of the dissolution of the Al(2)O(3) film in water. Subsequently, TiO(2) ALD was explored on copper at 120 °C using TiCl(4) and water as the reactants. The resulting TiO(2) films also did not prevent the water corrosion of copper. Fortunately, Al(2)O(3) films with a TiO(2) capping layer were much more resilient to dissolution in water and prevented the water corrosion of copper. Optical microscopy images revealed that TiO(2) capping layers as thin as 200 ? on Al(2)O(3) adhesion layers could prevent copper corrosion in water at 90 °C for ~80 days. In contrast, the copper corroded almost immediately in water at 90 °C for Al(2)O(3) and ZnO films by themselves on copper. Ellipsometer measurements revealed that Al(2)O(3) films with a thickness of ~200 ? and ZnO films with a thickness of ~250 ? dissolved in water at 90 °C in ~10 days. In contrast, the ellipsometer measurements confirmed that the TiO(2) capping layers with thicknesses of ~200 ? on the Al(2)O(3) adhesion layers protected the copper for ~80 days in water at 90 °C. The TiO(2) ALD coatings were also hydrophilic and facilitated H(2)O wetting to copper wire mesh substrates.     

Texture and sheet resistance of Al alloy thin films on Ti and TiN thin films

Ti films prepared by ionized physical vapor deposition (I-PVD) and TiN films prepared by metalorganic chemical vapor deposition (MOCVD) were examined as the underlayers of the Al interconnect films. The crystallographic texture of the Al films and the sheet resistance of the thin-film stacks were investigated at various thicknesses of the Ti or TiN thin film. The sheet resistance of the thin-film stacks was also measured after annealing at 400 °C in an N₂ ambient. For the I-PVD Ti underlayer, the excellent texture of the Al (1 1 1) was obtained even on a 5-nm thick Ti film. However, the sheet resistance of the multilayer structure increased after the annealing due to the reaction between Al and Ti. MOCVD TiN layers between the Ti film and the Al film could suppress the Al–Ti reaction without severe degradation of the Al (1 1 1) texture. Excellent texture of the Al film was obtained with thin MOCVD TiN films below 5 nm.     

Repeatability of the composition of titanium oxide films produced by evaporation of ti 2 o 3

Congruent vaporization is a process that yields constant vapor species. Ti(2)O(3) was continuously electron-beam evaporated to produce titanium oxide thin films. Rutherford backscattering spectrometry was employed to study the evolution of the composition of these films. It seems that congruent vaporization can be established in a coating plant. TiO(2) films produced by conventional reactive deposition tend to contain mixtures of titanium oxides. Increasing the transmission of TiO(2) films becomes an issue of increasing the TiO(2) component in the films by adequate reactive evaporation.     

Growth of TiO2 anti-reflection layer on textured Si (100) wafer substrate by metal-organic chemical vapor deposition method

Recently anti-reflective films (AR) have been intensely studied. Particularly for textured silicon solar cells, the AR films can further reduce the reflection of the incident light through trapping the incident light into the cells. In this work, TiO2 anti-reflection films have been grown on the textured Si (100) substrate which is processed in two steps, and the films are deposited using metal-organic chemical vapor deposition (MOCVD) with a precursor of titanium tetra-isopropoxide (TTIP). The effect of the substrate texture and the growth conditions of TiO2 films on the reflectance has been investigated. Pyramid size of textured silicon had approximately 2-9 microm. A well-textured silicon surface can lower the reflectance to 10%. For more reduced reflection, TiO2 anti-reflection films on the textured silicon were deposited at 600 degrees C using titanium tetra-isopropoxide (TTIP) as a precursor by metal-organic chemical vapor deposition (MOCVD), and the deposited TiO2 layers were then treated by annealing for 2 h in air at 600 and 1000 degrees C, respectively. In this process, the treated samples by annealing showed anatase and rutile phases, respectively. The thickness of TiO2 films was about 75 +/- 5 nm. The reflectance at specific wavelength can be reduced to 3% in optimum layer.     

IBAD钼膜与Al_2O_3(0001)单晶界面的HREM研究

采用中等能量离子束辅助沉积（IBAD）技术在单晶Al2O3（0001）基片上沉积钼膜，通过HREM等分析手段，在原子尺度上，对于钼膜及其与Al2O3单晶基体界面的显微结构进行了研究。结果表明：钼膜的晶粒呈细小柱状或纤维状，平均晶粒尺寸约为8nm，钼膜的致密度较高，膜内存在非晶组织。在钼膜与Al2O3单晶基片之间存在厚约10～15nm的非晶过渡层，在界面处未发现原子的长程扩散。非晶过渡层与钼膜界面处存在台阶，增加了钼膜的形核点。     

Control of ZnO thin film surface by ZnS passivation to enhance photoluminescence

To enhance the optical property of zinc oxide (ZnO) thin film, zinc sulfide (ZnS) thin films were formed on the interfaces of ZnO thin film as a passivation and a substrate layer. ZnO and ZnS thin films were deposited by atomic layer deposition (ALD) using diethyl zinc, H₂O, and H₂S as precursors. Investigations by X-ray diffraction and transmission electron microscopy showed that ZnS/ZnO/ZnS multi-layer thin films with clear boundaries were achieved by ALD and that each film layer had its own polycrystalline phase. The intensity of the photoluminescence of the ZnO thin film was enhanced as the thickness of the ZnO thin film increased and as ZnS passivation was applied onto the ZnO thin film interfaces.     

SiO2层上沉积的纳米多晶硅薄膜及其特性

采用低压化学气相沉积(LPCVD)系统以高纯SiH4为气源,在p型10.16 cm<100>晶向单晶硅衬底SiO2层上制备纳米多晶硅薄膜,薄膜沉积温度为620℃,沉积薄膜厚度分别为30 nm、63 nm和98 nm.对不同薄膜厚度的纳米多晶硅薄膜分别在700℃、800℃和900℃下进行高温真空退火.通过X射线衍射(XRD)、Raman光谱、扫描电子显微镜(SEM)和原子力显微镜(AFM)对SiO2层上沉积的纳米多晶硅薄膜进行特性测试和表征,随着薄膜厚度的增加,沉积态薄膜结晶显著增强,择优取向为<111>晶向.通过HP4145B型半导体参数分析仪对沉积态掺硼纳米多晶硅薄膜电阻I-V特性测试发现,随着薄膜厚度的增加,薄膜电阻率减小,载流子迁移率增大.     

Aluminum-induced crystallization of amorphous silicon films deposited by hot wire chemical vapor deposition on glass substrates

Aluminum-induced crystallization of amorphous silicon films is discussed. Amorphous Si films were deposited by hot wire chemical vapor deposition onto Al coated glass substrates at 430 °C. Complete crystallization of a-Si films was achieved during a-Si deposition by controlling Al and Si layer thicknesses. The grain structure of the poly-Si films formed on glass substrate was evaluated by optical and electron microscopy. Continuous poly-Si films were obtained using Al layers with a thickness of 500 nm or less. The average grain size was found to be 10-15 μm, corresponding to a grain size/thickness ratio greater than 20.     

Fabrication of 3-dimensional PbZr(1-x)Ti(x)O3 nanoscale thin film capacitors for high density ferroelectric random access memory devices

PbZr(x)Ti(1-x)O3 (PZT) thin films were deposited on 3-dimensional (3D) nano-scale trench structures for use in giga-bit density ferroelectric random access memories. PZT thin films were deposited by liquid delivery metalorganic chemical vapor deposition using Pb(thd)2, Zr(MMP)4, and Ti(MMP)4 precursors dissolved in ethyl cyclohexane. Iridium thin films were deposited by atomic layer deposition, and they exhibited excellent properties for capacitor electrodes even at a thickness of 20 nm. The trench capacitor was composed of three layers, viz. Ir/PZT/lr (20/60/20 nm), and had a diameter of 250 nm and a height of 400 nm. Almost 100% step coverage was obtained at a deposition temperature of 530 degrees C. The PZT thin film capacitors with a thickness of 60 nm on a planar structure exhibited a remnant polarization (Pr) of 28 microC/cm2, but the Pr value of the 3D PZT capacitors decreased slightly with decreasing 3D trench pattern size. The transmission electron microscope analysis indicated that the PZT thin films had compositional uniformity in the 3D trench region. Both columnar and granular grains were formed on the sidewalls of the trench capacitors, and their relative proportion exhibited strong size dependence. The trench capacitors with more columnar PZT grains showed good switching behavior under an external bias of 2.1 V and had a remnant polarization of 19-24 microC/cm2.     

Parallel core-shell metal-dielectric-semiconductor germanium nanowires for high-current surround-gate field-effect transistors

Core-shell germanium nanowires (GeNW) are formed with a single-crystalline Ge core and concentric shells of nitride and silicon passivation layer by chemical vapor deposition (CVD), an Al2O3 gate dielectric layer by atomic layer deposition (ALD), and an Al metal surround-gate (SG) shell by isotropic magnetron sputter deposition. Surround-gate nanowire field-effect transistors (FETs) are then constructed using a novel self-aligned fabrication approach. Individual SG GeNW FETs show improved switching over GeNW FETs with planar gate stacks owing to improved electrostatics. FET devices comprised of multiple quasi-aligned SG GeNWs in parallel are also constructed. Collectively, tens of SG GeNWs afford on-currents exceeding 0.1 mA at low source-drain bias voltages. The self-aligned surround-gate scheme can be generalized to various semiconductor nanowire materials.