Characterization of hafnium oxide grown on silicon by atomic layer deposition: Interface structure

Ultra-thin films of hafnium oxide deposited on Si(1 0 0) substrates by means of atomic layer deposition using tetrakis(diethylamino)hafnium as the hafnium precursor are characterized. These films and interface structures are probed using Fourier transform infrared spectroscopy along with Z-contrast imaging and electron energy loss spectroscopy (EELS) of a scanning transmission electron microscope. The interface structure of HfO₂/Si(1 0 0) is further investigated using angle resolved X-ray photoelectron spectroscopy to probe the core level orbitals (Hf 4f, Si 2p, O 1s) at high resolution. The interfacial differences are also examined by probing the Hf 4f bonding with normal incidence XPS in thin and thick films. The XPS studies show that the binding energies remain unchanged with film depth and that there is no apparent signature of silicate structure in the as-deposited films. EELS spectra taken at the interface and XPS measurements suggest the interface is mainly silicon oxide. Two different cleaning methods used show difference only in the thickness of the silicon oxide interlayer.     

Electrical characterization of hafnium oxide and hafnium-rich silicate films grown by atomic layer deposition

An electrical characterization comparative analysis between Al/HfO₂/n-Si and Al/Hf-Si-O/n-Si samples has been carried out. Hafnium-based dielectric films have been grown by means of atomic layer deposition (ALD). Interface quality have been determined by using capacitance–voltage (C–V), deep level transient spectroscopy (DLTS) and conductance transient (G-t) techniques. Our results show that silicate films exhibit less flat-band voltage shift and hysteresis effect, and so lower disordered induced gap states (DIGS) density than oxide films, but interfacial state density is greater in Hf–Si–O than in HfO₂. Moreover, a post-deposition annealing in vacuum under N₂ flow for 1 min, at temperatures between 600 and 730 °C diminishes interfacial state density of Hf–Si–O films to values measured in HfO₂ films, without degrade the interface quality in terms of DIGS.     

Optical and electrical characterization of hafnium oxide deposited by liquid injection atomic layer deposition

Optical and electrical properties of a set of high-k dielectric HfO₂ films, deposited by liquid injection atomic layer deposition (LI-ALD) and post deposition annealed (PDA) in nitrogen (N₂) ambient at various temperatures (400–600 °C), were investigated. The films were prepared using the cyclopentadienyl of hafnium precursor [Cp₂Hf(CH₃)₂] with water deposited at 340 °C. The spectroscopic ellipsometric (SE) results show that the characteristics of the dielectric functions of these films are strongly affected by annealing temperatures. I–V results show that N₂-based PDA enhances the average energy depth of the shallow trapping defects from Poole–Frenkel conduction fitting. This also correlated with the measured increase in MOS capacitance–voltage hysteresis.     

GaAs MOSFET with oxide gate dielectric grown by atomic layer deposition

For the first time, a III-V compound semiconductor MOSFET with the gate dielectric grown by atomic layer deposition (ALD) is demonstrated. The novel application of the ALD process on III-V compound semiconductors affords tremendous functionality and opportunity by enabling the formation of high-quality gate oxides and passivation layers on III-V compound semiconductor devices. A 0.65-/spl mu/m gate-length depletion-mode n-channel GaAs MOSFET with an Al/sub 2/O/sub 3/ gate oxide thickness of 160 /spl Aring/ shows a gate leakage current density less than 10/sup -4/ A/cm/sup 2/ and a maximum transconductance of 130 mS/mm, with negligible drain current drift and hysteresis. A short-circuit current-gain cut-off frequency f/sub T/ of 14.0 GHz and a maximum oscillation frequency f/sub max/ of 25.2 GHz have been achieved from a 0.65-/spl mu/m gate-length device.     

Nitrogen-doped ZnO/n-Si core–shell nanowire photodiode prepared by atomic layer deposition

Photodiodes made from core–shell nanowires (NWs) comprising n-type silicon (n-Si; core) and nitrogen-doped ZnO (ZnO:N; shell) were fabricated by atomic layer deposition of ZnO:N on vertically aligned Si NWs. The device properties were investigated as functions of nitrogen content of the ZnO:N shell. The electron-carrier concentration of ZnO:N was modulated by adjusting the concentration of the reactant, diluted ammonium hydroxide, from 0 to 30%. The rectification ratio and the reverse-current density of the ZnO:N/n-Si planar heterojunction were evaluated under dark condition for various NH₄OH concentrations. The ZnO:N/n-Si heterojunction prepared with NH₄OH 15% was found to have the lowest reverse-current density with a moderate resistivity. In order to realize an effective ZnO:N/n-Si photodiode, a ZnO:N layer prepared with 15% NH₄OH was deposited on well-aligned Si nanowires. The core–shell NW photodiode showed more sensitive photodetecting performance in UV light than the planar photodiode. Also, the significantly enhanced performances of the core–shell NW photodiode were evaluated by examining its spectral responsivity.     

原子层沉积法制备微通道板发射层的性能

随着微通道板的不断发展与完善,通过改善传统工艺提升其性能越来越困难,开发提升微通道板性能的新技术迫在眉睫。纳米薄膜材料的发展及其制备技术的成熟为微通道板的发展提供了契机,利用原子层沉积技术在通道内壁沉积一层氧化铝纳米薄膜,作为二次电子发射功能层,可以增强通道内壁的二次电子发射能力,从而提升微通道板的增益性能。通过优化原子层沉积工艺参数可以在微通道板的通道内壁沉积厚度均匀的氧化铝薄膜。研究结果表明,微通道板增益随沉积氧化铝厚度的变化而变化,在氧化铝厚度为60 cycles时,施加偏压800 V时增益可达56 000,约为正常微通道板增益的12倍。     

Near-edge conduction band electronic states in SiGe alloys

Spatially resolved electron energy loss spectroscopy (EELS) measurements in GeSi alloys illustrate the relationship of atomic structure to local electronic structure. Extending earlier measurements, where electronic structure was found to be controlled by composition in relaxed alloys, measurements in anisotropically strained alloys show splitting of normally degenerate band edges into two components. In a strained Si quantum well, this allows the engineered band offset to be followed from the GeSi substrate through the well to the alloy-capping layer. In the high-mobility conduction channel, the band edge is found to be very sharp, in spite of obvious composition roughness. Near a misfit dislocation under the Si well, the band edge can shift by as much as 0.25 eV due to local strain. Within the core of the defect, however, strictly local behavior dominates the observations. Local conduction band splitting and in-gap states are both observed.     

原子层沉积Al_2O_3纳米管弯曲模量的原位研究

本文使用原子层沉积技术以及模板法制备了厚度、成分和结构精确可控的氧化铝纳米管,结合SEM、TEM、SAED和XPS分析,可知所得为非晶态氧化铝纳米管状结构且薄膜致密无针孔,沉积速率为0.11 nm/cycle,实现了纳米管壁厚在纳米尺度精确可控制备。进一步使用自主设计的SEM/SPM(扫描电子显微镜/扫描探针显微镜)联合测试系统,对氧化铝纳米管进行了原位三点弯曲实验研究。结果表明外半径在50 nm左右的氧化铝纳米管的杨氏模量范围在400~600 GPa之间,且杨氏模量值随着纳米管壁厚的增大而递减。     

Thermal and voltage instabilities of hafnium oxide films prepared by sputtering technique

Hafnium oxide (HfO₂) films are not stable at a high-temperature thermal treatment and under high-field stressing. The thermally-induced instabilities might involve the formation of nanocrystalline phases, interface reactions, and out-diffusion of substrate silicon. Our results indicate that there exists an optimal thermal treatment temperature which compromises these effects and yields the best electrical properties of the HfO₂ films. This observation has a high practical value in deciding the processing temperatures for MOS device fabrication using a high-k material as the gate dielectric film.     

High-performance pentacene field-effect transistors using Al2O3 gate dielectrics prepared by atomic layer deposition (ALD)

High-performance pentacene field-effect transistors have been fabricated using Al₂O₃ as a gate dielectric material grown by atomic layer deposition (ALD). Hole mobility values of 1.5 ± 0.2 cm²/V s and 0.9 ± 0.1 cm²/V s were obtained when using heavily n-doped silicon (n⁺-Si) and ITO-coated glass as gate electrodes, respectively. These transistors were operated in enhancement mode with a zero turn-on voltage and exhibited a low threshold voltage (< −10 V) as well as a low sub-threshold slope (<1 V/decade) and an on/off current ratio larger than 10⁶. Atomic force microscopy (AFM) images of pentacene films on Al₂O₃ treated with octadecyltrichlorosilane (OTS) revealed well-ordered island formation, and X-ray diffraction patterns showed characteristics of a “thin film” phase. Low surface trap density and high capacitance density of Al₂O₃ gate insulators also contributed to the high performance of pentacene field-effect transistors.     

Microwave annealing effects on ZnO films deposited by atomic layer deposition

Zinc oxide thin films deposited on glass substrate at 150°C by atomic layer deposition were annealed by the microwave method at temperatures below 500 °C.The microwave annealing effects on the structural and luminescent properties of Zn O films have been investigated by X-ray diffraction and photoluminescence.The results show that the MWA process can increase the crystal quality of Zn O thin films with a lower annealing temperature than RTA and relatively decrease the green luminescence of Zn O films.The observed changes have demonstrated that MWA is a viable technique for improving the crystalline quality of Zn O thin film on glass.     

Remote plasma-enhanced atomic layer deposition of gallium oxide thin films with NH_3 plasma pretreatment

High quality gallium oxide(Ga_2O_3) thin films are deposited by remote plasma-enhanced atomic layer deposition(RPEALD) with trimethylgallium(TMG) and oxygen plasma as precursors. By introducing in-situ NH3 plasma pretreatment on the substrates, the deposition rate of Ga_2O_3 films on Si and GaN are remarkably enhanced, reached to 0.53 and 0.46 ?/cycle at 250 °C,respectively. The increasing of deposition rate is attributed to more hydroxyls(–OH) generated on the substrate surfaces after NH3 pretreatment, which has no effect on the stoichiometry and surface morphology of the oxide films, but only modifies the surface states of substrates by enhancing reactive site density. Ga_2O_3 film deposited on GaN wafer is crystallized at 250 °C, with an epitaxial interface between Ga_2O_3 and GaN clearly observed. This is potentially very important for reducing the interface state density through high quality passivation.     

Thin-film encapsulation of polymer-based bulk-heterojunction photovoltaic cells by atomic layer deposition

This study demonstrated thin-film encapsulation of bulk-heterojunction polymer photovoltaic cells, utilizing a process based on atomic layer deposition (ALD) that both prevented degradation caused by ambient gases and served as an annealing step that increased the initial efficiency of the cells. With the ALD temperature set at 140 °C and the total deposition time set at 1 h, the photovoltaic cells, based on blended poly-3-hexylthiophene (P3HT) and [6,6]-phenyl C₆₁ butyric acid methylester (PCBM), were optimally annealed during encapsulation, achieving a power conversion efficiency (PCE) of 3.66%. Encapsulating the cells with a 26 nm Al₂O₃/HfO₂ nanolaminated film overcoated with an epoxy resin protection layer enabled the cells to obtain an in-air degradation rate that was similar to cells that were stored in nominally O₂/H₂O-free atmosphere. The nanolaminated structure of the encapsulation film resolved the issue of hydrolysis-induced aging observed with Al₂O₃ films, owing to the hydrophobicity of the HfO₂ layers. Additionally, extended exposure of the ALD precursors during the ALD process significantly improved the coverage of the ALD films over the P3HT/PCBM active layer at the perimeter of the cells.     

原子层沉积薄膜之激光损伤性能分析

采用目前尚在国内鲜有报道的原子层沉积技术在熔石英和BK7玻璃基片上镀制了TiO2单层膜、AlO3单层膜以及TiO2/Al2O3增透膜,沉积温度在110℃和280℃.利用X射线粉末衍射仪对膜层微观结构进行了分析研究,并在激光损伤平台上进行了抗激光损伤阈值的测量.采用Nomarski微分干涉差显微镜和原子力显微镜对激光损伤...     

New selector based on zinc oxide grown by low temperature atomic layer deposition for vertically stacked non-volatile memory devices

We report on the fabrication of Schottky diodes based on n-type zinc oxide (ZnO) grown by atomic layer deposition (ALD) at low temperature (100 °C). These structures are suitable as selector elements in highly integrated non volatile memories based on crossbar architecture. The junctions are fully realized by optical lithography and the smallest investigated structures are 3 × 3 μm² area. Several metals have been tested to single out the most suitable ohmic and Schottky contact materials. The electrical characterisation shows good properties with a forward current above 10⁴ A/cm² and a rectifying ratio of 10⁵.     

Polymer solar cells with NiO hole-collecting interlayers processed by atomic layer deposition

We report on the photovoltaic properties of polymer solar cells that use NiO-coated indium tin oxide (ITO) as the hole-collecting electrode. The NiO films were prepared by atomic layer deposition (ALD) on top of ITO with thicknesses varying from 6 to 25 nm. The NiO films increase the work function (WF) of the ITO, allowing NiO-coated ITO to act as an efficient hole-collecting electrode. Devices made with pristine NiO showed poor current–voltage characteristics. However, subsequent O₂-plasma treatment further increased the WF of NiO, tuning NiO-coated ITO into an efficient hole-collecting electrode for polymer solar cells based on the donor poly(3-hexylthiophene-2,5-diyl) (P3HT). The polymer solar cells with the O₂-plasma treated NiO-coated ITO hole-collecting electrodes yield a power conversion efficiency of 4.1 ± 0.2% under simulated air mass 1.5 G 100 mW/cm² illumination, which is comparable to reference devices with poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS)-coated ITO hole-collecting electrodes.     

Surface passivation of GaAs nanowires by the atomic layer deposition of AlN

It is shown that the atomic layer deposition of thin AlN layers can be used to passivate the surface states of GaAs nanowires synthesized by molecular-beam epitaxy. Studies of the optical properties of samples by low-temperature photoluminescence measurements shows that the photoluminescence-signal intensity can be increased by a factor of up to five by passivating the nanowires with a 25-Å-thick AlN layer.     

Review of recent progresses on flexible oxide semiconductor thin film transistors based on atomic layer deposition processes

The current article is a review of recent progress and major trends in the field of flexible oxide thin film transistors (TFTs),fabricating with atomic layer deposition (ALD) processes.The ALD process offers accurate controlling of film thickness and composition as well as ability of achieving excellent uniformity over large areas at relatively low temperatures.First,an introduction is provided on what is the definition of ALD,the difference among other vacuum deposition techniques,and the brief key factors of ALD on flexible devices.Second,considering functional layers in flexible oxide TFT,the ALD process on polymer substrates may improve device performances such as mobility and stability,adopting as buffer layers over the polymer substrate,gate insulators,and active layers.Third,this review consists of the evaluation methods of flexible oxide TFTs under various mechanic al stress conditions.The bending radius and repetition cycles are mostly considering for conventional flexible devices.It summarizes how the device has been degraded/changed under various stress types (directions).The last part of this review suggests a potential of each ALD film,including the releasing stress,the optimization of TFT structure,and the enhancement of device performance.Thus,the functional ALD layers in flexible oxide TFTs offer great possibilities regarding anti-mechanical stress films,along with flexible display and information storage application fields.     

Thin film encapsulation for organic light emitting diodes using a multi-barrier composed of MgO prepared by atomic layer deposition and hybrid materials

We demonstrated an organic/inorganic multi-barrier and encapsulation for flexible OLED devices. The multi-barrier consisted of a silica nanoparticle-embedded hybrid nanocomposite, in short, S-H nanocomposite, and MgO, which were used as organic and inorganic materials, respectively. The S-H nanocomposite was spin-coated followed by UV curing. The thickness of the S-H nanocomposite was 200 nm, and 40 nm of MgO was deposited by atomic layer deposition (ALD) using Mg(CpEt)₂ and H₂O at 70 °C. The results of a Ca test showed that the 4.5 dyads of the MgO/S-H nanocomposite had a low water vapor transmission rate (WVTR) of 4.33 × 10^?6 g/m²/day and an optical transmittance of 84%. The normalized luminance degradation of the thin film encapsulated OLED was also identical to that of glass-lid encapsulation after 1000 h of the real operation time. We proposed low temperature ALD as a deposition method to create relatively thin film for OLED passivation without degradation, such as creation of dark spots. The results confirmed that it may be feasible for our multi-barrier to passivate flexible OLEDs devices.     

Nitridation of hafnium oxide by reactive sputtering

Hafnium oxide films were RF sputtered from HfO₂ target in Ar/O₂ or Ar/N₂ ambient on silicon substrates. The composition of the deposited films was analyzed by X-ray photoelectron spectroscopy (XPS). For samples sputtered in Ar/N₂, it was observed that nitrogen was incorporated in the bulk of hafnium oxide films in the form of HfON, and SiON layer was formed at the silicon-insulator interface. After annealing the hafnium oxide films at 600-700 °C, MOS structures were fabricated and used for electrical characterization. The effects of nitridation of hafnium oxide on both the capacitance-voltage and current-voltage characteristics of the MOS capacitors were discussed.