Cross-sectional High-resolution Transmission Electron Microscopy Research Articles

Morphological Evolution of Atomic Layer Deposited Hafnium Oxide on Aligned Carbon Nanotube Arrays.

Microscopic study of the nucleation and growth of atomic layer deposition (ALD) dielectrics onto carbon nanotubes (CNTs) is an essential while challenging task toward high-performance devices. Here, we capture the morphological evolution and growth behaviors of ALD-HfO2 onto SiO2/Si-supported aligned CNT arrays (A-CNTs) under three ALD recipes via cross-sectional high-resolution scanning transmission electron microscopy. The HfO2 in ALD I (200 °C) preferentially nucleates on the SiO2 substrate in heterogeneous growth mode, resulting in films with considerable pinholes, while ALD II (90 °C) and III (90 °C and extra H2O presoak) exhibit homogeneous growth with nucleation on both SiO2 and CNTs, yielding uniform films. Arrangement defects in A-CNTs exacerbate nonuniformity of HfO2 and tube-tube separation plays deterministic roles affecting the HfO2-CNT interfacial morphology. Electrical measurements from A-CNTs metaloxide-semiconductor devices validate these findings. Our investigation contributes valuable insights for optimizing ALD processes for enhanced dielectric integration on A-CNTs in next-generation electronics.

Enhanced device performance of GaN high electron mobility transistors with in situ crystalline SiN cap layer

In this paper, a ∼2 nm in situ SiN cap layer on AlGaN barrier layer is grown, which is revealed to be crystalline using high-resolution cross-sectional transmission electron microscopy. Benefitting from superior interface quality of epitaxial crystalline SiN/AlGaN interface, the gate diodes with in situ SiN cap layer feature lower interface trap state density than that with GaN cap layer. By comparing the GaN high electron mobility transistors (HEMTs) with the conventional GaN cap layer, the GaN HEMTs with in situ SiN cap layer exhibit improved device performance, showing higher electron mobility, higher drain current, larger on/off current ratio, and higher transconductance. For breakdown characteristics, the devices with in situ crystalline SiN cap layer show prominent advantages over the GaN cap layer with a 30% breakdown voltage increase to 810 V.

Achieving high sheet resistance and near-zero temperature coefficient of resistance in NiCr film resistors by Al interlayers

Thin film resistive materials with low temperature coefficients of resistance (TCR) and high sheet resistances are essential for various electronic applications, such as embedded resistors. In this study, Al inserting layers and NiCr resistive layers were sequentially deposited on alumina ceramic substrates via DC magnetron sputtering to fabricate Al/NiCr bilayer resistive materials. The electrical properties of the bilayer films were adjusted by varying the thicknesses of the Al inserting layers and annealing conditions. When the thickness of the Al inserting layer varied from 5 to 7.5 nm, and post-annealing treatments ranging from 200℃ to 400℃ were applied, evident Al-NiCr interdiffusion occurred, forming intermediate layers at the interfaces and oxides on the film surfaces. A mixture of partial crystalline phases and amorphous phases was also observed in the cross-sectional high-resolution transmission electron microscope (HRTEM) images. The formation of intermediate layers and surface oxides and the balance between partial crystalline phases and amorphous phases collectively enhanced the electrical performance of bilayer film resistors, achieving thin film resistors with a remarkably low TCR of −6.61 ppm/K and a sheet resistance of up to 265.95 Ω/sq. By rational design of Al layers, NiCr layers and thermal treatment, thin film resistors with near zero TCRs and extremely wide sheet resistance range of 93.34–1439.01 Ω/sq can be obtained.

Nonideality in Arrayed Carbon Nanotube Field Effect Transistors Revealed by High-Resolution Transmission Electron Microscopy.

High density and high semiconducting-purity single-walled carbon nanotube array (A-CNT) have recently been demonstrated as promising candidates for high-performance nanoelectronics. Knowledge of the structures and arrangement of CNTs within the arrays and their interfaces to neighboring CNTs, metal contacts, and dielectrics, as the key components of an A-CNT field effect transistor (FET), is essential for device mechanistic understanding and further optimization, particularly considering that the current technologies for the fabrication of A-CNT wafers are mainly laboratory-level solution-based processes. Here, we conduct a systematic investigation into the microstructures of A-CNT FETs mainly via cross-sectional high-resolution transmission electron microscopy and tentatively establish a framework consisting of up to 11 parameters which can be used for structure-side quality evaluation of the A-CNT FETs. The parameter ensemble includes the diameter, length (or terminal), and density distribution of CNTs, radial deformation of CNTs, array alignment defects, surface crystallography facets of contact metal, thickness distribution of high-k dielectrics (HfO2), and the contact ratios for the CNT-CNT, CNT-metal, CNT-dielectric, and CNT-substrate interfaces. Enriched array alignment defects, i.e., bundle, stacking, misorientation, and voids, are observed with a total ratio sometimes up to ∼90% in pristine A-CNTs and even up to ∼95% after the device fabrication process. Thus, they are suggested as the prevalent performance-limiting factors for A-CNT FETs. Complex interfacial structures are observed at the CNT-CNT, CNT-metal contact, and CNT-high-k dielectric interfaces, making the local environment and the property of each component CNT involved in an A-CNT FET distinct from others in terms of the diameters, radial deformation, and interactions with the local surroundings (mainly through van der Waals interactions). The present study suggests further improvements on the fabrication technology of A-CNT wafers and devices and mechanistic investigations into the impacts of complex array alignment defects and interface structures on the electrical performance of A-CNT FETs as well.

Synthesis of multilayered h-BN film on the molten Ni–B and the influence of underneath W substrate

High-quality two-dimensional hexagonal boron nitride (h-BN) film with tens of layers has been used as a universal substrate and capping layer for the van der Waals devices. Various approaches have been carried out for the synthesis of multilayered h-BN. Among them, the metal flux method is reliable in yielding h-BN crystals with high crystalline quality. However, this time- and energy-demanding method hinders its scale application. Herein, inspired by the metal flux method, we reported the time-effective growth of high-quality multilayered h-BN film (ca. 20 nm) on a molten Ni–B layer wetting on W substrate with chemical vapor deposition method. The film exhibits an excellent stacking sequence and a full-width at half maximum of the Raman E2g peak narrow to 9.5 cm−1. Cross-sectional high-resolution transmission electron microscopy and in-situ x-ray diffraction spectroscopy were carried out to investigate the crystal structure evolution of Ni–B layer wetting on W substrate. It is found that the low surface tension caused by the spreading of Ni–B alloy on the W substrate and the presence of the Ni subsurface may be responsible for the formation of multilayered h-BN with excellent crystalline quality. Meanwhile, the W diffusion in Ni–B-based melt can hinder the formation of h-BN under certain growth conditions. The approach demonstrates the feasibility of large-scale growth of multilayered h-BN, paving the way to future applications in van der Waals electronic and optoelectronic devices.

Angle-resolved X-ray photoelectron spectroscopy intensity modeling of SiNx ultrathin layer grown on Si (100) and Si (111) substrates by N2 plasma treatment

In this work, we investigate the silicon nitridation process using a N2 plasma Glow Discharge Source (GDS) in an ultra-high vacuum chamber. In situ Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS) measurements were performed to determine various chemical environments of the surface species. The main goals of this study are determination of the film chemical composition, to estimate its thickness and identify various phenomena taking place during the nitridation process under different experimental conditions. To achieve these objectives, we developed an ARXPS intensity model for an ultrathin SiNx overlayer. Based on the ARXPS results, which indicate that the silicon nitride film is not homogenous, we adopted a bi-layer model composed of two SixNyOz layers with varying thickness and chemical composition. The model is built from analysis of photoelectron intensities, considering a comparison between experimental and theoretical data. This bi-layer model revealed that the silicon nitride layer consists of a surface layer composed of approximately equal amounts of silicon and nitrogen (50% each), and an interfacial layer containing varying amounts of oxygen depending on experimental parameters. The presence of oxygen is due to residual air contamination in the vacuum chamber and/or to Si native oxide. The estimated thickness of silicon nitride film is less than 9 nm, depending on the nitridation time and temperature.The model developed in this work enabled us to study the effects of initial surface state (as received or chemically cleaned), Si substrate crystallographic orientation (such as (100) and (111)), and the nitridation temperature (room temperature and 500°C). The diffusing species (N+, N2+, O+), which play a crucial role during nitridation, were found to be influenced by temperature, treatment time, and substrate orientation. The diffusion phenomenon competed with other processes such as NO desorption, leading to a significant impact on formation of the SiNx film. Furthermore, we compared the thickness obtained from the ARXPS model using cross-sectional High-Resolution Transmission Electron Microscopy (HR-TEM) images. Additional Low-Energy Electron Diffraction (LEED) measurements indicated that the SiNx film was amorphous.

Plasma-activated high-strength non-isothermal anodic bonding for efficient fabrication of the micro atomic vapor cells

Microfabricated alkali metal vapor cells are the core components for miniaturizing quantum devices, such as atomic clocks, atomic gyroscopes, and atomic magnetometers. Alkali metals are prone to thermal migration at the bonding interface during the sealing of the vapor cell, which leads to bonding failure. In this study, a non-isothermal anodic bonding process based on plasma activation was developed to achieve high-strength bonding at low temperatures using the temperature gradient to keep the alkali metal away from the bonding interface. This procedure eliminates interference from the alkali metal and significantly increases the success rate of anodic bonding of vapor cells. Simulation results for the temperature field and the residual stresses during anodic bonding demonstrate that the procedure is theoretically feasible. The effect of plasma treatment on the contact angle and roughness of the bonding surface revealed a mechanism for improving the bond strength. In addition, the construction of an integrated processing platform made it possible to perform non-isothermal anode bonding, injection of alkali metal, filling of inert gases, and recovery and recycling of noble gases. The high strength and good hermeticity of the bonding interface were demonstrated by the bond strength, cross-sectional high-resolution transmission electron microscopy observations, and leakage rate tests. Finally, the absorption spectrum and free-induction decay signal of the fabricated vapor cell were measured.

Structure and electrical conductivity of Ti-Zr-Ni films of quasicrystalline and related crystalline phases

The temperature dependence of electrical resistivity in the temperature range from 4.4 to 300 K for Ti41Zr41Ni18 (at.%) thin coatings of various crystal perfection and phase compositions has been investigated. The films were deposited by the magnetron sputtering method. The following vacuum annealing in various modes provided several combinations of the film phases such as 1/1 and 2/1 crystal-approximant phases, the quasicrystalline icosahedral phase, Laves (Ti,Zr)2Ni phase and α-Ti(Zr) solid solution phase. The structure and composition of the films before and after annealing were studied in detail by X-ray diffractometry and cross-sectional high-resolution transmission electron microscopy. Samples with predominant amorphous, quasi-crystalline, and approximant 2/1 phases have a temperature coefficient of resistance less than zero, while samples dominated by crystalline phases exhibit the characteristic metallic conductivity. For the quasicrystalline Ti41Zr41Ni18 film, the temperature dependence of the electrical resistance turned out to be similar to that of bulk samples with the composition Ti40Zr40Ni20. A significant effect of the presence of phases with metallic conduction on the overall conductivity of the coating is described. The electrical resistance of the 2/1 approximant phase with a low content of the additional Laves phase in the film has an almost constant value over the entire temperature range under study.

Thick p-type Mg2Si film on Si: Growth, structure and transport properties

A ∼ 0.8–0.9 µm thick Mg2Si film was grown by pulsed deposition of Mg on Si(111) at 340 °C in UHV. The X-Ray Diffraction (XRD) and cross-sectional High-resolution Transmission Electron Microscopy (x-HRTEM) data demonstrate the high crystal quality and nearly 100% texture of the film. Energy Dispersive X-ray spectroscopy (EDX) and X-ray Photoelectron Spectroscopy (XPS) depth profiling show that the synthesized Mg2Si contains some oxygen. Hall measurements reveal the p-type conductivity of 130 S/cm and carrier concentration of 6 × 1018 cm−3 at room temperature (RT), the acceptor concentration of ∼ 1.4 × 1018 cm−3 at 190 K, hole activation energy Ea ≈ 26 meV, mobility μ∼5050 cm2/V∙s at 75 K and μ∼134 cm2/V∙s at RT. The p-type conductivity is related to either unintentional doping with oxygen or/and Mg vacancies occurred during the non-equilibrium process of silicide ultra-fast formation. The outstanding transport parameters of the film are explained by its high crystal quality and texture. The films with such thickness and transport properties are suitable for photovoltaic and thermoelectric applications.

Growth and characterization of GePb/Ge multiple quantum wells

GePb/Ge multiple quantum well (MQW) structures with a Pb content of up to 7.2% were successfully grown on Ge(100) substrates via sputtering epitaxy. Scanning electron microscopy revealed that both the Pb content in the GePb layer and Ge layer thickness affect the Pb surface segregation. High-resolution X-ray diffraction and cross-sectional transmission electron microscopy indicated that the GePb/Ge MQW structures had a high crystal quality. Moreover, the thermal stability of the GePb/Ge MQW structures was investigated, and the MQW structures were found to be stable at an annealing temperature of 500 °C. The band gaps of the GePb/Ge MQWs were measured, and the band gap regulation caused by the quantum confinement effect was verified. These results indicate that the MQW structure is a promising approach for realizing efficient GePb light sources.

Strong perpendicular magnetic anisotropy of Pt/Co/AlN structure

In this study, the perpendicular magnetic anisotropy (PMA) and microstructure of Pt/Co/AlN stacks were investigated. At a Co thickness of 0.5 nm, the magnetic moment was not observed in the as-deposited state, but after annealing, it increased significantly. Furthermore, a strong PMA was obtained in the annealed samples; after annealing at 300 °C and 400 °C, the effective PMA energy densities were 2.28 and 1.96 × 107 erg/cm3, respectively. Similar behavior was observed for samples with thicker Co layers. The magnetic dead layer and interfacial PMA energy density were also investigated to determine the interfacial effects on PMA. The occurrence of strong PMA was supported by high-resolution cross-sectional transmission electron microscopy results, demonstrating a well-defined layered structure for the annealed Pt/Co/AlN samples.

Effect of a Discontinuous Ag Layer on Optical and Electrical Properties of ZnO/Ag/ZnOStructures

ZnO/Ag/ZnO nanolaminate structures were deposited by consecutive RF sputtering at room temperature.The optical transparency, sheet resistance, and figure of merit are determined in relation to the deposition time of Ag and to the film thickness of the ZnO top layer. An improved transmittance has been found in the visible spectral range of the ZnO/Ag/ZnO structure compared to ZnO multilayers without Ag. High transmittance of 98% at 550 nm, sheet resistance of 8 Ω/sq, and figure of merit (FOM) of 111.01 × 10−3 Ω−1are achieved for an optimized ZnO/Ag/ZnO nanolaminate structure. It is suggested that the good optical and electrical properties are due to the deposition of the discontinuous Ag layer. The electrical metallic type conductivity is caused by planar located silver metal granules. The deposition of a discrete layer of Ag nano-granules is confirmed by atomic force microscopy (AFM) and cross-section high-resolution transmission electron microscopy (HRTEM) observations.

Interface effect on superlattice quality and optical properties of InAs/GaSb type-II superlattices grown by molecular beam epitaxy

We systematically investigate the influence of InSb interface (IF) engineering on the crystal quality and optical properties of strain-balanced InAs/GaSb type-II superlattices (T2SLs). The type-II superlattice structure is 120 periods InAs (8 ML)/GaSb (6 ML) with different thicknesses of InSb interface grown by molecular beam epitaxy (MBE). The high-resolution x-ray diffraction (XRD) curves display sharp satellite peaks, and the narrow full width at half maximum (FWHM) of the 0th is only 30–39 arcsec. From high-resolution cross-sectional transmission electron microscopy (HRTEM) characterization, the InSb heterointerfaces and the clear spatial separation between the InAs and GaSb layers can be more intuitively distinguished. As the InSb interface thickness increases, the compressive strain increases, and the surface “bright spots” appear to be more apparent from the atomic force microscopy (AFM) results. Also, photoluminescence (PL) measurements verify that, with the increase in the strain, the bandgap of the superlattice narrows. By optimizing the InSb interface, a high-quality crystal with a well-defined surface and interface is obtained with a PL wavelength of 4.78 μm, which can be used for mid-wave infrared (MWIR) detection.

Cross-sectional high-resolution transmission electron microscopy at Mo/Si multilayer stacks

Abstract Using a Mo/Si multilayer stack, capabilities and limits of high-resolution transmission electron microscopy with respect to thin film analysis are pointed out. Image processing is shown to provide non-subjective criteria for the determination of layer thicknesses. In comparison to measurements by X-ray reflectometry, an integrating method capable of determining multilayer periodicities, preparation and observation artefacts in transmission electron microscopy is discussed. Special emphasis is placed on cleavage as a powerful method for TEM sample preparation, its advantages and disadvantages.

Biotic Process Dominated the Uptake and Transformation of Ag+ by Shewanella oneidensis MR-1.

Silver ions (Ag+) directly emitted from industrial sources or released from manufactured Ag nanoparticles (AgNPs) in biosolid-amended soils have raised concern about the risk to ecosystems. However, our knowledge of Ag+ toxicity, internalization, and transformation mechanisms to bacteria is still insufficient. Here, we combine the advanced technologies of hyperspectral imaging (HSI) and single-particle inductively coupled plasma mass spectrometry to visualize the potential formed AgNPs inside the bacteria and evaluate the contributions of biological and non-biological processes in the uptake and transformation of Ag+ by Shewanella oneidensis MR-1. The results showed a dose-dependent toxicity of Ag+ to S. oneidensis MR-1 in the ferrihydrite bioreduction process, which was primarily induced by the actively internalized Ag. Moreover, both HSI and cross-section high-resolution transmission electron microscopy results confirmed that Ag inside the bacteria existed in the form of particulate. The Ag mass distribution in and around live and inactivated cells demonstrated that the uptake and transformation of Ag+ by S. oneidensis MR-1 were mainly via biological process. The bioaccumulation of Ag+ may be lethal to bacteria. A better understanding of the uptake and transformation of Ag+ in bacteria is central to predict and monitor the key factors that control Ag partitioning dynamics at the biointerface, which is critical to develop practical risk assessment and mitigation strategies.

Improved resistive switching characteristics of a multi-stacked HfO2/Al2O3/HfO2 RRAM structure for neuromorphic and synaptic applications: experimental and computational study.

Atomic Layer Deposition (ALD) was used for a tri-layer structure (HfO2/Al2O3/HfO2) at low temperature over an Indium Tin Oxide (ITO) transparent electrode. First, the microstructure of the fabricated TaN/HfO2/Al2O3/HfO2/ITO RRAM device was examined by the cross-sectional High-Resolution Transmission Electron Microscopy (HRTEM). Then, Energy Dispersive X-ray Spectroscopy (EDS) was performed to probe compositional mapping. The bipolar resistive switching mode of the device was confirmed through SET/RESET characteristic plots for 100 cycles as a function of applied biasing voltage. An endurance test was performed for 100 DC switching cycles @0.2 V wherein; data retention was found up to 104 s. Moreover, for better insight into the charge conduction mechanism in tri-layer HfO2/Al2O3/HfO2, based on oxygen vacancies (VOX), total density of states (TDOS), partial density of states (PDOS) and isosurface three-dimensional charge density analysis was performed using WEIN2k and VASP simulation packages under Perdew–Burke–Ernzerhof _Generalized Gradient approximation (PBE-GGA). The experimental and theoretical outcomes can help in finding proper stacking of the active resistive switching (RS) layer for resistive random-access memory (RRAM) applications.

Evolution of a notched surface under glancing-angle broad ion beam erosion

Recently, a novel approach to sample preparation for microstructure analyses has been introduced where a surface possessing initial notches is eroded by a broad ion beam at gracing angles. In this contribution, details of the evolution of the sample surface and the geometry obtained are investigated in depth, using both simulation and experiments on single-crystalline Si substrates. A framework is introduced which describes the surface by a linear model and allows easy application for given sample preparation tasks. Furthermore, the surface amorphization introduced during sample preparation is evaluated using cross-sectional high-resolution transmission electron microscopy.

Structural and electrical characterisation of PtS from H2S-converted Pt

A manufacturing-compatible 300 mm chamber reactor for atomic layer deposition or chemical vapour deposition, and pre-fitted with H2/H2S gases that can be uniformly delivered to the wafer surface, is employed to thermally convert Pt to PtS in a H2/H2S gaseous atmosphere for 7 hours at a chamber temperature of 550 °C. Prior to conversion, platinum layers 5 nm thick are uniformly deposited by electron beam evaporation onto ∼30 nm of amorphous aluminium sesquioxide deposited by atomic layer deposition on, (a) p-type silicon, and (b) c-plane sapphire. Structural characterisation is performed by high-resolution cross-sectional transmission-electron microscopy, scanning-electron microscopy and Raman spectroscopy, confirming the formation of continuous films of polycrystalline platinum monosulfide (PtS) with a ∼15 nm thickness. Electrical characterisation is performed by 4-point resistivity and Hall-effect transport measurements on van der Pauw structures of PtS on aluminium sesquioxide on c-plane sapphire, and by back-gate junctionless MOSFET device measurements for PtS on aluminium sesquioxide on p-type silicon, showing that PtS behaves as a semiconductor with a mobility of ∼16 cm2/V.s and with an n-type carrier concentration of ∼1.2 × 1015 cm−3. Advanced commercial-grade Sentaurus simulations, alongside density-functional theory calculations, agree well with the experimental observations and suggest a large bandgap of ∼1.58 eV may be possible that could lead to a low off-current and a high Ion/Ioff ratio, suggesting that PtS may be an advanced material candidate for future device integration with CMOS and for 3D integration applications in Beyond-CMOS and More-than-Moore technologies.

Nb Texture Evolution and Interdiffusion in Nb/Si-Layered Systems.

In this paper, we present a detailed study on the microstructure evolution and interdiffusion in Nb/Si-layered systems. Interlayer formation during the early stages of growth in sputter-deposited Nb-on-Si and Si-on-Nb bilayer systems is studied in vacuo using a high-sensitivity low-energy ion-scattering technique. An asymmetric intermixing behavior is observed, where the Si-on-Nb interface is ∼2× thinner than the Nb-on-Si interface, and it is explained by the surface-energy difference between Nb and Si. During Nb-on-Si growth, the crystallization of the Nb layer occurs around 2.1 nm as-deposited Nb thickness with a strong Nb(110)-preferred orientation, which is maintained up to 3.3 nm as-deposited Nb thickness. A further increase in the Nb layer thickness above 3.3 nm results in a polycrystalline microstructure with a reduced degree of texture. High-resolution cross-sectional transmission electron microscopy imaging is performed on Nb/Si multilayers to study the effect of the Nb layer texture on interdiffusion during low-temperature annealing. Nb/Si multilayers with amorphous 2 nm Nb layers and strongly textured 3 nm thick Nb layers, with limited grain-boundary pathways for diffusion, show no observable interdiffusion during annealing at 200 °C for 8 h, whereas in a Nb/Si multilayer with polycrystalline 4 nm thick Nb layers, a ∼1 nm amorphous Nb/Si interlayer is formed at the Si-on-Nb interface during annealing.

Growth of centimeter-scale single crystal MoO3 ribbons for high performance ultraviolet photodetectors

Molybdenum oxides have attracted much interest due to their unique electronic properties. Here, we report a convenient and efficient method to synthesize centimeter-scale single crystal of MoO3 ribbons through an atmospheric pressure physical vapor deposition approach. Optical microscopy, atomic force microscopy, high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction, and x-ray diffraction measurements reveal that the MoO3 ribbons grow along the MoO3⟨100⟩ direction and the top surface is MoO3(010) plane. Raman spectroscopy, x-ray photoelectron spectroscopy, and cross-sectional HRTEM results disclose that the surface of MoO3 ribbons can be transformed from MoO3 to MoO2 through H2 annealing treatment forming MoO2/MoO3 heterostructure. We found that the conductance and ultraviolet photoresponsivity of the MoO3 ribbons can be improved by ∼11 and ∼5 orders of magnitude, respectively, after H2 annealing treatment, which will be helpful for the applications of MoO3 in the optoelectronic field.