Harm C. M. Knoops

3D negative electrode stacks for integrated all-solid-state lithium-ion microbatteries

The deposition feasibility and electrochemical evaluation of highly structured negative electrode stacks for 3D-integrated batteries is demonstrated. The stacks comprise a TiN thin film, serving as both current collector and Li-barrier layer, covered by a polycrystalline Si (poly-Si) thin film as electrode material. In comparison with planar films, these poly-Si films present a storage capacity increase of about 5× for the highest pore aspect ratio electrodes. The step coverage of poly-Si can be considerably improved by growing TiN and poly-Si into wide trenches. This results in much smoother poly-Si films and significantly improved step coverage. Further optimization of the trench dimensions should result in poly-Si films with a Li-storage capacity increase of more than one order of magnitude with respect to planar films.

Electron Scattering and Doping Mechanisms in Solid-Phase-Crystallized In2O3:H Prepared by Atomic Layer Deposition

Hydrogen-doped indium oxide (In2O3:H) has recently emerged as an enabling transparent conductive oxide for solar cells, in particular for silicon heterojunction solar cells because its high electron mobility (>100 cm(2)/(V s)) allows for a simultaneously high electrical conductivity and optical transparency. Here, we report on high-quality In2O3:H prepared by a low-temperature atomic layer deposition (ALD) process and present insights into the doping mechanism and the electron scattering processes that limit the carrier mobility in such films. The process consists of ALD of amorphous In2O3:H at 100 °C and subsequent solid-phase crystallization at 150-200 °C to obtain large-grained polycrystalline In2O3:H films. The changes in optoelectronic properties upon crystallization have been monitored both electrically by Hall measurements and optically by analysis of the Drude response. After crystallization, an excellent carrier mobility of 128 ± 4 cm(2)/(V s) can be obtained at a carrier density of 1.8 × 10(20) cm(-3), irrespective of the annealing temperature. Temperature-dependent Hall measurements have revealed that electron scattering is dominated by unavoidable phonon and ionized impurity scattering from singly charged H-donors. Extrinsic defect scattering related to material quality such as grain boundary and neutral impurity scattering was found to be negligible in crystallized films indicating that the carrier mobility is maximized. Furthermore, by comparison of the absolute H-concentration and the carrier density in crystallized films, it is deduced that <4% of the incorporated H is an active dopant in crystallized films. Therefore, it can be concluded that inactive H atoms do not (significantly) contribute to defect scattering, which potentially explains why In2O3:H films are capable of achieving a much higher carrier mobility than conventional In2O3:Sn (ITO).

Atomic Layer Deposition of Silicon Nitride from Bis(tert-butylamino)silane and N2 Plasma

Atomic layer deposition (ALD) of silicon nitride (SiNx) is deemed essential for a variety of applications in nanoelectronics, such as gate spacer layers in transistors. In this work an ALD process using bis(tert-butylamino)silane (BTBAS) and N2 plasma was developed and studied. The process exhibited a wide temperature window starting from room temperature up to 500 °C. The material properties and wet-etch rates were investigated as a function of plasma exposure time, plasma pressure, and substrate table temperature. Table temperatures of 300-500 °C yielded a high material quality and a composition close to Si3N4 was obtained at 500 °C (N/Si=1.4±0.1, mass density=2.9±0.1 g/cm3, refractive index=1.96±0.03). Low wet-etch rates of ∼1 nm/min were obtained for films deposited at table temperatures of 400 °C and higher, similar to that achieved in the literature using low-pressure chemical vapor deposition of SiNx at >700 °C. For novel applications requiring significantly lower temperatures, the temperature window from room temperature to 200 °C can be a solution, where relatively high material quality was obtained when operating at low plasma pressures or long plasma exposure times.

Low-Temperature Plasma-Assisted Atomic Layer Deposition of Silicon Nitride Moisture Permeation Barrier Layers.

Encapsulation of organic (opto-)electronic devices, such as organic light-emitting diodes (OLEDs), photovoltaic cells, and field-effect transistors, is required to minimize device degradation induced by moisture and oxygen ingress. SiNx moisture permeation barriers have been fabricated using a very recently developed low-temperature plasma-assisted atomic layer deposition (ALD) approach, consisting of half-reactions of the substrate with the precursor SiH2(NH(t)Bu)2 and with N2-fed plasma. The deposited films have been characterized in terms of their refractive index and chemical composition by spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FTIR). The SiNx thin-film refractive index ranges from 1.80 to 1.90 for films deposited at 80 °C up to 200 °C, respectively, and the C, O, and H impurity levels decrease when the deposition temperature increases. The relative open porosity content of the layers has been studied by means of multisolvent ellipsometric porosimetry (EP), adopting three solvents with different kinetic diameters: water (∼0.3 nm), ethanol (∼0.4 nm), and toluene (∼0.6 nm). Irrespective of the deposition temperature, and hence the impurity content in the SiNx films, no uptake of any adsorptive has been observed, pointing to the absence of open pores larger than 0.3 nm in diameter. Instead, multilayer development has been observed, leading to type II isotherms that, according to the IUPAC classification, are characteristic of nonporous layers. The calcium test has been performed in a climate chamber at 20 °C and 50% relative humidity to determine the intrinsic water vapor transmission rate (WVTR) of SiNx barriers deposited at 120 °C. Intrinsic WVTR values in the range of 10(-6) g/m2/day indicate excellent barrier properties for ALD SiNx layers as thin as 10 nm, competing with that of state-of-the-art plasma-enhanced chemical vapor-deposited SiNx layers of a few hundred nanometers in thickness.

Role of surface termination in atomic layer deposition of silicon nitride

There is an urgent need to deposit uniform, high-quality, conformal SiN(x) thin films at a low-temperature. Conforming to these constraints, we recently developed a plasma enhanced atomic layer deposition (ALD) process with bis(tertiary-butyl-amino)silane (BTBAS) as the silicon precursor. However, deposition of high quality SiNx thin films at reasonable growth rates occurs only when N2 plasma is used as the coreactant; strongly reduced growth rates are observed when other coreactants like NH3 plasma, or N2-H2 plasma are used. Experiments reported in this Letter reveal that NH(x)- or H- containing plasmas suppress film deposition by terminating reactive surface sites with H and NH(x) groups and inhibiting precursor adsorption. To understand the role of these surface groups on precursor adsorption, we carried out first-principles calculations of precursor adsorption on the β-Si3N4(0001) surface with different surface terminations. They show that adsorption of the precursor is strong on surfaces with undercoordinated surface sites. In contrast, on surfaces with H, NH2 groups, or both, steric hindrance leads to weak precursor adsorption. Experimental and first-principles results together show that using an N2 plasma to generate reactive undercoordinated surface sites allows strong adsorption of the silicon precursor and, hence, is key to successful deposition of silicon nitride by ALD.

Optical modeling of plasma-deposited ZnO films: Electron scattering at different length scales

In this work, an optical modeling study on electron scattering mechanisms in plasma-deposited ZnO layers is presented. Because various applications of ZnO films pose a limit on the electron carrier density due to its effect on the film transmittance, higher electron mobility values are generally preferred instead. Hence, insights into the electron scattering contributions affecting the carrier mobility are required. In optical models, the Drude oscillator is adopted to represent the free-electron contribution and the obtained optical mobility can be then correlated with the macroscopic material properties. However, the influence of scattering phenomena on the optical mobility depends on the considered range of photon energy. For example, the grain-boundary scattering is generally not probed by means of optical measurements and the ionized-impurity scattering contribution decreases toward higher photon energies. To understand this frequency dependence and quantify contributions from different scattering ph...

Enhancing the Wettability of High Aspect-Ratio Through-Silicon Vias Lined With LPCVD Silicon Nitride or PE-ALD Titanium Nitride for Void-Free Bottom-Up Copper Electroplating

One of the critical steps toward producing void-free and uniform bottom-up copper electroplating in high aspect-ratio (AR) through-silicon vias (TSVs) is the ability of the copper electrolyte to spontaneously flow through the entire depth of the via. This can be accomplished by reducing the concentration gradient of cupric ions from the via mouth to the via bottom by enhancing the wettability of the vias sidewalls. In this paper, we report on a new dry technique to enhance the hydrophilicity in high AR (~15) TSVs as one of the key solutions to face the mass transport limitation, low pressure chemical vapor deposition silicon nitride and atomic layer deposition titanium nitride of composition SiN0.95 and TiN11, respectively, are used as both barrier layers and wetting surfaces in these vias. Ammonia plasma immersion is used to treat silicon nitride. X-ray photoelectron spectroscopy shows both a partial oxidation and grafting of hydrophilic components. Alternatively, a rapid flood ultraviolet exposure step in order to photocatalytically activate the surface and induce a partially oxidized titanium nitride is used to create a highly wettable interface with a contact angle close to zero. These wettability enhancement steps were incorporated in a TSV process to produce 3-D cross-Kelvin structures using bottom-up copper electroplating. The vias lined with silicon nitride and titanium nitride exhibited a low average resistance of 25 mΩ and 50 mΩ, respectively, making them very suitable for radio-frequency signal transmission. This all-dry technology to achieve superhydrophilic barrier layers can be employed in both high and low thermal budget processing, thus enabling via-last or via-first flowchart schemes for advanced 3-D interconnects.

Expanding thermal plasma chemical vapour deposition of ZnO:Al layers for CIGS solar cells

Aluminium-doped zinc oxide (ZnO:Al) grown by expanding thermal plasma chemical vapour deposition (ETP-CVD) has demonstrated excellent electrical and optical properties, which make it an attractive candidate as a transparent conductive oxide for photovoltaic applications. However, when depositing ZnO:Al on CIGS solar cell stacks, one should be aware that high substrate temperature processing (i.e., >200°C) can damage the crucial underlying layers/interfaces (such as CIGS/CdS and CdS/i-ZnO). In this paper, the potential of adopting ETP-CVD ZnO:Al in CIGS solar cells is assessed: the effect of substrate temperature during film deposition on both the electrical properties of the ZnO:Al and the eventual performance of the CIGS solar cells was investigated. For ZnO:Al films grown using the high thermal budget (HTB) condition, lower resistivities, ρ, were achievable (5 × 10 -4 Ω·cm) than those grown using the low thermal budget (LTB) conditions (2 × 10-3 Ω·cm), whereas higher CIGS conversion efficiencies were obtained for the LTB condition (up to 10.9%) than for the HTB condition (up to 9.0%). Whereas such temperature-dependence of CIGS device parameters has previously been linked with chemical migration between individual layers, we demonstrate that in this case it is primarily attributed to the prevalence of shunt currents. cop. 2014 K. Sharma et al.

Remote Plasma Atomic Layer Deposition of Co3O4 Thin Films

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Comparison of thermal and plasma-enhanced atomic layer deposition of niobium oxide thin films

Niobium pentoxide was deposited using tBuN=Nb(NEt2)3 as niobium precursor by both thermal atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PE-ALD) with H2O and O2 plasma as coreactants, respectively. The deposition temperature was varied between 150 and 350 °C in both ALD processes. Amorphous films were obtained in all cases. Self-limiting saturated growth was confirmed for both ALD processes along with high uniformity over a 200 mm Si wafer. The PE-ALD process enabled a higher growth per cycle (GPC) than the thermal ALD process (0.56 A vs 0.38 A at 200 °C, respectively), while the GPC decreases with increasing temperature in both cases. The high purity of the film was confirmed using Rutherford backscattering spectrometry, elastic recoil detection, and x-ray photoelectron spectroscopy, while the latter technique also confirmed the Nb+5 oxidation state of the niobium oxide films. The thermal ALD deposited films were substoichiometric due to the presence of oxygen vacancies (VO), of which a more dominant presence was observed with increasing deposition temperature. The PE-ALD deposited films were found to be near stoichiometric for all investigated deposition temperatures.Niobium pentoxide was deposited using tBuN=Nb(NEt2)3 as niobium precursor by both thermal atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PE-ALD) with H2O and O2 plasma as coreactants, respectively. The deposition temperature was varied between 150 and 350 °C in both ALD processes. Amorphous films were obtained in all cases. Self-limiting saturated growth was confirmed for both ALD processes along with high uniformity over a 200 mm Si wafer. The PE-ALD process enabled a higher growth per cycle (GPC) than the thermal ALD process (0.56 A vs 0.38 A at 200 °C, respectively), while the GPC decreases with increasing temperature in both cases. The high purity of the film was confirmed using Rutherford backscattering spectrometry, elastic recoil detection, and x-ray photoelectron spectroscopy, while the latter technique also confirmed the Nb+5 oxidation state of the niobium oxide films. The thermal ALD deposited films were substoichiometric due to the presence of oxygen vacancies (VO), ...