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.

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.

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 ß-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.

Single-step plasma synthesis of carbon-coated silicon nanoparticles.

We have developed a novel single-step technique based on nonthermal, radio frequency (rf) plasmas to synthesize sub-10 nm, core-shell, carbon-coated crystalline Si (c-Si) nanoparticles (NPs) for potential application in Li(+) batteries and as fluorescent markers. Hydrogen-terminated c-Si NPs nucleate and grow in a SiH4-containing, low-temperature plasma in the upstream section of a tubular quartz reactor. The c-Si NPs are then transported downstream by gas flow, and are coated with amorphous carbon (a-C) in a second C2H2-containing plasma. X-ray diffraction (XRD), X-ray photoelectron spectroscopy, and in situ attenuated total reflection Fourier transform infrared spectroscopy show that a thin, < 1 nm, 3C-SiC layer forms at the c-Si/a-C interface. By varying the downstream C2H2 plasma rf power, we can alter the nature of the a-C coating as well as the thickness of the interfacial 3C-SiC layer. The transmission electron microscopy (TEM) analysis is in agreement with the Si NP core size determined by Raman spectroscopy, photoluminescence spectroscopy, and XRD analysis. The size of the c-Si NP core, and the corresponding light emission from these NPs, was directly controlled by varying the thickness of the interfacial 3C-SiC layer. This size tunable emission thus also demonstrates the versatility of this technique for synthesizing c-Si NPs for potential applications in light emitting diodes, biological markers, and nanocrystal inks.