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Atmospheric pressure plasma deposition (APPD) of poly(ethylene oxide) (PEO)‐like antifouling coatings provides an attractive way to reduce biofouling for reliable biosensor operation. Cold atmospheric pressure plasma jets are designed to operate in open air. This paper demonstrates the impact of open‐air processing on the composition and properties of PEO‐like coatings by APPD with vinyl ether precursors. The open‐air environment inhibits polymerization as indicated by low deposition rates, oxygen incorporation in the coatings, and instability of the coatings in water. The composition and stability of the coatings improve by appropriate nozzle design and by deposition in an environment with lower air content. The resulting PEO‐like coatings are stable and antifouling for an antibody solution and inhibit adhesion of human fibroblast cells. [ABSTRACT FROM AUTHOR]

Area‐selective deposition (ASD) is a bottom‐up technique that provides numerous opportunities for nanoelectronic device fabrication. For example, advanced nano‐interconnect structures with barrierless metals like Ru in the contact holes can be created by Ru ASD with the bottom metals as growth surfaces and dielectrics as non‐growth surfaces. This work investigates Ru ASD by chemical vapor deposition (CVD) on industrially relevant substrates and nanopatterns and reveals how selectivity and growth rate are modulated by the CVD conditions and type of nanopattern. For low‐k dielectric/Cu substrate combinations, the selectivity reverses from metal‐on‐metal to metal‐on‐dielectric upon only changing the CVD co‐reagent from H2 to NH3. In contrast, NH3 is the preferred co‐reagent for SiO2‐TiN line patterns with critical dimension (CD) of 40 nm due to the more favorable adsorption and diffusion kinetics that cause growth rate and selectivity enhancement. Consistent with a diffusion‐mediated mechanism, the growth rate enhances even more for Ru CVD on nanoscale contact holes with CD of 10.5 nm, becoming 2.4 times higher as compared to unpatterned substrates. Thus, the ASD process changes drastically when pattern dimensions reach the nanoscale. The reported insights facilitate rational design of metal ASD processes for multiple applications in nanofabrication. [ABSTRACT FROM AUTHOR]

Area‐selective deposition (ASD) shows great promise for sub‐10 nm manufacturing in nanoelectronics, but significant challenges remain in scaling to ultrasmall dimensions and understanding feature‐dependent nonuniformity and selectivity loss. This work addresses these problems by simultaneously quantifying uniformity and selectivity for passivation/deposition/etch supercycles in 45 nm half‐pitch TiN/SiO2 line/space patterns. This work employs three selective processes that are uniquely suited for supercycle processing: dimethylamino‐trimethylsilane (DMA‐TMS) inhibition, TiO2 atomic layer deposition (ALD), and HBr/BCl3 plasma etch. The DMA‐TMS inhibition selectively passivates the SiO2 nongrowth surface without affecting deposition on the TiN and TiO2 growth surfaces. The plasma etch removes TiO2 defect particles at a faster rate than the conformal TiO2 film or SiO2 lines. Using three supercycles of this process, this work demonstrates 8 nm of TiO2 with 88% uniformity and ≈100% selectivity according to transmission electron microscopy (TEM), a 2×improvement in film thickness from previous reports in similar nanoscale patterns. Integrated consideration of uniformity and selectivity at specific feature scales will facilitate the effective design of selective deposition processes for nanoscale electronic devices. [ABSTRACT FROM AUTHOR]

Anisotropic growth of two-dimensional (2D) tungsten disulfide (WS2) crystals occurs during atomic layer deposition (ALD) from WS2 seeds at predetermined locations on large area dielectric substrates. The number of ALD reaction cycles determines the lateral dimensions of the WS2 crystals. This 2D synthesis approach is compatible with temperature sensitive structures due to the low deposition temperature and can be extended to other 2D materials and heterostructures thereof. The crystallinity of the seed and the selectivity of ALD precursors toward seeds and underlying starting surface affect the structural quality of the 2D crystals. [ABSTRACT FROM AUTHOR]

Area-selective atomic layer deposition (AS-ALD) is a coveted method for the fabrication of next-generation nano-electronic devices, as it can complement lithography and improve alignment through atomic scale control. Selective reactions of small molecule inhibitors (SMIs) can be used to deactivate growth on specific surface areas and as such enable AS-ALD. To investigate new applications of ASD, we need insight into the reactions of SMIs with a broad range of technology relevant materials. This paper investigates the reactions of aminosilane SMIs with a broad range of oxide surfaces and the impact on subsequent atomic layer deposition (ALD). We compare the reactions of two aminosilane SMIs, namely, dimethylamino-trimethylsilane (DMA-TMS) and hexamethyldisilazane (HMDS), with a hydroxylated SiO2 surface and the impact on subsequent ALD processes. The DMA-TMS reaction saturates faster than the HMDS reaction and forms a dense trimethylsilyl (TMS) layer with a higher TMS surface concentration. The higher TMS surface concentration yields better inhibition and higher selectivity during subsequent TiO2 ALD. We show that a wide range of surfaces, i.e., MgO, HfO2, ZrO2, Al2O3, TiO2 (TiN/TiOx), SiO2, SnO2, MoOx, and WO3 remain reactive after DMA-TMS exposure for conditions where SiO2 is passivated, indicating that DMA-TMS can enable AS-ALD on these surfaces with respect to SiO2. On these surfaces, DMA-TMS forms residual TMS and/or SiOxCyHz surface species that do not markedly inhibit ALD but may affect interface purity. Surfaces with lower, similar, and higher surface acidity than SiO2 all show less reactivity toward DMA-TMS, suggesting that surface acidity is not the only factor affecting the substrate-inhibitor interaction. Our study also compares a hybrid inorganic-organic SnOxCyHz and inorganic SnO2 material in view of their relevance as resist for extreme ultraviolet lithography. DMA-TMS can enable selective infiltration in SnOxCyHz, as opposed to selective deposition on SnO2, indicating tunable reactivity by bulk and surface composition. These insights into the reactivity of aminosilane SMIs may aid the design of new area-selective deposition processes, broaden the material space, and enable new applications. [ABSTRACT FROM AUTHOR]

Small-molecule inhibitors have recently been introduced for passivation during area-selective deposition (ASD). Small silanes like (N,N-dimethylamino)trimethylsilane (DMATMS) selectively react with −OH sites on SiO2 to form a less reactive –OSi(CH3)3 terminated surface. The –OSi(CH3)3 surface termination can inhibit many atomic layer deposition (ALD) processes, including TiCl4/H2O ALD. However, the mechanisms by which ALD is inhibited and by which selectivity is eventually lost are not well understood. This study uses in situ Fourier-transform infrared spectroscopy to probe the adsorption of DMATMS on SiO2 and the subsequent reactions when the passivated surface is exposed to TiCl4/H2O ALD. The chemisorption of DMATMS on isolated –OH groups on SiO2 is shown to inhibit the reaction with TiCl4. Further, we find that starting with an inherently inhibiting H-terminated Si surface, DMATMS can also react with residual –OH groups and reduce the extent of nucleation. Finally, using Rutherford backscattering spectrometry, the effectiveness of DMATMS passivation on SiO2 and H-terminated Si is quantified during extended ALD cycle numbers. The insight into the mechanisms of passivation by DMATMS and passivation loss can enable the rational design of highly selective ASD processes by carefully matching compatible surfaces, passivating agents, and ALD precursors. [ABSTRACT FROM AUTHOR]

Nanoelectronics holds significant promise for two-dimensional (2D) semiconducting transition metal dichalcogenide (TMD) applications. On a polycrystalline WS2 monolayer created by metal-organic chemical vapor deposition (MOCVD) at 950 °C, we studied the nucleation, growth, and development of Al2O3 atomic layer deposition (ALD) on a SiO2/Si substrate. In this investigation, we used various complementary characterization methods, such as Raman spectroscopy, elastic recoil detection, atomic force microscopy, and time-of-flight secondary ion mass spectrometry, to understand thoroughly the intrinsic reactivity of WS2. Strong peak intensity changes at the interfaces in the Raman line scans of the SiO2/Si patterns suggest extremely crystalline WS2. After multiple ALD cycles, triangular WS2 crystals were decorated to provide a two-dimensional growth mode with a great selectivity for grain boundaries and step edges. The results of this work can be used for further exploration of the TMD monolayer structure and properties, which is essential for tailoring 2D materials for a specific application in devices. [ABSTRACT FROM AUTHOR]

During TiO2 atomic layer deposition (ALD) using TiCl4 and H2O at ∼150 °C, nucleation proceeds rapidly on hydroxylated SiO2 but is inherently delayed on passivated surfaces such as H-terminated silicon (Si-H) and trimethylsilyl-passivated SiO2 (SiO2-TMS) formed using dimethylamino-trimethylsilane (DMA-TMS) as a small molecule inhibitor. In this work, we explore details of TiO2 nucleation on both Si-H and SiO2-TMS and show that the mechanisms leading to unwanted nuclei depend strongly on the passivation mechanism. Initial growth is observed as a function of ALD cycles using scanning electron microscopy to obtain average particle size, density, and overall surface coverage fraction. Also, average film thickness vs cycle is estimated using ellipsometry or Rutherford backscattering spectrometry. Data are compared to an analytical model that considers that either nucleation sites are present on the starting non-growth surface or sites are generated during the ALD process. On the Si-H surface, data and modeling indicate that nucleation occurs predominantly from a fixed number of nucleation sites present on the starting growth surface that start to immediately grow. However, on TMS-passivated SiO2, nucleation sites are predominantly generated during the growth process so that the density of nucleation sites increases as growth proceeds. Results indicate that nucleation sites are created when adsorbed ALD reactants become kinetically trapped on the SiO2-TMS surface. This demonstrates that mechanisms associated with unwanted nucleation during area-selective deposition (ASD) can depend on details of the surface passivation scheme, thereby providing insight to help to improve ASD strategies for advanced applications. [ABSTRACT FROM AUTHOR]

The impact of chlorine residue concentration in thin Hf[O.sub.2] films on the MOSFET device time-dependent dielectric breakdown (TDDB) is discussed. The results have shown that the presence of chlorine residue has no important impact on the trap generation and reliability of atomic layer deposition (ALD) Hf[O.sub.2] layers.

An effective technique and methodology for the estimation of fixed charge components in high-kappa stacks was demonstrated by varying both the SiO[sub 2] and high-kappa dielectric thicknesses. Layers with different thickness of both the nitrided and non-nitrided hafnium-silicate layers were grown on wafers to estimate the entire interfacial and bulk charge components. This method was used to compare the fixed charge levels in Hf-silicates (HfSiO) and nitrided-Hf-silicate (HfSiON) layers.

Low equivalent oxide thickness (EOT) and high-performing n-channel transistors with a Hf[O.sub.2]/TaN gate stack and a low thermal-budget process is demonstrated using solid-phase epitaxial regrowth of the source and drain junctions. The thinnest devices have an EOT of 8 Angstrom, a leakage current of 1.5/a[cm.sup.2] at [V.sub.G] = 1 V, a peak mobility of 190 [cm.sup.2]/V .s and a drive current of 815 [mu]A/[mu]m at an OFF-state current of 0.1 [mu]A/mum for [V.sub.DD]= 1.2V.

Germanium combined with high-k dielectrics is put forth as a potential replacement for planar silicon transistors by the semiconductor industry. A study is carried out on the atomic layer deposition (ALD) of HfO2 high-k dielectric layers on HF-cleaned Ge substrates.

Area‐selective deposition (ASD) is a promising bottom‐up approach for fabricating nanoelectronic devices. However, a challenge is to prevent the undesired growth of nanoparticles in the nongrowth area. This work uses kinetic Monte Carlo (KMC) methods to investigate the defectivity in ruthenium ASD by (ethylbenzyl)(1‐ethyl‐1,4‐cyclohexadienyl)Ru/O2 (EBECHRu) atomic layer deposition (ALD) in line‐space nanopatterns with different dimensions. Ru ASD is governed by adsorption as well as diffusion. The defectivity depends on the pattern dimensions, as nanoparticles can diffuse and reach the interface with the growth area where they aggregate. For linewidths of 50 nm and smaller, all Ru adspecies are captured at the growth interface before growth by precursor adsorption is catalyzed. The synergetic effect of diffusion and size‐dependent reactivity reduces defectivity below 1010 Ru atoms cm−2 for at least 1000 ALD cycles. This is more than 1000 times lower than for patterns with a linewidth of 200 nm and larger, where the Ru content decreases significantly only near the interface with the growth surface. The predicted depletion zone is confirmed by experiments in nanoscale line‐space patterns. Overall, this mechanism results in smaller and fewer Ru nanoparticles for smaller patterns, facilitating the development of passivation‐deposition‐etch ASD processes for nanoelectronic device fabrication. [ABSTRACT FROM AUTHOR]

Alkyl-terminated surfaces have received significant interest as growth-blocking surfaces in area-selective deposition (ASD). Gas-phase chemical functionalization is attractive in this context due to its short process times, potentially wide applicability, and ease of integration in industrial process flows. However, the relation between the surface chemistry, the passivating agent, and the growth-blocking efficacy of such treatments is not well understood which can lead to suboptimal passivation performance. This work investigates the reaction between dimethylamino-trimethylsilane (DMA-TMS) and SiO2 surfaces with varying composition, and identifies the impact of surface composition on passivation efficacy and selectivity. DMA-TMS reacts rapidly with Si–OH groups on SiO2 in a self-limiting surface reaction, resulting in an –O–Si(CH3)3 covered surface. In contrast, Si–O–Si groups are either unreactive or significantly less reactive towards DMA-TMS. Increasing the number of Si–OH versus Si–O–Si groups on the initial SiO2 surface therefore results in a higher –O–Si(CH3)3 density after DMA-TMS treatment. As a consequence, the selectivity of an ASD process towards SiO2 improves, as demonstrated for ruthenium atomic layer deposition from 1-ethylbenzyl-1,4-cyclohexadienyl-ruthenium and oxygen. This work illustrates the impact of tuning surface composition on passivation and selectivity for ASD. [ABSTRACT FROM AUTHOR]

The direct reaction of trimethylaluminum (TMA) on a Ge(100) surface and the effects of monolayer H2O pre-dosing were investigated using ultrahigh vacuum techniques, such as scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). At room temperature (RT), a saturation TMA dose produced 0.8 monolayers (ML) of semi-ordered species on a Ge(100) surface due to the dissociative chemisorption of TMA. STS confirmed the chemisorption of TMA passivated the bandgap states due to dangling bonds. By annealing the TMA-dosed Ge surface, the STM observed coverage of TMA sites decreased to 0.4 ML at 250 °C, and to 0.15 ML at 450 °C. XPS analysis showed that only carbon content was reduced during annealing, while the Al coverage was maintained at 0.15 ML, consistent with the desorption of methyl (-CH3) groups from the TMA adsorbates. Conversely, saturation TMA dosing at RT on the monolayer H2O pre-dosed Ge(100) surface followed by annealing at 200 °C formed a layer of Ge-O-Al bonds with an Al coverage a factor of two greater than the TMA only dosed Ge(100), consistent with Ge-OH activation of TMA chemisorption and Ge-H blocking of CH3 chemisorption. The DFT shows that the reaction of TMA has lower activation energy and is more exothermic on Ge-OH than Ge-H sites. It is proposed that the H2O pre-dosing enhances the concentration of adsorbed Al and forms thermally stable Ge-O-Al bonds along the Ge dimer row which could serve as a nearly ideal atomic layer deposition nucleation layer on Ge(100) surface. [ABSTRACT FROM AUTHOR]

Atomic layer deposition (ALD) is used in applications where inorganic material layers with uniform thickness down to the nanometer range are required. For such thicknesses, the growth mode, defining how the material is arranged on the surface during the growth, is of critical importance. In this work, the growth mode of the zirconium tetrachloride/water and the trimethyl aluminum/water ALD process on hydrogen-terminated silicon was investigated by combining information on the total amount of material deposited with information on the surface fraction of the material. The total amount of material deposited was measured by Rutherford backscattering, x-ray fluorescence, and inductively coupled plasma–optical emission spectroscopy, and the surface fractions by low-energy ion scattering. Growth mode modeling was made assuming two-dimensional growth or random deposition (RD), with a “shower model” of RD recently developed for ALD. Experimental surface fractions of the ALD-grown zirconium oxide and aluminum oxide films were lower than the surface fractions calculated assuming RD, suggesting the occurrence of island growth. Island growth was confirmed with transmission electron microscopy (TEM) measurements, from which the island size and number of islands per unit surface area could also be estimated. The conclusion of island growth for the aluminum oxide deposition on hydrogen-terminated silicon contradicts earlier observations. In this work, physical aluminum oxide islands were observed in TEM after 15 ALD reaction cycles. Earlier, thicker aluminum oxide layers have been analyzed, where islands have not been observed because they have already coalesced to form a continuous film. The unreactivity of hydrogen-terminated silicon surface towards the ALD reactants, except for reactive defect areas, is proposed as the origin of island growth. Consequently, island growth can be regarded as “undesired surface-selective ALD.” [ABSTRACT FROM AUTHOR]

The reactions of (super 1)S and (super 3)D Cu(super +) ions with N2O are studied using the help of ab initio methods. The calculations showed that bare (super 1)S Cu(super +) ions are relatively inert with respect to N2O.

The reaction of 3d transition metal atoms with N2O is studied to examine charge transfer process in the reaction mechanism by combination of density functional theory and the coupled cluster method CCSD(T). Results showed no charge transfer from the transition metal toward N2O for Sc, Ti and V transition state, whereas charge transfer between the metal 4s orbital and the in-plane N2O LUMO is an important process, when moving from Cr to Cu in the 3d transition series.

SnS2 and SnS are two-dimensional (2D) semiconductors with distinct properties, as they exhibit a different type of conduction. They are of interest for applications in nanoelectronics, optoelectronics and sensors. To enable these applications, the deposition of SnS2 and SnS layers with a well-controlled phase, crystallinity and thickness at the nanometer level is required on large-area substrates. Chemical vapor deposition (CVD) of SnS2 and SnS using SnCl4 and H2S has previously been reported to give micrometer level polycrystalline SnS2 and SnS layers, which were insulating due to the uncontrolled grain orientations. In this work, we investigate the formation mechanism and phase control of nanometer level 2D SnS2 and SnS by SnCl4/H2S CVD. Nanometer level and phase-pure 2D hexagonal SnS2 and orthorhombic SnS layers are obtained. The SnSx phase depends on both the temperature and the H2S/SnCl4 concentration ratio. Compared to the formation of the SnS2 phase, the formation of the SnS phase is favorable at higher temperature and, surprisingly, at a higher H2S/SnCl4 concentration ratio. This is explained by the catalytic decomposition of H2S by SnS2 with the formation of H2, where the as such generated H2 reduces SnS2 to SnS at temperatures equal to or higher than 350 °C. By adjusting the conditions of the CVD process, the product can be tuned to either n-type SnS2 or p-type SnS, as demonstrated by back-gated field effect transistors. [ABSTRACT FROM AUTHOR]

The deposition of ultra-thin tungsten films and their related 2D chalcogen compounds on large area dielectric substrates by gas phase reactions is challenging. The lack of nucleation sites complicates the adsorption of W-related precursors and subsequent sulfurization usually requires high temperatures. We propose here a technique in which a thin solid amorphous silicon film is used as reductant for the gas phase precursor WF6 leading to the conversion to metallic W. The selectivity of the W conversion towards the underlying dielectric surfaces is demonstrated. The role of the Si surface preparation, the conversion temperature, and Si thickness on the formation process is investigated. Further, the in situ conversion of the metallic tungsten into thin stoichiometric WS2 is achieved by a cyclic approach based on WF6 and H2S pulses at the moderate temperature of 450 °C, which is much lower than usual oxide sulfurization processes. [ABSTRACT FROM AUTHOR]

The structure, crystallinity and properties of as-deposited two-dimensional (2D) transition metal dichalcogenides are determined by nucleation mechanisms in the deposition process. 2D materials grown by atomic layer deposition (ALD) in the absence of a template are polycrystalline or amorphous. Little is known about their nucleation mechanisms. Therefore, the nucleation behavior of WS2 during plasma enhanced ALD from WF6, H2 plasma and H2S at 300 °C is investigated on amorphous ALD Al2O3 starting surface and on monocrystalline, bulk sapphire. Preferential interaction of the precursors with the Al2O3 starting surface promotes fast closure of the WS2 layer. The WS2 layers are fully continuous at WS2 content corresponding to only 1.2 WS2 monolayers. On amorphous Al2O3, (0002) textured and polycrystalline WS2 layers form with grain size of 5 to 20 nm due to high nucleation density (∼1014 nuclei/cm2). The WS2 growth mode changes from 2D (layer-by-layer) growth on the initial Al2O3 surface to three-dimensional (Volmer-Weber) growth after WS2 layer closure. Further growth proceeds from both WS2 basal planes in register with the underlying WS2 grain and from or over grain boundaries of the underlying WS2 layer with different in-plane orientation. In contrast, on monocrystalline sapphire, WS2 crystal grains can locally align along a preferred in-plane orientation. Epitaxial seeding occurs locally albeit a large portion of crystals remain randomly oriented, presumably due to the low deposition temperature. The WS2 sheet resistance is 168 MΩμm, suggesting that charge transport in the WS2 layers is limited by grain boundaries. [ABSTRACT FROM AUTHOR]

In this paper, the deep levels found by Deep-Level Transient Spectroscopy in Si-O superlattices (SLs) on n-type silicon are reported. Samples have been grown with one, two or five silicon-oxygen layers, separated by 3 nm of silicon. A Cr Schottky barrier (SB) is thermally evaporated on top of the SL. Similar as for p-type silicon, no deep levels have been found for a bias pulse in depletion, while a broad distribution of electron traps shows up when pulsing into forward bias. At the same time, these bands are absent in a zero SL reference sample. Similar as for the p-type results, the trap filling of the electron states exhibits a logarithmic capture. The possible origin of this slow filling will be discussed. [ABSTRACT FROM AUTHOR]

The presence of deep levels in a silicon-oxygen (Si-O) superlattice (SL) deposited on p-type silicon substrates has been investigated by deep-level transient spectroscopy (DLTS) on thermally evaporated Cr Schottky barriers (SBs). The SLs have been fabricated with different thicknesses of the silicon interlayers, formed by chemical vapor deposition. It is shown that a broad band of hole traps is present near the surface of the SB, which is associated with the SL. In addition, the activation energy corresponding with the peak maximum shifts to higher values with respect to the valence band and gives rise to a higher trap concentration with increasing silicon interlayer thickness. It is proposed that these states are associated with the structural defects found in similar SL structures, that is, with the epitaxial quality and not with the SiO bonds in the atomic layers. The change in the DLT-spectra with silicon thickness could be related with the transformation of the structural defects from small self-interstitial clusters to stacking faults. [ABSTRACT FROM AUTHOR]