Markus Heyne

Multilayer MoS2 growth by metal and metal oxide sulfurization

We investigated the deposition of MoS2 multilayers on large area substrates. The pre-deposition of metal or metal oxide with subsequent sulfurization is a promising technique to achieve layered films. We distinguish a different reaction behavior in metal oxide and metallic films and investigate the effect of the temperature, the H2S/H2 gas mixture composition, and the role of the underlying substrate on the material quality. The results of the experiments suggest a MoS2 growth mechanism consisting of two subsequent process steps. At first, the reaction of the sulfur precursor with the metal or metal oxide occurs, requiring higher temperatures in the case of metallic film compared to metal oxide. At this stage, the basal planes assemble towards the diffusion direction of the reaction educts and products. After the sulfurization reaction, the material recrystallizes and the basal planes rearrange parallel to the substrate to minimize the surface energy. Therefore, substrates with low roughness show basal plane assembly parallel to the substrate. These results indicate that the substrate character has a significant impact on the assembly of low dimensional MoS2 films.

Quantitative characterization of pore stuffing and unstuffing for postporosity plasma protection of low-k materials

The problem of k-value degradation (plasma damage) is a key issue for the integration, and it is becoming more challenging as the dielectric constant of low-k materials scales down. One way to circumvent this issue is temporarily conversion of low-k material from a porous to a dense state by filling the pores with a sacrificial polymer after the deposition and curing of the low-k material. A detailed process scheme for the pore stuffing and postetch polymer removal of PMMA is described in this work. The filling temperature was optimized according to the molecular weight of the PMMA. To remove the polymer after plasma-etching in a purely thermal environment, a temperature of at least 430 °C had to be applied. Annealing assisted by variable frequency microwaves could remove the polymer already at 380 °C and with a He–H2 afterglow plasma the polymer could be removed at 280 °C. Laser annealing allowed the removal at a stage temperature of 200 °C with an only surface-limited heating of about 500 °C and higher ...

Vacuum ultra-violet damage and damage mitigation for plasma processing of highly porous organosilicate glass dielectrics

Porous organosilicate glass thin films, with k-value 2.0, were exposed to 147 nm vacuum ultra-violet (VUV) photons emitted in a Xenon capacitive coupled plasma discharge. Strong methyl bond depletion was observed, concomitant with a significant increase of the bulk dielectric constant. This indicates that, besides reactive radical diffusion, photons emitted during plasma processing do impede dielectric properties and therefore need to be tackled appropriately during patterning and integration. The detrimental effect of VUV irradiation can be partly suppressed by stuffing the low-k porous matrix with proper sacrificial polymers showing high VUV absorption together with good thermal and VUV stability. In addition, the choice of an appropriate hard-mask, showing high VUV absorption, can minimize VUV damage. Particular processing conditions allow to minimize the fluence of photons to the substrate and lead to negligible VUV damage. For patterned structures, in order to reduce VUV damage in the bulk and on feature sidewalls, the combination of both pore stuffing/material densification and absorbing hard-mask is recommended, and/or the use of low VUV-emitting plasma discharge.

Two-dimensional WS2 nanoribbon deposition by conversion of pre-patterned amorphous silicon

We present a method for area selective deposition of 2D WS2 nanoribbons with tunable thickness on a dielectric substrate. The process is based on a complete conversion of a pre-patterned, H-terminated Si layer to metallic W by WF6, followed by in situ sulfidation by H2S. The reaction process, performed at 450 °C, yields nanoribbons with lateral dimension down to 20 nm and with random basal plane orientation. The thickness of the nanoribbons is accurately controlled by the thickness of the pre-deposited Si layer. Upon rapid thermal annealing at 900 °C under inert gas, the WS2 basal planes align parallel to the substrate.

Thermal recrystallization of short-range ordered WS2 films

The integration of van der Waals materials in nanoelectronic devices requires the deposition of few-layered MX2 films with excellent quality crystals covering a large area. In recent years, astonishing progress in the monolayer growth of WS2 and MoS2 was demonstrated, but multilayer growth resulted often in separated triangular or hexagonal islands. These polycrystalline films cannot fully employ the specific MX2 properties since they are not connected in-plane to the other domains. To coalesce separated islands, ultrahigh-temperature postdeposition anneals in H2S are applied, which are not compatible with bare silicon substrates. Starting from the deposition of stoichiometric short-ordered films, the present work studies different options for subsequent high-temperature annealing in an inert atmosphere to form crystalline films with large grains from stoichiometric films with small grains. The rapid thermal annealing, performed over a few seconds, is compared to excimer laser annealing in the nanosecond range, which are both able to crystallize the thin WS2. The WS2 recrystallization temperature can be lowered using metallic crystallization promoters (Co and Ni). The best result is obtained using a Co cap, due to the circumvention of Co and S binary phase formation below the eutectic temperature. The recrystallization above a critical temperature is accompanied by sulfur loss and 3D regrowth. These undesired effects can be suppressed by the application of a dielectric capping layer prior to annealing. A SiO2 cap can suppress the sulfur loss successfully during annealing and reveals improved material quality in comparison to noncapped films.The integration of van der Waals materials in nanoelectronic devices requires the deposition of few-layered MX2 films with excellent quality crystals covering a large area. In recent years, astonishing progress in the monolayer growth of WS2 and MoS2 was demonstrated, but multilayer growth resulted often in separated triangular or hexagonal islands. These polycrystalline films cannot fully employ the specific MX2 properties since they are not connected in-plane to the other domains. To coalesce separated islands, ultrahigh-temperature postdeposition anneals in H2S are applied, which are not compatible with bare silicon substrates. Starting from the deposition of stoichiometric short-ordered films, the present work studies different options for subsequent high-temperature annealing in an inert atmosphere to form crystalline films with large grains from stoichiometric films with small grains. The rapid thermal annealing, performed over a few seconds, is compared to excimer laser annealing in the nanosecond ...

The conversion mechanism of amorphous silicon to stoichiometric WS2

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.

WS 2 transistors on 300 mm wafers with BEOL compatibility

For the first time, WS2-based transistors have been successfully integrated in a 300 mm pilot line using production tools. The 2D material was deposited using either area selective chemical vapor deposition (CVD) or atomic layer deposition (ALD). No material transfer was required. The major integration challenges are the limited adhesion and the fragility of the few-monolayer 2D material. These issues are avoided by using a sacrificial Al2O3 capping layer and by encapsulating the edges of the 2D material during wet processing. The WS2 channel is contacted with Ti/TiN side contacts and an industry-standard back end of line (BEOL) flow. This novel low-temperature flow is promising for integration of back-gated 2D transistors in the BEOL.