The influence of hydrogen concentration in amorphous carbon films on mechanical properties and fluorine penetration: a density functional theory and ab initio molecular dynamics study.

Amorphous carbon (a-C) films have attracted significant attention due to their reliable structures and superior mechanical, chemical and electronic properties, making them a strong candidate as an etch hard mask material for the fabrication of future integrated semiconductor devices. Density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations were performed to investigate the energetics, structure, and mechanical properties of the a-C films with an increasing sp3 content by adjusting the atomic density or hydrogen content. A drastic increase in the bulk modulus is observed by increasing the atomic density of the a-C films, which suggests that it would be difficult for the films hardened by high atomic density to relieve the stress of the individual layers within the overall stack in integrated semiconductor devices. However, the addition of hydrogen into the a-C films has little effect on increasing the bulk modulus even though the sp3 content increases. For the F blocking nature, the change in the sp3 content by both atomic density and H concentration makes the diffusion barrier against the F atom even higher and suppresses the F diffusion, indicating that the F atom would follow the diffusion path passing through the sp2 carbon and not the sp3 carbon due to the significantly high barrier. For the material design of a-C films with adequate doped characteristics, our results can provide a new straightforward strategy to tailor the a-C films with excellent mechanical and other novel physical and chemical properties.

First principles investigation on energetics, structure, and mechanical properties of amorphous carbon films doped with B, N, and Cl.

Amorphous carbon (a-C) films have received significant attention due to their reliable structures and superior mechanical, chemical and electronic properties, making them a strong candidate as a hard mask material. We investigated the energetics, structure, and electronic and mechanical properties of the B, N, and Cl doped a-C films based on density functional theory (DFT) calculation. Our DFT calculated results clearly show that introducing B and N atoms into a-C films makes the bulk modulus slightly reduced as a function of the concentration increases. Interestingly, it is noted that introducing Cl atom into a-C films makes the bulk modulus is drastically reduced, which suggests that the films softened by Cl doping would relieve residual stress of the individual layers within the overall stacks in integrated semiconductor devices. These requirements become more important and increasingly more challenging to meet as the device integrity grows. In the perspective of F blocking nature, B doping into a-C films pulls in and captures the F atom due to the strong bonding nature of B‒F bond than C-F bond. Unlike the B doping, for the N doped a-C film, F atom has extremely large diffusion barrier of 4.92 eV. This large diffusion barrier is attributed to the electrostatically repulsive force between both atoms. The Cl doped a-C film shows consistently the similar results with the N doped a-C film because both N and Cl atoms have large electro-negativity, which causes F atom to push out. If one notes the optimized designing with the suitable doped characteristics, our results could provide a new straightforward strategy to tailor the a-C films with excellent mechanical and other novel physical and chemical properties.

Effects of H2 and N2 treatment for B2H6 dosing process on TiN surfaces during atomic layer deposition: an ab initio study.

For the development of the future ultrahigh-scale integrated memory devices, a uniform tungsten (W) gate deposition process with good conformal film is essential for improving the conductivity of the W gate, resulting in the enhancement of device performance. As the memory devices are further scaled down, uniform W deposition becomes more difficult because of the experimental limitations of the sub-nanometer scale deposition even with atomic layer deposition (ALD) W processes. Even though it is known that the B2H6 dosing process plays a key role in the deposition of the ALD W layer with low resistivity and in the removal of residual fluorine (F) atoms, the roles of H2 and N2 treatments used in the ALD W process have not yet been reported. To understand the detailed ALD W process, we have investigated the effects of H2 and N2 treatment on TiN surfaces for the B2H6 dosing process using first-principles density functional theory (DFT) calculations. In our DFT calculated results, H2 treatment on the TiN surfaces causes the surfaces to become H-covered TiN surfaces, which results in lowering the reactivity of the B2H6 precursor since the overall reactions of the B2H6 on the H-covered TiN surfaces are energetically less favorable than the TiN surfaces. As a result, an effect of the H2 treatment is to decrease the reactivity of the B2H6 molecule on the TiN surface. However, N2 treatment on the Ti-terminated TiN (111) surface is more likely to make the TiN surface become an N-terminated TiN (111) surface, which results in making a lot of N-terminated TiN (111) surfaces, having a very reactive nature for B2H6 bond dissociation. As a result, the effect of N2 treatment serves as a catalyst to decompose B2H6. From the deep understanding of the effect of H2 and N2 during the B2H6 dosing process, the use of proper gas treatment is required for the improvement of the W nucleation layers.

Overall reaction mechanism for a full atomic layer deposition cycle of W films on TiN surfaces: first-principles study.

We investigated the overall ALD reaction mechanism for W deposition on TiN surfaces based on DFT calculation as well as the detailed dissociative reactions of WF6. Our calculated results suggest that the overall reactions of the WF6 on the B-covered TiN surfaces are energetically much more favorable than the one on the TiN surfaces, which means that the high reactivity of WF6 with the B-covered TiN surface is attributed to the presence of B-covered surface made by B2H6 molecules. As a result, an effect of the B2H6 flow serves as a catalyst to decompose WF6 molecules. Two additional reaction processes right after WF6 bond dissociation, such as W substitution and BF3 desorption, were also explored to clearly understand the detailed reactions that can occur by WF6 flow. At the first additional reaction process, W atoms can be substituted into B site and covered on the TiN surfaces due to the stronger bonding nature of W with the TiN surface than B atoms. At the second additional reaction process, remaining atoms, such as B and F, can be easily desorbed as by-product, that is, BF3 because BF3 desorption is an energetically favorable reaction with a low activation energy. Furthermore, we also investigated the effect of H2 post-treatment on W-covered TiN surface in order to remove residual F adatoms, which are known to cause severe problems that extremely degrade the characteristics of memory devices. It was found that both H2 dissociative reaction and HF desorption can occur sufficiently well under somewhat high temperature and H2 ambience, which is confirmed by our DFT results and previously reported experimental results. These results imply that the understanding of the role of gas molecules used for W deposition gives us insight into improving the W ALD process for future memory devices.

Detection and characterization of nanomaterials released in low concentrations during multi-walled carbon nanotube spraying process in a cleanroom.

Release of nanomaterials was assessed in a cleanroom workplace designed for the handling of multi-walled carbon nanotubes. During the process, the nanotubes were sprayed in a chamber fitted with an exhaust duct system. The front door of the spraying chamber was completely closed, but rear end of the chamber was partially open. Throughout a series of spray processes, three detectors - an optical particle counter, a nanoparticle aerosol monitor, and an aethalometer - counted and characterized particles escaping the chamber. Concentrations of particle surface area and black carbon emitted by the spraying were assessed assuming zero background aerosol concentration in the cleanroom. Very low concentrations of black carbon, 0.4 µg/m(3), were observed. In conclusion, in a cleanroom, low concentrations of nanomaterials were detected to be emitted from a spraying chamber into the workplace. The level of particles reaching the workplace was sufficiently low to have made their detection difficult in a normal environment. Both target nanomaterial and non-intended incidental nanomaterials were released during spraying. Despite the use of exhaust duct system in the process chamber, workers would be exposed to some particles if the chamber were partially open. The exhaust duct system was not enough to remove all the particles released in the chamber.

Detection of acetone vapor using graphene on polymer optical fiber.

Recently, many studies have been focused on the development of fiber optic sensor systems for various gases and vapors. In the present study, an intrinsic polymer optical fiber (POF) sensor using graphene is described for the purpose of acetone vapor sensing for the first time. Observations on the continuous measurement of acetone vapor in dehydrated air are presented. The principle of operation of sensor transduction relies on the dependence of the reflectance on the optical and geometric properties of the sensitive over layered when the vapor molecules are adsorbed on the graphene film. For the same purpose the CVD synthesized graphene film was transferred on the POF end. The synthesized graphene film thickness was evaluated using atomic force microscopy (AFM), Raman spectroscopy and transmission electron microscopy (TEM). For the preliminary evaluation using volatile organic compounds, we evaluated the sensor performance for acetone. Upon the interaction of the sensor with acetone vapor, the variation in the reflected light was monitored as a function of the acetone concentration. The sensor response shows a significant change in sensitivity as compared with the POF probe without a graphene coating. The present sensor shows a satisfactory response upon exposure to various concentrations of acetone vapor from 44 ppm to 352 ppm. To the best of our knowledge, the use of graphene film along with POF for the sensing of volatile organic compounds has not previously been reported.