Deposition Of Ru Research Articles

Ru nanoparticles on mesostructured carbon for glucose hydrogenation; catalysts synthesis and characterization

Ru-containing hydrogenation catalysts based on functionalized carbon material CMK-3 (Carbon Mesostructured by KAIST) were developed. Mesostructured silicate SBA-15 with enlarged wall channels was used as a template for the carbon replica synthesis. The effect of carbon material functionalization via moist air oxidation and sulfonation on the morphology, physicochemical properties and activity of the catalyst was studied. The dispersion, localization, and electronic state of supported ruthenium were determined depending on the support functionalization method. The initial support structure preservation after Ru deposition was confirmed by a set of physicochemical methods. Metal particles are finely distributed with no agglomerated present, providing a high active site accessibility and ensures a superb catalyst activity. The catalysts were tested in glucose to sorbitol hydrogenation. The results showed that pore morphology and carbon support initial structure preservation account for the catalytic activity of Ru nanoparticles.

Area-Selective Atomic Layer Deposition of Ru Using Carbonyl-Based Precursor and Oxygen Co-Reactant: Understanding Defect Formation Mechanisms.

Area selective deposition (ASD) is a promising IC fabrication technique to address misalignment issues arising in a top-down litho-etch patterning approach. ASD can enable resist tone inversion and bottom-up metallization, such as via prefill. It is achieved by promoting selective growth in the growth area (GA) while passivating the non-growth area (NGA). Nevertheless, preventing undesired particles and defect growth on the NGA is still a hurdle. This work shows the selectivity of Ru films by passivating the Si oxide NGA with self-assembled monolayers (SAMs) and small molecule inhibitors (SMIs). Ru films are deposited on the TiN GA using a metal-organic precursor tricarbonyl (trimethylenemethane) ruthenium (Ru TMM(CO)3) and O2 as a co-reactant by atomic layer deposition (ALD). This produces smooth Ru films (<0.1 nm RMS roughness) with a growth per cycle (GPC) of 1.6 Å/cycle. Minimizing the oxygen co-reactant dose is necessary to improve the ASD process selectivity due to the limited stability of the organic molecule and high reactivity of the ALD precursor, still allowing a Ru GPC of 0.95 Å/cycle. This work sheds light on Ru defect generation mechanisms on passivated areas from the detailed analysis of particle growth, coverage, and density as a function of ALD cycles. Finally, an optimized ASD of Ru is demonstrated on TiN/SiO2 3D patterned structures using dimethyl amino trimethyl silane (DMA-TMS) as SMI.

Palladium/Platinum/Ruthenium Trimetallic Dendritic Nanozymes Exhibiting Enhanced Peroxidase-like Activity for Signal Amplification of Lateral Flow Immunoassays.

Developing ultrasensitive lateral flow immunoassays (LFIAs) has garnered significant attention in the field of point-of-care testing. In this study, a trimetallic dendritic nanozyme (Pd@Pt-Ru) was synthesized through Ru deposition on a Pd@Pt core and utilized to enhancing the sensitivity of LFIAs. Pd@Pt-Ru exhibited a Km value of 5.23 mM for detecting H2O2, which indicates an H2O2 affinity comparable with that of horseradish peroxidase. The Ru surface layer reduces the activation energy barrier, which increases the maximum reaction rate. As a proof of concept, the proposed Pd@Pt-Ru nanozyme was incorporated into LFIAs (A-Pd@Pt-Ru-LFIAs) for detecting human chorionic gonadotropin (hCG). Compared with conventional gold nanoparticle (AuNP)-LFIAs, A-Pd@Pt-Ru-LFIAs demonstrated 250-fold increased sensitivity, thereby enabling a visible detection limit as low as 0.1 IU/L. True positive and negative rates both reached 100%, which renders the proposed Pd@Pt-Ru nanozyme suitable for detecting hCG in clinical samples.

Si precursor inhibitors for area selective deposition of Ru

Area-selective atomic layer deposition (AS-ALD) using highly process-compatible precursor inhibitors (PIs) has garnered attention because of the need to overcome three-dimensional nanofabrication bottlenecks. The main advantages of precursor inhibitor (PI) molecules are their high process compatibility and their inherent bifunctionality as inhibitors and precursors. Herein, we examined the inhibition properties, adsorption mechanisms, and adsorption configurations of two PIs, bis(N,N-dimethylamino)dimethylsilane (PI1) and tris(dimethylamino)silane (PI2). Both PIs selectively inhibited the SiO2 surface but not the Cu surface, which enabled the AS-ALD of Ru films on the latter. The inhibition mechanisms were elucidated on the basis of chemical reactivity and steric hindrance considerations using density functional theory calculations and Monte Carlo simulations. PI1 featured a larger areal coverage than PI2 because of the favorable adsorption configuration of the former, inducing a stronger steric hindrance effect and achieving a higher inhibition performance against Ru ALD, although the two PIs had similar chemical reactivities toward the examined surface. Furthermore, PI1 and PI2 formed SiO2 ALD films when ozone was used as a reactant. The differences in the growth characteristics of the corresponding ALD SiO2 films were explained by the different adsorption configurations of PIs. Thus, our work elucidates the adsorption configurations of silane-based PIs and thus paves the way for the more effective utilization of their bifunctionality, inhibition properties, and growth characteristics in future AS-ALD processes.

Ultrathin Ru-CdIn2S4 nanosheets for simultaneous photocatalytic green hydrogen production and selective oxidation of furfuryl alcohol to furfural

Biomass is an important sustainable carbon source and converting biomass intermediates into value-added chemicals/fuels using a green technology is a promising sustainable pathway. Dual-functional photocatalysis can be used to “hit two birds with one stone” via the simultaneous production of hydrogen (H2) and valorisation of the biomass intermediates. CdIn2S4 (CIS) is an exciting photocatalytic material because of its high visible-light harvesting capacity. Herein, ultrathin CIS nanosheets were fabricated via a solvothermal method with in situ deposition of Ru (Ru-CIS). The photocatalytic performance of Ru-CIS toward the selective oxidation of furfuryl alcohol (FOH, a biomass intermediate), to a value-added product (Furfural, FCHO) with concurrent generation of hydrogen was investigated. Ru incorporation resulted in up to 50-fold enhancement in H2 production rate and higher FOH to FCHO conversion% and selectivity%. This enhancement was attributed to the enhanced charge separation due to the incorporated Ru species, as supported by density functional theory (DFT) calculations.

Electrodeposition of Ru on Nanoscale Trench Patterns

Ru deposition in advanced technology nodes can improve performance by providing low resistance in nanoscale features. In this study, we reported the electrochemical reactions of Ru3+ on an Ru surface using multi-cyclic voltammetry (CV) and behavior of additives during Ru electrodeposition using linear sweep voltammetry (LSV) and potentiostatic measurements. Disodium 3,3’-dithiobis(1-propanesulfonate) (SPS), polyvinylpyrrolidone (PVP), and a bromide ion (Br−) were added for bottom-up filling. We investigated the suppression behavior of PVP. The current density and the onset potential of suppressor breakdown were affected by the suppressor concentration. PVP interacted synergistically with Br− and showed additional suppression. PVP formed a suppressing layer with Br− after formation of a bromide layer. SPS could reduce roughness during electrodeposition of Ru. Based on these results, nano-trenches were filled with Ru using the optimized additive condition.

Area-selective atomic layer deposition of Ru thin films by chemo-selective inhibition of alkyl aldehyde molecules on nitride surfaces

Area-selective atomic layer deposition (AS-ALD) on pre-defined areas is of crucial importance nowadays in significantly reducing complexities associated with current top-down fabrication processes. In this work, we report the effects of surface modification using various alkyl aldehyde inhibitors with different chain lengths—hexanal, decanal, and undecanal—on nitride surfaces such as TiN and SiN to achieve AS-ALD. On the basis of density functional theory calculations and experimental analysis, including water contact angle and X-ray photoelectron spectroscopy, it is evident that aldehydes would chemo-selectively react with the –NH2 functional groups present on the nitride surfaces. Then, we further investigate their blocking ability against subsequent Ru ALD, a promising next-generation electrode material. It is worth noting that the Ru deposition thickness decreased by 4–10 nm with the presence of undecanal adsorbed on SiN and TiN substrates. Finally, we successfully demonstrate AS-ALD of Ru thin films over 8 nm on a patterned TiN/SiO2 substrate. These results hold potential for applications in bottom-up nanofabrication techniques for next-generation nanoelectronic applications.

Ru/Attapulgite as an Efficient and Low-Cost Ammonia Decomposition Catalyst

On-site hydrogen generation from ammonia decomposition is a promising technology to address the challenges of direct transportation and storage of hydrogen. The main problems with the existing support materials for ammonia decomposition catalysts are their high cost and time-consuming preparation process. In this work, ammonia decomposition catalysts consisting of in situ-formed nano-Ru particles supported on a naturally abundant mineral fiber, attapulgite (ATP), were proposed and studied. Also, 1 wt.% Ru was uniformly dispersed and anchored onto the surface of ATP fibers via the chemical method. We found that the calcination temperatures of the ATP support before the deposition of Ru resulted in little difference in catalytic performance, while the calcination temperatures of the 1Ru/ATP precursor were found to significantly influence the catalytic performance. The prepared 1 wt.% Ru/ATP catalyst (1Ru/ATP) without calcination achieved an ammonia conversion efficiency of 51% at 500 °C and nearly 100% at 600 °C, with the flow rate of NH3 being 10 sccm (standard cubic centimeter per minute). A 150 h continuous test at 600 °C showed that the 1Ru/ATP catalyst exhibited good stability with a degradation rate of about 0.01% h−1. The 1Ru/ATP catalyst was integrated with proton ceramic fuel cells (PCFCs). We reported that PCFCs at 650 °C offered 433 mW cm−2 under H2 fuel and 398 mW cm−2 under cracked NH3 fuel. The overall results suggest low-level Ru-loaded ATP could be an attractive, low-cost, and efficient ammonia decomposition catalyst for hydrogen production.

(Invited) Ru Selective Metal Deposition for Hybrid Metallization in Nano-Interconnect Applications

The connection of semiconductor devices happens through metal interconnects at the back end of line (BeOL) in integrated circuits. The BeOL consists of multiple metal levels that are vertically connected through small contact holes, or so-called vias. Especially at the lower metal levels, the vias are becoming much smaller in critical dimension, which increases their resistance significantly while more of these vias are needed to make the more complex connections in future device architectures. For these reasons, the vias resistance is becoming the dominating part of the total resistance of the stack and may become the limiting factor in keeping resistance-capacitance delay under control.In this work, the metal-on-metal area selective metal deposition is studied to make low resistive vias. The via is first prefilled with the Ru before performing the Cu metallization of the remainder of the vias and wires. Ru is chosen as the preferred metal [1] because it can be used without a metal barrier (it does not electromigrate) and this provides a large resistance benefit as compared to the Cu metallization which needs a TaN barrier combined with a Co liner. The combination of the different metals for the via (here Ru) and the metallization of wires (here Cu), is called a hybrid metallization scheme.We will discuss the challenges for the Ru selective deposition on the metal (growth area) towards different dielectrics as the non-growth area. The selectivity studies to optimize the Ru chemical vapour deposition (CVD) recipe and surface treatments are performed on blanket level (non-patterned wafers). A small molecule inhibitor dimethylamino-trimethylsilane (DMA-TMS) is used to passivate the dielectric surface which makes the dielectrics less reactive towards the Ru deposition improving thereby the selectivity of the CVD process (see also Fig.a).[2] We demonstrate that the growth rate and selectivity of Ru ASD depend on the CVD process conditions (type of co-reactant and process temperature) and the type of nanopattern (line spaces or via holes).[3]The most selective Ru process found with the line-space pattern (45/45nm line-space width) was also tested in nanoscale patterns with via holes of ~10.5nm.[4] It was found that the Ru growth rates in the patterned structures are enhanced as compared to the blanket substrates. The CVD Ru growth rates are ~ 1.3x higher in line-space nanopatterns as compared to flat metal substrates, and up to 3x higher in the small contact holes.[4] The growth enhancement of the CVD process is beneficial for the technological implementation of the process. The results show that the growth rate and the selectivity are different from the behavior on blankets and are also pattern dependent, which is consistent with a growth mechanism that is based on diffusion in addition to adsorption.[2] Therefore, the metal-on-metal selective deposition process may need to be optimized and adjusted to the patterned structure used in the interconnect application.[1] D. Gall et al, J. Appl. Phys. 2016, 119, p.085101.[2] F. Grillo and J. Soethoudt et al, Chem. Mater. 2020, 32, 22, 9560–9572.[3] A. Kumar Mandal et al, “Ruthenium Area-Selective Deposition for Nano-interconnect Structures: Process and nanopattern dependent selectivity and growth rate” Manuscript in submission 2023.[4] M.H. van der Veen et al, Proc. of the IITC 2021, S7-2.. Figure 1

Growth behavior and mechanism of atomic layer deposition of Ru for replacing Cu-interconnects

The growth behavior and nucleation mechanism of Ru films on various substrates using Ru(EtCp)2 as the precursor and O2 as the reactant were studied systematically. The results show that the Ru films grow rapidly on TiN substrates with almost no incubation time. Different of the segregation and combustion mechanism reported in the previous literature, we established the adsorption and combustion mechanism of ALD-Ru on TiN substrates. SEM and XPS confirmed that the grown Ru films were polycrystalline (average grain size of 16.53 nm, negligible impurities). The Ru films annealed at 600 °C showed significantly low resistivity of 9.73 μΩ•cm, which is one of the lowest resistivities reported in the literature so far. Suppressing electron scattering at grain boundaries is crucial factor to preparing Ru films with low resistivity. The work uses a simple plasma-free technique to construct high-quality Ru films with extremely low resistivity and low impurities, making them one of the ideal candidates for replacing Cu in future ultrafine-pitch interconnects. Furthermore, the work is significant for understanding the growth behaviors and nucleation mechanisms of Ru films on different substrates.

Ru–Co alloy coatings electrodeposited on a MAX phase substrate as efficient catalysts for the hydrogen evolution reaction

This study investigates the structure, electrochemical behavior and hydrogen evolution reaction (HER) performance of electrodeposited Ru–Co alloy coatings. The alloys were prepared from a 0.75 M Co2+ + 0.025 M Ru3+ solution at various potentials ranging from −0.5 to −1.2 V vs. SCE. Results reveal that the Ru and Co deposition processes are interdependent. The deposition of nobler Ru from the mixed metal solution reaches pure diffusion control already at −0.7 V compared to −1.0 V from a single Ru bath. On the other hand, Co deposition is significantly facilitated in the presence of Ru in the solution. Consequently, as the deposition potential changes from −0.6 to −1.0 V, Ru–Co solid solution coatings characterized by a distinct globular morphology are formed, with their Co content increasing from 22.1/7.4 to 70.2/86.1 wt% for the Cu/Ti2AlC MAX phase substrate applied. The alloy catalysts are found to show much better HER activity and stability in alkaline than in acidic solutions. The best Ru–Co@Ti2AlC sample, electrodeposited at −0.6 V, requires an overpotential of only −95 mV to deliver a current density of −100 mA cm−2 in 1 M KOH, thus outperforming most Ru–Co-based HER electrocatalysts reported to date.

Alkali Wet Chemicals for Ru with Advanced Semiconductor Technology Nodes

Wet chemicals for ruthenium (Ru) etching are required for the formation of reliable Ru interconnects in advanced semiconductor technology nodes. In the present study, a novel alkali wet etchant, referred to as TK-1, has been developed in order to overcome issues with conventional Ru etchants, such as a low etch rate and the formation of toxic RuO4 gas. Regardless of the Ru deposition process, TK-1 exhibits a high Ru etching selectivity of greater than 100 relative to dielectric and liner materials. It also suppresses the production of RuO4 during the etching process. TK-1 has potential applications for Ru recess etching during fully self-aligned via fabrication.

Nucleation of Co and Ru Precursors on Silicon with Different Surface Terminations: Impact on Nucleation Delay.

Early transition metals ruthenium (Ru) and cobalt (Co) are of high interest as replacements for Cu in next-generation interconnects. Plasma-enhanced atomic layer deposition (PE-ALD) is used to deposit metal thin films in high-aspect-ratio structures of vias and trenches in nanoelectronic devices. At the initial stage of deposition, the surface reactions between the precursors and the starting substrate are vital to understand the nucleation of the film and optimize the deposition process by minimizing the so-called nucleation delay in which film growth is only observed after tens to hundreds of ALD cycles. The reported nucleation delay of Ru ranges from 10 ALD cycles to 500 ALD cycles, and the growth-per-cycle (GPC) varies from report to report. No systematic studies on nucleation delay of Co PE-ALD are found in the literature. In this study, we use first principles density functional theory (DFT) simulations to investigate the reactions between precursors RuCp2 and CoCp2 with Si substrates that have different surface terminations to reveal the atomic-scale reaction mechanism at the initial stages of metal nucleation. The substrates include (1) H:Si(100), (2) NHx-terminated Si(100), and (3) H:SiNx/Si(100). The ligand exchange reaction via H transfer to form CpH on H:Si(100), NHx-terminated Si(100), and H:SiNx/Si(100) surfaces is simulated and shows that pretreatment with N2/H2 plasma to yield an NHx-terminated Si surface from H:Si(100) can promote the ligand exchange reaction to eliminate the Cp ligand for CoCp2. Our DFT results show that the surface reactivity of CoCp2 is highly dependent on substrate surface terminations, which explains why the reported nucleation delay and GPC vary from report to report. This difference in reactivity at different surface terminations may be useful for selective deposition. For Ru deposition, RuCp2 is not a useful precursor, showing highly endothermic ligand elimination reactions on all studied terminations.

Enhanced CO Functionality on Carbon Papers Ensures Lowering Nucleation Delay of ALD for Ru towards Unprecedented Alkaline HER Activity.

The success in lowering the nucleation delay for Atomic Layer Deposition (ALD) of Ru on carbon surfaces is mitigated by constructive pretreatments resulting enhancement of CO functionality. Treatment of the carbon papers (CP) allowed Ru species deposition for minimum number of ALD cycles (25 cycles) with good conformality. The development of electrocatalysts from single atoms to nanoparticles (NPs) on conductive supports with low metal loadings, thus improving performance, is essential in electrocatalysis. For alkaline hydrogen evolution reaction, ALD decorated CPs with Ru exhibit low onset potentials of ≈4.7mV versus reversable hydrogen electrode (RHE) (at 10mAcm-2 ) and a high turnover frequency of 1.92 H2 s-1 at 30mV versus RHE. The Ru decorated CPs show comparable to higher catalytic activity than of Platinum (Pt) decorated CP also developed by ALD. The current representation of unfamiliar catalytic activities of Ru active centers developed by ALD, pave a bright and sustainable path for energy conversion reactions.

Phase-Controlled Deposition of Ru on Pd Nanocrystal Templates: Effects of Particle Shape and Size

Phase-Controlled Deposition of Ru on Pd Nanocrystal Templates: Effects of Particle Shape and Size

Area-selective atomic layer deposition of high-quality Ru thin films by chemo-selective adsorption of short alkylating agents

We report the effects of surface modification by vapor dosing of (N,N-diethylamino)trimethylsilane (DEATMS) molecules as short alkylating agents on technologically important substrates of Si, SiO2, TiN, and W. In this study, tricarbonyl(trimethylenemethane) ruthenium [Ru(TMM)(CO)3] was employed as a metal–organic precursor for atomic layer deposition (ALD) of Ru, which produced high-quality Ru films with significantly low resistivity and high growth-per-cycle. Through surface modification of vapor-dosed DEATMS molecules, significant growth retardation against the ALD Ru process was selectively found on SiO2 and TiN in contrast to Si(-H) and W substrates. With applying chemo-selectively inhibitory characteristics, we successfully demonstrate area selective deposition of ALD Ru films on a patterned TiN/Si substrate.

Spatially Templated Nanolines of Ru and RuO2 by Sequential Infiltration Synthesis

Nanoscale patterning of inorganics is crucial for the fabrication of advanced electronic, photonic, and energy devices. The emerging sequential infiltration synthesis (SIS) method fabricates nanofeatures by block-selective vapor-phase growth in block copolymer templates with tunable patterns. Yet, SIS has been demonstrated mainly for Al2O3 and a few other metal oxides, while deriving metal nanostructures from a single SIS process is a challenge. Here, we present SIS of the Ru metal in polystyrene-block-polymethyl methacrylate (PS-b-PMMA) templates without any pretreatment, using alternating infiltration of RuO4 and H2. RuO4 interacts selectively and strongly with the aromatic C═C and C–H groups in PS, leaving the PMMA domains inert. Density functional theory calculations corroborate that the PS–RuO4 interaction is energetically favorable, with a calculated interaction energy of −1.65 eV, whereas for PMMA–RuO4, the calculated energy of −0.05 eV indicates an unfavorable interaction. Morphological analysis on the di-BCP after the RuO4-H2 process indicates an increase in contrast as a function of SIS cycles and templated Ru incorporation. The crystalline nature of the Ru deposits is confirmed using grazing incidence wide-angle X-ray scattering. Plasma-aided removal of the organic components yields Ru nanolines with lateral dimensions of ca 20 nm. We further highlight the broad potential of RuO4 as a reactant for SIS by generating RuO2 nanopatterns via alternating RuO4 and methanol infiltration.

Carbon supports for the oxidative cleavage of oleic acid: Influence of textural properties

Microporous oxidized activated carbon (ACO) and macroporous oxidized carbon black (CBO) were assessed in the complexation of Ru for the oxidative cleavage of oleic acid. This reaction breaks carbon-carbon double bond to produce azelaic and pelargonic acids (highly demanded in pharmacology). Both carbon materials were treated with HNO3 prior Ru deposition by wet impregnation method. Carbon supports were characterized by FTIR, Boehm's titration and N2 physisorption, while Ru complexation was determined by ICP and XPS spectroscopy. Activated carbon catalyst displayed a low conversion (∼53%) in comparison to carbon black catalyst (>99%). The reason is related to the molecular length of oleic acid (2.2 nm), estimated by ab initio Hartree-Fock calculation, which is larger than micropores from activated carbon (∼0.7 nm). Despite Ru losses during the catalytic tests, CBO was more active and stable than ACO, confirming that a macroporous support is more suitable to perform the oxidative cleavage of oleic acid.

A multi-functional Ru Mo bimetallic catalyst for ultra-efficient C3 alcohols production from liquid phase hydrogenolysis of glycerol

Ru and Mo bimetallic catalysts supported on active carbon modified by phosphotungstic acid (PW) were designed and applied in glycerol hydrogenolysis reaction. The physicochemical properties of the catalysts were characterized and the presence of active sites was investigated from the perspective of the glycerol hydrogenolysis performance. The MoO x is highly selective for the C—O bond cleavage of glycerol molecules, which can reasonably regulate the strong C—C bond cleavage activity of Ru nanoparticles. By using sequential deposition of Ru and Mo supported on mesoporous PW-C, the characterization results show that the combination of isolated low-valence MoO x with metal Ru particles can form “MoO x -Ru-PW”, which provides highly catalytic activity toward C—O bond cleavage, selectively producing more C3 alcohols (mainly 1,2(3)-propanediol). The glycerol conversion of 1% Mo/Ru/PW-C catalyst was 59.6%, the selectivity of C3 alcohol was 96.1%, and the selectivity of propanediol (1,2(3)-propanediol) was 94.9%. It is noteworthy that the selectivity of 1,3-propanediol reached 20.7% when the PW was 21.07% (mass). This study provides experimental evidence for the tandem dehydration and hydrogenation mechanism of the multifunctional Mo/Ru/PW-C catalyst.

Size-dependent activity of supported Ru catalysts for ammonia synthesis at mild conditions

Ammonia (NH3) synthesis is a structure-sensitive reaction, where a minute variation of catalyst structure would lead to a dramatic change of activity. To date, the roles of Ru size on NH3 synthesis still remain elusive, and it remains a major challenge. Herein, a series of Ru catalysts with sizes ranging from 1.4 to 5.0 nm were prepared by colloidal Ru deposition, which allows the investigation of size influence on NH3 synthesis. Through analyses of the geometric and electronic properties of variable-sized Ru particles, it shows that the reduction of Ru particle size could increase the proportion of corner sites while decrease that of terrace sites, which can decrease the work function and thus promote N2 for its activation. Isotopic investigations show that the decrease of dissociative contribution but the increase of associative contribution as Ru particle size was decreased from 5.0 to 1.4 nm. Meanwhile, the NH3 synthesis rate increases when the size of Ru catalysts decreases from 5.0 to 1.4 nm. Using a suite of elaborate characterizations, we have observed that 1.4 nm Ru nanoclusters (NCs) with ample corner sites are conducive to activate N2 via an associative route. As a result, the 1.4 nm Ru NCs catalyst shows the highest NH3 synthesis rate (up to 17.13 mmolNH3 gcat−1h−1) at 400 ℃ and 1 MPa.