Atomic Layer Deposition Precursors Research Articles

Aluminum tri-isopropoxide as an alternative precursor for atomic layer deposition of aluminum oxide thin films

Due to the safety challenges associated with the use of trimethylaluminum as a metal precursor for the deposition of alumina, different chemicals have been investigated over the years to replace it. The authors have investigated the use of aluminum tri-isopropoxide (TIPA) as an alternative alkoxide precursor for the safe and cost-effective deposition of alumina. In this work, TIPA is used as a stable Al source for atomic layer deposition (ALD) of Al2O3 when different oxidizing agents including water, oxygen plasma, water plasma, and ozone are employed. The authors have explored the deposition of Al2O3 using TIPA in ALD systems operating in vacuum and atmospheric pressure conditions. For thermal and plasma processes in vacuum ALD, a growth rate of 1.1–2 Å/cycle achieved over a range of 140–300 °C is shown. Film density, roughness, and composition have been tested using various characterization techniques confirming comparable film properties to the thermal ALD of trimethylaluminum and water. The thermal water process at atmospheric pressure ALD (AP-ALD) resulted in a growth rate of up to 1.1 Å/cycle with residual carbon below the XPS detection limit. AP-ALD on nanoparticles shows different growth modes on TiO2 versus SiO2 nanoparticle surfaces confirmed by transmission electron microscopy analysis. Using TIPA as an ALD precursor would open up the possibility for a safer and cost-effective process for deposition of Al2O3 in various applications.

In Situ Photoluminescence of Colloidal Quantum Dots During Gas Exposure-The Role of Water and Reactive Atomic Layer Deposition Precursors.

Colloidal quantum dots (QDs) are a promising material for optoelectronic applications. Typically, device integration requires QDs to be embedded in a host material. Atomic layer deposition (ALD) is often considered as a deposition technique for such purposes. However, it is known that ALD and vacuum processes often influence the optical properties of QDs in a negative way. Here, we describe an in situ photoluminescence (PL) measurement setup and use it to monitor the PL of QDs under vacuum and during ALD. For CdSe-based core/shell QDs, a reduction in the QD PL was observed upon exposure to vacuum. Water was identified as crucial for maintaining a high PL as evidenced by re-exposure to different gases. Furthermore, we addressed the influence of vacuum, different plasmas (O2, H2O, H2, H2S/Ar, and Ar), precursors (trimethylaluminum, diethylzinc, tetrakis(dimethylamido)titanium, and tetrakis(ethylmethylamido)hafnium), reactants (H2O, H2S, and O3), and ALD processes (Al2O3, TiO2, HfO2, and ZnS) on QDs. We observed a PL reduction by up to 90% upon plasma treatments. Furthermore, we found that trimethylaluminum and diethylzinc reduced the PL efficiency by more than 70% while exposure to tetrakis(dimethylamido)titanium and tetrakis(ethylmethylamido)hafnium lowered the PL by only 10-20%. Surprisingly, tetrakis(dimethylamido)titanium and H2O, which by themselves had only a minor influence on the QD PL, still caused an 80% drop of the PL efficiency when combined as an ALD process. On the other hand, ALD growth of HfO2 by combining tetrakis(ethylmethylamido)hafnium and O3 preserved 80% of the initial PL quantum yield, making it a promising process for QD embedding. These results put forward in situ PL measurements as a versatile technique to identify suitable precursors, reactants and ALD processes for QD embedding and investigate the interaction between QDs and reactive gaseous species in general.

Effects of surface pretreatment and deposition conditions on the gas permeation properties and flexibility of Al2O3 films on polymer substrates by atomic layer deposition

The effects of surface pretreatment and deposition conditions on the gas permeation properties—including permeability of He, O2, and H2O; the size; and the density of permeation-enhancing defects—and mechanical flexibility of Al2O3 films on polymer substrates by atomic layer deposition (ALD) were investigated to develop flexible gas barrier films for organic and flexible electronics. Pretreating polyimide (PI) and poly(ethylene terephthalate) (PET) substrates with an aqueous KOH solution greatly lowered the gas permeability of the ALD Al2O3 films as a result of improved affinity between the substrate surface and the ALD precursors. Varying the ALD conditions—including lengthening the precursor exposure, elevating the deposition temperature, and changing the precursor sequence—enhanced physisorption of ALD precursors on the polymer substrate, which improved nucleation of the ALD films to reduce defects in the films and lower their gas permeability. Activation energy for permeation determined from the temperature dependence of the permeability of the ALD films indicated that the ALD films deposited under the optimized condition contained smaller and few permeation-enhancing defects. The optimized ALD films possessed a low water vapor transmission rate of ~ 10−6 g/m2 day that met the stringent requirement of organic and flexible electronics, while also exhibiting excellent mechanical flexibility by withstanding repeated bending with small increases in gas permeability. Our results provide valuable insights into the development of flexible barrier thin films for the encapsulation of organic and flexible electronics.

Atomic Layer Deposition Nucleation on Isolated Self-Assembled Monolayer Functional Groups: A Combined DFT and Experimental Study

We computationally design and experimentally corroborate the atomic layer deposition (ALD) of metal oxides with tailorable nucleation on selected self-assembled monolayers (SAMs) decorated with terminal functional groups. The low-temperature ALD processes for Al2O3, MnO, and especially ZnO are inhibited on nonpolar alkyl-terminated SAMs with high efficacy, in agreement with the thermodynamics calculated for reactivity with the alkyl-terminated SAMs as well as for potentially physisorbed precursors. Functional-SAM surfaces are also considered for the uniform nucleation of ALD oxides, while mixed alkyl-/functional-group-terminated SAMs are considered for the site-directed synthesis of metal oxide clusters. Long alkyl-chain SAMs with functional group termination including OH, COOH, and SH are predicted to react exergonically over a variable energy barrier which depends strongly on ALD precursor chemistry as well as functional group density. Experiments confirm that more efficient nucleation may be catalyzed via a single ALD precursor cycle of a more reactive precursor (e.g., trimethylaluminum) followed by growth of targeted metal oxides (ZnOx and MnOx). The computational strategy and experimental approach may be applicable to the selective deposition of technologically important hybrid organic–inorganic barrier films as well as catalytically relevant metal oxide and mixed-metal oxide precision few-atom clusters.

Atomic Layer Deposition of NiO to Produce Active Material for Thin-Film Lithium-Ion Batteries

Atomic layer deposition (ALD) provides a promising route for depositing uniform thin-film electrodes for Li-ion batteries. In this work, bis(methylcyclopentadienyl) nickel(II) (Ni(MeCp)2) and bis(cyclopentadienyl) nickel(II) (NiCp2) were used as precursors for NiO ALD. Oxygen plasma was used as a counter-reactant. The films were studied by spectroscopic ellipsometry, scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray reflectometry, and X-ray photoelectron spectroscopy. The results show that the optimal temperature for the deposition for NiCp2 was 200–300 °C, but the optimal Ni(MeCp)2 growth per ALD cycle was 0.011–0.012 nm for both precursors at 250–300 °C. The films deposited using NiCp2 and oxygen plasma at 300 °C using optimal ALD condition consisted mainly of stoichiometric polycrystalline NiO with high density (6.6 g/cm3) and low roughness (0.34 nm). However, the films contain carbon impurities. The NiO films (thickness 28–30 nm) deposited on stainless steel showed a specific capacity above 1300 mAh/g, which is significantly more than the theoretical capacity of bulk NiO (718 mAh/g) because it includes the capacity of the NiO film and the pseudo-capacity of the gel-like solid electrolyte interface film. The presence of pseudo-capacity and its increase during cycling is discussed based on a detailed analysis of cyclic voltammograms and charge–discharge curves (U(C)).

Use of a New Non-Pyrophoric Liquid Aluminum Precursor for Atomic Layer Deposition.

An Al2O3 thin film has been grown by vapor deposition using different Al precursors. The most commonly used precursor is trimethylaluminum, which is highly reactive and pyrophoric. In the purpose of searching for a more ideal Al source, the non-pyrophoric aluminum tri-sec-butoxide ([Al(OsBu)3], ATSB) was introduced as a novel precursor for atomic layer deposition (ALD). After demonstrating the deposition of Al2O3 via chemical vapor deposition (CVD) and ‘pulsed CVD’ routes, the use of ATSB in an atomic layer deposition (ALD)-like process was investigated and optimized to achieve self-limiting growth. The films were characterized using spectral reflectance, ellipsometry and UV-Vis before their composition was studied. The growth rate of Al2O3 via the ALD-like process was consistently 0.12 nm/cycle on glass, silicon and quartz substrates under the optimized conditions. Scanning electron microscopy and transmission electron microscopy images of the ALD-deposited Al2O3 films deposited on complex nanostructures demonstrated the conformity, uniformity and good thickness control of these films, suggesting a potential of being used as the protection layer in photoelectrochemical water splitting.

Fabrication of Top-Gate MoS2 FET with Transferred Al2O3 Gate Dielectric

This study describes the fabrication of top-gate molybdenum disulfide (MoS2) field-effect transistor (FET) using transfer printing of an Al2O3 gate dielectric. Semiconducting MoS2 has been considerable attention for applications as channel materials of FETs because a two-dimensional (2D) crystal is free from dangling bonds at the surface [1]. On the other hand, atomic layer deposition (ALD) of high-k gate dielectric is incompatible with MoS2 since an ALD precursor cannot be chemisorbed onto the surface of MoS2 due to the absence of dangling bonds [2]. Furthermore, ALD disrupts the surface structure and induces the oxidation of the channel layer [2], leading to the degradation of FET characteristics or the failure of devices. This study addresses these issues by utilizing the transfer printing of a high-k gate dielectric on a MoS2 layer [2], [3]. Transfer printing can avoid the deposition of a high-k gate dielectric directly on a fragile MoS2 surface. An abrupt and sharp interface can be anticipated by implementing the transfer printing of high-k gate dielectric.A key component for developing the transfer printing of the Al2O3 gate dielectric is to find out an appropriate sacrificial layer on the handling substrate. In this study, nickel (Ni) metal was adopted as the sacrificial layer for the transfer printing of the Al2O3 gate dielectric. It was revealed that the adhesion strength at Ni and thermally grown SiO2 interface is reduced by immersion in deionized water (DIW) [3]. The penetration of water into the interface results in the separation of Ni from the SiO2 surface. This Ni layer can be etched by using dilute nitric acid (HNO3). On the other hand, HNO3, which is an oxidizing agent, cannot etch an oxide gate dielectric.A 50-nm-thick Ni layer was deposited on the SiO2 (400 nm)/Si substrate by thermal evaporation (Fig. 1 (a)). The Al2O3 gate dielectric was deposited on the Ni layer by ALD with trimethylaluminum (TMA) and a H2O oxidant at a substrate temperature of 300 oC. Polymethyl methacrylate (PMMA) was prepared on Al2O3 by spin-coating as a protective layer. Next, a thermal release tape was attached to the PMMA layer. Then, the entire substrate was immersed in DIW for 5 min to weaken the adhesion strength between Ni and SiO2. The laminated structure was peeled off from the SiO2 surface in DIW. After the etching of Ni layer with dilute HNO3 (60% HNO3 : H2O = 1 : 10), the Al2O3 gate dielectric was transferred on MoS2 flakes. The Al2O3 gate dielectric and PMMA bilayer can be released from the thermal release tape by baking on a hot plate. After the removal of PMMA by oxygen plasma ashing, Al (40 nm) for the gate and Au (40 nm)/Ti (10 nm) for the source/drain were fabricated by the lift-off process. Finally, forming gas annealing (FGA) was performed in ambient (H2 : N2 = 3% : 97%) at 300 oC for 30 min to improve the electrical contacts at source/drain.The fabricated FET has small hysteresis, low leakage current, a subthreshold slope of 120 mV/dec, and a carrier mobility of 7.3 cm2/Vs (Fig. 1 (b)). The abrupt and sharp interface was demonstrated for transfer printing of the Al2O3 gate dielectric on the MoS2 channel layer. Process mismatches including temperature and chemical compatibility are avoidable by adopting the transfer printing method. The use of transferred high-k gate dielectrics is not restricted to MoS2 FETs. It is also applicable to various 2D layered materials. This study opens up the interesting direction for the research and development of 2D material-based functional devices. AcknowledgmentsThe authors would like to thank Professor Y. Kawano, Professor T. Hoshii, Professor I. Muneta, Professor K. Kakushima, Professor K. Tsutsui, and Professor H. Wakabayashi of Tokyo Institute of Technology for their continuous support in the experiments. This study was supported by JST CREST (Grant No. JPMJCR16F4) and a JSPS Grant-in-Aid for Young Scientists (B) (Grant No. 17K14662).

Room Temperature Atomic Layer Deposition of ZnO Observed By in Situ IR Absorption Spectroscopy

Zinc oxide (ZnO) is an attractive material for flexible electronics since it has various merits of nontoxicity, wide bandgap, low resistivity, and a high optical transmittance. The ZnO deposition has been intensively studied as transparent conductive films for the liquid crystal displays and thin film solar cells. Furthermore, ZnO has been used as buffer layers for gas barrier films on organic electronics devices. The ZnO deposition has been already reported by DC magnetron sputtering, chemical vapor deposition (CVD), and metal organic CVD (MOCVD). However, it was difficult to control the film thickness with a nanometer precision. In addition, these require high-temperature treatments exceeding 300 ºC, which might be problems for organic electronics and micromachines. To achieve the room temperature growth with a nanometer scale precision, we developed RT atomic layer deposition (ALD). In this study, we report a new RT ALD with dimethyl zinc (DMZ) and an oxidation gas of plasma excited humidified Ar. We used an in-situ multiple-internal-reflection IR absorption spectroscopy (MIR-IRAS) equipped ALD system to investigate the saturation behavior in precursor adsorption and oxidization. We determined injection conditions of the precursor and oxidization gas for the RT ALD based on the IRAS experiment. The RT ALD of ZnO was performed to confirm the ZnO formation on a silicon substrate. In figure 1, we show ZnO thicknesses as a function of ALD cycle which were measured by spectroscopic ellipsometry. The growth per cycle was estimated as 0.046 nm/cycle. We evaluate its composition by using X-ray photoelectron spectroscopy and confirmed that it was fully oxidized. We assume that the deposited film was amorphous from the X-ray diffraction pattern. In addition, we discuss the reaction mechanism in this ALD with Langmuir equation fitting applied to the saturation curve plotted from the result of IR absorption spectroscopy. We depict the surface reaction scheme of the ZnO RT ALD in this paper. Acknowledgment; This work was partly supported by JST-CREST Grant Number JPMJCR14F3, Japan. It was also partly supported by JSPS KAKENHI Grant Numbers 15H03536 and 16K17494. Figure 1 Growth thicknesses of ZnO as a function of the ALD cycle number. Figure 1

Potential Precursor Alternatives to the Pyrophoric Trimethylaluminium for the Atomic Layer Deposition of Aluminium Oxide.

New precursor chemistries for the atomic layer deposition (ALD) of aluminium oxide are reported as potential alternatives to the pyrophoric trimethylaluminium (TMA) which is to date a widely used Al precursor. Combining the high reactivity of aluminium alkyls employing the 3-(dimethylamino)propyl (DMP) ligand with thermally stable amide ligands yielded three new heteroleptic, non-pyrophoric compounds [Al(NMe2 )2 (DMP)] (2), [Al(NEt2 )2 (DMP)] (3, BDEADA) and [Al(NiPr2 )2 (DMP)] (4), which combine the properties of both ligand systems. The compounds were synthesized and thoroughly chemically characterized, showing the intramolecular stabilization of the DMP ligand as well as only reactive Al-C and Al-N bonds, which are the key factors for the thermal stability accompanied by a sufficient reactivity, both being crucial for ALD precursors. Upon rational variation of the amide alkyl chains, tunable and high evaporation rates accompanied by thermal stability were found, as revealed by thermal evaluation. In addition, a new and promising plasma enhanced (PE)ALD process using BDEADA and oxygen plasma in a wide temperature range from 60 to 220 °C is reported and compared to that of a modified variation of the TMA, namely [AlMe2 (DMP)] (DMAD). The resulting Al2 O3 layers are of high density, smooth, uniform, and of high purity. The applicability of the Al2 O3 films as effective gas barrier layers (GBLs) was successfully demonstrated, considering that coating on polyethylene terephthalate (PET) substrates yielded very good oxygen transmission rates (OTR) with an improvement factor of 86 for a 15 nm film by using DMAD and a factor of 25 for a film thickness of just 5 nm by using BDEDA compared to bare PET substrates. All these film attributes are of the same quality as those obtained for the industrial precursor TMA, rendering the new precursors safe and potential alternatives to TMA.

Reactivity of Atomic Layer Deposition Precursors with OH/H2O-Containing Metal Organic Framework Materials

Metal organic frameworks (MOFs) are a class of three-dimensional porous architectures that can be chemically functionalized. The ability of atomic layer deposition (ALD) to incorporate metal atoms or functional groups into MOFs offers an interesting alternative to chemically modify MOFs for applications such as catalysis and gas separation, for which transport, adsorption, and the reaction of gases are critical. Optimization of these deposition processes requires an understanding of the underlying reaction mechanisms that is best derived from in situ characterization. We have therefore combined in situ infrared spectroscopy, X-ray photoelectron spectroscopy with in situ sputtering, and ab initio calculations to elucidate the reaction mechanisms of the common ALD precursors trimethylaluminium (TMA), diethylzinc (DEZ), and TiCl4 with several Zr-MOFs containing hydroxyl (OH) and water (H2O) groups. Focusing on the OH and H2O groups is particularly revealing because it makes it possible to explore the reactivity dependence on the chemical and structural (i.e., sterics) environments. We find that the reactivity of the OH groups in the Zr6(μ3–OH)4(μ3–O)4(OH)x(OH2)y cluster node is highly dependent on their location, accessibility, and chemical environment. For instance, the activation temperature for the reaction of the OH groups of Zr6 clusters with TMA decreases with the node connectivity: 200, 150, and 24 °C for UiO-66-NH2, Zr-abtc, and MOF-808, respectively. Interestingly, the hydroxyl groups in unfunctionalized UiO-66 do not react with TMA molecules. Ab initio calculations reveal that the NH2 group is directly responsible for catalyzing this reaction by anchoring the TMA molecule in close proximity to the target OH group. Finally, we show that TMA easily reacts with water adsorbed on the external surfaces of wet MOF crystals at room temperature, forming a thick Al2O3 blocking layer on the periphery of the MOF crystals. These findings provide a basis for the design and modification of MOFs by ALD processes.

Conformal deposition of GeTe films with tunable Te composition by atomic layer deposition

Atomic layer deposition (ALD) of chalcogenide amorphous films has attracted attention, thanks to its ability to deposit highly conformal and uniform thin films on three-dimensional structures; these film properties are critical for the development of ultrahigh-density integrated electronic circuits such as nanoscale 3D cross-point memory stacks. Control over the composition of chalcogenide compounds is indispensable for fabricating functional electronic devices. In this work, the authors used trichlorogermane (HGeCl3) and bis(trimethylsilyl)telluride [(Me3Si)2Te] as ALD precursors to develop conformal and uniform germanium telluride (GeTe) films at low temperature (60 °C). The growth of GeTe resulted in moderately Ge rich films independently of the ALD precursor injection time and the use of single or discrete (Me3Si)2Te doses. To achieve control over the GeTe film composition, the authors developed a unique ALD of elemental tellurium (Te) using tellurium ethoxide [Te(OEt)4] and (Me3Si)2Te as precursors. Combining GeTe and elemental Te in an ALD supercycle fashion, they obtained GeTex films with a controllable Te content showing a uniform and conformal morphology on high aspect ratio trench structures. A detailed analysis of the variations in Ge and Te contents upon exposure of GeTex films to Te(OEt)4 revealed that an interfacial replacement of Ge atoms to form volatile Ge(OEt)2 takes place and produces a decrease in Ge and an increase in Te content. The ALD studies of GeTe and Te films described in this work provide a facile route for deposition of GeTe with controllable composition. This material system is important for the development of ovonic threshold switching selectors and phase change memories.

Chemical Analysis of the Interface between Hybrid Organic-Inorganic Perovskite and Atomic Layer Deposited Al2O3.

Ultrathin metal oxides prepared by atomic layer deposition (ALD) have gained utmost attention as moisture and thermal stress barrier layers in perovskite solar cells (PSCs). We have recently shown that 10 cycles of ALD Al2O3 deposited directly on top of the CH3NH3PbI3–xClx perovskite material, are effective in delivering a superior PSC performance with 18% efficiency (compared to 15% of the Al2O3-free cell) with a long-term humidity-stability of more than 60 days. Motivated by these results, the present contribution focuses on the chemical modification which the CH3NH3PbI3–xClx perovskite undergoes upon growth of ALD Al2O3. Specifically, we combine in situ Infrared (IR) spectroscopy studies during film growth, together with X-ray photoelectron spectroscopy (XPS) analysis of the ALD Al2O3/perovskite interface. The IR-active signature of the NH3+ stretching mode of the perovskite undergoes minimal changes upon exposure to ALD cycles, suggesting no diffusion of ALD precursor and co-reactant (Al(CH3)3 and H2O) into the bulk of the perovskite. However, by analyzing the difference between the IR spectra associated with the Al2O3 coated perovskite and the pristine perovskite, respectively, changes occurring at the surface of perovskite are monitored. The abstraction of either NH3 or CH3NH2 from the perovskite surface is observed as deduced by the development of negative N–H bands associated with its stretching and bending modes. The IR investigations are corroborated by XPS study, confirming the abstraction of CH3NH2 from the perovskite surface, whereas no oxidation of its inorganic framework is observed within the ALD window process investigated in this work. In parallel, the growth of ALD Al2O3 on perovskite is witnessed by the appearance of characteristic IR-active Al–O–Al phonon and (OH)–Al=O stretching modes. Based on the IR and XPS investigations, a plausible growth mechanism of ALD Al2O3 on top of perovskite is presented.

Controlled TiO2 Growth on Reverse Osmosis and Nanofiltration Membranes by Atomic Layer Deposition: Mechanisms and Potential Applications.

Enhancing the chemical and physical properties of the polyamide active layer of thin-film composite (TFC) membranes by surface coating is a goal long-pursued. Atomic layer deposition (ALD) has been proposed as an innovative approach to deposit chemically robust metal oxides onto membrane surfaces due to its unique capability to control coating conformality and thickness with atomic scale precision. This study examined the potential to coat the surface of TFC reverse osmosis (RO) and nanofiltration (NF) membranes via ALD of TiO2. Our results suggest that the optimal ALD conditions, the film growth kinetics, and the depth of deposition are different for RO and NF membranes due to the different diffusive transport of ALD precursors through the membrane pores. The TiO2 coating mainly located at the surface of the RO membrane; in contrast, the TiO2 coating extended to the depth of the NF membrane. The TiO2 coating degraded membrane water permeability and salt rejection beyond 10 cycles of ALD, the condition commonly employed in previous ALD-based membrane modification studies. Instead, this study showed that with fewer than 10 cycles, the TiO2 coating of RO membrane increased the membrane surface charge without negatively impacting water permeability and salt rejection. For the NF membranes, the coating of TiO2 inside their pores led to the tuning of pore sizes and increased the rejection of selected solutes.

Atomic Layer Deposition of Molybdenum and Tungsten Oxide Thin Films Using Heteroleptic Imido-Amidinato Precursors: Process Development, Film Characterization, and Gas Sensing Properties

Heteroleptic bis(tert-butylimido)bis(N,N′-diisopropylacetamidinato) compounds of molybdenum and tungsten are introduced as precursors for atomic layer deposition of tungsten and molybdenum oxide th...

Area-Selective Atomic Layer Deposition Using Si Precursors as Inhibitors

Short-chain aminosilanes, namely, bis(N,N-dimethylamino)dimethylsilane (DMADMS) and (N,N-dimethylamino)trimethylsilane (DMATMS), have been used as Si precursors for atomic layer deposition (ALD) of SiO2. In this work, the DMADMS and DMATMS Si precursors are utilized as inhibitors for area-selective ALD (AS-ALD). The inhibitors selectively adsorb on a SiO2 surface but not on H–Si, so that SiO2 becomes selectively deactivated toward subsequent ALD. The deactivation of the SiO2 surface by the inhibitors was investigated using various experimental and theoretical methods, including surface potential measurements, spectroscopic ellipsometry, and X-ray photoelectron spectroscopy. Better inhibition was observed for ALD of Ru and Pt than for ALD of Al2O3 and HfO2. Through quantum mechanical and stochastic simulations, the difference in the blocking ability for noble metal and metal oxide ALD by the aminosilane inhibitors could be attributed to the inherently partial surface coverage by the inhibitors at their saturation and the reactivity of the subsequent ALD precursors. As silane inhibitors can be easily integrated with vacuum-based processes to facilitate high volume manufacturing of upcoming electronic devices, the current study provides a potential approach for the utilization of AS-ALD in pattern fabrication inside 3D nanostructures.

Influence of carbon impurities and oxygen vacancies in Al2O3 film on Al2O3/GaN MOS capacitor characteristics

Effects of carbon impurities and oxygen vacancies in Al2O3 film on the characteristics of Al2O3/GaN MOS capacitors were studied using the different atomic layer deposition (ALD) precursor and high-pressure water vapor annealing (HPWVA). Trimethyl aluminum (TMA: Al(CH3)3) and dimethyl aluminum hydride (DMAH: Al(CH3)2H) were used as ALD precursors to control the carbon impurities. On the other hand, oxygen vacancies in Al2O3 film were suppressed using the HPWVA. The DMAH precursor reduced the concentration of carbon impurities in the ALD Al2O3 film. It was found that the interface trap density (Dit) was mainly affected by the carbon impurities rather than the oxygen vacancies at the Al2O3/GaN interface. On the other hand, voltage stress induced flat band voltage (VFB) shift was attributed to both the carbon impurities and the oxygen vacancies.

Design of Molecular Water Oxidation Catalysts Stabilized by Ultrathin Inorganic Overlayers—Is Active Site Protection Necessary?

Anchored molecular catalysts provide a good step towards bridging the gap between homogeneous and heterogeneous catalysis. However, applications in an aqueous environment pose a serious challenge to anchoring groups in terms of stability. Ultrathin overlayers embedding these catalysts on the surface using atomic layer deposition (ALD) are an elegant solution to tackle the anchoring group instability. The propensity of ALD precursors to react with water leads to the question whether molecules containing aqua ligands, such as most water oxidation complexes, can be protected without side reactions and deactivation during the deposition process. We synthesized two iridium and two ruthenium-based water oxidation catalysts, which contained an aqua ligand (Ir–OH2 and Ru–OH2) or a chloride (Ir–Cl and Ru–Cl) that served as a protecting group for the former. Using a ligand exchange reaction on the anchored and partially embedded Ru–Cl, the optimal overlayer thickness was determined to be 1.6 nm. An electrochemical test of the protected catalysts on meso-ITO showed different behaviors for the Ru and the Ir catalysts. The former showed no onset difference between protected and non-protected versions, but limited stability. Ir–Cl displayed excellent stability, whilst the unprotected catalyst Ir–OH2 showed a later initial onset. Self-regeneration of the catalytic activity of Ir–OH2 under operating conditions was observed. We propose chloride ligands as generally applicable protecting groups for catalysts that are to be stabilized on surfaces using ALD.

(Invited) Atomic Layer Deposition of Tungsten-Rich Tungsten Carbide Films Using WCl6 and AlH2(tBuNCH2CH2NMe2) as Precursors

Atomic layer deposition (ALD) is a thin film deposition procedure where growth occurs in a layer-by-layer fashion. Growth of a binary material AB occurs first by passing a gaseous stream of a precursor containing element A over the substrate, to afford a monolayer of the precursor on the surface. Then, an inert gas purge is carried out to remove excess precursor and any reaction products. Next, a gaseous stream of a precursor containing element B is passed over the substrate. This precursor reacts with the monolayer on the surface containing element A to afford the desired material AB. Finally, a second inert gas purge is conducted to remove any excess precursor and reaction products. These four steps constitute a growth cycle. A key feature of ALD is its self-limiting nature, in which the precursor containing element A reacts with surface reactive sites until they are all consumed. At this point, growth ceases, to afford a monolayer of the precursor on the substrate surface. Self-limiting growth gives excellent conformal coverage of high aspect ratio features because the growth is controlled by surface reactive sites, and also allows sub-nanometer control of film thicknesses by adjusting the number of growth cycles. The success of ALD is directly related to the chemical precursors that are used to deliver the desired elements for a given material. ALD precursors must combine good volatility, thermal stability at the deposition temperature, as well as high reactivity toward a second precursor to afford the desired material. The reaction products must be volatile so that they are not incorporated into the growing film. Moreover, chemical precursors must have chemical reaction paths built into them so that the desired materials are obtained. These properties are difficult to incorporate into molecules, and lack of appropriate precursors represents a major bottleneck for the wider applications of ALD. This tutorial will review ALD precursors that have been reported for a variety of materials. Emphasis will be focused on obtaining volatility, high thermal stability, and high reactivity toward a second precursor. Examples will be chosen where chemical reactivity is designed into the precursors to obtain desired materials with high purities. Difficult current challenges in ALD include design of precursors for the growth of electropositive element films, integration of appropriate ALD precursor chemistry into manufacturing processes, and the possibility of precursor design to achieve inherent area-selective deposition. Additional future challenges related to ALD precursors and chemistry encompass the emerging atomic layer etching (ALE) and atomic layer clean (ALC) techniques. The importance of precursors and chemistry in future ALD, ALE, and ALC processes will be highlighted.

Platinum atomic layer deposition on metal substrates: A surface chemistry study

The surface chemistry associated with the atomic layer deposition (ALD) of platinum films on metallic nickel substrates using trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPtMe3) and oxygen was characterized by using X-ray photoelectron spectroscopy (XPS). The uptake of the MeCpPtMe3 ALD precursor was found to be self-limiting between 525 and 625 K, but to lead to multilayer deposition at 675 K. The adsorbed species display a C:Pt ratio of approximately 5:1, suggesting that all methyl moieties are lost upon activated bonding to the surface but that the methylcyclopentadienyl group remains coordinated to the adsorbed Pt atoms. Oxygen treatment of that surface leads to the complete removal of the carbon-containing species from the surface and to the formation of a thin NiO film. Further dosing with MeCpPtMe3, in the next ALD cycle, fully reduces that NiO film to metallic Ni(0) and adds more Pt to the surface. However, no Pt film buildup was seen after several ALD cycles. Angle-resolved XPS data suggested that the deposited Pt migrates below the NiO that forms during the O2 exposures and possibly alloys with the metallic Ni substrate at that stage.

Preventing carbon contamination of Ge (001) during atomic layer deposition with a barium-based Zintl layer

Carbon contamination of the clean Ge (001) 2 × 1 surface occurs during atomic layer deposition (ALD) of perovskite oxides and introduces impurities that can affect device performance. Zintl layers are formed by exposing a bare Ge (001) 2 × 1-reconstructed surface to 0.5-monolayers of elemental Ba, with the Ba atoms occupying the fourfold sites between Ge-dimer rows. The bare Ge (001) and Ba-Zintl layer surfaces feature a 2 × 1-reconstructed structure. Exposure of bare 2 × 1-reconstructed Ge (001) to 0.5 monolayers of elemental Sr leads to an 8 × 1- or 9 × 1-reconstructed Ge (001) surface. Bare Ge (001) and Ba-Zintl layer Ge (001), and 0.5-monolayer Sr-dosed Ge (001) surfaces were exposed to background molecules in the ALD chamber at 225 °C. Bare Ge (001) and Ba-Zintl layer Ge (001) were also exposed to barium bis(triisopropylcyclopentadienyl) at 225 °C and changes in the surface composition were monitored with x-ray photoelectron spectroscopy. The 2 × 1-reconstructed Ba-Zintl surface protects Ge (001) from carbon accumulation associated with ALD background molecules and cyclopentadienyl-based ligands originating from the ALD precursor. Surface structure is important in protecting Ge (001); the 8 × 1- or 9 × 1-reconstructed Ge (001) surface formed from 0.5-monolayers of Sr does not prevent carbon accumulation.