The Role of Low-Energy Electron Interactions in cis-Pt(CO)2Br2 Fragmentation.

Platinum coordination complexes have found wide applications as chemotherapeutic anticancer drugs in synchronous combination with radiation (chemoradiation) as well as precursors in focused electron beam induced deposition (FEBID) for nano-scale fabrication. In both applications, low-energy electrons (LEE) play an important role with regard to the fragmentation pathways. In the former case, the high-energy radiation applied creates an abundance of reactive photo- and secondary electrons that determine the reaction paths of the respective radiation sensitizers. In the latter case, low-energy secondary electrons determine the deposition chemistry. In this contribution, we present a combined experimental and theoretical study on the role of LEE interactions in the fragmentation of the Pt(II) coordination compound cis-PtBr2(CO)2. We discuss our results in conjunction with the widely used cancer therapeutic Pt(II) coordination compound cis-Pt(NH3)2Cl2 (cisplatin) and the carbonyl analog Pt(CO)2Cl2, and we show that efficient CO loss through dissociative electron attachment dominates the reactivity of these carbonyl complexes with low-energy electrons, while halogen loss through DEA dominates the reactivity of cis-Pt(NH3)2Cl2.

Dissociation of the FEBID precursor cis-Pt(CO)2Cl2 driven by low-energy electrons.

In this study, we present experimental and theoretical results on dissociative electron attachment and dissociative ionisation for the potential FEBID precursor cis-Pt(CO)2Cl2. UHV surface studies have shown that high purity platinum deposits can be obtained from cis-Pt(CO)2Cl2. The efficiency and energetics of ligand removal through these processes are discussed and experimental appearance energies are compared to calculated thermochemical thresholds. The present results demonstrate the potential effectiveness of electron-induced reactions in the deposition of this FEBID precursor, and these are discussed in conjunction with surface science studies on this precursor and the design of new FEBID precursors.

Electron induced surface reactions of (η5-C5H5)Fe(CO)2Mn(CO)5, a potential heterobimetallic precursor for focused electron beam induced deposition (FEBID).

Electron-induced surface reactions of (η5-C5H5)Fe(CO)2Mn(CO)5 were explored in situ under ultra-high vacuum conditions using X-ray photoelectron spectroscopy and mass spectrometry. The initial step involves electron-stimulated decomposition of adsorbed (η5-C5H5)Fe(CO)2Mn(CO)5 molecules, accompanied by the desorption of an average of five CO ligands. A comparison with recent gas phase studies suggests that this precursor decomposition step occurs by a dissociative ionization (DI) process. Further electron irradiation decomposes the residual CO groups and (η5-C5H5, Cp) ligand, in the absence of any ligand desorption. The decomposition of CO ligands leads to Mn oxidation, while electron stimulated Cp decomposition causes all of the associated carbon atoms to be retained in the deposit. The lack of any Fe oxidation is ascribed to either the presence of a protective carbonaceous matrix around the Fe atoms created by the decomposition of the Cp ligand, or to desorption of both CO ligands bound to Fe in the initial decomposition step. The selective oxidation of Mn in the absence of any Fe oxidation suggests that the fate of metal atoms in mixed-metal precursors for focused electron beam induced deposition (FEBID) will be sensitive to the nature and number of ligands in the immediate coordination sphere. In related studies, the composition of deposits created from (η5-C5H5)Fe(CO)2Mn(CO)5 under steady state deposition conditions, representative of those used to create nanostructures in electron microscopes, were measured and found to be qualitatively consistent with predictions from the UHV surface science studies.

Low energy electron-induced decomposition of (η5-Cp)Fe(CO)2Mn(CO)5, a potential bimetallic precursor for focused electron beam induced deposition of alloy structures.

The production of alloyed nanostructures presents a unique problem in focused electron beam induced deposition (FEBID). Deposition of such structures has historically involved the mixing of two or more precursor gases in situ or via multiple channel gas injection systems, thereby making the production of precise, reproducible alloy compositions difficult. Promising recent efforts to address this problem have involved the use of multi-centred, heterometallic FEBID precursor species. In this vein, we present here a study of low-energy electron interactions with cyclopentadienyl iron dicarbonyl manganese pentacarbonyl ((η5-Cp)Fe(CO)2Mn(CO)5), a bimetallic species with a polyhapto ligand (Cp) and seven terminal carbonyl ligands. Gas phase studies and coupled cluster calculations of observed low-energy electron-induced reactions were conducted in order to predict the performance of this precursor in FEBID. In dissociative electron attachment, we find single CO loss and cleavage of the Fe-Mn bond, leading to the formation of [Mn(CO)5]-, to be the two dominant channels. Contributions through further CO loss from the intact core and the formation of [Mn(CO)4]- are minor channels. In dissociative ionization (DI), the fragmentation is significantly more extensive and the DI spectra are dominated by fragments formed through the loss of 5 and 6 CO ligands, and fragments formed through cleavage of the Fe-Mn bond accompanied by substantial CO loss. The gas phase fragmentation channels observed are discussed in relation to the underlying processes and their energetics, and in context to related surface studies and the likely performance of this precursor in FEBID.

Synthesis and Characterization of Tungsten Nitrido Amido Guanidinato Complexes as Precursors for Chemical Vapor Deposition of WNxCy Thin Films.

Tungsten nitrido amido guanidinato complexes of the type WN(NR2)[(NR')2C(NR2)]2 (R = Me, Et; R' = i Pr, Cy) were synthesized as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WNxCy thin films. The reaction of tungsten nitrido amido complexes of the type WN(NR2)3 (R = Me, Et) with two equivalents of a carbodiimide R'N=C=NR' (R' = i Pr, Cy) resulted in two insertions of a carbodiimide into W-N(amido) bonds, affording bis(guanidinato) amido nitrido tungsten complexes. These compounds were characterized by 14N NMR, indicating distinctive chemical shifts for each type of N-bound ligand. Crystallographic structure determination of WN(NMe2)[(N i Pr)2C(NMe2)]2 showed the guanidinato ligands to be non-equivalent. The complex WN(NMe2)[(N i Pr)2C(NMe2)]2 was demonstrated to serve as a precursor for AACVD of WNxCy thin films, resulting in featureless, X-ray amorphous thin films for growth temperatures 200 - 400 °C.

Low energy electron-induced decomposition of (η3-C3H5)Ru(CO)3Br, a potential focused electron beam induced deposition precursor with a heteroleptic ligand set.

Here we describe in detail low energy electron induced fragmentation of a potential focused electron beam induced deposition (FEBID) precursor, π-allyl ruthenium tricarbonyl bromide, i.e. (η3-C3H5)Ru(CO)3Br, specially designed to allow comparison of the effect of different ligands on the efficiency of low energy electron induced fragmentation of FEBID precursors. Specifically, we discuss the efficiency of dissociative electron attachment (DEA) and dissociative ionization (DI) with respect to electron-induced removal of the allyl, bromide and carbonyl ligands. We place this in perspective with a previous surface study on the same precursor and we propose a design strategy for FEBID precursor molecules to increase their susceptibility towards DEA.

Photochemical CVD of Ru on functionalized self-assembled monolayers from organometallic precursors.

Chemical vapor deposition (CVD) is an attractive technique for the metallization of organic thin films because it is selective and the thickness of the deposited film can easily be controlled. However, thermal CVD processes often require high temperatures which are generally incompatible with organic films. In this paper, we perform proof-of-concept studies of photochemical CVD to metallize organic thin films. In this method, a precursor undergoes photolytic decomposition to generate thermally labile intermediates prior to adsorption on the sample. Three readily available Ru precursors, CpRu(CO)2Me, (η3-allyl)Ru(CO)3Br, and (COT)Ru(CO)3, were employed to investigate the role of precursor quantum yield, ligand chemistry, and the Ru oxidation state on the deposition. To investigate the role of the substrate chemistry on deposition, carboxylic acid-, hydroxyl-, and methyl-terminated self-assembled monolayers were used. The data indicate that moderate quantum yields for ligand loss (φ ≥ 0.4) are required for ruthenium deposition, and the deposition is wavelength dependent. Second, anionic polyhapto ligands such as cyclopentadienyl and allyl are more difficult to remove than carbonyls, halides, and alkyls. Third, in contrast to the atomic layer deposition, acid-base reactions between the precursor and the substrate are more effective for deposition than nucleophilic reactions. Finally, the data suggest that selective deposition can be achieved on organic thin films by judicious choice of precursor and functional groups present on the substrate. These studies thus provide guidelines for the rational design of new precursors specifically for selective photochemical CVD on organic substrates.

Electron Induced Surface Reactions of cis-Pt(CO)2Cl2: A Route to Focused Electron Beam Induced Deposition of Pure Pt Nanostructures.

Using mechanistic data from surface science studies on electron-induced reactions of organometallic precursors, cis-Pt(CO)2Cl2 (1) was designed specifically for use in focused electron beam induced deposition (FEBID) of Pt nanostructures. Electron induced decomposition of adsorbed 1 under ultrahigh vacuum (UHV) conditions proceeds through initial CO loss as determined by in situ X-ray photoelectron spectroscopy and mass spectrometry. Although the Pt-Cl bonds remain intact during the initial decomposition step, larger electron doses induce removal of the residual chloride through an electron-stimulated desorption process. FEBID structures created from cis-Pt(CO)2Cl2 under steady state deposition conditions in an Auger spectrometer were determined to be PtCl2, free of carbon and oxygen. Coupled with the electron stimulated removal of chlorine demonstrated in the UHV experiments, the Auger deposition data establish a route to FEBID of pure Pt. Results from this study demonstrate that structure-activity relationships can be used to design new precursors specifically for FEBID.

Dioxo-Fluoroalkoxide Tungsten(VI) Complexes for Growth of WOx Thin Films by Aerosol-Assisted Chemical Vapor Deposition.

The soluble bis(fluoroalkoxide) dioxo tungsten(VI) complexes WO2(OR)2(DME) [1, R = C(CF3)2CH3; 2, R = C(CF3)3] have been synthesized by alkoxide-chloride metathesis and evaluated as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WOx. The (1)H NMR and (19)F NMR spectra of 1 and 2 are consistent with an equilibrium between the dimethoxyethane (DME) complexes 1 and 2 and the solvato complexes WO2(OR)2(CD3CN)2 [1b, R = C(CF3)2CH3; 2b, R = C(CF3)3] in acetonitrile-d3 solution. Studies of the fragmentation of 1 and 2 by mass spectrometry and thermolysis resulted in observation of DME and the corresponding alcohols, with hexafluoroisobutylene also generated from 1. DFT calculations on possible decomposition mechanisms for 1 located pathways for hydrogen abstraction by a terminal oxo to form hexafluoroisobutylene, followed by dimerization of the resulting terminal hydroxide complex and dissociation of the alcohol. AACVD using 1 occurred between 100 and 550 °C and produced both substoichiometric amorphous WOx and a polycrystalline W18O49 monoclinic phase, which exhibits 1-D preferred growth in the [010] direction. The work function (4.9-5.6 eV), mean optical transmittance (39.1-91.1%), conductivity (0.4-2.3 S/cm), and surface roughness (3.4-7.9 nm) of the WOx films are suitable for charge injection layers in organic electronics.

Tungsten nitrido complexes as precursors for low temperature chemical vapor deposition of WN(x)C(y) films as diffusion barriers for Cu metallization.

Tungsten nitrido complexes of the form WN(NR2)3 [R = combinations of Me, Et, (i)Pr, (n)Pr] have been synthesized as precursors for the chemical vapor deposition of WN(x)C(y), a material of interest for diffusion barriers in Cu-metallized integrated circuits. These precursors bear a fully nitrogen coordinated ligand environment and a nitrido moiety (W≡N) designed to minimize the temperature required for film deposition. Mass spectrometry and solid state thermolysis of the precursors generated common fragments by loss of free dialkylamines from monomeric and dimeric tungsten species. DFT calculations on WN(NMe2)3 indicated the lowest gas phase energy pathway for loss of HNMe2 to be ß-H transfer following formation of a nitrido bridged dimer. Amorphous films of WN(x)C(y) were grown from WN(NMe2)3 as a single source precursor at temperatures ranging from 125 to 650 °C using aerosol-assisted chemical vapor deposition (AACVD) with pyridine as the solvent. Films with stoichiometry approaching W2NC were grown between 150 and 450 °C, and films grown at 150 °C were highly smooth, with a RMS roughness of 0.5 nm. In diffusion barrier tests, 30 nm of film withstood Cu penetration when annealed at 500 °C for 30 min.

Formylation of amines.

Methods to convert amines to formamides are of interest due to the many uses of formamides as synthetic intermediates. These methods include stoichiometric reactions of formylating reagents and catalytic reactions with CO as the carbonyl source. This review discusses the reported stoichiometric and catalytic approaches for preparation of formamides.

Aerosol-Assisted Chemical Vapor Deposition of 2H-WS2 From Single-Source Tungsten Dithiolene Precursors.

The tungsten carbonyl dimethyldithiolene (dmdt) complexes W(CO)4(dmdt), W(CO)2(dmdt)2, and W(dmdt)3 were evaluated as potential single-source precursors for the chemical vapor deposition of WS2. The results of TGA-MS, DIP-MS, and pyrolysis with NMR analysis were consistent with a thermal decomposition pathway in which loss of 2-butyne through a retro[3+2]cycloaddition of the dithiolene ligand generated terminal sulfido ligands. Aerosol-assisted chemical vapor deposition onto silicon substrates was performed using all three complexes, yielding 2H-WS2 thin films as characterized by Raman spectroscopy and GI-XRD. Film morphology and elemental composition of the films were determined using SEM, EDS, and XPS. Four-point probe measurements afforded a film resistivity of 8.37 Ωcm for a sample deposited from W(dmdt)3 in toluene at 600 °C.

Electron-induced deposition using Fe(CO)4MA and Fe(CO)5 - effect of MA ligand and process conditions.

The electron-induced decomposition of Fe(CO)4MA (MA = methyl acrylate), which is a potential new precursor for focused electron beam-induced deposition (FEBID), was investigated by surface science experiments under UHV conditions. Auger electron spectroscopy was used to monitor deposit formation. The comparison between Fe(CO)4MA and Fe(CO)5 revealed the effect of the modified ligand architecture on the deposit formation in electron irradiation experiments that mimic FEBID and cryo-FEBID processes. Electron-stimulated desorption and post-irradiation thermal desorption spectrometry were used to obtain insight into the fate of the ligands upon electron irradiation. As a key finding, the deposits obtained from Fe(CO)4MA and Fe(CO)5 were surprisingly similar, and the relative amount of carbon in deposits prepared from Fe(CO)4MA was considerably less than the amount of carbon in the MA ligand. This demonstrates that electron irradiation efficiently cleaves the neutral MA ligand from the precursor. In addition to deposit formation by electron irradiation, the thermal decomposition of Fe(CO)4MA and Fe(CO)5 on an Fe seed layer prepared by EBID was compared. While Fe(CO)5 sustains autocatalytic growth of the deposit, the MA ligand hinders the thermal decomposition in the case of Fe(CO)4MA. The heteroleptic precursor Fe(CO)4MA, thus, offers the possibility to suppress contributions of thermal reactions, which can compromise control over the deposit shape and size in FEBID processes.

Surface plasmon mediated chemical solution deposition of gold nanoparticles on a nanostructured silver surface at room temperature.

Sub-15 nm Au nanoparticles have been fabricated on a nanostructured Ag surface at room temperature via a liquid-phase chemical deposition upon excitation of the localized surface plasmon resonance (SPR). Measurement of the SPR-mediated photothermal local heating of the substrate surface by a molecular thermometry strategy indicated the temperature to be above 230 °C, which led to an efficient decomposition of CH(3)AuPPh(3) to form Au nanoparticles on the Ag surface. Particle sizes were tunable between 3 and 10 nm by adjusting the deposition time. A surface-limited growth model for Au nanoparticles on Ag is consistent with the deposition kinetics.

Evaluation of multisite polypyridyl ligands as platforms for the synthesis of Rh/Zn, Rh/Pd, and Rh/Pt heterometallic complexes.

Ligands containing linked dipicolylamine (dpa) and bipyridine (bpy) sites have been utilized in the synthesis of monometallic and heterometallic complexes. The two sites have different selectivities for metal binding, which allows preferential formation of singly metalated complexes. The dpa site of the ligands has been observed to bind selectively to Zn(2+), Pd(2+), and Pt(2+), while the bpy site binds selectively to Rh(+). Addition of a second metal then results in the formation of heterometallic products. In the presence of CD3OD, the heterometallic Rh/Pt and Rh/Pd complexes undergo rapid selective H/D exchange of one of the diastereotopic protons of the dpa methylene group.

Heterobimetallic complexes of polypyridyl ligands containing paramagnetic centers: synthesis and characterization by IR and EPR.

Ligands containing linked dipicolylamine (dpa) and bipyridine sites have been explored as platforms for the synthesis of heterometallic complexes containing the paramagnetic metals Cu(2+) and Co(2+). IR and EPR studies on the bimetallic complexes and simplified model compounds support dpa-selective binding by both of these metals. The IR spectra have also been compared to those of diamagnetic Rh(+), Zn(2+), and Pd(2+) complexes whose metal binding sites had been independently determined through NMR techniques. The binding preferences have been used to control selective metalation in the synthesis of heterometallic Pt/Cu, Pd/Cu, and Rh/Cu complexes.

Aerosol-Assisted Chemical Vapor Deposition of MoS2 with a Thiourea Sulfur Source: Single-Source Precursors vs Coreactant Mixtures.

Aerosol-assisted chemical vapor deposition of MoS2 from solutions containing the single-source precursors cis-Mo(CO)4(TMTU)2 and Mo(CO)5(TMTU) in toluene was compared to depositions from the coreactant solution containing Mo(CO)6 and uncoordinated TMTU in toluene. The results were used to assess the significance of ligand precoordination on the properties of the deposited films. Raman spectra and GI-XRD patterns of the films show that the single-source precursors produced more intense and sharper signals for 2H-MoS2 as compared to the coreactant system of Mo(CO)6 and TMTU, which is indicative of improved crystallinity. SEM and XPS were also used to assess morphology and film composition. Thermolysis of cis-Mo(CO)4(TMTU)2 and analysis of the pyrolysis products by GC-MS and 1H NMR suggested a decomposition mechanism of the TMTU ligand where a terminal sulfido is generated on the molybdenum center with loss of a heteroatom stabilized carbene.

Molybdenum(III) Amidinate: Synthesis, Characterization, and Vapor Phase Growth of Mo-Based Materials.

The synthesis, characterization, and thermogravimetric analysis of tris(N,N'-di-isopropylacetamidinate)molybdenum(III), Mo(iPr-AMD)3, are reported. Mo(iPr-AMD)3 is a rare example of a homoleptic mononuclear complex of molybdenum(III) and fills a longstanding gap in the literature of transition metal(III) trisamidinate complexes. Thermogravimetric analysis (TGA) reveals excellent volatilization at elevated temperatures, pointing to potential applications as a vapor phase precursor for higher temperature atomic layer deposition (ALD), or chemical vapor deposition (CVD) growth of Mo-based materials. The measured TGA temperature window was 200-314 °C for samples in the 3-20 mg range. To validate the utility of Mo(iPr-AMD)3, we demonstrate aerosol-assisted CVD growth of MoO3 from benzonitrile solutions of Mo(iPr-AMD)3 at 500 °C using compressed air as the carrier gas. The resulting films are characterized by X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy. We further demonstrate the potential for ALD growth at 200 °C with a Mo(iPr-AMD)3/Ar purge/300 W O2 plasma/Ar purge sequence, yielding ultrathin films which retain a nitride/oxynitride component. Our results highlight the broad scope utility and potential of Mo(iPr-AMD)3 as a stable, high-temperature precursor for both CVD and ALD processes.