Mass spectrometry as a tool study CVD process

Mass spectrometry as a tool study CVD process. Application of two mass spectrometric (MS) techniques to study chemical vapour deposition from organometallic precursors is described. CpCuPEt3 (Cp = η5-C5H5, Et =C2H5) was used as a model precursor in this work

Thermal behaviour of CpCuPEt3 in gas phase and Cu thin films processing

Decomposition of CpCuPEt3 (Cp=NNN(η5-C5H5)) and MOCVD of Cu films from CpCuPEt3 have been investigated in the frame of an ongoing project on the processing of Cu-containing coatings. The behaviour of CpCuPEt3 vapours under heating conditions was studied by in situ mass spectrometry. It was established that this compound is monomeric in gas phase. Its decomposition mechanism on hot surface was proposed. From mass spectroscopy experiments, it was established that decomposition in vacuum begins at 150 °C with evolution of PEt3. Beyond 270 °C, formation of cyclopentadiene is observed, indicating that a change in decomposition mechanism occurs. The saturating vapour pressure of CpCuPEt3 was estimated through static method, in order to optimize transport conditions and to control the molar fraction of the precursor in the gas phase. Finally, growth rate and microstructure of MOCVD processed Cu films from CpCuPEt3 have been investigated

Decomposition Schemes of Copper(I)N1′-Diisopropylacetamidinate During Chemical Vapor Deposition of Copper

Copper(I) N1N′-diisopropylacetamidinate [Cu(amd)]2 (amd = CH(CH352NC(CH35NCH(CH3525, an oxygen and halogen-free compound, was previously tested as precursor for pure copper CVD and ALD films. The present work deals with the investigation of the composition and of the reactivity of the gas phase during the CVD process. The work was performed by mass spectrometry as a function of temperature in two different, though complementary environments: (A) in a miniature, low pressure hot wall CVD reactor, (B) in a cold wall reactor operating at subatmospheric pressure. (A) revealed that the onset of thermal decomposition is 140°C and 130°C in vacuum and in the presence of hydrogen, respectively; maximal decomposition degree is reached at temperature higher than 200°C. The protonated ligand H(amd) is the main gaseous decomposition by-product; propene CH2 CHCH3, acetonitryle CH3C≡N and iminopropane CH3C(CH35 NH are also observed in vacuum. Heterogeneous decomposition mechanism both in vacuum and hydrogen presence is discussed

Chemical vapor deposition of iron, iron carbides, and iron nitride films from amidinate precursors

Iron bis(N,N-diisopropylacetamidinate) [Fe2(µ-iPr-MeAMD)2(2-iPr-MeAMD)2] and iron bis(N,N-di-tert-butylacetamidinate) [Fe(tBu-MeAMD)2] were used as precursors for the metallorganic chemical vapor deposition (MOCVD) of iron-containing compounds including pure iron, iron carbides, Fe3C and Fe4C, and iron nitrides Fe4C. Their decomposition mechanism involves hydrogen migration followed by dissociation of the Fe–N bond and the release of free hydrogenated ligand (HL) and radicals. Surface intermediates are either released or decomposed on the surface providing Fe–N or Fe–C bonds. MOCVD experiments were run at 10 Torr, in the temperature ranges of 350–450°C with Fe2(µ−iPr-MeAMD)2(2-iPr-MeAMD)2 and 280–350°C with Fe(tBu-MeAMD)2. Films prepared from Fe2(µ−iPr-MeAMD)2(2-iPr-MeAMD)2 contain Fe, Fe3C, and Fe4C. Those prepared from Fe(tBu-MeAMD)2 contain Fe, Fe3C, and also Fe4C or Fe4N, depending on the temperature and hydrogen to precursor ratio (H/P) in the input gas. The room-temperature coercive field of films processed from Fe(tBu-MeAMD)2 is 3 times higher than that of the high temperature processed Fe4N films

Iron amidinates as precursors for the MOCVD of iron-containing thin films

Iron amidinates as precursors for the MOCVD of iron-containing thin film

Direct liquid injection chemical vapor deposition of ZrO2 films from a heteroleptic Zr precursor: Interplay between film characteristics and corrosion protection of stainless steel

The direct liquid injection chemical vapor deposition (DLI-CVD) of uniform and dense zirconium oxide (ZrO2) thin films applicable as corrosion protection coatings (CPCs) is reported. We present the entire development chain from the rational choice and thermal evaluation of the suitable heteroleptic precursor [Zr(OiPr)2(tbaoac)2] over the detailed DLI-CVD process design and finally benchmarking the CPC behavior using electrochemical impedance spectroscopy (EIS). For a thorough development of the growth process, the deposition temperature (Tdep) is varied in the range of 400 – 700 °C on Si(100) and stainless steel (AISI 304) substrates. Resulting thin films are thoroughly analyzed in terms of structure, composition, and morphology. Grazing incidence X-ray diffractometry (GIXRD) reveals an onset of crystallization at Tdep ≥ 500 °C yielding monoclinic and even cubic phase at low temperatures. At Tdep = 400 °C, isotropic growth of XRD amorphous material is shown to feature cubic crystalline domains at the interfacial region as revealed by electron diffraction. Corrosion results obtained through EIS measurements and further immersion tests revealed improved CPC characteristic for the 400 °C processed ZrO2 coatings compared to the ones deposited at Tdep ≥ 500 °C, yielding valuable insights into the correlation between growth parameter and CPC performance which are of high relevance for future exploration of CPCs

Thermal decomposition of tungsten hexacarbonyl: CVD of W-containing films under Pd codeposition and VUV assistance

Experiments on chemical vapor deposition of W(CO)6- derived films on silicon substrates were carried out at total pressure of 5-10 Torr within the temperature range of 250-350 oС in Ar or H2 flow. Metallic, carbide and oxide phases composed the obtained films. Deposition in presence of hydrogen results in the increase of the metal content in the film. Sublimed palladium hexafluoracetylacetonate Pd(hfa)2 was used for Pd catalytic promotion of the deposition process. Codeposition with Pd(hfa)2 in hydrogen increases W-metal fraction and oxygen content while the Pd content is up to 10 at.%. Influence of vacuum ultraviolet (VUV) radiation from Xe excimer lamp (λ~172 nm) on the quality of the obtained films was investigated. It was found that VUV irradiation can reduce the oxygen-content in the film while W-metal fraction slightly increases. In all films, oxygen was in the form of WO3 and carbon was mainly incorporated as a graphite metastable phase. The influence of other chemical additives is discussed

MONITORING COMPOSITION AND STRUCTURE OF MOCVD ZrO2-BASED MULTICOMPONENT FILMS BY INNOVATIVE MIXED METAL-ORGANIC PRECURSORS

Three volatile mixed-metal precursors [ZrL4Pb(hfa)2] (1), [ZrL4PbL2] (2), and [ZrL4La(dpm)3] (3) (L = 2-methoxy-2,6,6-trimethyl-3,5-heptanedionate; dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate; hfa = 1,1,1,5,5,5-hexafluore-2,4-pentanedionate) are used to prepare ZrO2-based multicomponent films by metalorganic chemical vapor deposition (MOCVD). The deposition experiments are carried out in a hot-wall reactor at 600-750 °C on silicon substrates under 20 Torr in the presence of oxygen. According to X-ray powder diffraction, the main crystal phases in the films prepared from precursors 1 and 2 are solid solutions based on tetragonal and cubic ZrO2. Lead does not form separate crystal phases but is dissolved in the oxide form within the ZrO2 matrix, as is indicated by X-ray photoelectron spectroscopy data. La2Zr2O7 films are prepared from 3 using two ways of precursor supply: evaporation in argon and by direct liquid injection (DLI). It is shown that the composition and structure of obtained films are determined by the precursor composition. The results obtained for thermal behavior of precursors in condensed and gas phases are discussed

Volatile Heterobimetallic Complexes from PdIIand CuIIβ-Diketonates: Structure, Magnetic Anisotropy, and Thermal Properties Related to the Chemical Vapor Deposition of Cu-Pd Thin Films

A novel approach for preparing volatile heterometallic complexes for use as precursors for the chemical vapor deposition of various materials is reported. New Cu¢Pd complexes based on b-diketonate units were prepared, and their structures and compositions were determined. [PdL2*CuL2] (1) and [PdL2*Cu(tmhd)2] (2) (L=2-methoxy-2,6,6-trimethylheptane-3,5-dionate; tmhd=2,2,6,6- tetramethylheptane-3,5-dionate) are 1D coordination polymers with alternating metal complexes, which are connected through weak interactions between the Cu atoms and the OCH3 groups from the ligand of the Pd complexes. The volatility and thermal stability were studied using thermogravimetric and differential thermal analyses and mass spectrometry. Compound 1 vaporizes without decomposition into monometallic complexes. It exhibits magnetic anisotropy, which was revealed from the angular variations in the EPR spectrum of a single crystal. The vapor thermolysis process for 1 was investigated using mass spectrometry, allowing the process to be framed within the temperature range of 200–3508C. The experimental data, supported by QTAIM calculations of the allowed intermolecular interactions, suggest that 1 likely exists in the gas phase as bimetallic molecules. Compound 1 proved to be suitable as a single-source precursor for the efficient preparation of Cu¢Pd alloy films with tunable Cu/Pd ratio. A possible mechanism for the film growth is proposed based on the reported data

Chemical vapor deposition of Pd/Cu alloy films from a new single source precursor

International audienceCu/Pd alloys were deposited onto Si(100) and SiO2 (fused silica) substrates by MOCVD from PdL2×CuL2, (L=2-methoxy-2,6,6-trimethylheptane-3,5-dionate), a new single source bimetallic precursor. Deposition was performed at 10 Torr in a temperature range between 200 °C and 350 °C and was assisted by vacuum ultraviolet (VUV) irradiation of the precursor vapor from an excimer Xe-lamp. It was shown that the elemental and phase composition of the films can be controlled by varying the deposition temperature and by stimulating by VUV the precursor decomposition. The bulk compositional properties of the obtained films confirmed the feasibility of proposed approach and precursor to prepare Pd alloy membrane materials by the CVD method