Charge transport and optical properties of MOCVD-derived highly transparent and conductive Mg- and Sn-doped In2O3 thin films

Mg- and Sn-doped In2O3 (MgIn(x)Sn(y)O(z), 6.0 < x < 16.0; 3.0 < y < 8.0) thin films were grown by low-pressure metal-organic chemical vapor deposition using the volatile metal-organic precursors tris(2,2,6,6-tetramethyl-3,5-heptanedionato)indium(III) [In(dpm)3], bis(2,4-pentanedionato)tin(II) [Sn(acac)2], and bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(N,N,N',N'-tetramethylethylenediamine)magnesium(II) [Mg(dpm)2(TMEDA)]. Films in this compositional range retain the cubic In2O3 bixbyite crystal structure. The highest conductivity is found to be approximately 1000 S/cm for an as-grown film with a nominal composition MgIn14.3Sn6.93O(z). Annealing of such films in a vacuum raises the conductivity to approximately 2000 S/cm. The optical transmission window of the present films is significantly wider than that of typical indium tin oxide (ITO) films from 300 to 3300 nm, and the transmittance is also greater than or comparable to that of commercial ITO films.     

Surface morphology and electrical properties of copper thin films prepared by MOCVD

Thin copper films have been grown in a vertical MOCVD (Metal-Organic Chemical Vapor Deposition) reactor using bis(2,2,6,6-tetramethyl-3,5-heptanedionato) copper(II), Cu(thd)₂, as precursor. Deposition has been carried out in a pure hydrogen atmosphere (pressure: 3, 20 mbar) at different substrate temperatures (350–750 ° C). The films have been investigated by profilometry, four-point resistivity measurements, ESCA, AES, XRD, AFM, and Normarsky microscopy. An unusual dependence of the film thickness with deposition time has been observed. Rapid growth occurred in the first minutes resulting in badly conducting films (thickness below 1000 Å). Good electrical resistivities have been obtained above 2000 Å. AFM has been used to gain information about the surface morphology of the films with different thicknesses. The grain size and surface roughness increased with increasing film thickness. Small grains grew in the beginning and the electrical properties have been governed by the highly Ohmic bridges between the individual grains.     

Electronic structure of a metal-organic copper spin-1/2 molecule: bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II)

The metal-organic molecule bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (Cu(CNdpm)2) (C24H36N2O4Cu, Cu(II)) is a copper spin-1/2 system with a magnetic moment of 1.05 +/- 0.04 muB/molecule, slightly smaller than the 1.215+/-0.02 muB/molecule for the larger size copper spin-1/2 system C36H48N4O4Cu.C4H8O (bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) 4,4'-bipyridylethene-THF). There is generally good agreement between photoemission from vapor-deposited thin films of the C24H36N2O4Cu on Cu(111) and Co(111) and model calculations. Although this molecule is expected to have a gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, the molecule remains surprisingly well screened in the photoemission final state.     

Chemical vapor deposition using lanthanide β-diketone chelates with difluorodichloromethane

Preparation of lanthanide fluoride and chloride films has been studied by chemical vapor deposition (CVD) using Ln(thd)₃ (Ln=lanthanide(III); thd=2,2,6,6-tetramethyl-3,5-heptanedionato ligand) and Y(thd)₃ with gas mixture systems of CF₂Cl₂ (difluorodichloromethane)/O₂ and CF₂Cl₂/H₂. Two kinds of fluorides, LnOF oxyfluoride and LnF₃ triffluoride, were obtained separately along a CVD tube at atmospheric pressure and temperature as low as 300–600°C by the reaction of Ln(thd)₃ chelates with CF₂Cl₂/O₂ gas system. The chemical characteristics of the CVD products were considered from the thermochemical point of view.     

Synthesis and Characterization of Pr（DPM）3 Served as Precursor for MOCVD

Praseodymium β-diketone chelate, Pr(DPM)3 [DPM=2,2,6,6-tetramethyl-3,5-heptanedionato], was successfully synthesized from the inorganic salt praseodymium chloride and HDPM(2,2,6,6-tetramethyl-3,5-heptane-dione) in an ethanol/aqueous solution followed distillation at low pressure and recrystallization from toluene. The physical and thermal properties of the chelate, including volatility, stability, and thermal decomposition, were investigated by elemental analyses, 1H NMR spectroscopy, XRD, TG/DTG/DTA analysis, infrared spectroscopy, and mass spectroscopy. The chelate with high purity prepared by thes of this study also shows sufficient volatility and stability in inert gases, which could be used as the precursor for metal-organic chemical vapor deposition(MOCVD).     

Preparation of lanthanide sulfide films by chemical vapor deposition using β-diketone chelates

Preparation of thin films of lanthanide (Ln) sulfides has been studied by the chemical vapor deposition (CVD) method, using metal -diketonato chelates with 2,2,6,6-tetramethyl-3,5-heptanedione and reactant H₂S gas as starting materials. Two kinds of sulfides, Ln₂O₂S oxysulfides and EuS monosulfide, were obtained as thin films at temperatures as low as 390–570 °C. The CVD method was confirmed to be suited for the above purpose.     

Structure and properties of films based on HfO<Subscript>2</Subscript>-Sc<Subscript>2</Subscript>O<Subscript>3</Subscript> double oxide

The results of the investigation of the chemical constitution and structure of (HfO₂) _x (Sc₂O₃)_1−x thin films are reported. The films are obtained by chemical vapor deposition (CVD) from hafnium 2,2,6,6-tetramethyl-3,5-heptandionate (Hf(thd)₄) and scandium 2,2,6,6-tetramethyl-3,5-heptandionate (Sc(thd)₃) coordination compounds. It is demonstrated by powder X-ray diffraction and infrared spectroscopy that depending on the scandium content in the films the structure is changed from monoclinic to cubic. Voltage-capacity dependences of test Al/(HfO₂) _x (Sc₂O₃)_1−x /Si structures are used to calculate the dielectric constant of the films. For the films with the cubic structure it is found that k = 21, while for the films with the monoclinic structure k = 9.     

Co(thd)2: a superior catalyst for aerobic epoxidation and hydroperoxysilylation of unactivated alkenes: application to the synthesis of spiro-1,2,4-trioxanes

Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)cobalt(II) (Co(thd)₂), a β-diketonate prepared in a simple one-step procedure, is an excellent catalyst for aerobic epoxidation and Mukaiyama-Isayama hydroperoxysilylation of unactivated alkenes. For hydroperoxysilylation, Co(thd)₂ is superior to Co(acac)₂ and can catalyse oxidation of cyclic alkenes in excellent yield. Chiral β-diketonate or keto iminato catalysts failed to catalyse this reaction in an enantioselective manner and a free radical mechanism consistent with this observation is proposed. Hydroperoxysilylation of cyclohex-1-enylmethanol by Co(thd)₂ followed by addition of a ketone/TsOH provides a simple one-pot procedure for the synthesis of spiro-1,2,4-trioxane antimalarials.     

CVD of metal organic and other rare-earth compounds

Three major applications have been found for rare-earth compounds in Metal Organic Chemical Vapour Depostion (MOCVD) or Chemical Vapour Deposition (CVD). Yttrium 2,2,6,6-tetramethyl-3,5-heptanedionates and 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionates have been used in conjunction with barium and copper(II) β-diketonates to deposit YBa₂Cu₃O_7−δ as superconducting thin films. Rare-earth fluorides and chlorides have been used for CFD doping of rare earths into MOCVD-deposited ZnS, whilst yttrium chloride has been used, with barium iodide and copper(I) chloride, to produce YBa₂Cu₃O_7−δ superconducting material by CVD. Lanthanoid (Ln) tris(cyclopentadienyl) compounds, Ln(C₅H₅)₃ or Ln(C₅H₄Me)₃, have been used for doping of rare earths into 13–15 (III–V) semiconductors. Their volatility, structure/volatility relationships, and preparations are discussed. Possible alternative reagents and problems to be faced in doping 12–16 (II–VI) semiconductors are also considered.     

Comparison of characteristics of solid oxide fuel cells with YSZ and CGO film solid electrolytes formed using magnetron sputtering technique

The work describes the methods of manufacturing single cells of solid oxide fuel cell (SOFC) with thin–film YSZ and CGO electrolytes and also with the bilayer YSZ/CGO electrolyte. Formation of YSZ and CGO films on the supporting NiO–YSZ anode of SOFC was carried out using the combined electron–ionic–plasma deposition technique. The microstructure and phase composition of the formed coatings are studied and also comparative analysis of electrochemical characteristics of single fuel cells with different electrolytes is performed. It is shown that the maximum power density of 1.35 W/cm² at the temperature of 800°C is obtained for the cell with bilayer YSZ/CGO electrolyte. However, the highest performance at lower working temperatures (650–700°C) is characteristic for the fuel cell with single–layer CGO electrolyte; its power density is 600–650 mW/cm².     

Nonradiative intramolecular deactivation of Tb3+ fluorescence in a vapor phase terbium(III) complex

For the first time, fluorescence lifetime studies are reported for a trivalent rare-earth gas: specifically, for the ⁵D₄ state of Tb³⁺ in the vapor phase chelate 2,2,6,6-tetramethyl-3,5-heptanedione. Measurements of the fluorescence decay as a function of temperature and pressure demonstrate that intermolecular collisional deactivation is unimportant and that nonradiative deactivation by intramolecular processes dominates the fluorescence lifetime at temperatures of 230–300°C. The rate for the latter processes is well described by an Arrhenius equation and suggests that the Tb³⁺ relaxation occurs via transfer to low-lying excited states of the chelate.     

Structure of a new chelate complex MO<Subscript>2</Subscript>O<Subscript>3</Subscript>(dpm)<Subscript>4</Subscript>

A new Mo₂O₃(dpm)₄ compound (I) is synthesized by the interaction of Mo(CO)₆ with 2,2,6,6-tetramethylheptanedione-3,5 (dpm). The structure of complex I determined by the XRD method is as follows: triclinic crystal system, space group P–1, a = 10.1780(7) Å, b = 10.1817(6) Å, c = 13.3255(9) Å, α = 110.562(2)°, β = 102.233(2)°, γ = 93.9041(19)°, V = 1248.17(14) ų. The compound is characterized by IR spectroscopy, mass-spectrometry and thermogravimetric analysis (TGA).     

Decomposition behavior of M(DPM)n (DPM = 2,2,6,6-tetramethyl-3,5-heptanedionato; n = 2, 3, 4)

The decomposition behavior of M(DPM)n (DPM = 2,2,6,6-tetramethyl-3,5-heptanedionato; M = Sr, Ba, Cu, Sm, Y, Gd, La, Pr, Fe, Co, Cr, Mn, Ce, Zr; n = 2-4) was studied in detail with infrared spectroscopy and mass spectrometry. The results indicated that the chemical bonds in these compounds dissociate generally following the sequence of C-O > M-O > C-C(CH3)3 > C-C and C-H at elevated temperatures. The decomposition processes of M(DPM)n are strongly influenced by the coordination number and central metal ion radius. In addition, the decomposed products, in air atmosphere, varied from metal oxides to metal carbonates associated with different M(DPM)n.     

Volatile Heteroligand Complexes of Copper(II): New Precursors for Chemical Vapor Deposition of Copper Films

Two heteroligand ketoiminate–diketonate complexes of copper(II), CuL(hfa) (1), L = pentane-2-imino-4-onato, CH₃COCHCNHCH ₃ ^– , and CuL′(hfa) (2), L′ = 2,2,6,6-tetramethyl-3-iminoheptane-5-onato, C(CH₃)₃COCHCNHC(CH)^–, were studied as precursors for chemical vapor deposition of copper films. The flow method was employed to measure the temperature dependences of a saturated vapor pressure of these compounds, the thermodynamic parameters of evaporation–sublimation were calculated, and the volatilities of these compounds and thermal behaviors in the condensed and gaseous phases were compared. The copper films were compared, and it was shown that comparatively high growth rates are reached when (2) is used to obtain copper films in hydrogen.     

Palladium-Catalyzed C−H Bond Arylation of Cyclometalated Difluorinated 2-Arylisoquinolinyl Iridium(III) Complexes

The utility of C−H bond functionalization of metalated ligands for the elaboration of aryl-functionalized difluorinated-1-arylisoquinolinyl Ir(III) complexes has been explored. Bis[(3,5-difluorophenyl)isoquinolinyl](2,2,6,6-tetramethyl-3,5-heptanedionato) iridium(III) undergoes Pd-catalyzed C−H bond arylation with aryl bromides. The reaction regioselectively occurred at the C−H bond flanked by the two fluorine atoms of the difluoroaryl unit, and on both cyclometalated ligands. This post-functionalization gives a straightforward access to modified complexes in only one manipulation and allows to introduce thermally sensitive functional groups, such as trifluoromethyl, nitrile, benzoyl, or ester. The X-ray crystallography, photophysical, and electrochemical properties of the diarylated complexes were investigated. Whatever the nature of the incorporated substituted aryl groups is, all obtained complexes emit red phosphorescence (622–632 nm) with similar lifetimes (1.9–2 μs).     

Nanostructured ZrO2 and Zr‐C‐N Coatings from Chemical Vapor Deposition of Metal‐Organic Precursors

Nanocrystalline zirconium carbonitride (Zr‐C‐N) and zirconium oxide (ZrO₂) films were deposited by chemical vapor deposition (CVD) of zirconium‐tetrakis‐diethylamide (Zr(NEt₂)₄) and ‐tert‐butyloxide (Zr(OBu^t)₄), respectively. The films were deposited on iron substrates and characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The Zr‐C‐N films show blue, golden brown or bronze colours, with colour stability depending upon the precursor composition (pure metal amide or mixed with Et₂NH). The deposition temperature showed no pronounced effect on the granular morphology of the Zr‐C‐N films. The XRD data of the films correspond to the formation of carbonitride phase whereas the XPS analyses revealed a strong surface oxidation and incorporation of oxygen in the film. The films deposited using a mixture of Zr(NEt₂)₄ and Et₂NH showed higher N content, better adhesion and scratch resistance when compared to films obtained from the CVD of pure Zr(NEt₂)₄. Subject to the precursor composition and deposition temperature (550‐750 °C), the microhardness values of Zr‐C‐N films were found to be in the range 2.11‐5.65 GPa. For ZrO₂ films, morphology and phase composition strongly depend on the deposition temperature. The CVD deposits obtained at 350 °C show tetragonal ZrO₂ to be the only crystalline phase. Upon increasing the deposition temperature to 450 °C, a mixture of tetragonal and monoclinic modifications was formed with morphology made up of interwoven elongated grains. At higher temperatures (550 and 650 °C), pure monoclinic phase was obtained with facetted grains and developed texture.     

Tailored vapor-phase growth of Cu(x)O-TiO2 (x = 1, 2) nanomaterials decorated with Au particles

We report on the fabrication of Cu(x)O-TiO(2) (x = 1, 2) nanomaterials by an unprecedented vapor-phase approach. The adopted strategy involves the growth of porous Cu(x)O matrices by means of chemical vapor deposition (CVD), followed by the controlled dispersion of TiO(2) nanoparticles. The syntheses are performed on Si(100) substrates at temperatures of 400-550 °C under wet oxygen atmospheres, adopting Cu(hfa)(2)·TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N',N'-tetramethylethylenediamine) and Ti(O-(i)Pr)(2)(dpm)(2) (O-(i)Pr = isopropoxy; dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate) as copper and titanium precursors, respectively. Subsequently, finely dispersed gold nanoparticles are introduced in the as-prepared systems via radio frequency (RF)-sputtering under mild conditions. The synthesis process results in the formation of systems with chemical composition and nano-organization strongly dependent on the nature of the initial Cu(x)O matrix and on the deposited TiO(2) amount. The decoration with low-size gold clusters paves the way to the engineering of hierarchically organized nanomaterials.     

Synthesis and crystal structures of dichlorocyclopentadienyl β-diketonate titanium complexes

Complexes of acetylacetonatodichlorocyclopentadienyltitanium(IV) (1) and dichlorocyclopentadienyl(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium(IV) (2) have been prepared and their crystal structures determined by X-ray diffraction methods. Complex 1 crystallizes in space group P2₁/m with a?=?7.1893(10), b?=?11.7680(17), c?=?7.6129(11) Å, β?=?109.901(12)°; complex 2 crystallizes in space group P2₁/n with a?=?10.065(2), b?=?16.322(3), c?=?12.219(2) Å, β?=?110.99(3)°. The molecular structures of 1 and 2 can be described as square-based pyramidal, with the centroid of the C₅H₅ ring occupying the apical site and the bidentate β-diketonate and two chloride ligands occupying the basal positions. The average distances between titanium and oxygen atoms are 1.991(2) and 1.967(3) Å in compounds 1 and 2, respectively.     

Microstructure and ionic conductivity of lithium-aluminum titanophosphate

Synthesis from aqueous peroxide solutions provides lithium-aluminum titanophosphate Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) with particles of submicron size and conductivity of (4–5) × 10^?4 S/cm at the room temperature. LATP were characterized using the methods of XRD, DTA/TG, measurement of specific surface area, ionic and electronic conductivity. According to XRD, a single-phase crystalline product with the specific surface area of 8.2 m²/g is formed as a result of precursor sintering at 700°C (the average particle size of electrolyte was 250 nm). Sizes of coherent-scattering region were calculated on the basis of the values of intrinsic broadening of diffraction maximums. Analysis of broadening of diffraction maximums indicates that the size of primary LATP crystallites after sintering at 700°C was 90 nm according to peak (113) (2θ = 24.5°) and 110 nm according to peak (104) (2θ = 20.9°). The synthesized submicron LATP powders are suitable for formation of solid electrolyte films using the method of aerosol deposition.     

Investigations into the preparation of sila-β-diketones via 2-trimethylsilyl-1,3-dithianes: structural characterization of a second polymorph of bis(2,2,6,6-tetramethyl-2-sila-3,5-heptanedionato)copper(II)

The sila-β-diketone, 2,2,6,6-tetramethyl-2-silaheptane-3,5-dione (tmshdH), was synthesized by the condensation of the anion of 2-trimethylsilyl-1,3-dithiane with 1-bromo-3,3-dimethylbutan-2-one, followed by unmasking of the latent carbonyl moiety with HgO/HgCl₂. A monoclinic polymorph of the known copper(II) complex, Cu(tmshd)₂, was crystallized and studied by X-ray diffraction methods and found to be disordered like the orthorhombic one. Attempts to synthesize the disilylated β-diketone, 2,2,6,6-tetramethyl-2,6-disilaheptane-3,5-dione and monosilylated 4,4-dimethyl-4-sila-3-oxo-pentanal using the dithiane method were not successful. However, the 1,3-dithianyl precursors, along with the impurity 2,2^′-bis(trimethylsilyl)-2,2^′-bi-1,3-dithiane, were studied crystallographically. Large stereoelectronic and steric effects on the solid-state bonding parameters were observed for these molecules.