Proton-Coupled Reduction of N2 Facilitated by Molecular Fe Complexes

The activation of Fe-coordinated N₂ via the formal addition of hydrogen atom equivalents is explored in this thesis. These reactions may occur in nitrogenase enzymes during the biological conversion of N₂ to NH₃. To understand these reactions, the N₂ reactivity of a series of molecular Fe(N₂) platforms is investigated. A trigonal pyramidal, carbon-ligated Fe^I complex was prepared that displays a similar geometry to that of the resting state 'belt' Fe atoms of nitrogenase. Upon reduction, this species was shown to coordinate N₂, concomitant with significant weakening of the C-Fe interaction. This hemilability of the axial ligand may play a critical role in mediating the interconversion of Fe(N_xH_y) species during N₂ conversion to NH₃. In fact, a trigonal pyramidal borane-ligated Fe complex was shown to catalyze this transformation, generating up to 8.49 equivalents of NH₃. To shed light on the mechanistic details of this reaction, protonation of a borane-ligated Fe(N₂) complex was investigated and found to give rise to a mixture of species that contains an iron hydrazido(2-) [Fe(NNH₂)] complex. The identification of this species is suggestive of an early N-N bond cleavage event en route to NH₃ production, but the highly-reactive nature of this complex frustrated direct attempts to probe this possibility. A structurally-analogous silyl-ligated Fe(N₂) complex was found to react productively with hydrogen atom equivalents, giving rise to an isolable Fe(NNH₂) species. Spectroscopic and crystallographic studies benefited from the enhanced stability of this complex relative to the borane analogue. One-electron reduction of this species initiates a spontaneous disproportionation reaction with an iron hydrazine [Fe(NH₂NH₂)] complex as the predominant reaction product. This transformation provides support for an Fe-mediated N₂ activation mechanism that proceeds via a late N-N bond cleavage. In hopes of gaining more fundamental insight into these reactions, a series of Fe(CN) complexes were prepared and reacted with hydrogen-atom equivalents. Significant quantities of CH₄ and NH₃ are generated in these reactions as a result of complete C-N bond activation. A series of Fe(CNH_x) were found to be exceptionally stable and may be intermediates in these reactions. The stability of these compounds permitted collection of thermodynamic parameters pertinent to the unique N-H bonds. This data is comparatively discussed with the theoretically-predicted data of the N₂-derived Fe(NNH_x) species. Exceptionally-weak N-H bond enthalpies are found for many of these compounds, and sheds light on their short-lived nature and tendency to evolve H₂. As a whole, these works both establish and provide a means to understand Fe-mediated N₂ activation via the addition of hydrogen atom equivalents.

Deposición de carbono en las superficies de películas delgadas de Fe sumergidas en tolueno en condiciones ambientales

Las nanoestructuras han sido muy estudiadas debido a su importancia en aplicaciones tecnológicas y biomédicas, como por ejemplo el recubrimiento de los sensores y biosensores. Estas necesitan ser recubiertas para su protección y/o funcionalización. Un estudio sobre las superficies de nanopartículas magnéticas y esféricas (MNPs) de Fe y Ni reveló que el tolueno actúa como catalizador de reacciones de condensación de los componentes aromáticos formando estructuras gigantes, policíclicas e irregulares, creando así una especie de recubrimiento de carbono. También se ha estudiado la posibilidad de formar recubrimientos con carbono en películas de hierro y permalloy (FeNi) en tiempos largos de tratamiento de 1 año. En el presente trabajo, debido a los resultados anteriores para las películas delgadas de hierro, se ha estudiado el desarrollo del proceso de deposición del grafeno defectuoso a temperatura ambiente, sobre las superficies de las películas delgadas de hierro en periodos de entre unos días hasta medio año aproximadamente. Se ha hecho un estudio en función del tiempo de inmersión en tolueno de las propiedades estructurales y magnéticas de las películas de hierro depositadas sobre vidrio. Las películas de hierro han sido preparadas por el método de pulverización catódica y después sumergidas en tolueno. Las técnicas utilizadas para la caracterización estructural han sido, la difracción de Rayos-X, los estudios de microscopia electrónica de barrido (SEM) y la perfilómetría. La caracterización magnética se ha hecho con un magnetómetro de Kerr (MOKE) y un magnetómetro vibrante (VSM). Las muestras cristalizaban en el sistema cúbico FCC del grupo espacial Fm-3m, con parámetro de celda de 3.5922Ǻ. El tamaño de dominio coherente para los índices de Miller (110) ha ido aumentando a lo largo del tratamiento. Para el índice de Miller (211) el tamaño de dominio coherente ha disminuido. Este comportamiento se explica tendiendo en cuenta el modelo propuesto en la literatura científica del proceso de formación de las estructuras de grafeno defectuoso. El análisis de las imágenes de SEM y los correspondientes datos de la emisión de Rayos-X han confirmado la presencia del carbono en la superficie. La cantidad del carbono en la superficie de las películas de hierro aumenta con el incremento del tiempo de inmersión en tolueno. Ha sido posible detectar la presencia del carbono en la superficie después de 9 días de inmersión (por lo tanto, el proceso de las estructuras policíclicas e irregulares es relativamente rápido). La deposición del carbono no resulta en una formación de estructura uniforme, así que cuanto más largo es el tratamiento, más complicadas son las estructuras. Como resultado del tratamiento superficial durante aproximadamente medio año, se observa un aumento de rugosidad de un micrómetro aproximadamente. La diferencia entre las medidas de MOKE y VSM para el campo coercitivo y la remanencia, se explica teniendo en cuenta el proceso de oxidación de la superficie y la interacción de algunas partes de la película de hierro con el tolueno, que pueden causar la relajación de las tensiones. La imanación de saturación obtenida para las películas después del tiempo de tratamiento de 135 días es de 192 emu por gramo. La disminución de la imanación de saturación es debida a la oxidación de las películas por el contacto con la atmósfera y el tolueno. En un cálculo aproximado se ha llegado a la conclusión que dicha capa tiene un espesor de 50 nm, repartida en dos capas de 25 nm. De todo lo anterior y de la base de análisis de las propiedades estructurales y magnéticas de las películas delgadas de hierro sumergidas en tolueno para hacer el tratamiento superficial a temperatura ambiente, se concluye, que las estructuras policíclicas e irregulares de grafeno defectuoso se forman relativamente rápido. El tratamiento con el tolueno no causa muchos cambios en la estructura y en las propiedades magnéticas, se trata de procesos superficiales. La modificación in situ de películas de hierro en tolueno, puede ser candidato a método de protección y funcionalización de los sensores magnéticos.

I. Anisotropy and crystal structure of ferromagnetic thin films. II. Investigations into magnetic microstructure by Lorentz microscopy

The induced magnetic uniaxial anisotropy of Ni-Fe alloy films has been shown to be related to the crystal structure of the film. By use of electron diffraction, the crystal structure or vacuum-deposited films was determined over the composition range 5% to 85% Ni, with substrate temperature during deposition at various temperatures in the range 25° to 500° C. The phase diagram determined in this way has boundaries which are in fair agreement with the equilibrium boundaries for bulk material above 400°C. The (α+ ɤ) mixture phase disappears below 100°C.

The measurement of uniaxial anisotropy field for 25% Ni-Fe alloy films deposited at temperatures in the range -80°C to 375°C has been carried out. Comparison of the crystal structure phase diagram with the present data and those published by Wilts indicates that the anisotropy is strongly sensitive to crystal structure. Others have proposed pair ordering as an important source of anisotropy because of an apparent peak in the anisotropy energy at about 50% Ni composition. The present work shows no such peak, and leads to the conclusion that pair ordering cannot be a dominant contributor.

Width of the 180° domain wall in 76% Ni-Fe alloy films as a function of film thickness up to 1800 Å was measured using the defocused mode of Lorentz microscopy. For the thinner films, the measured wall widths are in good agreement with earlier data obtained by Fuchs. For films thicker than 800 Å, the wall width increases with film thickness to about 9000 Å at 1800 Å film thickness. Similar measurements for polycrystalline Co films with thickness from 200 to 1500 Å have been made. The wall width increases from 3000 Å at 400 Å film thickness to about 6000 Å at 1500 Å film thickness. The wall widths for Ni-Fe and Co films are much greater than predicted by present theories. The validity of the classical determination of wall width is discussed, and the comparison of the present data with theoretical results is given.

Finally, an experimental study of ripple by Lorentz microscopy in Ni-Fe alloy films has been carried out. The following should be noted: (1) the only practical way to determine experimentally a meaningful wavelength is to find a well-defined ripple periodicity by visual inspection of a photomicrograph. (2) The average wavelength is of the order of 1µ. This value is in reasonable agreement with the main wavelength predicted by the theories developed by others. The dependence of wavelength on substrate deposition temperature, alloy composition and the external magnetic field has been also studied and the results are compared with theoretical predictions. (3) The experimental fact that the ripple structure could not be observed in completely epitaxial films gives confirmation that the ripple results from the randomness of crystallite orientation. Furthermore, the experimental observation that the ripple disappeared in the range 71 and 75% Ni supports the theory that the ripple amplitude is directly dependent on the crystalline anisotropy. An attempt to experimentally determine the order of magnitude of the ripple angle was carried out. The measured angle was about 0.02 rad. The discrepancy between the experimental data and the theoretical prediction is serious. The accurate experimental determination of ripple angle is an unsolved problem.

Spin wave resonance in ferromagnetic films

The objective of this investigation has been a theoretical and experimental understanding of ferromagnetic resonance phenomena in ferromagnetic thin films, and a consequent understanding of several important physical properties of these films. Significant results have been obtained by ferromagnetic resonance, hysteresis, torque magnetometer, He ion backscattering, and X-ray fluorescence measurements for nickel-iron alloy films.

Taking into account all relevant magnetic fields, including the applied, demagnetizing, effective anisotropy and exchange fields, the spin wave resonance condition applicable to the thin film geometry is presented. On the basis of the simple exchange interaction model it is concluded that the normal resonance modes of an ideal film are expected to be unpinned. The possibility of nonideality near the surface of a real film was considered by means of surface anisotropy field, inhomogeneity in demagnetizing field and inhomogeneity of magnetization models. Numerical results obtained for reasonable parameters in all cases show that they negligibly perturb the resonance fields and the higher order mode shapes from those of the unpinned modes of ideal films for thicknesses greater than 1000 Å. On the other hand for films thinner than 1000 Å the resonance field deviations can be significant even though the modes are very nearly unpinned. A previously unnoticed but important feature of all three models is that the interpretation of the first resonance mode as the uniform mode of an ideal film allows an accurate measurement of the average effective demagnetizing field over the film volume. Furthermore, it is demonstrated that it is possible to choose parameters which give indistinguishable predictions for all three models, making it difficult to uniquely ascertain the source of spin pinning in real films from resonance measurements alone.

Spin wave resonance measurements of 81% Ni-19% Fe coevaporated films 30 to 9000 Å thick, at frequencies from 1 to 8 GHz, at room temperature, and with the static magnetic field parallel and perpendicular to the film plane have been performed. A self-consistent analysis of the results for films thicker than 1000 Å, in which multiple excitations can be observed, shows for the first time that a unique value of exchange constant A can only be obtained by the use of unpinned mode assignments. This evidence and the resonance behavior of films thinner than 1000 Å strongly imply that the magnetization at the surfaces of permalloy films is very weakly pinned. However, resonance measurements alone cannot determine whether this pinning is due to a surface anisotropy, an inhomogeneous demagnetizing field or an inhomogeneous magnetization. The above analysis yields a value of 4πM=10,100 Oe and A = (1.03 ± .05) x 10^-6 erg/cm for this alloy. The ability to obtain a unique value of A suggests that spin wave resonance can be used to accurately characterize the exchange interaction in a ferromagnet.

In an effort to resolve the ambiguity of the source of pinning of the magnetization, a correlation of the ratio of magnetic moment and X-ray film thickness with the value of effective demagnetizing field 4πNM as determined from resonance, for films 45 to 300 Å has been performed. The remarkable agreement of both quantities and a comparison with the predictions of five distinct models, strongly imply that the thickness dependence of both quantities is related to a thickness dependent average saturation magnetization, which is far below 10,100 Oe for very thin films. However, a series of complementary experiments shows that this large decrease of average saturation magnetization cannot be simply explained by either oxidation or interdiffusion processes. It can only be satisfactorily explained by an intrinsic decrease of the average saturation magnetization for very thin films, an effect which cannot be justified by any simple physical considerations.

Recognizing that this decrease of average saturation magnetization could be due to an oxidation process, a correlation of resonance measurements, He ion backscattering, X-ray fluorescence and torque magnetometer measurements, for films 40 to 3500 Å thick has been performed. On basis of these measurements it is unambiguously established that the oxide layer on the surface of purposefully oxidized 81% Ni-19% Fe evaporated films is predominantly Fe-oxide, and that in the oxidation process Fe atoms are removed from the bulk of the film to depths of thousands of angstroms. Extrapolation of results for pure Fe films indicates that the oxide is most likely α-Fe₂O₃. These conclusions are in agreement with results from old metallurgical studies of high temperature oxidation of bulk Fe and Ni-Fe alloys. However, X-ray fluorescence results for films oxidized at room temperature, show that although the preferential oxidation of Fe also takes place in these films, the extent of this process is by far too small to explain the large variation of their average saturation magnetization with film thickness.

Effects of magnetostriction and superlattice formation in ferromagnetic thin films

The contribution to the magnetic uniaxial perpendicular anisotropy which arises from substrate constraint through magnetostrictive effects has been measured in Ni-Fe and Ni-Co thin films evaporated on substrates at room temperature. This was accomplished by measuring the perpendicular anisotropy before and after removal of the film from the substrate. Data are given for the fcc crystal structure regions of both alloy systems, but data for Ni-Co include compositions with less than 60% Ni which have a small percentage of the hcp phase mixed with the fcc phase. The constraint contribution to the perpendicular anisotropy correlates well with the value of the bulk magnetostriction constant using the equation ∆K_˔=3/2λ_sσ. Measured values of isotropic stress for films thicker than 600 Å were 1.6 x 10¹⁰ dyn/cm². In films less than 600 Å thick the isotropic stress decreased with decreasing thickness. After removal of the films from the substrates, the measured perpendicular anisotropy deviated from the expected geometrical shape anisotropy near pure Ni in both alloys. This indicates that additional significant sources of anisotropy exist at these compositions.

The effect of substrate constraint on the crystalline anisotropy K₁ of Ni-Fe epitaxial films has been studied by use of a film removal technique, which involves the evaporation of an epitaxial layer of LiF on MgO, the epitaxial growth of the metallic film on the LiF, and the stripping of the film with water soluble tape. Films ranging in composition from 50% to 100% Ni have been studied. For compositions below 90% Ni the experimental values agree reasonably well with the first order theoretical prediction, ∆K₁=[-9/4(C₁₁-C₁₂)λ² 100+9/2C₄₄λ²111].

In order to compare the magnetic properties of epitaxial thin films more completely with the properties of bulk single crystals, Ni-Fe films ranging in composition from 60% to 90% Ni, which were evaporated epitaxially on (100) MgO substrates, have been subsequently annealed at 400°C in a vacuum of less than 10^-7 Torr to form the ordered Ni₃Fe structure near the 75% composition. This ordered structure has been confirmed by electron diffraction.

The saturation magnetization at Ni₃Fe increased about 6% with ordering which is in good agreement with previous bulk data. Measurements of the magnetocrystalline anisotropy energy K₁ for the epitaxial films show the same large changes with ordering as observed in bulk single crystal samples. In the (001) plane the magnetostriction constants ^λ100, ^λ111 are directly related to the induced anisotropy due to a uniform uniaxial strain in the [100] and [110] directions respectively. Assuming that the elastic constants of a film are the same as in bulk material and are unchanged by ordering, the changes in strain sensitivity with ordering for the epitaxial films are found to be in good agreement with values predicted from bulk data. The exchange constant A as measured by ferromagnetic resonance has been measured at the Ni₃Fe composition and found to increase 25% with ordering. This seems to indicate a significant increase in the Curie temperature which has only been inferred indirectly for bulk material.

Write-once medium with Fe-Doped BiOx thin films for blue laser recording

Fe:BiOx films are fabricated on K9 glass substrates by rf-magnetron sputtering of a BiFeO target under argon atmosphere with increasing sputtering power from 80 to 200 W at room temperature. It is found that the thin films grown at the sputtering power of 160W can be formed at an appropriate deposition rate and have an improved surface morphology. The XPS result reveals that the films investigated are comprised of Bi, Fe and O elements. A typical XRD pattern shows that no phase transition occurs in the films up to 400 degrees C. The results of the blue laser recording test demonstrate that the Fe:BiOx films have good writing sensitivity for blue laser beam (406.7 nm) and good stability after reading 10000 times. The recording marks of 200nm or less are obtained. These results indicate that the introduction of Fe into BiOx films can reduce the mark size and improve the stability of the films.

Low-Power Super-resolution Readout with Antimony Bismuth Alloy Film as Mask layer

Sb-Bi alloy films are proposed as a new kind of super-resolution mask layer with low readout threshold power. Using the Sb-Bi alloy film as a mask layer and SiN as a protective layer in a read-only memory disc, the super-resolution pits with diameters of 380 nm are read out by a dynamic setup, the laser wavelength is 780 nm and the numerical aperture of pickup lens is 0.45. The effects of the Sb-Bi thin film thickness, laser readout power and disc rotating velocity on the readout signal are investigated. The results show that the threshold laser power of super-resolution readout of the Sb-Bi mask layer is about 0.5 mW, and the corresponding carrier-to-noise ratio is about 20 dB at the film thickness of 50 nm. The super-resolution mechanism of the Sb-Bi alloy mask layer is discussed based on its temperature dependence of reflection.