Alloy films composition

Some other points worth noting in connection with alloy film composition are The loss in weight from separate sources is a guide to mean composition but not an exact measure because the sources become themselves alloyed. It is often important to determine the composition of the actual specimen on which other characterizing measurements have been made. If there is confidence that the films are reasonably homogeneous, lattice constants determined by X-ray diffraction can be used to examine the uniformity of composition (69), but the change of lattice constant with composition may be inconveniently small. 

Intermetallic compound films, alloy films. Composite films etc. 

Takahashi et al. [220] first reported the formation of Bi-Te alloy films with varying chemical composition by means of cathodic electrodeposition from aqueous nitric acid solutions (pH 1.0-0.7) containing Bi(N03)3 and Te02. The electrodeposition took place on Ti sheets at room temperature under diffusion-limited conditions for both components. In a subsequent work [221], it was noted that the use of the Bi-EDTA complex in the electrolyte would improve the results, since Bi " is easily converted into the hydrolysis product, Bi(OH)3, a hydrous polymer, thus impairing the reproducibility of electrodeposition. The as-produced films were found to consist of mixtures of Te and several Bi-Te alloy compounds, such as Bi2Tc3, Bi2+xTe3 x, Bi Tee, and BiTe. Preparation of both n- and p-type Bi2Te3 was reported in this and related works [222]. 

It was assumed that the nickel crystallites are rapidly enveloped in a skin of a copper-rich alloy, from which diffusion towards the center of each crystallite then takes place. If xx and x2 are the atomic fractions of copper in the two equilibrium phases and x is the atomic fraction of copper in the alloy film under consideration, then the crystallites in the annealed film may have a variety of forms. Solid solutions occur at either end of the composition range but the values of Xi and x2 at 200°C are <0.1 and 0.8. Hence, over much of the composition range (i.e., where x lies between X and xi), the Cu-Ni films should consist of crystallites with a kernel which is almost pure nickel (composition xi) enveloped in a skin of a copper-rich alloy (composition x2). Eventually, when x is only slightly larger than Xi, the alloy skin does not completely surround the nickel crystallites small patches of alloy (x2) and almost pure nickel ( ci) are both exposed. 

Finally, with respect to successive evaporation, Pd-Rh films used for CO oxidation (34) are an example of preparing alloy films where a miscibility gap exists and interdiffusion rates are slow. These Pd-Rh films were prepared by depositing layers of palladium and rhodium at 0°C, followed by annealing in 50 Torr hydrogen at 400°C for 21 hr. The apparent surface compositions, evaluated from the CO oxidation rate as described in Section IV, and information on film structure obtained by X-ray diffraction (XRD) are recorded in Table II. 

Evaporation from an alloy source largely avoids the problems of source geometry which may be encountered in simultaneous evaporation from separate pure metal sources. The success of the method depends on the relative vapor pressures of the component metals in the alloy source because one component metal with a substantially higher vapor pressure will evaporate preferentially. The alloy film will then be rich in the more volatile component compared with the composition of the source and may also be stratified into layers of different composition. Evaporation from alloy sources is discussed in detail by Dushman (43) and Holland (44) on the basis of Raoult s law, and it is possible to predict which metal pairs... 

According to the data in Table III, the value of the ratio P)Mm is approximately the same for the metals Au, Fe, Co, Ni, and Pd. Binary alloys formed from any pair of these metals can therefore be expected to evaporate without substantial fractionation. On the other hand, films evaporated from Ag-Pd and Cu-Ni alloys can be expected to be enriched in Ag and Cu, respectively. These predictions are largely confirmed by experiment. For example, the composition of Pd-Au films was found to be the same as the wires which were evaporated (46), but in the case of Pd-Ag, evaporation of a 30% Ag-Pd alloy ware yielded a 50% Ag-Pd alloy film (47)- Alexander and Russell evaporated a number of alloys from pellets in the reaction vessel as shown in Fig. 5 (48) The alloy pellet was placed in a small quartz cup with its surface equidistant from the hemispherical top of the reaction vessel. The pellet was evaporated by... 

Hence, the decision to use a heated substrate with simultaneous evaporation of the component metals as an aid to homogenization requires consideration of whether or not it might have an adverse effect, i.e., causing preferential nucleation of one component, which interdiffusion may not be able to remedy. It was believed (60) that in preparing Pd-Rh alloys by simultaneous deposition on a substrate at 400°C, rhodium nucleated preferentially and that crystallites grew by the addition of palladium (and rhodium) atoms. The diffusion of palladium atoms into this kernel formed a phase with 88 =t 5% Rh (phase II). The outer shell of the crystallite, phase I, was in effect a solid solution deficient in rhodium compared with the overall film composition, and the Rh content of phase I therefore increased as the Rh flux was increased. 

The characterization of evaporated alloy films can be carried out at widely different levels of sophistication. At the very least, it is necessary to determine the bulk composition, probably after the film has been used for an adsorption or catalytic experiment. Then various techniques can be applied, e.g., X-ray diffraction, electron diffraction, and electron microscopy, to investigate the homogeneity or morphology of the film. The measurement of surface area by chemisorption presents special problems compared with the pure metals. Finally, there is the question of the surface composition (as distinct from the bulk or overall composition), and a brief account is given of techniques such as Auger electron spectroscopy which might be applied to alloy films. 

With due regard to the lateral variations in composition which can arise as a consequence of source geometry and positioning (discussed in Section II), it is vise to analyze the alloy film at a number of representative points. For example, if a catalytic reaction was carried out over an alloy film deposited inside a spherical vessel maintained at a constant temperature over its entire area, then the mean alloy composition (and the uniformity of composition) is required. A convenient procedure is to cut glass reaction vessels carefully into pieces at the end of the experiment and to determine the composition by X-ray fluorescence analysis of a number of representative pieces. Compositions of Pd-Ag alloy films (40) determined at 12 representative parts of a spherical vessel from the intensities of the AgK 12 and PdKau fluorescent X-ray emissions are shown in Table V mean compositions are listed in the first column. (The Pd and Ag sources were separate short concentric spirals.) In other applications of evaporated alloy films to adsorption and catalytic studies, as good or better uniformity of composition was achieved. Analyses of five sections of a cylindrical... 

Figure 7 (a, b, d, and e) shows transmission electron micrographs from Pd-Ag films of comparable weight, prepared and annealed at 400°C, and used once to catalyze the oxidation of ethylene at 240°C (40). The structure of this series of alloy films varied consistently with composition. Silver-rich films (e.g., Fig. 7a, 13% Pd) showed extensive coalescence of the crystallites, while at the other end of the composition range (e.g., Fig. 7e,...

In earlier work with pure metals, it was generally accepted that the area of films deposited at, say, 0°C was proportional to their weight (with the exception of group IB and low melting-point metals). Information was available on the surface areas of films of Ni, Pt, Pd, Rh, etc. (71), and hence absolute reaction rates could be calculated. It would be a considerable undertaking to establish similar data for alloy systems, bearing in mind that various compositions would have to be examined and also a method for preparing exact compositions would be required. However, for sintered alloy films, approximate methods can be proposed. 

Sintered alloy films of reasonable thickness, e.g., opaque, mirrorlike films, can provide an adequate number of diffraction peaks for the determination of a lattice constant of adequate accuracy for present purposes. Thus, the apparent lattice constants calculated from the centroids of individual diffraction peaks, observed with a counter-diffractometer, may be extrapolated to 0 = 90°, using the Nelson-Riley function to give a value of a0. There has been some discussion about differences in lattice constants for thin films compared with bulk metals values of ao for pure silver films ( 1000 A nominal thickness) were found (74) to be consistently small compared with bulk silver but only by 0.05%. For alloy films a similar deviation would correspond to a variation of 1% in the composition of the alloy. Larger deviations have been reported for very thin films, e.g., —0.2% in copper films of 100 A nominal thickness (75).]... 

It has indeed been found (83a) that the work function of Ag-Pd alloy films equilibrated at 300°C only changes from 4.38 eV at pure silver to 4.50 eV at 86% Pd (increasing to 5.22 at pure Pd). It was proposed (83a) that this work function pattern is a consequence of surface enrichment by silver and so confirmation of the theory awaits further work function measurements on alloy surfaces for which compositions have been determined by, say, Auger electron spectroscopy. 

Further progress in the study of the Cu-Ni system awaited the preparation and careful characterization of alloy films of known bulk and surface composition. The essential step was taken by Sachtler and his co-workers 28, 88, 114) who prepared Cu-Ni alloy films by successive evaporation of the component metals in UHV. After evaporation the films were homogenized by heating in vacuum at 200°C. The bulk composition of the alloys was derived from X-ray diffraction, and the photoelectric work function of the films was also measured. A thermodynamic analysis, summarized by Fig. 13, indicated that alloy films sintered at 200°C should consist, at equilibrium, of two phases, viz., phase I containing 80% Cu and phase II containing 2% Cu. Evidence was presented that alloys within the... 

Fig. 14. Adsorption ratio a as a function of composition for Cu-Ni alloy films Ni deposited on Cu (O), Cu deposited on Ni (A), both sintered at 200°C Cu deposited on Ni and sintered at 300°C (V) (70).

Copper-nickel alloy films similarly deposited at high substrate temperatures and annealed in either hydrogen or deuterium were used to study the hydrogenation of buta-1,3-diene (119) and the exchange of cyclopentane with deuterium (120). Rates of buta-1,3-diene hydrogenation as a function of alloy composition resemble the pattern for butene-1 hy-... 

Fig. 19. Rate of H2-D2 exchange (at -40°C) divided by nickel content as a function of composition for Cu-Ni alloy films deposited at 300°C and sintered at 400°C 84).

Gold forms a continuous series of solid solutions with palladium, and there is no evidence for the existence of a miscibility gap. Also, the catalytic properties of the component metals are very different, and for these reasons the Pd-Au alloys have been popular in studies of the electronic factor in catalysis. The well-known paper by Couper and Eley (127) remains the most clearly defined example of a correlation between catalytic activity and the filling of d-band vacancies. The apparent activation energy for the ortho-parahydrogen conversion over Pd-Au wires wras constant on Pd and the Pd-rich alloys, but increased abruptly at 60% Au, at which composition d-band vacancies were considered to be just filled. Subsequently, Eley, with various collaborators, has studied a number of other reactions over the same alloy wires, e.g., formic acid decomposition 128), CO oxidation 129), and N20 decomposition ISO). These results, and the extent to which they support the d-band theory, have been reviewed by Eley (1). We shall confine our attention here to the chemisorption of oxygen and the decomposition of formic acid, winch have been studied on Pd-Au alloy films. 

The decomposition of formic acid over evaporated Pd-Au alloy films has been studied by Clarke and Rafter (69) the same reaction on Pd-Au alloy wires was studied by Eley and Luetic (128). The alloy films were prepared in a conventional high vacuum system by simultaneous evaporation of the component metals from tungsten hairpins. The alloy films were characterized by X-ray diffraction and electron microscopy. The X-ray diffractometer peaks were analyzed by a method first used by Moss and Thomas (SO). It was found that alloys deposited at a substrate temperature of 450°C followed by annealing for one hour at the same temperature were substantially homogeneous. Electron microscopy revealed that all compositions were subject to preferred orientation (Section III). 

Fig. 27. C2H4 oxidation on Pd-Rh alloy films at 150°C as a function of bulk composition (73).

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