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By Richard I. Petritz

A brief review of today's processing of integvated circuits is given. The major trends in the development of advanced integvated electronics are identified as 1) the broadening of the integvated circuit concept to a large class of circuit function, 2) the processing of more complex circuits within relatively small chips of silicon, and 3) the processing of very large electronic functions on complete slices of silicon. This latter trend, called array technology, is then developed in detail. Emphasis is given to defining the key tech-nological problems. Current progress being made is illustrated. THIS paper will endeavor to identify the major trends in advanced integrated electronics technology. One of these, array technology, will be developed in some detail. The array technology discussion will identify the key problem areas. Since it is the scope of the entire meeting' to present specific progress in the science and technology of integrated electronics, we shall indicate general directions being explored rather than discuss comprehensively solutions to the problems. In order to set the stage for the discussion of future trends in integrated-electronics technology, let us briefly compare the processes by which circuits are fabricated through discrete-device technology with that of integrated circuits technology. The reader is referred to the December 1964 issue of Proceedings of IEEE2 for a comprehensive review of integrated electronics. The article3 by Jay Lathrop is an excellent discussion of integrated-circuits technology. A discussion of the history of semiconductor technology is contained in Ref. 4. A) Current Status of Integrated Electronics. Fig. 1 (top) shows the process by which circuits are constructed from discrete devices. Key points are: 1) Slices containing large numbers of transistors or diodes are processed separately. 2) The slices are scribed into small chips (on the order of 15 mils on a side is about as small as can be conveniently handled) each chip containing one transistor. 3) Each device is specified separately—circuit -function specs are derived largely from device specs. 4) Circuits are formed by connecting together the discrete devices. 5) The number of circuit connections required is approximately equal to the number of devices. 6) There are potentially many more discrete devices per inch2 of semiconductor—only our lack of ability to handle them in discrete form prevents us from going to several orders of magnitude higher density iin Fig. 1, 400,000 transistors are discussed at 1.5 mils on a side). The bottom part of Fig. 1 illustrates the integrated circuit process. Key points are: 1) On the same slice of silicon, transistors, diodes, and resistors are processed grouped to do a complete circuit function. 2) While still in slice form, the components are interconnected into circuit functions by an evaporation process, eliminating the need for separate interconnection steps later. Dramatic improvements in cost and reliability are realized. With a simple flash of metalization thousands of interconnections are reliably made. 3) The slices are scribed into chips which contain complete circuit functions. 4) The circuit functions are specified-not each component in the circuit. This important point was missed by some of the early opponents to integrated circuitry. They argued that, with device yields at x pct, integrated circuit yields would be pct, where n is the required number of devices to make a circuit. This argument leads to extremely low yields for integrated circuits. The fallacy of the argument is that in integrated circuits each device is not specified separately. Furthermore, since a device is forever integrated into a specific circuit function, it need meet only the requirements for that particular function. Discrete devices, on the other hand, are tightly specified so that they can be applied to a variety of circuit functions. 5) Extremely high packing densities are achievable because one need only make the basic devices as large as the circuit demands. Their size is not dictated by handling requirements. A current example

Jan 1, 1967

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By Richard H. Bube

Photoelectronic radiation detectors may be conveniently classified as homogeneous intrinsic, homogeneom extrinsic, or junction type. Highly photosensitive homogeneous intrinsic photodetectors may be prepared from a number of different II-VI, III-V, or IV materials. Such materials require the presence of specific imperfections that can act as sensitizing centers to provide long majority carrier lifetime. Homogeneous extrinsic photodetectors are of interest primarity for infrared detection, and consist principully of germaniuim and silicon with suitable inpurities. A vaviety of junction photodetectors exist, with silicon us the most common material for them all. The following extrema in performance are found: 1) highest photoconductivity gain in homogeneous intrinsic photodetectors; 2) smallest response time (highest frequency response) in p-i-n junctions; 3) largest gain-bandwidth product in avalanche diodes. ALTHOUGH the total number of materials exhibiting photoconductivity effects is very large, only a relatively few of these have appropriate properties for a practical photoelectronic radiation detector. In fact if one surveys the commercial detectors currently available, one finds that the field is dominated by some ten or fewer materials. These are summarized in Table 1 in terms of the other important variable in detector fabrication, the structure of the material, i.e., whether the material is used as a single crystal or in polycrystalline form, and whether the material is used as a homogeneous detector or whether the detector depends upon the existence of a junction or barrier in the material. The principal wavelength range for each type of material is also shown, together with an indication of the utilization of intrinsic or extrinsic excitation. For the purposes of the present comparison of various detectors, it will be convenient to discuss two main topics: homogeneous photodetectors and junction photodetectors. The performance of a photoelectronic radiation detector is measured in terms of two parameters: the photoconductivity gain, and the response time of the detector. A convenient figure-of-merit is given by the ratio of gain to response time, often called the gain-bandwidth product. The photoconductivity gain is a device parameter since it varies in many cases with the applied voltage and the detector geometry, and should be distinguished from the actual photosensitivity of the material involved. This photosensitivity can be conveniently given as the product of free carrier lifetime and mobility in the material. The photoconductivity gain is defined as the number of charge carriers which pass between the electrodes per second for each photon absorbed per second, where G is the photoconductivity gain, is the pho-tocurrent in amperes, e is the electronic charge in coulombs, and F is the total number of electron-hole pairs created in the photo conductor per second by the absorption of light. The gain may also be expressed as the ratio of the lifetime of a free carrier to the transit time for that carrier, i.e., the time required for the carrier to move between the electrodes. For a material in which one-carrier conductivity dominates, where T is the lifetime of a free carrier, ttr is the transit time for this carrier, p is the carrier mobil-ity, V is the applied voltage, and L is the electrode spacing. From Eq. [2] it follows that the photoconductivity gain is proportional to the photosensitivity of the material (tP), the proportionality constant being The photosensitivity of a material, and hence the photoconductivity gain of a device utilizing the material, depends on the lifetime of the free carriers as a critical parameter. In a homogeneous material this lifetime is determined by the nature of imperfections in the material, and in an inhomogeneous material the lifetime is determined by the specific junction structure. The speed of response, the other basic photodetec-tor parameter, is determined by factors quite similar to those important for photoconductivity gain. Imperfections are of primary importance in homogeneous materials, and the structure of the junction is a determining factor in junction devices. For infrared detectors it has become common to define another quantity designed to indicate directly how effective the detector is in distinguishing between a small photoconductivity signal and random noise due to the detector and its environment. The detectivity D* is given by

Jan 1, 1968

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum&apos; of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have&apos; any appreciable absorption in the short or long uv regions. When P0&apos;t3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.&apos;-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU&apos;3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total&apos; band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By Louis G. Bailey

This paper .reviews some of the key developments which have been made in the synthesis of the III-V compound semiconductors and the associated progress in obtaining high-quality material for device development. The history of the investigation of the semi-conducting properties of these materials has indicated the need for synthesis techniques capable of producing rnaterial of high chemical purity and physical perfection. The progress in the area is described, and the present status of quality of several compounds is discussed. In addition, recent studies of localized epitaxial deposition of GaAs into semi-insulating GaAs substvates for the development of arrays of devices ave reviewed. In conclusion, some important areas for future research and developrnent are discussed. INTEREST in III-V compounds as semiconductors dates back to the period 1950 to 1952, when Goryunova, Ioffe, and, in particular, Welker determined that 111-V compounds were structural analogs of the group IV elements carbon, silicon, germanium, and tin and that they were also semiconductors.&apos;-3 Since that time interest in the properties of these materials has ex- panded rapidly. During 1953 and 1954, the first reports of rectification, photoconductivity, and optical absorption in these materials came from several investigators. In 1955, recombination radiation from samples of GaAs, InP, and GaSb was reported by ~raunstein .&apos; This radiation was produced by injected minority carriers from point and large-area contacts. From 1955 to 1960, efforts increased on preparing large, pure specimens of these materials for the study of basic physical phenomena and device exploration. By 1960, materials preparation and the understanding of the physics of some of the materials had advanced to where some very interesting and potentially useful phenomena came under study. The first observation of electric-field-induced changes in the optical absorption edge (Franz -Keldysh effect) of 111-V compounds was reported for GaAs by Moss in 1961.&apos; In 1962 the study of recombination radiation advanced rapidly. Keyes and Quist6 and Pankove and Berkey-heiser7 reported high radiative efficientices obtained from recombination, and then the first injection electroluminescent lasers in GaAs were announced by Hall ef al.,&apos; by Nathan et al.,O and by Quist ef al.,&apos;O and in Ga(As, P) alloys by Holonyak and Bevacqua." Hil-sum has reviewed the early work leading to the first observations of laser action in GaAS." Recombination processes in GaAs, Gap, and the other 111-V com-

Jan 1, 1968

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"&apos; wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-&apos;sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-&apos; cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews&apos; have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77&apos;~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By I. J. Hegyi, J. J. Tietjen, H. Nelson, J. I. Pankove

The fabrication of p-n junctions in GaAsl-,P, alloys by a vapor-phase gowth technique has for the first tirne resulted in room-temperature injection lasers capable of operating over a broad range of wavelengths extending into the visible region of the spectrum. The shortest wavelength achieved to date is 6750A at room tetnperature. In addition, at 78°K the threshold current density values for these lasers are generally the lo~vest reported, and the emitted radiation extends to the lozc,est wavelength ever attained (6350A). With lasers fabricated from material containing 14 pct Gap, quanticm efficiencies of 26 pct and peak power outputs of 25 zu were obtained at room temperature. ALTHOUGH room-temperature operation of GaAs injection lasers has been well-documented,&apos;-5 the operation of GaAsl-,P, (x > 0) laser diodes has been restricted to relatively low temperatures.8-&apos;0 This has been previously attributed5, 7, 10-12 partially to the difficulty of preparing single-crystalline GaAsl-& alloys having a high degree of chemical homogeneity and purity. Also, with these materials it has been difficult to prepare high-quality, abrupt p-12 junctions by diffusion techniques; and, in turn, this has made it difficult to obtain optimum electrical properties for room-temperature operationL3 in the resulting laser diodes. As a result, GaAsl-,P, laser diodes have not been efficient enough to permit operation at room temperature. For example, using diffused structures, only a few diodes were obtained which could be operated even close to room temperature (255K)." Recently, a vapor-phase growth method of preparing epitaxial deposits of GaAsl - .P, alloys has been described,14 and the high-purity and homogeneity of these materials has been previously demonstrated. Of special significance, with this technique, n- or p -type doping can be initiated or discontinued at any time and at almost any rate during the crystal growth so that the donor and the acceptor concentrations can be easily controlled to obtain desired impurity profiles. This permits high-quality, abrupt p-TZ junctions to be vapor-phase grown entirely during the crystal growth process, so that diffusion or other p-n junction fabrication processes are unnecessary. After growth, the device does not have to be heated to elevated temperatures, which avoids the possible unwanted introduction and motion of both impurities and lattice defects. Using the vapor-phase growth method cited above, over 300 room-temperature injection lasers have been prepared from GaAsl-,P, alloys having compositions in the range of 0 5 x 5 0.41. These lasers have emitted cohe~ent radiation in the spectral range of 8350 to 6350A at 78°K or from 9000 to 6750A at room temperature. The threshold current densities of the best lasers are independent of the alloy composition over the range 0 < x < 0.2 and compare favorably with values for good GaAs lasers.&apos; MATERIAL PREPARATION Multilayer, epitaxial deposits of GaAsl-,P, alloys are prepared by a vapor-growth technique described elsewhere.14 With this technique, the individual layers which comprise the multilayer structure are prepared sequentially in the deposition apparatus without interrupting the crystal growth. The epitaxial layers are deposited on GaAs substrate surfaces oriented normal to the ( 100) direction. The substrate wafers employed in this study were usually doped with tellurium to an electron concentration of approximately 2 x 10" per cu cm. To avoid strains, the first 10 to 15 p of the deposited material is uniformly graded from pure GaAs to the specific GaAsl- ,P, alloy composition of interest. The GaAsl - ,P, alloy growth is then continued to form a layer of constant composition having a thickness in the range of 25 to 75 p. Both the graded region and the layer of constant composition are doped with selenium to an electron concentration of about 2 x 10" per cu cm. The p region of the diode is then incorporated in the crystal by abruptly changing the dopant concentrations in the vapor phase to facilitate doping with zinc. This layer has a hole concentration of approximately 3 X 1019 per cu cm and typically is 50 p thick. DEVICE FABRICATION In general, the GaAs substrate and the region of graded composition are removed. Ohmic contacts are made to the n-type side by tin evaporation and to the p-type side by an electrodeless nickel deposition. This is followed by an electrodeless deposition of gold on both sides. The crystal wafer is then cleaved along (110) planes and sawed into rectangular parallelepipeds. Typical dimensions are 100 by 300 for the junction area and 100 µ for the diode height. The diodes are either soldered to a copper stud or pressure-mounted in a copper clip. RESULTS AND DISCUSSION Approximately 400 laser diodes having compositions in the range of 0.41 have been prepared by the method described above. Each laser was routinely tested at liquid-nitrogen temperature. The lasers were operated with l-psec current pulses at a repetition rate of 60 pulses per sec. The parameters of greatest practical interest are the photon energy or wavelength of the laser output and the threshold current density. Fig. 1 shows the variation of photon energy with alloy composition at 78°K. The composition was determined from the lattice constant of the material obtained by X-ray back-reflection measurements. Although there

Jan 1, 1968

By Kurt Kennedy

A method is described by which three elements can be condensed simirltaneously on a common substrate in such a way that the composition varies with position on the substrate. Almost all possible combinations of three solid elements can be formed in a single evaporation. The three elements are heated by magnetically deflected electron beams. The alloys and cornpounds formed by this method generally correspond to those trade by other methods; however, many exceptions exist. Simple symmetric crystallographic phases tend to form in preference to more complex phases. The Nb-Sn. Cr-Fe-Nt, and other systems of alloys made by this method will be discussed. Phases that form very slowly, such as the o phase in Cr-Fe alloys, may be formed rapidly by this method when certain substrate temperatures are used. STUDYING all the mixtures and compounds of two or more elements by the preparation of individual samples forces the investigator to make sampling sufficiently close together so that the properties of the intermediate compositions can be inferred. A completely unknown system will require a dis c our aging ly large number of preparations in order to fully know all its properties. For the purpose of expediting this type of investigation, methods have been devised to prepare samples that have a continuous variation in composition over some predefined area. The code-position of two elements onto suitable substrates has been used to produce alloys or compounds that have variable compositions depending on their positions on the substrates Composition gradients have been formed by depositing a wedge-shaped layer of one element and then depositing a second wedge-shaped layer on top of it such that the total film thickness is kept constant. Concentration equilibrium perpendicular to the surface is then established by annealing.4 This paper describes a method for the simultaneous condensation of three volatile components on a substrate such that there is a regular variation of composition with position on the substrate. The arrangement of the evaporation sources and the substrate is shown schematically in Fig. 1. Materials to be evaporated are placed in three water-cooled crucibles located at the corners of a 10-in. equilateral triangle. Electron beams from cathodes located below the crucibles are bent 180 deg by magnetic fields and focused on the material to be evaporated. The cathodes are connected in parallel to a constant-current 12-kv power supply. The distribution of emission current from each cathode is controlled by filament temperature. When materials that sublime are to be evaporated, the electron beam is deflected by an auxiliary ac magnetic field so that the beam moves over the surface of the evaporating material rather than digging a hole in one spot. The substrate is a 10-in. triangle of 2-mil stainless steel or molybdenum which is stretched against a slightly curved heat sink by a frame as shown in Fig. 2. This frame and heat sink are located so that each corner is directly above an evaporation source. The heat sink has three radiant heaters at each corner that can be separately controlled permitting the

Jan 1, 1967

Jan 1, 1967

Jan 1, 1968

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnXTe have been grown from The melt under liquid B2O3 using the Czochralski technique. The PbTe-SnTe crystals were grown from near-stoichiometric melts and from melts with slight deviations from sloichiometry. Crystal growth rates ranging from 1 mm per hr to 1 cm per hr were employed, the latter being generally used. Several investigations were performed to characterize the single crystals grown In this study. The phase diagram of the PbTe-SnTe system was examined. X-ray analyses verified the single-crystal character of the crystals, and powder pattern lattice parameter determinations showed that Vegard&apos;s law was followed within the limits of the experimental error. The as-grown crystals were p-type with apparent carrier concentrations of -8 x 1018 to -8 x 1020 carriers per cu cm. Hall coefficients, resistivities, and carrier mobilities were determined as a function of composition. Dislocations were revealed by an electrolytic etch, and the crystals were found typically to contain 2 to 4 x 105 dislocations per sq cm. Microhardness measurements were performed; no maximum in the Vickers hardness us composition curve was seen. Mass spectrometry was used for impurity analyses, and the crystals were found to contain 1 to 2 x 1017 total p-type impurities per cubic centimeter. Distribution coefficients were calculated for the major impurities which were Na, Mg, Al, Si, Cl, and Zn. RECENTLY interest has been stimulated in the preparation and characterization of many alloys of the binary compound semiconductors. This interest is due primarily to the almost unlimited possibilities of adjusting the semiconducting characteristics of these materials by varying the alloy compositions. One alloy system which has been receiving extensive investigation is the PbTe-SnTe system, since these alloys show promise of being useful as emitters and detectors of electromagnetic radiation in the spectral range of 8 to 14 µ. This paper reports on the growth of PbTe-SnTe single crystals by the Czochralski technique and investigations of the general properties of these crystals. The phase diagram of the PbTe-SnTe system was investigated so that specific alloy compositions could be attained. I) CRYSTAL GROWTH The PbTe-SnTe single crystals were pulled from the melt using the Czochralski technique. Generally, the crystals were grown from near-stoichiometric melts, although special growth runs were made from both lead-rich and tellurium-rich melts. Growth of single crystals from up to 5 pct lead-rich melts presented no problems; however, melts with tellurium in excess of -1 pct caused volatilization problems which generally made crystal growth impossible. All melts were prepared from high-purity materials as follows: 1) lead— 6 N— Cominco (Cominco Products, Inc., Spokane, Wash.); 2) tin—5N—Cominco; and 3) tellurium— 5N+— American Smelting & Refining Co., Plainfield, N.J. No further purification of materials was undertaken in this study. The elements were reacted at -1000°C in a vacuum-sealed silica tube for a few hours, a gentle rocking action being used to ensure thorough reaction. The cast ingots were then transferred to a silica crucible for crystal growth. A schematic diagram of the growth apparatus is shown in Fig. 1. The Vycor tube is sealed at both ends by O-ring flanges so that a vacuum or a positive pressure may be maintained in the growth chamber. The pull rod and crucible may be rotated; all crystals produced in this study were grown with the crucible sta-

Jan 1, 1969

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.&apos; This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By L. R. Weisberg, E. A. Miller

Single-crystalline films of silicon of good quality were vacuum-deposited on sapphire. The improved crystallinity was achieved by the strict exclusion of oxygen from the evaporation system, including the use of a "oxygen-free" silicon source. To minimize possible contamination of the source, the silicon was sublimed from the solid at about 1390° C. using a simple electron bombardment system to heat the silicon. This resulted in deposition rates of about 5 to 7 µ per hr and film thicknesses of 4 to 20 µ. The vacuum during deposition was ordinarily about 5x 10-8 Torr, DESPITE the success achieved in the chemical vapor deposition of silicon on sapphire using Silane,1-4 vacuum deposition has not provided comparable properties. For example, Chu et a1.5 vacuum-deposited silicon on single-crystalline substrates of A12O3, Sic, ThO2, and other compounds, and, although some epi- but the use of ultrahigh vacuum (about 1 to 3 x10-9 Torr) during deposition did not significantly improve the results in the oxygen-free system. The crystalline quality of films deposited on (0001) sapphire was found to be considerably superior to (1102) sapphire surfaces. Using (0001) sapphire, single-crystalline films were deposited at temperatures as low as 780° C and as high as 1075°C, with the best crystalline quality obtained at about 1000°C. At this temperature, hole mobilities over 250 sq cm per v-sec were achieved. taxy was indicated, single-crystalline films were not produced. More recently, Salama, Tucker, and young6 evaporated silicon on single-crystalline sapphire, but only poor crystallinity was observed, and low carrier mobilities were measured. In the present experiments, good-quality single-crystalline films of silicon on sapphire have been achieved by specifically excluding oxygen from the evaporation. This included not only the use of a "clean" vacuum system but, of special importance, the use of an oxygen-free silicon source. This has also been shown to provide a dramatic improvement in silicon homoepi-taxy.7 As a result, silicon-on-sapphire films with hole mobilities over 250 sq cm per v-set were achieved, and single-crystal films were grown as low as 780°C and as

Jan 1, 1969

By Richard O. Carlson

Ions of p31 and B 11 were implanted in natural insulating diamond macles. The thin (-0.4µ) layers showed sheet resistances of 107 to 1011 ohm per sq and activation energies of 0.17 to 0.34 ev above room temperature. However, no Hall effect could be measured, indicating that mobilities were less than I to 10 sq cm per (v-sec). Such low mobilities may be due to excessive scattering due to radiation damage in the bombarded layer or to very high concentrations of active compensating impurities. Annealing did not materially change the room -temperature properties, but the temperature was limited to -800°C by surface graphitization, the latter process probably being accelerated by lattice damage in our diamonds arising from the ion bombardment. A weak n-type thermoelectric power was detected after p31 irradiation, but it cannot be presumed that we have made the phosphorus ions active as donors in diamond. The natural diamonds have a high and uncontrolled concentration of impurities and, when coupled with the radiation damage and graphitization problems, would appear to seriously limit the quality of semiconductor that we can presently achieve by ion implantation in diamond. ALTHOUGH diamonds are usually thought of as insulating in terms of their electrical conductivity, it was found about 15 years ago that natural semiconducting diamonds do occur rarely, and these were designated as type IIb diamonds. These p-type semiconducting diamonds were found to be dominated by an impurity level 0.37 ev from the valence band. Evidence today based on correlation of the concentration of acceptor states from Hall effect measurements with the impurity concentrations determined by neutron activation analysis point to aluminum as the dominant acceptor impurity.&apos; The compensating donor is believed to be nitrogen, which has a donor level 1.6 ev above the valence band.&apos; However, only a small fraction of the total nitrogen content in the diamond is electrically active. An infrared absorption band at 7.8 p and ultraviolet absorption near 4 ev have been associated with nitrogen, the former providing a quantitative measure of nitrogen content.3 The nitrogen content is -l020 cm-3 in insulating or type I diamonds, but is less than 10&apos;&apos; in natural semiconducting diamonds. Much of this nitrogen is distributed in platelets oriented in (100) planes and not atomically dispersed in the diamond lattice.4 Semiconducting diamonds have been deliberately formed by incorporating impurities into the graphite charge in the high-pressure apparatus used to form diamonds.5 These manufactured semiconducting diamonds are always p-type, and while some show the 0.37 ev level due to aluminum, most such samples have been ascribed to impurity banding effects.6 The best natural or manufactured semiconducting diamonds have hole mobilities near 1500 sq cm per (v-sec) at room temperature, and those with the 0.37-ev level can be analyzed to reveal an acceptor concentration of 3 to 8 X 1016 cm-3 and a donor concentration 3 to 10 times lower.&apos; NO bulk n-type diamonds have ever been reported, but the electron mobility has been measured as 1900 sq cm per (v-sec) by irradiating a diamond with ultraviolet to excite electrons out of the deep nitrogen donor level or other levels.7 New hope for the formation of n-type diamond has emerged from the ion-implantation method whereby desired impurities are introduced into a crystal lattice by bombardment with a high-energy beam of the impurity ion. It was found in the case of silicon that the usual donors such as phosphorus and arsenic and acceptors such as boron and gallium could be implanted into silicon. Wentorf and arrow&apos; produced semiconducting layers on diamonds by an ionic bombardment in a glow discharge at potentials of about 2 kv. The observed typeness from thermoelectric probing seemed to depend on the atmosphere gas (nitrogen, argon, or hydrogen) rather than on the electrode material, but the nature of the conduction process in the thin damaged surface layer is completely unknown. A Russian group under Vavilov has attempted high-energy ion implantation in natural diamonds using boron and lithium ions9 and later also phosphorus, aluminum, and carbon ions.10 Their papers claim n-type layers from lithium, phosphorus, and carbon implant and a p-type layer from boron and aluminum implant, though the methods of type determination are not described in detail. Under government contract support, the Ion Physics Corp. has studied ion implantation in several semiconductors. While the bulk of their study1&apos; was devoted to the irradiation of silicon, they did carry out a short study on boron and phosphorus implantation into natural diamonds. They did observe surface conducting layers but did not determine the typeness of the layers. For our experiments, phosphorus and boron were chosen as the dopant ions because of their respective donor and acceptor behavior in germanium and silicon. Moreover, they are the lightest mass dopants of the shallow level donors and acceptors from columns 111 and V of the Periodic Table (excluding nitrogen which is already present in diamond), and will have the largest depth penetration into the diamond lattice. EXPERIMENTAL Diamonds. As the target diamonds for our ion implantation study, we chose commercially available macles, which are flat, twinned diamond crystals. By scanning through the stock of a wholesale distributor

Jan 1, 1970

By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood&apos;s metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1&apos;"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood&apos;s metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood&apos;s metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood&apos;s metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By B. D. Lichter

In a previous paper, Oelsen, Schuermann, and Hey-nertl pointed out the possibility of obtaining complete thermodynamic functions for alloy systems from calorimetric measurements alone. Specifically, if the heat content of a heterogeneous, multicomponent system is known as a function of temperature and composition, then it is possible to derive the heats, entropies, and free energies of formation of liquid phases and of solid intermediate phases of fixed composition. The authors present equations and graphical techniques applicable to eutectic systems and systems with intermediate phases without solid solubility at lower temperatures. eijering has considered possible extension of the treatment to systems with complete solid-state miscibility at lower temperatures; however, experimental difficulties practically restrict the method to systems with very limited miscibility in the solid state. The purpose of this note is to present an alternative derivation of the heats and entropies of formation of liquid phases and of solid intermediate phases from heat-content measurements alone. Fig. 1 shows three types of phase diagram to which the analysis may be applied. If the heat content is determined as a function of composition x, at temperature T, we have quite generally and the heat of mixing of the liquid is obtained directly from heat-content measurements. If the temperature T lies in a two-phase region (solid-liquid) then

Jan 1, 1967

By N. A. Gjostein

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors&apos; conclusion.

Jan 1, 1968

By A. Hansson, G. E. Tardiff

WHILE it is generally known that cold-worked low-and medium-carbon steels exhibit substantial increases in tensile rupture ductility with increased deformation velocity172 (up to the von Karman limit), the observations for annealed or normalized steel do not permit simple generalization. Various investigators, for example, have reported both small increases1,3 and small decreases4,5&apos; in rupture ductility with increased rates of deformation of normalized low-carbon steel. The purpose of the present note is to report on the dependence observed for strain-aged steel since preliminary work here indicates that strain aging results in the development of a consistent type of behavior that is understandable in the light of current knowledge of the lower yield dynamics for steels which deform inhomogeneously.6 This realization throws additional light on the influences responsible for the behavior of normalized steel. The results presented here were obtained for a 0.21 pct C, 0.012 pct N sheet (0.012 in. thick) steel which was received in a temper-rolled condition (approximately 3 pct reduction in thickness after process annealing); the as-received material had a spherodized structure with a ferritic grain size of ASTM 8. The material was selected for testing after 6 months room temperature aging, at which time the static lower yield and ultimate tensile strength measured 79 and 82 kpsi, respectively. ASTM 2-in. reduced section, 1/2-in.-wide specimens were used in smooth bar tests and 3/4-in.-wide specimens containing two 60-deg opposed edge notches (root radii = 0.002 in.) were used in notched bar tests. To facilitate strain measurement, the smooth bars were blued with ink and marked at 0.1-in. intervals along the gage length; the notched

Jan 1, 1968

By A. S. Argon, G. East

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors&apos; conclusion.

Jan 1, 1968