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By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

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 A. D. McMaster, M. L. Gimpl, N. Fuschillo

Low-power, high-speed, radiation-resistant, monolithic thin-film integrated circuits require thin-film resistors of high sheet resistance which are compatible with the processing requirements for monolithic silicon devices. For this purpose the structure and electrical resistance as a function of temperature were investigated for Nichrome-silicon monoxide cermet films on passivated single-crystal silicon substrates. A suitable material was found to be a mixture of 50 vol pct Nichrome-50 vol pct silicon monoxide. This mixture, when evaporated onto 300°C substrates. showed a low temperature coefficient up to 400°C, at both 270 and 1100 ohms per square. Resistors deposited on room-temperature, 300°, and 500°C substrates were heat-treated at 600°C in air for short periods of H- seed, low-power, radiation-re sis tant, monolithic thin-film integrated circuits'-3 require thin-film resistors of high sheet resistance and low temperature coefficients of resistance which are compatible with the processing requirements for monolithic silicon active devices. The present investigation is directed towards the replacement of the Nichrome in the sandwich-type SO2-Nichrome-SiO resistors, currently used for DTL monolithic thin-film integrated circuits, with codeposited Nichrome-SiO cermet resistors. These Nichrome-SiO resistors are provided with an overcoat of SiO and are deposited onto thermally oxidized silicon wafers used in monolithic mi-crocircuit technology. The cermet resistors are shown to provide a lower temperature coefficient of time totaling up to 45 min. Electron nzicrogvaphs and diffraction patterns were taken of the as - deposited and heat-treated films. These results were then compared with electrical-resistance measurements for each condition. The room-temperature and 300°C substrate films showed a large decrease in resistance. The 500°C substrate film remained stable throughout the entire cycle. Electron-microscopy results show that the increased stability after heating to 600°C is largely due to crystallization of the films which begins in the vicinity of 400°C. The slight oxidation of the films when heated in air had a negligible effect on the resistance. The resistance of the film was a function of the substructure. resistance and a more versatile compatibility with silicon monolithic processing. Previous work3, on chromium-SiO coevaporated cermet resistors on glass and ceramic substrates without overcoats of SiO has been reported. For the present application, the thin films should possess the following ideal requirements: a) a temperature coefficient of resistance as near zero as possible up to 300°C; b) have a sheet resistance higher than 200 ohms per sq to conserve space on the chip; c) be easy to evaporate; d) be oxidiation- and radiation-resistant; e) show long-time stability at 100°C; } be stable in N2 atmospheres up to 600°C for short periods of time (5 to 45 min). Requirements a to e are well-known. The last requirement was optional and was due to a mask elimi-

Jan 1, 1967

By J. M. Blank, V. A. Russell

When the nucleation of silicon on a sapphire substrate is accomplished by gradually decreasing the substrate temperature while subjecting it to a constant impingement rate of hydrogen and silicon tetrachloride, the resulting deposit is characterized by widely separated islands of silicon scattered over an "open sea" of sapphire. Analysis shows that nucleation takes place mainly on sites of large adsorption energy, about 85 kcal per mole, and small surface concentration, about 108 cm-2. Crystal growth proceeds rapidly on these nuclei and results in enough depletion of Sicl4 from the ambient gas to suppress further nucleation. The technological importance of single-crystal films on dielectric substrates has prompted considerable work on the deposition of silicon on sapphire. This paper is concerned with the deposition of silicon, by the reduction of silicon tetrachloride with hydrogen, onto heated sapphire substrates. The apparatus consisted of a temperature-controlled container for the silicon tetrachloride along with gas lines and flow meters necessary to convey a hydrogen-silicon tetrachloride mixture to a reaction chamber constructed of quartz tubing. Heat for the substrate was provided by means of an inductively heated graphite susceptor. The observations pertinent to the present discussion were made with an American Optical Co. high-temperature microscope which allowed us to make motion pictures of the deposition process at a magnification of approximately 50 times. Two main categories of experiments were carried out: one on determination of critical condensation temperatures and the other on the deposition of epitaxial silicon films on the sapphire substrates. Critical condensation temperatures were determined in the traditional way by raising the substrate temperature well above that at which condensation could be expected at the impingement rates being studied and then gradually lowering the temperature until the condensation of the first silicon was observed. This was done initially with ellipsometry-type detection but it was soon discovered that the deposits were occurring as widely separated islands and groups of islands scattered over an "open sea" of sapphire. We have called these archipelago formations. They were most easily detected by optical microscopy. Data gathered from experiments of this type have been collected in Table I. Motion pictures of the formation of archipelago patterns show that the nucleation period lasts about 10 sec if the substrate temperature and impingement rate are kept constant. Essentially all of the nuclei are formed in a few seconds and all subsequent silicon deposition merely adds to the size of the established nuclei. After an archipelago formation has matured at a given substrate temperature and impingement rate, it is very difficult to stimulate any further nucleation in the open space between islands. Lowering the substrate temperature will occasionally stimulate nucleation but increasing the impingement rate hardly ever produces any more new nuclei. It should also be emphasized that the nucleation rates appear to be very small, about 104 cm-2 sec-1. They will receive special attention in the analysis section. Another series of experiments was performed employing a systematic variation of substrate temperatures and impingement rates approximating those expected to produce epitaxy. Sapphire substrates with surfaces normal to the 2233 direction were used. In contrast to the procedure that produces archipelago patterns, these films were deposited by raising the substrate temperature to a desired value at which time the silicon tetrachloride and hydrogen flow was begun. Of course, these depositions produced mainly films that were continuous. After removal from the deposition chamber, the substrate and silicon film were examined microscopically to determine the nature of the deposit and by X-ray diffraction to determine the extent to which a single-crystal film had been achieved. Results of these experiments are summarized in Table 11. Of interest for the present analysis is the fact that epitaxy appears to be confined to a fairly narrow temperature range between about 1050" and 1150°C. This also will be discussed in the analysis section. ANALYSIS In this section we shall apply nucleation theory to the data presented above with the objective of testing

Jan 1, 1967

By A. D. McMaster, M. L. Gimpl, N. Fuschillo

There is interest in the use of rhenium metal films as resistive elements in thin-film circcits, and already some zvork has been done using er)aporated rhenium films. It has been found that rheniim films protected from the atmosphere by an evaporated layer of silicon monoxide show excellent electrical stability. Unprotected films, however, are subject to aging- effects, notably the increase in electrical resistivity as a function of time. This phenomenon can be understood as primarily one of oxidation of the thin films. This paper is concerned with the study of the oxidation and crystallization behavior of such unprotected films. It has been found that the oxidation rates are a function of the substrate temperatures used during the deposition of Lhe metal films. The strictures observed in the films are correlated with the film resistivities and some data are presented to establish the existence of the various types of oxides of rhenium. ThERE is some interest in the use of thin films of rhenium metal as resistive elements in monolithic, thin-film integrated circuits. Some work has been done using evaporated films and it has been found that such films, if protected from the atmosphere by an evaporated layer of silicon monoxide, show excellent electrical stability up to temperatures of 500"." Rhenium films unprotected from the atmosphere tend to age and the electrical resistivity of the films increases as a function of time. Rhenium films, of the order of <100A thick, prepared by electron-beam evaporation techniques are found to oxidize very readily when exposed to dry air at room temperature. It would seem, therefore, that this aging phenomenon could be attributed to the oxidation of the metal films. In this investigation, the oxidation and crystallization behavior of thin films of rhenium evaporated onto silicon monoxide substrates were studied as a function of the substrate temperatures used during the evaporation. The films were examined using electron-microscopy and electron-diffraction techniques. EXPERIMENTAL RESULTS Rhenium metal was evaporated onto suitable prepared substrates which were heated to various temperatures. The evaporations were performed in a vacuum of approximately 5 x 1CT5 torr. The evaporation was carried out at a rate of approximately 10A per omin. The final film thickness was approximately lOOA and the resistance ranged from 5000 to 10,000 ohms per square. The substrates used for supporting the metal films were made by evaporating 75A of silicon monoxide onto freshly cleaved mica. The silicon monoxide film was then floated off the mica by immersing the composite in water. The film could then be picked up on a clean nickel grid. Silicon monoxide substrates were chosen because of their similarity to quartz and glass substrates commonly used for making thin-film resistors. Fuschillo, Gimpl, and McMas-ter have also shown that silicon monoxide films have only minor structural changes at temperatures up to 800°C. This fact simplified the interpretation of any changes observed in the electron micrographs or electron-diffraction patterns obtained from the deposited rhenium films. After the evaporations were completed, the substrates were cooled to room temperature, except where noted differently, before the coated substrates were removed from the vacuum system. All aging of the deposited films was done in a desiccator. The evaporated films were examined in an electron microscope equipped with a hot stage that would permit continuous observations of the samples up to temperatures of 1000°C. RESULTS A series of electron micrographs of the rhenium films deposited on the silicon monoxide substrates are shown to Figs. 1 to 3. In all cases, the metal films are approximately 100A thick and the micrographs were taken 1 hr after the deposition was completed. here was no apparent structure in the films deposited on the substrates held at the higher temperatures. The

Jan 1, 1967

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 W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

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 P. Hudock

Thin films of PbS and CdS have been deposited on insulutiug- sapphire substrates by euzploying a subliwzation technique rising near-equilibriurum conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have mobilities approachitzg values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. By performing the depositiotz of a compound within a small chamber heated to a UNiform temperature within a Vacuum systerrz, it is possible to approach equiilibrium cod-tions r.~litl~irs the chamber. In this way; the sublimation and condensation proceed under near equilibrium co?zditions, and it was found that the properties of dePosited corrzpounds were similar to those of the source material. Oriented PbS films on sapphire have a roor?l- temperature unobility of 700 sq cm per v sec and a T-5/2 temperature dependence characteristic of bulk crrystnls. CdS layers on sapphive Izazse a resistivity ~uhich is corrlpamble to the resistivity of the souvce crystals over a range of four ordem of rrlagnitude. Irz contrast, Ihe resistivity of CdS films prepared by conventional evaporation depends largely upon the substrate terrzperat~ire and postheating treatrrletlt, vather than upon the properties of&apos; the solirce rrraterial. In the case oj the CdS films the achievment of high carrier mobility required the cargful exclusion of cont~~~~ii~unts from the films. The steps taken to accomplish this included presublimation of the source material, performance of the deposition at a backg-m~ozd pressure less than 10-8 Torr, and a solvent extraction with liquid cadminum, similar to that described by Aven and woodbury. The deposition of ,films under near-equilibrium conditions is being op-plied to other classes oj COmpounds. II should he of 1:allce ,tor llle deposition of nny matevial that decomposes in the vapor state. THIN films of PbS and CdS have been deposited on insulating sapphire substrates by employing a sublimation technique using near-equilibrium conditions in ultrahigh vacuum. Oriented polycrystalline PbS and CdS films on sapphire have Hall mobilities approaching values characteristic of bulk crystals. In the case of CdS, special purification procedures were crucial in obtaining high-mobility films. Depositions were performed in a small quartz sublimation cell shown in Fig. 1 that contained the compound and the single-crystal sapphire substrate. The substrates were etched in tapered solutions of hot phosphoric acid, rinsed in deionized water, dried, and transferred to the cell under dry nitrogen. Graphite crucibles and substrates were used in experiments where it was necessary to provide an inert test vehicle for the analytical determination of impurities in the source crystals and deposited films. The crucibles and substrates were machined out of spectrographic-grade graphite having less than 1 ppm of impurities. A quartz mask was sometimes used to define a pattern which could be used for Hall and resistivity measurements. Close spacing between the compound and substrate was maintained to insure better transport of each component from the source material.

Jan 1, 1968

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.&apos; The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-&apos; cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By R. C. Himes, K. Zanio, J. B. Wagner, J. W. Moody, J. F. Miller, W. Johnson

The recent research with which this paper deals has been concerned with the preparation of pure PbTe crystals suitable for control of radiative processes and othe.v electronic applications. The research has been directed toward the developrnent of methods for the preparation of puve, homogeneous, loul-ca,wier-density PbTe crystals suitable for use in the fabrication of optically pumped and electrically pumped diode lasers. Steps in the preparation of the crystals include 1) purification of the starting materials, 2) synthesis and purification of the PbTe, 3) growoth of PbTe crystals, and 4) adjustt~zertt of composition of the crystals This Paper describes the general preparation procedure employed and discusses some investigntiotzs of purification processes. THE as-received lead and tellurium are nominally 99.999 to 99.9999 pct pure. Assays furnished by the suppliers, obtained by emission spectrographic analysis, show only the presence of about 2 ppm Mg in the tellurium. Such analyses are not very informative, however, since they give no information on the concentrations of normally gaseous impurity elements such as oxygen. Both the lead and the tellurium in the as-received state usually contain appreciable concentrations of oxygen—primarily in the form of oxides on the surfaces of the material. To reduce the oxygen content, the lead is held in the molten state in hydrogen at -700°C for several hours. For this treatment, the lead is contained in a graphite boat which is rf-heated, and the hydrogen is passed through a liquid-nitrogen trap prior to use. Tellurium is subjected to multiple distillation in hydrogen to remove oxygen and other foreign impurities. If, in conducting the distillation, approximately the last 10 pct of the charge at each "stage" is left as the discard cut, purification of the tellurium proceeds as indicated in Fig. 1.l Tellurium used in this work has been distilled two or three times to reduce carrier concentration to about 10" per cu cm. The PbTe is prepared from the purified elements by reacting them in the molten state in sealed, evacuated, or hydrogen-filled silica ampoules. The charge is usually held above the melting point of PbTe (923°C) at 1000 C for 24 hr to ensure that it has been homogenized. Two methods have been employed for the growth of the required single crystals of PbTe: growth from the melt, which will be discussed first, and growth from the vapor phase. Large single crystals of p-type PbTe can be grown readily from the melt by the Bridgman method. For this method of crystal growth, the PbTe is synthesized in situ from proper proportions of the purified elements. Growth (dropping) rates in the range 1.3 to 6.5 mm per hr are employed. Material near the maximum melting composition (about 50.012 at. pct Te) is utilized to avoid composition change on freezing, and thus to obtain crystals of nearly uniform composition. Crystals prepared by use of procedures described up to this point were sufficiently pure and perfect that they could be used for the preparation of laser crystals in studies at Lincoln Laboratory.2-5 ADJUSTMENT OF COMPOSITION Good n-type crystals of PbTe cannot readily be grown from the melt. Further, growth from the melt of crystals of any compositions (n or p type) other than those near the maximum melting composition is difficult because of the large composition changes that must occur on freezing.&apos;" However, melt-grown crystals can rapidly be brought to other desired compositions by isothermal equilibration through the vapor phase with a two-phase Pb-Te stock material, essentially as described by Brebrick and Allgaier.1 The work to be discussed has been concerned with the preparation of n-type crystals; thus, the two-phase stock which was employed contained excess lead, and all ensuing discussion is of the preparation and properties of n-type crystals. The equilibration was designed to the shift composition to the lead-rich limit of stability at the selected temperature. Initial treatment of the crystals at high temperature was employed to minimize the total time required for the equilibration. Final adjustments of the composition and state of the crystals were made by use of low-temperature heat treatment at temperatures in the range 200" to

Jan 1, 1968

By P. Nyul, S. Caplan, M. F. Lamorte, T. Gonda

Therrnal resistance is measured on GaAs laser diodes in the temperature range 77" to 300°K. These data show that typically the thermal resistance increases fifteen times from 77 to 300°K. The increase is attributed to the decrease in thermal conductivity of Gds. Nornzalized thermal-resistance experimental and calculated from published thermal-conductivity data) values are compared and good agreement shown. In many practical applications, it is desirable to obtain high average power output from laser diodes. Average power output is determined in large measure by the external efficiency and thermal resistance of the diode.&apos;-3 The average input power with which a laser diode may be pumped is dependent on the thermal resistance. Thermal resistance has been studied over the temperature range from 77" to 300°K which is usually of interest in practical applications. This correspondence presents data on thermal resistance for GaAs laser diodes and compares them to values calculated from thermal-conductivity data. Junction heating arises from three distinct components: 1) joule heating, 2) nonradiative recombinations, and 3) reabsorption of radiation. In high-threshold lasers, joule heating predominates.4 Typically, the nonradiative recombination is not negligible and contributes significantly to junction heating. The loss caused by reabsorption may be of the order of the joule-heating loss.&apos; The fabrication and the geometry of laser diodes have been described in other publications.5 The data presented were obtained from diodes which were fabricated from the same region of a wafer to minimize differences. Fig. 1 shows four types of heat sinks employed in this study. In types 1 and 2, the laser cavities are alloyed; pressure contacts are employed in types 3 and 4, and indium is plated on the inside faces to improve the intimacy of contact between the diode and the heat sink. The thermal resistance R is defined by the following relationship: where AT is the junction-temperature rise above the heat-sink temperature for the diode power dissipation Pd. For measurement of thermal resistance, a direct current is passed through the junction, in the range from 1 to 50 pct of threshold. The diode is placed in the laser mode by superimposing a current pulse of low-duty cycle on the direct current.3 Junction-temperature rise is obtained from the time-resolved laser spectrum at the leading edge of the current pulse.&apos; Typically, the laser line shift is 2.5A per OK. The resolution employed in these experiments is 0.5A; therefore, the accuracy in the temperature measurement is 0.2K. Typically, the temperature rise is 2" to 20°K. The power dissipation is the difference between the dc power input, and the radiation power exiting the diode. The measurement accuracy is less than 1

Jan 1, 1968

By Charles C. Peterson, Ronald E. Enstrom

Significant improvements have been made in the ursine systern for epitaxial vapor gvowtlz of Gds. The electron concentration has been reduced to below 1015 cm-3 with electron-mobility values as high as 7200 sq on per v-sec at 30PK and 60,000 sq cw7 per v-sec at 77°K. These high-purity layers have been successfully gvown on n&apos; layers with thicknesses as snzall as 1 p and as large as 125 p. Furthermore, high-purity layers have been incorporated into an structure without degradation of electrical properties. Different impurity gradients at the n&apos; to n interface were achieved. Using these structures, Gunn oscillators have been operated at frequencies as low as 0.4 GHz and as high as 40 GHz, which equals the highest valzle yet reported. The frequencies nleasured are in reasonable apeenlent with those calculated fron7 the n-layer widths and the transit times. CW operatiolz has been achieved from 3 to 20 GHz. In Gunn devices for >40 GHz operation (i.e., witk an n-layer tkickness below 2.5p), the n layer has been generally too pure to permit oscillations to occuv. ThE mechanism of the Gunn oscillator&apos; is now generally understood.2-5 Electron transfer from the (000) minimum to the ( 100) minima leads to a voltage-controlled negative resistance, which results in the formation of domains of high and low electric fields which travel through the crystal with a characteristic velocity of about 107 cm per sec. When a constant voltage is applied to the sample, this domain motion generaliy leads to oscillations at the transit time frequency, fT = 107/L, where L is the thickness of the active n layer.&apos; In this case, a single high-field domain is nucleated at the cathode and grows until it reaches the anode, where it is absorbed; a new domain then forms at the cathode.5 There are related modes of oscillation of the same device in which a tuned circuit causes a periodic variation of the voltage across the device. The frequency then may be either above or below fT. It has been shown that oscillations will occur when n • L 2 1012 cm"2, where n is the carrier concentration in the active region. At lower doping densities, 10" 5 n . L 5 lo&apos;&apos;, the doping is said to be subcritical for oscillation and the description of the device operation changes since the domains become comparable in thickness to the device thickness, L. Nevertheless, such devices have been found to be "active" and, in fact, are useful as amplifiers.778 For CW operation, one wishes to minimize the power dissipation, which is related to the electric field, E, and the low-field resistivity, p. Below threshold, the power dissipation density is approximately Typically, at threshold where E -- 3 x 103 v per cm, the dissipation density is 107/p watts per cu cm, p in ohm-cm. Furthermore, it is desirable to provide good conduction of the heat generated in the active region. The temperature rise, AT, across the active layer of a sandwich structure, with a heat sink on one side, is given by AT = (E&apos;/P)(L~/~~) where it is assumed that the thermal conductivity, u, and resistivity, p, of GaAs do not vary appreciably over the range of temperature and electric fields existing in the layer. This expression shows that, subject to maintaining an appropriate (n . L) product, CW operation is favored by a higher resistivity, a lower threshold field, and a thinner device. The above device requirements place some severe restrictions on the materials to be used, especially for high-frequency (>10 GHz) operation. Here, it is necessary to prepare very thin (<10 µ) layers of GaAs, in a state of high purity (-1 ohm-cm), complete with very low-resistance ohmic contacts. Problems of handling such thin and fragile samples become inereasingly severe as the frequency is raised. Furthermore, while good low-resistance ohmic contacts are easily applied to low-resistivity GaAs, contacting difficulties are encountered for these higher-resistivity materials.

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 G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-&apos; have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.&apos; Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)&apos; molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),&apos; which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.&apos; This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

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

By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The &apos;system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and &apos;p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By C. W. Covington, H. C. Cook, J. F. Libsch

Sputtered aluminum thin films were prepared in each of two conventional bell-jar vacuum systems. One system utilized an inner "getter sputtering" enclosure; the second system was a standard diode sputterirlg arrangement. Consistent and repeatable film properties were obtained in both systems provided sufficient cleanup and presputter time was allowed. The various problems associated with aluminum sputtering are discussed, with pavticular attention to the vzinimization of film contamination by outgassing and oxidation. The growth and structure of the aluminum thin films were studied with the aid of electron wzicroscopy and related to deposition rate, substrate temperature, and film thickness. The resistivity of the films was correlated to film structure and surface roughness. Resistiuities as low as 3.5 microhm-cm (2.3 x bulk resistiuity) were measured for relatively thick films (20,000). THIS investigation was undertaken to explore the problems and film characteristics associated with the sputtering of aluminum. Earlier work reported on aluminum sputtering has stressed the contamination of both the cathode and film as well as abnormally low deposition rates.&apos; Data on sputtering yields,3 however, indicate that aluminum sputtering could be practical. Recently, it was shown by Theuerer and Hauser3 that aluminum sputtering was feasible in a conventional oil-diffusion pumped vacuum system provided an inner "getter sputtering" enclosure was employed to minimize gaseous contamination. This technique employs the getter action of aluminum to produce extremely low reactive gas partial pressures in the deposition zone. Aluminum films have already found use in solid-state electronic devices such as transistors and integrated microcircuits. To the present time, most aluminum films have been prepared by evaporation due to the ease with which this metal can be evaporated. Controlled sputtering of aluminum offers a number of advantages over evaporation, however, such as 1) manufacturing compatibility with other metals which must be sputtered, 2) better control of process variables resulting in more repeatable and uniform films, 3) generally better adhesion resulting from higher-energy metal atoms, 4) built-in material supply for continuous operation, and 5) the ability to deposit alloys. The data presented in this paper are the result of two separate studies. One study utilized a small "getter sputtering" enclosure (System A) and was concerned with the structure and properties of thin aluminum films up to about 1600A thick. In this thickness range, study of the film structure was possible with transmission electron microscopy. The second study was conducted with a conventional diode sputtering apparatus (System B) and covered $ much wider range of film thickness up to about 34,000A. Emphasis was placed on developing techniques which would extend aluminum sputtering to an existing in-line continuous deposition process.4 I) EQUIPMENT AND PROCEDURE System A. Fig. 1 shows a schematic of the "getter sputtering" inner chamber used and Fig. 2 is a photograph of this chamber mounted on an 18-in. access ring of a standard liquid-nitrogen trapped bell-jar vacuum system. This chamber was designed after a similar system used by Theuerer and auser.3 The configuration allowed the glow to emanate in all directions from the cathode. Argon (99.99&apos;) was allowed to enter only at the top of the chamber such that most of the reactive gases entering with the argon were reacted with the aluminum vapor and deposited on the chilled walls of the chamber before reaching the deposition zone. Provision was also made as shown, Fig. 1, for heating and cooling the substrate from about 20" to 400°C. Two substrate materials were used: Corning 7059 glass (12 by 12 by 0.048 in.) and carbon films about

Jan 1, 1967