PROCESS OF PRODUCING A HALL ELEMENT OR MAGNETORESISTIVE ELEMENT COMPRISING AN INDIUM-ANTIMONY COMPLEX CRYSTAL SEMICONDUCTOR

Abstract: An indium-antimony complex crystalline semiconductor consisting essentially of crystals of an indium-antimony compound and crystals of indium alone is disclosed. The atomic ratio of the total indium content to the antimony content in the semiconductor is in the range of from 1.1/1 to 1.7/1. A process for producing such semiconductor is also disclosed. In the process, the vapors of indium and antimony are deposited on a substrate in such a manner that the arrival rate ratio of indium to antimony is controlled to be within the range of from 1.1/1 to 1.7/1.

Description: Field of the invention The present invention relates to a process of producing a Hall element or magnetoresistive element comprising an indium-antimony complex crystal semiconductor. Background of the invention A thin film of indium-antimony compound has a higher mobility (78,000 cm²/V · sec) than other semiconductor compounds, such as an indium-arsenic compound (30,000 cm²/V · sec) and gallium-arsenic compound (7,000 cm²/V · sec). Because of this property, a thin film of indium-antimony compound is known to be advantageous for use as a Hall element or magneto-resistive element, and has been getting the increasing attention of researchers as a device that can be used in a position detector for a direct drive motor, or as a component of video tape recorder or acoustic equipment. Two important parameters for the Hall effect of a semiconductor are the Hall coefficient (R H ) and Hall mobility (µ H ). Figure 1 shows an arrangement for measurement of these two parameters, which consists of a test conductor A having a length I, width w, and a thickness t (not illustrated), on which gold is vacuum-deposited to form input electrodes a, a′ and output electrodes b, b′. A voltage V Hi is developed between the output electrodes when the input electrodes are connected to a constant current supply I, and a voltage V HV is developed when they are connected to a constant voltage supply V. The two voltages are represented by the following equations: wherein B is the magnetic flux density of an external magnetic field applied, and f is a factor dependent on the configuration of the sample. As equation (1) shows, V Hi is in inverse proportion to the thickness of the material through which the current flows, and it can be seen that the thickness of an indium-antimony wafer to be used as a high-sensitivity Hall element or magneto-tesistive element should be as small as possible. Since the indium-antimony semiconductor has a small forbidden band, its Hall coefficient (R H ) in equation (1) varies greatly with temperature, and V Hi , the output voltage under constant current, is largely dependent on temperature in practical applications. On the other hand, the Hall mobility (µ H ) in equation (2) is fairly independent with respect to temperature and almost all commercial indium-antimony Hall elements are used under constant voltage. Hence, an indium-antimony semiconductor having high Hall mobility rather than high Hall coefficient is desired. However, no industrial process has to date been known for producing a thin film of indium-antimony crystalline structure. US-A-3,850,685 describes a thin layer semiconductor device comprising a mixed crystal, InSb (1 _ x) AS x composed of indium, antimony and arsenic. The amount of arsenic therein satisfies the relationship 0 < x < 0.3. Arsenic is necessary in order to avoid areas being indium-rich and instead of that results in a ternary mixture of the three components. Heretofore, it has been considered essential that in a compound semiconductor such as indium-antimony, the atomic ratio of the element of group IIIB in the Periodic Table to the element of group VB should be 1/1 (see Z. Naturforschung , Vol. 7a, p. 744, 1952). To make a wafer of indium-antimony crystal having an In to Sb atomic ratio of 1/1 for use as a Hall element or magnetoresistive element, a slice of a single crystal of indium-antimony is polished into a thin film, or an indium-antimony composition having a thickness of about 10 µm layer is formed on a substrate by vacuum deposition or other suitable means, crystallized by zone melting and then polished to a thin film (see Japanese Patent Application (OPI) No. 9373/75 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application")). However, slicing a wafer of InSb single crystal is not an industrially advantageous method, since a large amount of expensive material must be used. In the second method wherein the vacuum-deposited InSb layer is crystallized, controlling the In to Sb atomic ratio at 1/1 is very difficult and requires complex procedures, and these are two great limiting factors on the effort to use this method on an industrial scale. K. G. Günther proposed in U.S. Patent 3,172,778 a process for making a thin layer of IIIB-VB compound semiconductor by vacuum deposition. In that process. Günther suggests presetting the temperature of the substrate higher than the decomposition temperature of the compound semiconductor, and depositing more element of VB group than the element of IIIB by controlling the arrival rate ratio of the two elements (hereunder referred to as A In /A Sb ) to be 1 or less. The arrival rate ratio (A In /A Sb ) as used herein means the ratio of the flux density of In atoms to that of Sb atoms that reach the substrate in the process of vacuum deposition (see Physics Status Solid , (a). Vol. 54, p. 707, 1979). But even this method requires a complex procedure to control the atomic ratio of In to Sb to be 1.0/1 and has the above described defects of the conventional art. In phys. stat. sol. (a), Vol. 54, No. 1, pages 391-4 there is disclosed an investigation on the effect of non-stoichiometric excess of In on the electrical transport properties of polycrystalline p-Type InSb thin film by P. C. Mathur et al. The disclosure shows 1.9% of indium at maximum (see table I). Further, the reference deals with p-type semi-conductor properties. JP-A-55-77131 and JP-A-55-77130 relate to growth of a film in a gaseous phase. The method of film growth in a gaseous phase is a method wherein compounds containing two or more kinds of group III and V elements (organometallic compounds) are decomposed and reacted, and it is known as an effective method for forming a fairly thick epitaxial film having a 1/1 composition in use of two elements. JP-A-55-77130 discloses an excess of group III element in amounts of at least 3/1 in the composition ratio. Noting that in the prior art the problem in producing a thin film of indium-antimony semiconductor is the necessity of strictly controlling the In to Sb atomic ratio, and that therefore the process control can be simplified and hence the desired thin film can be easily produced by expanding the latitude in selection of the In to Sb atomic ratio, the present inventors have conducted various studies to develop an industrial process for making a thin film of indium-antimony crystalline structure. Summary of the invention One object of the present invention is to provide a process of producing a Hall elementt or magnetoresistive element comprising a binary indium-antimony complex crystalline semiconductor and a thin film thereof, which is free from the above problems on an industrial scale. Other objects of the present invention will be apparent from the description hereinbelow. As a result of extensive studies, it has now unexpectedly been found that an indium-antimony binary compound that has an excess of indium, and particularly which has an In to Sb atomic ratio in the range of from 1.1/1 to 1.7/1 has high crystallinity and exhibits high mobility. This fact disproves the established theory in the art. It has been found that such compound can be produced easily by depositing the vapor of antimomy and indium on a substrate in such a manner that the arrival rate ratio of indium atoms to antimony atoms is held at 1.0/1 or less during the initial stage of the vacuum deposition, this being the period in which the semiconductor film attains a thickness of about 100 nm or 200 nm, and at the same time, the temperature of the substrate T is held at a level that satisfies the relation wherein Tc is the critical temperature of the substrate on the absolute scale (°K) that is given by the formula wherein P is the pressure in the vacuum deposition system (expressed in Torrs), the temperature of the substrate also being held in the initial stage of the vacuum deposition at a level lower than the limiting temperature given by the formula wherein T L is the limiting temperature of the substrate on the absolute scale (°K) and P is the pressure during the vacuum deposition system (expressed in Torrs), and wherein the average arrival rate ratio of the indium atoms to antimony atoms during the deposition is controlled to be within the range of from 1.1/1 to 1.7/1. The present invention has been accomplished on these findings. Brief description of the drawings Figure 1 is a pattern for measuring the electrical characteristics of a semiconductor. Figure 2 is a graph showing the relation between F In /F Sb (defined below) and Hall mobility of the thin semiconducting films made in Example 1. Figure 3 is a graph shoving the relation of A In /A Sb and F In /F Sb . Figure 4 is a graph showing the relation between the pressure (degree of vacuum) in a vacuum deposition system and the limiting temperature of the substrate. Figure 5 is an illustration of an apparatus for use in producing the thin semiconducting film of the present invention. Detailed description of the invention Specific embodiments of the present invention are listed below: A process of producing a Hall element or magnetoresistive element comprising an indium-antimony complex crystalline semiconductor thin film consisting of crystals of an indium-antimony binary compound and crystals of indium alone by depositing the vapors of indium and antimony on a substrate in such a manner that the A In /A Sb , is held at 1.0/1 or below in the initial stage of the vacuum deposition, this being the period in which the semiconductor film attains a thickness of about 100 nm or 200 nm, and, at the same time, the temperature of the substrate (T) is held at a level that satisfies the relation wherein T C is the critical temperature of the substrate on the absolute scale (°K) that is given by the formula wherein P is the pressure in the vacuum deposition system (expressed in Torr), that the temperature of the substrate is held in the initial period of the vacuum deposition, at a level lower than the limiting temperature given by the formula wherein T L is the limiting temperature of the substrate on the absolute scale (°K), and P is the pressure in the vacuum deposition system (expressed in Torr) and wherein the average arrival rate ratio of the indium atoms to antimony atoms during the deposition is controlled to be within the range of from 1. 1/1 to 1. 7/1. A process as above, wherein the vacuum deposition is performed in the presence of nitrogen. The essential feature of the present invention is to provide a process of producing a Hall element or magnetoresistive element comprising an indium-antimony complex crystalline semiconductor wherein the atomic ratio of total indium, i.e., indium in the In-Sb compound and indium as the indium crystal, to antimony (or film composition ratio of indium to antimony which is hereunder referred to as F In /F Sb ) is in the range of from 1.1/1 to 1.7/1, For the purposes of the present invention, the value of F In /F Sb of the indium-antimony complex crystalline semiconductor must be in the range of from 1.1/1 to 1.7/1 because the semiconductor having a value of F In /F Sb in this range exhibits a particularly higher mobility than those which have a value outside this range, and it is easier to make a thin film thereof that suits practical purposes. The relation between the F In /F Sb and mobility of a thin semiconducting film is shown in Figure 2, wherein the F In /F Sb is plotted on the x-axis and a fairly accurate measurement of the factor could be made by atomic absorption spectroscopy. The mobility of the thin film is plotted on the y-axis. In Figure 2, the symbol A indicates a line for the mobility of 10,000 cm²/ V · sec, and the region above this line is practical. The thin film has a mobility higher than this line when it has a value of F In /F Sb between 1.1/1 and 1.7/1. If the value of F In /F Sb is less than 1.1/1, the resulting thin film is fragile and has a high noise level. If the F In /F Sb is above 1.7/1, a heterogeneous thin film is made and the commercial productivity of the film is decreased. A particularly preferred range is from 1.2/1 to 1.6/1. If this range is observed, a highly crystalline thin film having high mobility and uniformity, and yet which has a low noise level, is produced. As described above, the complex crystalline semiconductor of the present invention has an excess of indium, and the indium content is variable over a fairly wide range. Therefore, the desired thin film can be produced by an industrially efficient technique of vacuum deposition since there is no need of using excess antimony having high vapor pressure and yet there is an increased latitude in selection of process conditions. The process of the present invention is based on the new finding that if the F In /F Sb is in the range of from 1.1/1 to 1.7/1, it agrees substantially with the value of A In /A Sb , the difference being within experimental error. The process of the present invention that produces a thin film of indiumantimony complex crystalline semiconductor that is very rich in indium is based on the idea of controlling the value of A In /A Sb to be within the range of from 1.1/1 to 1.7/1, and this idea is very much different from the established theory. Figure 3 shows how the value of F In /F Sb agrees with that of A In /A Sb . In Figure 3, the A In /A Sb is plotted on the x-axis and the F In /F Sb is plotted on the y-axis. In Figure 3, the symbol A represents a line for B represents a case for a substrate temperature of 440°C. C represents a case for a substrate temperature of 350°C, D represents a case for a substrate temperature of 460°C, and E represents a case for a substrate temperature of 400°C. The values of A In /A Sb could be determined by a simple preliminary experiment: first, the relation between the amounts of indium and antimony that were vaporized from their respective boats and the amounts of their vapor deposited on the substrate was determined for the case where the temperature of the substrate was low, say, at room temperature; the flux density of the respective atoms could be determined from the amounts of deposition, and hence, the relation between the amounts of the respective elements that were vaporized from the boats and their flux densities could be determined. The points in Figure 3 relate the F In /F Sb and A In /A Sb to the actual temperatures at which thin In-Sb complex crystalline films were made. As is clear from Figure 3, the values of A In /A Sb substantially agree with those of F In /F Sb within the range contemplated by the present invention where the F In /F Sb is between 1.1/1 and 1.7/1, so the composition of the thin film produced can be controlled by controlling the A In /A Sb . Since the A In /A Sb can be controlled simply by controlling the amounts of the respective elements that are vaporized from their boats, the process of the present invention is very useful for industrial purposes. Furthermore, the variation in the mobility of the thin film produced can be reduced to a surprisingly low level by holding the A In /A Sb constant. Therefore, the greatest industrial advantage of the present invention is that it provides a process for making a thin film of indium-antimony complex crystalline semiconductor having the least variation in its characteristics. A thin film of indium-antimony complex crystalline semiconductor having a further increased mobility can be produced if the temperature of the substrate is held in the initial state of vacuum deposition to be at a level lower than the limiting temperature of the substrate given by the formula wherein T L is the limiting temperature of the substrate on the absolute scale, and P is the pressure in the vacuum deposition system (expressed in Torrs). The term "initial stage" used herein means the initial period until the film having a thickness of about 100 nm (1000 Å) is formed, with the proviso that when the final film having a relatively large thickness (e.g., 2 µ or more) is desired), it is preferred that the same condition as that of the initial stage be maintained until the film having a thickness of about 200 nm (2000 Å) is formed. As described hereinafter, the limiting substrate temperature T L given by the formula (3) corresponds to the decomposition point of the crystal of an indium-antimony compound, and according to the studies of the present inventors, the substrate temperature is desirable held in the initial stage of vacuum deposition at a level at least 20°C lower than this decomposition point. When a thin film is formed by vacuum deposition, the substrate temperature becomes higher than the preset level, and even in such a case, the substrate temperature must be held below the melting point of the In-Sb compound which is about 530°C. For this purpose, the substrate temperature may be increased continuously at a given rate, or it may be elevated incrementally (stepwise). As indicated by the formula (3), the limiting temperature of the substrate is dependent on the pressure, and it is a temperature at which the amounts of deposition of indium and antimony vapors are decreased suddenly for the unit amount of vaporization (the amounts of indium and antimony vaporized from their boats) per given area. Therefore, the limiting substrate temperature can be defined as the temperature of the substrate at which the ratio of deposition to vaporization is decreased suddenly for a given degree of vacuum. The present inventors studied the relation between the limiting substrate temperature and the pressure, and obtained the results shown in Figure 4, wherein the logarithm of pressure is plotted on the y-axis and the reciprocal of the substrate temperature is plotted on the x-axis. In Figure 4, the straight line 1 is the theoretical decomposition line given by the formula (3), and the numerals 2, 2′ and 2″ represent sets of experimental values that were obtained at different pressures. One can easily see that these experimental values are virtually on the theoretical decomposition line. The present inventors have found that these values well coincide with the theoretical curve of the decomposition of an indium-antimomy compound that is very similar to the formula (3) and which is calculated on the basis of the thermal data for In-Sb compound prepared by Lichter et al (see Trans. Metallurgical Soc ., AIME Vol. 245, p. 99, 1969) and the thermal data for the elements prepared by Stull et al (see Thermodynamic Properties of the Element s, ACS, 1956). In other words, for a given degree of vacuum in the vacuum deposition system, the limiting substrate temperature substantially corresponds to the decomposition point. Therefore, the process of this embodiment differs essentially from the "three-temperature method" proposed by Günther. In the three-temperature method, A In /A Sb is held at 1.0/1 or below, and, at the same time, the substrate temperature must be held higher than the decomposition point of the In-Sb compound, but in the process of this embodiment, A In /A Sb is held between 1.1/1 and 1.7/1, and at the same time the substrate temperature in the initial period of vacuum deposition is held below the decomposition point of the In-Sb compound. If the vapors of indium and antimony are deposited on the substrate at an A In /A Sb between 1.1/1 and 1.7/1 by presetting the substrate temperature higher than the decomposition point of the In-Sb compound semiconductor, a non-glossy and non-uniform film having pinholes results, and, what is worse, the mobility, which is an important factor of the resulting film, is only 10,000 cm²/V · sec or less. Formula (3) also indicates that the limiting temperature of the substrate can be varied by changing the degree of vacuum. To be more specific, the degree of vacuum may be reduced if the substrate temperature need be preset at a high level. The degree of vacuum may be reduced by holding down the performance of the evacuating system used, or by introducing a gas into the vacuum deposition system through a needle valve or the like. Nitrogen, argon, hydrogen, helium and many other gases can be used, but according to the studies of the present inventors, a thin film having a remarkably high mobility can preferably be obtained by using nitrogen. The inventors therefore conducted a close study on the gas to be introduced in the vacuum deposition system, and found the following: (1) rare gases such as argon and helium decrease, rather than increase, the mobility; (2) if nitrogen is supplied in an amount that is greater than its content in atmosphere, higher mobility is obtained. The amount of nitrogen relative to other gases varies with the degree of vacuum achieved at the start of vacuum deposition and that achieved by introduction of nitrogen. For instance, if the initial degree of vacuum which is 133.32 × 10 _6 Pa (10 _6 Torr) is reduced to 666.6 × 10 _6 Pa (5 × 10 _6 Torr) by supplying nitrogen, the nitrogen content is about 90 mol%. Surprisingly enough, such a small change in the composition of the atmosphere in the vacuum deposition system from 80 mol% of nitrogen that is the nitrogen content of air to 90 mol%) is sufficient to provide the desired improvement in mobility. In other words, the mobility can be increased significantly by using an atmosphere for vacuum deposition whose nitrogen content is greater than 80%, the nitrogen content of air. But if the nitrogen content is less than 80 mol%, the mobility is not improved at all, and it is even decreased depending on the amounts of other gases contained in the vacuum deposition atmosphere. Several methods can be used to increase the nitrogen content of the vacuum deposition atmosphere. In one method, the system is evacuated to an adequately high degree of vacuum, then nitrogen is introduced, and the system is again evacuated to a high degree of vacuum. In another method, a nitrogen supply valve is connected to the vacuum deposition equipment, and the initial degree of vacuum of the system is reduced by supplying a small amount of nitrogen. A preferred method is to first increase the degree of vacuum up to 133.32 × 10 _7 Pa (10 _7 Torr), then supply nitrogen to obtain a pressure of 133.32 × 10 _5 Pa (10 _5 Torr), and perform the vacuum deposition with the supply of nitrogen continued. A thin film of indium-antimony complex crystalline semiconductor having an even higher mobility can be produced in a nitrogen-rich atmosphere by depositing the vapors of indium and antimony on a substrate that is held in the initial stage of the deposition at a level lower than the limiting substrate temperature given by the formula (3). When it is desired to provide the thin film of indium-antimony complex crystalline semiconductor of the present invention with a mobility as high as that of a bulk device, A In /A Sb must be held at 1.0/1 or lower in the initial stage of vacuum deposition and at the same time, the substrate temperature (T) must be preset at a level that satisfies the relation wherein Tc is the critical temperature of the substrate on the absolute scale that is given by the formula wherein P is the pressure in the vacuum deposition system (expressed in Torrs). The formulae (4) and (5) are empirical formulae that show the relation between the preset temperature of the substrate and the degree of vacuum for producing a thin semiconducting film having a very high mobility. As far as the present inventors know, the formula (5) corresponds to the equilibrium vaporization temperature (Tv) of Sb with a degree of vacuum in the range of from 133.32 × 10 _6 _133.32 × 10 _3 Pa (10 _6 to 10 _3 Torr). It is believed that the formula slightly differs from, but substantially corresponds to, the value calculated from the thermal data for the elements prepared by Stull et al. ( Thermodynamic Properties of the Elements , ACS, 1956). Formula (4) allows some variation in the preset value of the substrate temperature because said value must be varied depending upon the position of the monitor for the substrate temperature or the degree of vacuum, as well as upon the vacuum deposition rate. In this case, the value of A In /A Sb in the initial stage of the vacuum deposition must be held at 1.0/1 or lower. But it is absolutely necessary that the average value of A In /A Sb be maintained between 1.1/1 and 1.7/1 throughout the process of vacuum deposition. The particularly preferred average value of A In /A Sb is between 1.1/1 and 1.5/1. The studies of the present inventors have shown that it is essential for the purpose of making a thin film of In-Sb semiconductor having a very high mobility that the value of A In /A Sb be held in the initial stage of vacuum deposition to he at 1.0/1 or below. The inventors made a series of experiments in which vacuum deposition was conducted by controlling the power supplied to indium and antimony boats for achieving a mobility as high as that of a bulk device and the deposition was stopped in a few minutes. The inventors found that in every experiment, the value of A In /A Sb was 1.0/1 or less, and in an extreme case, the value was less than 0.5/1. However, the requirement of holding the value of A In /A Sb to be 1.0 or less applies only to the initial period of vacuum deposition during which a semiconducting film having a thickness of 100 nm (1000 A) is formed. If the value of A In /A Sb is held at 1.0/1 or lower in the subsequent stage, the resulting film is very brittle and has a very low mobility. If the above two requirements for the substrate temperature and A In /A Sb are met, a thin film of indium-antimony complex crystalline semiconductor is produced wherein both the crystal of indium-antimony compound and the indium crystal have grown to a size visible to the naked eye. If the substrate temperature in the initial stage of vacuum deposition is lower than the critical substrate temperature, the resulting crystal is not visible to the naked eye at all, or only a blue-white film is formed. If the substrate temperature is higher than the upper limit specified by the formula (4), some of the crystal grains formed are visible but there occurs a variation is not only the mobility but also the film thickness, or a transparent area is formed in the film. If vacuum deposition is performed by the process of this embodiment, the resulting thin film of indium-antimony complex crystalline semiconductor has a mobility as high as that of a bulk device and the crystal grains formed are visible to the naked eye. It is very surprising that this film has a value of F In /F Sb in the range of from 1.1/1 to 1.7/1. The compound semiconductor of the present invention has a high Hall mobility and is very suitable for use as the material of a Hall element or magnetoresistive element. In this connection, it should be remembered that the formula (1) shows the desirability of making a thin film of the semiconductor if it is used in a Hall element or magnetoresistive element. For this purpose, the compound semiconductor of the present invention is made in a thin film whose thickness is preferably from 500 nm (5000 Å) to 10 µm, more preferably from 0.8 to 5.0 µm. The thinner the film, the greater the output voltage produced, but, on the other hand, an excessively thin film has low mobility. According to one step of the process of the present invention, a thin film of high-mobility, indium-antimony complex crystalline semiconductor having a value of F In /F Sb of from 1.1/1 and 1.7/1 can be produced by depositing the vapors of indium and antimony on a substrate under such conditions that the value of A In /A Sb is held in the range from 1.1/1 to 1.7/1. This method is advantageous in that it can be performed on an industrial scale such more easily than the conventional method of making an indium-antimony crystalline compound having an A In /A Sb of 1.0/1, and that it is capable of producing a thin semiconducting film that has high mobility and which yet has a very small variation in the composition and characteristics of the film. There is no particular limitation on the substrate that can be used in the process of the present invention, but an electrically insulating substrate is preferred, and an insulating crystalline substrate is particularly preferred. Illustrative substrates include silica glass, borosilicate glass, sodium glass, sapphire, calcium fluoride, sodium chloride and mica, and sapphire, calcium fluoride, sodium chloride and mica are particularly preferred. Mica is advantageous since it is fairly easily available and is completely insulating single crystal that easily forms a cleavage plane with minimum contamination or defect. The process of the present invention can be performed by any of the known techniques that comply with the purposes of the present invention. Suitable examples are vacuum deposition by heating with an electric heater, electron beams, by flash evaporation, sputtering, molecular beam epitaxy and by ion beam plating. The rate of forming a thin film can be selected from a fairly wide range, i.e., from 0.01 to 100 nm/sec (0.1 to 1000 A/sec), but for easy control of the A In /A Sb , the rate of 0.1 to 1 nm/sec (1 to 10 Å/sec) is particularly advantagous. The substrate may be heated to any temperature below T L if the relation A In /A Sb = F In /F Sb is satisfied, and it is generally heated to 530°C or less. The vapor deposition temperature seems to have some relation with the pressure in the evaporation equipment, and, generally, the lower the pressure, the lower the maximum temperature for vapor deposition. The optimum source of evaporation is elemental indium and antimony. The power supplied to the respective boats may be so controlled that the ratio of evaporation of indium to antimony provides an A In /A Sb between 1.1/1 and 1.7/1. Therefore, an antimony-containing compound such as InSb or GaSb may be used as an antimony source. Such compounds can be satisfactorily used as an antimony source since the vapor pressure of indium or gallium is much lower than that of antimony Figure 5 is a schematic representation of an apparatus suitable for use in producing the indium-antimony complex crystalline semiconductor of the present invention. In Figure 5, the temperature of a substrate (e.g., mica plate) denoted as 1 is detected by a thermocouple 3 attached to the substrate through an indium material 2, and is held constant by a substrate temperature control system (not shown). The substrate 1 is heated to a predetermined temperature by heating elements 5, 5′, and boats 4, 4′ are heated to a predetermined temperature by heating elements 6, 6′. The boats 4, 4′ are charged with elemental indium and antimony: Thereafter the apparatus is evacuated with a vacuum suction system 7 to a pressure of 133.32 × 10 _3 Pa _133.32 × 10 _6 Pa (10 _3 to 10 _6 Torr). By heating the boats 4, 4′ to a higher temperature, the desired thin film of InSb complex crystalline semiconductor is formed on the substrate 1. The thus-prepared thin film of InSb complex crystalline semiconductor of the present invention is fabricated into a semiconductor device such as a Hall element or magnetoresistive element by, optionally pasting or transferring the film onto another substrate such as ferrite, patterning and connection to electrodes. The present invention is now described in greater detail by reference to the following examples and comparative examples which are given here for illustrative purposes only, and are not intended to limit its scope. The electric characteristics of the thin semiconducting films made in the following examples and comparative examples were measured by applying a constant current of 5 mA, a constant voltage of 1 V, and magnetic field of 500 gauss to films that were shaped as shown in Figure 1 (lengh: 10 mm, width: 5 mm). The composition of the crystal grains was analyzed by the wet process of atomic absorption spectroscopy, wherein a predetermined amount of the thin film was dissolved in dilute nitric acid and the light absorbance of the indium and antimony in that solution was measured with an atomic absorption spectroscope (Model AA-646 of Shimadzu Seisakusho, Ltd.). In the analysis, calibration curves were depicted using two separate solutions of indium and antimony, and on the basis of those curves, the value of F In /F Sb was calculated from the measured values of light absorbance. Reference Example 1 Forty eight thin films of indium-antimony complex crystalline semiconductor having a thickness between 1.0 and 2.0 µm and varying values of F In /F Sb were made by depositing controlled amounts of the vapors of indium (6-N of Furuuchi Chemical Co., Ltd.) and antimony (6-N of the same company) onto a mica substrate in the apparatus of Figure 5. The substrate temperature was 420°C, the degree of vacuum, 66.6 × 10 _6 -399.9 × 10 _6 Pa @ 2.0 to 3.0 × 10 _6 Torr), and the deposition rate, 0.1 to 0.3 nm/sec (1.0 to 3.0 Å/sec). The electric characteristics and F In /F Sb of the respective samples were measured, and the result is shown in Figure 2 as a graph depicting the relation between F In /F Sb and Hall mobility (µ H ) in cm²/V · sec. As one can see from the graph of Figure 2, a maximum mobility of 20,100 cm²/V · sec was obtained when the F In /F Sb was 1.4411, and the Hall coefficient was 346 cm³/C. In the F In /F Sb range of from 1.1/1 to 1.7/1, the mobility was between 9,500 and 20,100 cm²/ V · sec, and the Hall coefficient was between 254 and 346 cm³/C. Analysis of each film with an X-Ray diffractometer showed the presence of two peaks for an indium-antimony compound and elemental indium, and they were found to have high degree of selective orientation. Further, Laue photographs of each film revealed that those having a value of F In /F Sb in the range of from 1.1/1 to 1.7/1 had no ring characteristic of polycrystals and hence were found to have high degree of crystalline orientation. But those films which had values of F In /F Sb outside this range had the characteristic ring. This data shows that the semiconductor of the present invention formed thin semiconducting films having high crystallinity. Reference Example 2 Thin films of indium-antimony complex crystalline semiconductor having values of F In /F Sb in the range of from 1.31/1 to 1.48/1 were prepared as in Reference Example 1 except that the mica substrate was replaced by a glass plate (Corning 7059). The Hall mobilities of the films were in the range of from 2,700 to 5,500 cm²/V · sec. Comparative Example 1 Three thin films of indium-antimony complex crystalline semiconductor having F In /F Sb values of 0.98/1, 1.03/1 and 1.82/1, respectively, were prepared as in Reference Example 1 except that a glass plate (Corning 7059) was used as substrate. The films had the Hall mobilities of 1,200, 1,900 znd 1,700 cm²/V · sec, respectively. Reference Exemple 3 Seven thin films of indium-antimony complex crystalline semiconductor were prepared by depositing the vapors of indium and antimony (both being 6-N of Furuuchi Chemical Co., Ltd.) on a mica substrate in the apparatus of Figure 5 wherein both the substrate and the respective boats were heated with a tungsten heater and the temperature of the substrate was held at 440°C by proportional, integral and differential control. The degree of vacuum in the vapor deposition system was preset at 199.9 × 10 _6 Pa (1.5 × 10 _6 Torr), the boats were charged with the same amounts of indium and antimony for the seven films so that the A In /A Sb value was 1.45/1, and the power supplied to the boats was so controlled that the film thickness became 1 micron in 30 minutes. Each film was analyzed for its composition by subjecting part of each film to atomic absorption spectroscopy. The seven films had values of F In /F Sb in the range of from 1.42/1 to 1.49/1. There was little variation in the Hall mobility of the seven films: the respective values were within the range of from 20.000 to 21,500 cm²/V · sec. Additional three groups of seven thin semiconducting films were prepared as in above except that the amounts of indium and antimony were so changed that the values of A In /A Sb were 1. 15/1, 1.3/1 and 1.6/1, respectively. The composition analysis and mobility data for the films of the respective groups are indicated in Table I below. For comparison, thin semiconducting films were prepared by controlling the value of A In /A Sb to be at 0.9/1 and 1.8/1. As shown in Table 2 below, there was not a high degree of agreement between A In /A Sb and F In /F Sb , the films had low values of mobility, and there was great variation in the mobility. What is more, the films prepared by controlling the A In /A Sb at 0.9/1 were brittle and had high offset voltage. Those which were prepared by controlling the A In /A Sb at 1.8/1 were apparently not uniform and even contained at transparent area. Laue photographs were taken of the thin films of indium-antimony complex crystalline semiconductor that were prepared according to the process of the present invention and these films (A In /A Sb = 0.9/1 and 1.8/1) which were prepared by not using the present invention. The first group of films had no characteristic ring, whereas the second group of films had a distinct ring. Clearly, the process of the present invention is very effective for use in industrial applications: as an immediate advantage, the film composition can be controlled by controlling the value of A In /A Sb , and as a secondary merit, the process is capable of making a thin semiconducting film whose mobility is sufficiently high for practical purposes and varies little from batch to batch. Reference Examples 4 to 6 Vacuum deposition was effected as in Reference Example 3 except that a sapphire (0001) substrate was used. The sapphire substrate was subjected to the following preliminary treatment: its surface was treated with a 9: 1 mixture of H₂SO₄ and H₃PO₄ at 80°C for 2 hours, then immersed in 1 N KOH, washed with water and dried. Immediately after the preliminary treatment, the substrate was mounted in a vacuum enclosure, and three groups of five thin films of indium-antimony complex crystalline semiconductor were prepared by controlling the value of A In /A Sb to be at 1. 2/1 (Reference Example 4), 1.4/1 (Reference Example 5) and 1.6/1 (Reference Example 6), respectively. The mobilities of the respective groups of films are shown in Table 3 below. Comparative Example 2 Thin films of indium-antimony complex crystalline semiconductor were prepared as in Example 3 except that a sapphire (0001) substrate was used. Vacuum deposition was conducted by controlling the A In /A Sb at 0.95/1 and 1.8/1. Those films prepared by controlling the A In /A Sb at 0.95/1 had the mobilities in the range of from 1,700 to 2,800 cm²/V · sec, and those which were prepared by controlling the A In /A Sb at 1.8/1 had the mobilities in the range of from 1,000 to 2,500 cm²/V · sec. Reference Example 7 A thin film of indium-antimony complex crystalline semiconductor having an F In /F Sb of 1.54/1 was formed on a mica substrate as in Reference Example 3. The film was then bonded to a ferrite plate, patterned, connected to electrodes, wirebonded and moded to fabricate 340 Hall elements each measuring 3 mm long and 2.5 mm wide. The output voltages from the Hall elements were measured at a constant current of 5 mA or a constant voltage of 1 V, and in a magnetic field of 500 gauss. The results were: and The |V Hio | and |V Hvo | were offset voltages as produced in the absence of magnetic field with a constant current and voltage applied, respectively. Comparative Example 3 A thin film of indium-antimony complex crystalline semiconductor having an F In /F Sb of 1.04/1 was formed on a mica substrate as in Reference Example 3, and Hall elements were fabricated from the film as in Reference Example 7. The output voltages from the respective samples were measured as in Reference Example 7, and the results were: Reference Example 8 A vacuum deposition apparatus having a rotary substrate holder capable of supporting six wafers on the circumference was used. A mica substrate was used, and its temperature was detected by a Pt-Rh thermocouple positioned 10 mm above each wafer. Another thermocouple was positioned above each wafer but at different heights for controlling the substrate temperature. Since the detected substrate temperature differs from the actual substrate temperature, it was corrected for the value of the stationary holder. The values of the substrate temperature indicated in the following examples are those after correction by thixsmethod. Elemental indium and antimony to be deposited were 6-N of Furuuchi Chemical Co., Ltd. Six thin semiconducting films were formed at degree of vacuum of 1 × 10 _6 Torr; the substrate temperature was preset at 380°C, and indium and antimony were vaporized so that the A In /A Sb was controlled at 1.45/1, and a deposited film having a thickness of 1.1 µ was formed in a period of 30 minutes, during which the substrate temperature was increased to 460°C. The six wafers were patterned as shown in Figure 1 and their characteristics were measured: the mobility was between 23,000 and 24,500 cm²/V · sec and the Hall coefficient was as high as 390 to 420 cm³/C. All films had high gloss. Reference Example 9 Thin semiconducting films were prepared by vacuum deposition as in Example 8 except that the substrate temperature was held at 420°C. The films had the mobilities of 17,100 to 18,900 cm²/V · sec, and the Hall coefficients of 270 to 280 cm³/C. Reference Example 10 Thin semiconducting films were prepared as in Reference Example 8 except that the substrate temperature was preset at 480°C that was higher than the limiting temperature of the substrate. The average mobility of the films was 3.000 cm²/ V · sec, and the Hall coefficient was between 230 and 250 cm³/C. The films were non-glossy and had great offset voltage. Reference Examples 11 to 13 Three groups of thin conducting films were prepared as in Reference Example 8 except that the A In /A Sb was varied to 1.15/1 (Reference Example 11), 1.3/1 (Reference Example 12) and 1. 6/1 (Reference Example 13). The mobility data for the three examples is given in Table 4 below. Comparative Example 4 Thin films of indium-antimony compound semiconductor were prepared as in Reference Example 8 except that the A,n/Asb was controlled to be at 0.9/1 and 1.8/1. Both types of films had a mobility much lower than 10,000 cm²/V · sec: the first type (A In /A Sb = 0.9/1) had an average mobility of 6,000 cm²/V · sec, and the second type (A In /A Sb = 1.8/1) had an average of 3,000 cm²/V · sec. The first type of films had large offset voltage, and the second type of films were not uniform and had pinholes here and there. Reference Examples 14 to 17 Thin semiconducting films were prepared by vacuum deposition as in Example 8 by controlling the A In /A Sb at 1.45/1 except that the degree of vacuum was held at 8 × 10 _7 Torr and the final substrate temperature was 480°C whilst the initial substrate temperatures were 400°C (Reference Example 14), 420°C (Reference Example 15), 440°C (Reference Example 16) and 470°C (Reference Example 17), respectively. The results are shown in Table 5 below. Reference Examples 18 to 21 Thin semiconducting films were prepared as in Reference Example 8 except that the substrate temperature was held at the average substrate temperatures in Reference Examples 14 to 17, i.e., 440°C (Reference Example 18), 450°C (Reference Example 19), 460°C (Reference Example 20) and 475°C (Reference Example 21). The results are shown in Table 6 below. Reference Example 22 Six wafers of indium-antimony semiconductor were prepared using the same apparatus, substrate and vaporizable materials as in Reference Example 8. First, the degree of vacuum and the substrate temperature were preset at 133.32 × 10 _6 Pa at (1 × 10 _6 Torr) and 400°C, respectively. Then, the needle valve was opened to introduce nitrogen gas to increase the pressure to 133.32 × 10 _4 Pa (1 × 10 _4 Torr). Elemental indium and antimony were vaporized in such a manner that the A In /A Sb was held at 1.4/1, and thin films each having a thickness of 1.1 µm were formed over a period of 3o minutes, during which the substrate temperature was elevated to 480°C and nitrogen gas was continuously supplied through the needle valve. The resulting six wafers were patterned as depicted in Figure 1, and their mobility was measured. The result was: 29,800-32,500 cm²/V · sec. Reference Example 23 Thin semiconducting films were prepared as in Reference Example 22 except that the substrate temperature was held at 440°C. The films had the mobilities of from 24,400 to 26,200 cm²/V · sec. Reference Examples 24 to 26 Three groups of thin semiconducting films were prepared using the same apparatus, substrate and vaporizable material as in Example Reference 8. First, the degree of vacuum and the substrate temperature were preset at 133.32 × 10 _6 Pa (1 × 10 _6 Torr) and 400°C, respectively. Then the needle valve was opened to introduce nitrogen gas to increase the pressure to 933.24 × 10 _5 Pa (7 × 10 _5 Torr). Elemental indium and antimony were vaporized and condensed on the substrate to form a film about 1 µm thick over a period of 30 minutes while the substrate temperature was elevated to 500°C and nitrogen gas was continuously supplied through the needle valve. The rate of increasing the substrate temperature in the period of vacuum deposition was as follows: 1-2°C/min for the first 10 minutes, from 12 to 20 minutes, and from 22 to 30 minutes; 12-14°C/min from 10 to 12 minutes; and 6-7°C/ min from 20 to 22 minutes. During the vacuum deposition, the A In /A Sb was controlled to be at 1. 20/1 (Reference Example 24), 1. 41/1 (Reference Example 25) and 1.53/1 (Reference Example 26). The mobility data for the resulting films is given in Table 7 below. Example 1 A vacuum deposition apparatus having a rotary substrate holder capable of supporting six wafers on the circumference was used. The substrate temperature was detected by three Pt-Rh thermocouples located 10 mm above the wafers, and the average of the detected values was taken. Two other thermocouples were located for the control of the substrate temperature: one was positioned 5 mm above the wafers, and the other 15 mm above. The degree of vacuum was measured with a B-A gauge inserted into a pipe connecting the bell jar and the evacuating device. a mica plate was used as substrate and elemental indium and antimony, 6-N, of Furuuchi Chemical Co., Ltd. were used as vaporizable materials. First, the pressure in the bell jar was reduced to 199.9 × 10 _6 Pa (1.5 × 10 _6 Torr), and the substrate temperature was preset at 395°C. Power was supplied to the indium and antimony boats so that the A In /A Sb was held at 0.6/1 for the first 8 minutes, and at 1.40/1 for the remaining period of the vacuum deposition. The vacuum deposition was continued for 40 minutes until the film thickness became 1.2 µm. The final substrate temperature was 500°C. After the deposition, the average A In /A Sb was calculated from the amounts of indium and antimony vaporized, and was found to be 1.35/1. The six wafers were patterned as depicted in Figure 1 and their characteristics were measured: the Hall coefficient was between 330 and 390 cm³/C, and the mobility was between 49,200 and 55,700 cm²/V · sec. The wafers had whitish silver gloss, and were comprised of crystal grains of a size of several hundred microns which were visible to the naked eye. Example 2 Thin semiconducting films qere prepared as in Example 1 except that power was supplied to the indium and antimony boats so that the A In /A Sb was held at 1.30/1 throughout the period of vacuum deposition. The films had no crystal grain and had a mobility between 19,000 and 23,600 cm²/V · sec. Comparative Example 5 Thin semiconducting films were prepared as in Example 1 except that the initial substrate temperature was 370°C. The average value of A In /A Sb was 1.32/1, and the films obtained had mobilities in the range of from 23,300 to 23,800 cm 2 /V · sec. Example 3 Six wafers of indium-antimony semiconductor were prepared using the same apparatus, substrate and vaporizable materials as in Example 1. First, the pressure in the bell jar was reduced to 266.6 × 10 _6 Pa (2 × 10 _6 Torr, then the needle valve was opened to introduce 4-N nitrogen gas to increase the pressure of 666.6 × 10 _6 Pa (5 × 10 _5 Torr). Then, the substrate temperature was preset at 420°C, and the power supplied to the indium and antimony boats was so controlled that the A In /A Sb was held at 1.0/1 or less for the first 8 minutes, and at 1.30/1 for the remaining period. The vacuum deposition was continued for 30 minutes until the film thickness became 0.9 µm. Nitrogen gas was supplied throughout the period of the deposition. The final substrate temperature was 510°C, and the average A In /A Sb was 1.23/1. Four samples of semiconductor element having the pattern of Figure 1 were made from each wafer, and their characteristics were measured: the Hall coefficient was between 380 and 450 cm³/C and the mobility was between 54,300 and 61,400 cm²/ V · sec. The wafers had silver white gloss and were comprised of crystal grains of a size of several millimeters and having a hexagonal section. X-ray diffractiometry gave a strong diffraction line for both indium-antimony compound (111) and indium crystal (101). The F In /F Sb values of the films as measured by atomic absorption spectroscopy were in the range of from 1. 18/1 to 1.24/1. Reference Example 27 Thin semiconducting films were prepared by vacuum deposition as in Example 3 except that the initial substrate temperature was 445°C. The resulting films had crystalline areas and transparent areas. The variation in the amount of deposition on the substrate was as great as 20% or more. The mobility of the films varied over a fairly wide range of from 21,700 to 48.000 cm²/ V · sec. Comparative Example 6 Thin semiconducting films were prepared by vacuum deposition as in Example 3 except that the initial substrate temperature was 405°C. The resulting films were bluish. Their mobility was in the range of from 14,500 to 17,000 cm²/V · sec. Example 4 Thin semiconducting films were prepared by vacuum deposition as in Example 3. except that the 4-N nitrogen gas was replaced by 4-N argon gas. The average value of A In /A Sb was 1.20/1. The mobility of the films was between 37,000 and 46,000 cm²/V · sec. Example 5 Six thin films of indium-antimony semiconductor were prepared by using the same apparatus, substrate and vaporizable materials as in Example 1. The bell jar was supplied with 4-N nitrogen gas until the pressure in the bell jar was 8 × 10 _5 Torr. The substrate temperature was initially set at 425°C, and the power supplied to the indium and antimony boats was so controlled that the A In /A Sb was held at 1.0/1 or less for the first 5 minutes and at 1.45/1 for the remaining period. The deposition of indium and antimony vapors was continued for 30 minutes until the film thickness became 1.0 µm. The final substrate temperature was 515°C, and the average value of A In /A Sb was 1.38/1. The six wafers were patterned as shown in Figure 1 and their characteristics were measured: the Hall coefficient was between 360 and 430 cm³/C and the mobility was between 48,700 and 56,600 cm²/V · sec. While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims: 1. A process for producing a Hall element or magnetoresistive element comprising an indium-antimony complex crystalline semiconductor thin film consisting of crystals of an indium-antimony binary compound and crystals of indium alone by vacuum depositing vapors of indium and antimony on a substrate in such a manner that the arrival rate ratio of indium atoms to antimony atoms is held at 1.0/1 or less during the initial stage of the vacuum deposition, this being the period in which the semiconductor film attains a thickness of about 100 nm or 200 nm, and at the same time, the temperature of the substrate T is held at a level that satisfies the relation wherein Tc is the critical temperature of the substrate on the absolute scale (°K) that is given by the formula wherein P is the pressure in the vacuum deposition system (expressed in Torrs), the temperature of the substrate also being held in the initial stage of the vacuum deposition at a level lower than the limiting temperature given by the formula wherein Tc is the limiting temperature of the substrate on the absolute scale (°K) and P is the pressure during the vacuum deposition system (expressed in Torrs), and wherein the average arrival rate ratio of the indium atoms to antimony atoms during the deposition is controlled to be within the range of from 1.1/1 to 1.7/1. 2. A process according to claim 1, wherein the vacuum deposition is performed in the presence of nitrogen. 3. A process as in claim 1 or 2, wherein the vacuum depositing is conducted in such a manner that the average arrival rate ratio of indium atoms to antimony atoms is controlled to be within the range of from 1.1/1 to 1.5/1.

Inventors: KIMURA, TAKEO, KUBOYAMA, KEIJI, MATSUI, TAKEKI
Applicants: ASAHI KASEI KOGYO KABUSHIKI KAISHA
Application year: 1982
Main classification: H01L43
IPC codes: H01L43