P-type GaAs single crystal and method for manufacturing the same

Abstract: Disclosed are a P-type GaAs single crystal having an average dislocation density of 500 cm -2 or lower, and a manufacturing method therefor. The P-type GaAs single crystal is characterized by containing, as dopants, Si at an atomic concentration of from 1 x 10 17 to 1 x 10 19 cm -3 and Zn at an atomic concentration of from 2 x 10 18 to 6 x 10 19 cm -3 . Further, as another example, B is contained at an atomic concentration of from 1 x 10 17 to 1 x 10 20 cm -3 .

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a P-type GaAs single crystal having low dislocation, and a manufacturing method therefor. Related Arts P-type GaAs single crystals have been widely used as sliced and epitaxially grown for use in manufacturing a compound semiconductor laser or a light-emitting diode (LED). It is well known that the P-type GaAs single crystals widely used for compound semiconductor lasers and LEDs can be manufactured using various methods, such as the horizontal Bridgman (HB) method, the horizontal gradient freeze (GF) method, the liquid encapsulated crystal growth (LEC) method, the vertical Bridgman (VB) method, and the vertical gradient freeze (VGF) method. Since high light emission efficiency and long service life are requisite qualities for a compound semiconductor laser, a P-type GaAs single crystal having a lower dislocation density is required. Therefore, generally, the horizontal Bridgman (HB) method, the gradient freeze (GF) method, the vertical Bridgman (VB) method, or the vertical gradient freeze (VGF) method is employed to manufacture a P-type GaAs single crystal. JP-A-57-059735 and JP-A-58-009790 describe compositions and thermal conditions for manufacturing a P-type GaAs single crystal with a low dislocation density. Doping with Si and Zn is investigated, as is doping with Zn and S. However, when using any of these methods, the average dislocation density is equal to or greater than 1000 cm -2 , and it is difficult to obtain a high yield when manufacturing P-type GaAs single crystals having an average dislocation density of 500 cm -2 or lower. On the contrary, it is known that doping a crystal with S and Si can effectively reduce dislocation. Vertical and horizontal methods of growing doped GaAs single crystals are compared, in Hagi et al . (Proc. 9T Conf. (SIMC), Toulouse, pp 279-282, 24 April 1996), for their ability to produce crystals containing few defects. Doping with Si and B is investigated. As example means for resolving the above shortcomings, doping GaAs crystal with Zn and S using the horizontal Bridgman (HB) method is described in JP-A-63-57079. However, although a P-type GaAs single crystal having an average dislocation density of 100 cm -2 or lower can be obtained using this method, it is difficult to manufacture a P-type GaAs single crystal having an average dislocation density of 500 cm -2 . It has been reported that In, which is a neutral impurity, can contribute to the reduction of the dislocation of GaAs crystal (Proc. 12 th Intern. Symp. on GaAs and Related Compounds, London-Bristol, 1986, p. 7-2). As related in this report, a 2-inch GaAs wafer which was doped with Zn, at a density of 1.5 x 10 19 cm -3 , and In, at a density of 4.0 x 10 19 cm -3 , served as a semiconductor wafer having no dislocation. However, since the segregation coefficient of In is small, i.e., 0.1, in order to perform the high density doping of a crystal with In, a single crystal must be manufactured from melt-GaAs to which a large amount of In has been added in advance. However, if a crystal is manufactured under these conditions, cell growth is begun due to constitutional supercooling during the solidifying of the crystal, and there is a considerable reduction in productivity. SUMMARY OF THE INVENTION It is, therefore, one objective of the present invention to provide a P-type GaAs single crystal which resolves the conventional problems, and a manufacturing method therefor. It is another objective of the present invention to provide a P-type GaAs single crystal having an average dislocation density of 500 cm -2 . In one aspect, according to the present invention, there is provided a P-type GaAs single crystal as set out in claim 1. Preferably the atomic ratio, for said P-type dopant to Si, is 2 to 100. Particularly, when the dopant has an atomic concentration of 1 x 10 17 to 1 x 10 20 cm -3 , a P-type GaAs single crystal having a lower dislocation can be obtained. Preferably, the carrier concentration is 1 x 10 18 to 5 x 10 19 cm -3 . The average dislocation density of such a P-type GaAs single crystal can be equal to or lower than 500 cm -2 . Furthermore, at least part of the Si can be replaced by Se and/or Te, e.g. by up to 50 atomic %. The doping method is not limited to the use of any of the above dopants. A doping source can be, for example, a metal, a compound, an oxide, or an impurity in polycrystal or in a container, and can take the form of a solid, a liquid or a gas. In a second aspect the invention provides a method of manufacture of a P-type GaAs single crystal as set out in claim 12. The P-type dopant may be loaded at a density of from 1 x 10 18 to 5 x 10 20 cm -3 . The horizontal boat growth method or the vertical boat growth method can be employed. Other features and effects of the present invention will become apparent during the course of the descriptions given for the following embodiments of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram illustrating an apparatus used to manufacture a single crystal according to a first embodiment of the present invention; Fig. 2 is a schematic diagram illustrating an apparatus used to manufacture a single crystal according to a second embodiment of the present invention; Fig. 3 is a schematic diagram illustrating an apparatus used to manufacture a single crystal according to a third embodiment of the present invention; and DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will now be described in detail while referring to the accompanying drawings. As previously described, a P-type GaAs single crystal which has been grown is sliced and is used for an epitaxial semiconductor wafer. In the explanation for the present invention, except where otherwise specified, the meanings of terms for the P-type GaAs single crystal and the scope of the present invention include those for a P-type GaAs single crystal which has been grown and a P-type GaAs single crystal semiconductor wafer which has been prepared as a substrate by slicing the P-type GaAs single cristal. The present inventor has studied the above described problem, which is present in the prior art. As a result, it has been found that when the doping with Si and a P-type dopant of a GaAs single crystal is doubled, in particular when both dopants are present at a specific ratio, i.e., at an atomic ratio of the P-type dopant to Si ranging from 1.5 to 200, preferably 2 to 200 and even more preferably 2 to 50, Si effectively restricts the dislocation movement, and a P-type GaAs single crystal having low dislocation can be obtained. Normally, when the densities established for Si and a P-type dopant, such as an impurity, fall within a predetermined range, a P-type GaAs single crystal can be manufactured which has a preferable, average dislocation density. According to one embodiment of the present invention, since as an impurity the Si content fell in an atomic range of from 1 x 10 17 to 5 x 10 19 cm -3 , in particular, from 1 x 10 17 to 1 x 10 19 cm -3 , and a P-type dopant content fell in an atomic range of from 1.1 x 10 17 to 1 x 10 20 cm -3 , in particular, from 1 x 10 18 to 1 x 10 20 cm -3 , preferably from 2 x 10 18 to 6 x 10 19 cm -3 , more preferably, from 2 x 10 18 to 5 x 10 19 cm -3 , a P-type GaAs single crystal having a low dislocation density was obtained. When the Si atomic concentration is equal to or higher than 1 x 10 18 cm -3 , greater low dislocation effects can be obtained. Further, if the Si atomic concentration exceeds 1 x 10 19 cm -3 , a tiny deposited substance tends to be generated due to an impurity, and cell growth induced by constitutional supercooling is begun. Therefore, as an impurity, a practical Si atomic concentration content ranges from 1 x 10 18 to 1 x 10 19 cm -3 . Generally, one element is selected as a P-type dopant from C, Be, Zn, Cd, Li, Ge, Au, Mn, Ag, Pb, Co, Ni, Cu and Fe. Zn is the element which is most preferred. In particular, Zn is preferable because, if its content ranges from 2 x 10 18 to 6 x 10 19 cm -3 , constitutional supercooling seldom occurs during crystal growth, and a low dislocation density can be obtained. When the atomic concentration exceeds 6 x 10 19 cm -3 , constitutional supercooling tends to occur during crystal growth and the manufacturing yield tends to be reduced. It is preferable that the carrier concentration be from 1 x 10 18 cm -3 to 5 x 10 19 cm -3 for the P-type semiconductor wafer. For manufacturing a P-type GaAs single crystal having an average dislocation density which is equal to or lower than 500 cm -2 , according to the present invention only the Si and P-type dopant need be double doped, as is described above. However, in order to manufacture a single crystal having a lower dislocation density, it is preferable that B be contained at an atomic ratio relative to Si which ranges from 0.001 to 1000, in particular, 0.001 to 100, or more preferably 0.05 to 50. Generally, the B atomic concentration content ranges from 1 x 10 17 to 1 x 10 20 cm -3 , and preferably from 1 x 10 18 to 5 x 10 19 cm -3 . Further, either a horizontal boat method, such as the horizontal Bridgman (HB) method or the horizontal gradient freeze (GF) method, or a vertical boat method, such as the vertical Bridgman (VB) method or the vertical gradient freeze (VGF) method, may be employed as the method used for the manufacture of a P-type GaAs single crystal having an average dislocation density of 500 cm -2 or lower. According to the horizontal boat method (HB, GF), a horizontal (boat-shaped) deposition container is employed, and a seed crystal is positioned at one end of the container. Whereas, in accordance with the vertical boat method (VB or VGF), a vertically disposed long deposition container, similar to a crucible, is employed, and a seed crystal is positioned at the lower end. Either method constitutes a P-type GaAs single crystal manufacturing method which comprises the steps of: positioning a GaAs single seed crystal at one end of a deposition container, and positioning, in the deposition container, at least one part of a GaAs crystal growing material and a dopant; heating the deposition container and its vicinity, and adjusting, in the deposition container, melt-GaAs in which the dopant is contained; performing seeding; and cooling the deposition container in order to limit the growth of a P-type GaAs single crystal. The feature of the present invention is that a dopant is so positioned in a deposition container that in a GaAs single crystal for the Si and the P-type dopant the density content for the atomic ratio of the P-type dopant relative to Si ranges from 1.5 to 200, as described above, and so that normally the Si and the P-type dopant content densities respectively range from 1 x 10 17 to 5 x 10 19 cm -3 , and from 1 x 10 18 to 1 x 10 20 cm -3 . When Zn is employed as the P-type dopant, it is preferable that the Zn content have a density of from 2 x 10 18 to 6 x 10 19 cm -3 . When B is employed as a dopant, it is so disposed at a specific atomic ratio relative to Si of from 0.001 to 1000. Normally, B is disposed at the atomic concentration of from 1 x 10 17 to 1 x 10 20 cm -3 . While the present invention is effective when applied for either the vertical or the horizontal boat growing method, its application for the vertical boat method is the most preferable because then the disk wafer manufacturing process can provide a high yield, larger wafers can be manufactured, and single crystals having a lower dislocation density can be produced. According to the present invention, a large P-type GaAs single crystal semiconductor wafer can be fabricated for which the average dislocation density is equal to or lower than 500 cm -2 , the surface area (the dimensions for one face) is greater than 20 cm 2 , the total surface area for both faces is grater than 40 cm 2 , and the diameter exceeds 50.8 mm (2 inches), and is actually equal to or greater than 2.5 inches(the area equal to or greater than 31 cm 2 for one face) or 3 inches(the area equal to or greater than 45 cm 2 for one face). A single crystal semiconductor wafer having a round shape can be efficiently fabricated by the above explained boat growing methods according to present invention. However, the present invention is not limited to obtain such the round shaped single crystal semiconductor wafer, and can be applied to other single crystal semiconductor wafers having any type of shapes such as square, as far as characteristics of the wafer is satisfied according to the present invention. When at least one part of Si is replaced by doping with an impurity of Se and/or Te, the same effect can be also obtained as is obtained when using only Si. As is described above, according to the present invention, a P-type GaAs single crystal having a low dislocation density can be obtained when a GaAs single crystal contains Si and a P-type dopant, or when the crystal is doped with Si, and a B or a P-type dopant. Since Si provides low dislocation effects at a density which is approximately 1/10 that of In, doping with only a small amount of Si is required, and constitutional supercooling due to segregation seldom occurs during the fabrication of a crystal. Therefore, a high yield can be obtained for a P-type GaAs single crystal which has a low dislocation density. Compared with conventional crystals, the thus obtained P-type GaAs single crystals and P-type GaAs single crystal wafers have low dislocation densities of 500 cm -2 , or particularly, of lower than 400 cm -2 . When such a semiconductor wafer is employed as a compound semiconductor laser wafer, a laser having high light emission efficiency and a long service life can be obtained. Embodiment 1 As is shown in Fig. 1, a GaAs seed crystal (3) was loaded at the bottom of a pBN (thermally decomposed boron nitride) crucible (1) having a 3-inch diameter, and 4000 grams of GaAs polycrystal (4) and 50 grams of B 2 O 3 (5) were loaded above it. Then, 1.5 grams of Zn (6) and 0.5 gram of Si (7) were added, and in a vacuum the crucible (1) was sealed inside a quartz ampoule (2). The quartz ampoule (2) was inserted into a growth furnace where it was heated by a heater (8), and seeding occurred when the GaAs polycrystal (4) and a part of the seed crystal (3) were melted. The quartz ampoule (2) was cooled while a temperature gradient of from 3 to 5°C/cm was maintained, and a GaAs single crystal was obtained. The single crystal was sliced, and a 3-inch GaAs wafer, having the area of 45 cm 2 for one face and a crystal face (100), was obtained for which melt-KOH etching was performed for thirty minutes. The dislocation density was then measured by observing the wafer using an optical microscope. The etched pits in a 1 x 1 mm area within the visual field of the microscope were counted, and the result was multiplied by 100 to obtain the dislocation density for 1 cm 2 . Measurements were conducted at 37 locations at intervals of 10 mm to acquire the average dislocation density. The average dislocation density was 180 cm -2 . The carrier concentration of the wafer was 1.2 x 10 19 cm -3 , which is indicative of a P-type conductive wafer. And the impurity densities, as determined when the wafer was measured using an SIMS, were those shown in table I. Five crystals were grown under the above described conditions, and all the obtained crystals were single crystals. Comparative Example 1 As is shown in Fig. 2, a GaAs seed crystal (3) was loaded at the bottom of a quartz crucible (1) having a 3-inch diameter, and 4000 grams of GaAs polycrystal (4) was loaded above it. Then, 1.5 grams of Zn (6) and 0.2 gram of Si (7) were added, and in a vacuum, the crucible (1) was sealed inside a quartz ampoule (2). The quartz ampoule (2) was inserted into a growth furnace where it was heated by a heater (8), and seeding occurred when the GaAs polycrystal (4) and a part of the seed crystal (3) were melted. The quartz ampoule (2) was cooled while a temperature gradient of 3 to 5°C/cm was maintained, and a GaAs single crystal was obtained. The single crystal was sliced, and a 3-inch GaAs wafer having a crystal face (100) was obtained for which melt-KOH etching was performed for thirty minutes. The dislocation density was then measured in the same manner as in Embodiment 1, and the average dislocation density was found to be 380 cm -2 . The carrier concentration of the wafer was 1.5 x 10 19 cm -3 , which is indicative of a P-type conductive wafer. And the impurity densities, as determined when the wafer was measured using an SIMS, were those shown in table I. Five crystals were grown under the conditions described above, and all the obtained crystals were single crystals. Comparative Example 2 As is shown in Fig. 3, 2750 grams of Ga (9), 3.0 grams of Zn (6), and 0.2 gram of Si (7) were loaded in a horizontal quartz boat (10), at one end of which was disposed a GaAs seed crystal (3). In a vacuum, the quartz boat (10) and metal arsenic (11) were then sealed in a quartz ampoule (2). The quartz ample (2) was inserted into a growth furnace where it was heated by a heater (8) to composite melt-GaAs, and seeding occurred when a part of the GaAs seed crystal (3) was melted. The quartz ampoule (2) was cooled while a temperature gradient of 0.5 to 3°C/cm was maintained, and a GaAs single crystal was obtained. The single crystal was sliced and a 2-inch GaAs wafer having a face (100) was obtained for which melt-KOH etching was performed for thirty minutes. Then, the dislocation density was measured in the same manner as in Embodiment 1, except that measurements were conducted at 69 locations at intervals of 5 mm. The average dislocation density was 420 cm -2 . The carrier concentration of the GaAs wafer was 2.1 x 10 19 cm -3 , which is indicative of a P-type conductivity. The impurity densities, as determined when the wafer was measured using an SIMS, were those shown in table I. And when five crystals were grown under the conditions described above, all the obtained crystals were single crystals. Comparative Example 3 Growing of a GaAs single crystal was performed in the same manner as in Embodiment 1, with the exception that 0.01 gram of Si was added. The dislocation density of the thus obtained GaAs wafer was measured under the same conditions as in Embodiment 1, and the average density in a plane was found to be 1810 cm -2 . The impurity densities, as determined when the wafer was measured using an SIMS, were those shown in table I. Comparative Example 4 Growing of a GaAs single crystal was performed five times in the same manner as in Embodiment 1, with the exception that 1.5 grams of Si were added. Many tiny deposits of substances were generated by impurities, and only one single crystal was obtained. The dislocation density of a GaAs wafer, which was obtained by cutting the single crystal that was produced, was measured under the same conditions as in Embodiment 1, and the average density in a plane was found to be 2840 cm -2 . The impurity densities, as determined when the wafer was measured using an SIMS, were those shown in table of I. As is apparent from the Table I when the result obtained for Embodiment 1 of the present invention is compared with the results obtained for Comparative Examples 1 to 4, it is obvious that for a unit area a low etch pit density can be obtained by using a combination of densities for Zn and Si and B. As is described above in the embodiment, according to the present invention a P-type GaAs single crystal having a low dislocation density can be obtained by doping with Si, a P-type dopant and B. As a result, a compound semiconductor laser or a light emitting diode having high efficiency and a long service life can be produced by using the thus obtained P-type GaAs single crystal semiconductor wafer.

Claims: A P-type GaAs single crystal containing Si, a P-type dopant and B, wherein said P-type dopant is present at an atomic ratio relative to Si of from 1.5 to 200, and said B is present at an atomic ratio relative to Si, of from 0.001 to 1000. The P-type GaAs single crystal according to claim 1, wherein the atomic ratio of said P-type dopant relative to Si is in the range from 2 to 100. The P-type GaAs single crystal according to claim 1 or 2, wherein the Si content has an atomic concentration of from 1 x 10 17 to 5 x 10 19 cm -3 . The P-type GaAs single crystal according to claim 3, wherein said Si content has an atomic concentration of from 1 x 10 17 to 1 x 10 19 cm -3 . The P-type GaAs single crystal according to claim 1 or 2, wherein the content of said P-type dopant has an atomic concentration of from 1.1 x 10 17 to 1 x 10 20 cm -3 . The P-type GaAs single crystal according to claim 5, wherein said content of said P-type dopant has an atomic concentration of from 2 x 10 18 to 6 x 10 19 cm -3 . The P-type GaAs single crystal according to any one of claims 1 to 6, wherein said P-type dopant is an element selected from C, Be, Zn, Cd, Li, Ge, Au, Mn, Ag, Pb, Co, Ni, Cu and Fe. The P-type GaAs single crystal according to claim 7, wherein said P-type dopant is Zn. The P-type GaAs single crystal according to any one of claims 1 to 8, wherein said B content has an atomic concentration of from 1 x 10 17 to 1 x 10 20 cm -3 . The P-type GaAs single crystal according to claim 1, wherein at least a part of Si is replaced by Se and/or Te. The P-type GaAs single crystal according to any one of claims 1 to 10, wherein the carrier concentration is from 1 x 10 18 to 5 x 10 19 cm -3 . A method for manufacturing a P-type GaAs single crystal using a boat growth method comprising Si, a P-type dopant and B, the method including the step of: loading, in a deposition container, Si, a P-type dopant and B, so that in said P-type GaAs single crystal which is formed there is present Si at an atomic concentration of from 1 x 10 17 to 5 x 10 19 cm -3 , said P-type dopant at an atomic ratio relative to Si of 1.5 to 200, and said B at an atomic ratio relative to Si, of from 0.001 to 1000. The method according to claim 12 for manufacturing a P-type GaAs single crystal further comprising the steps of: positioning a GaAs single seed crystal at one end of the deposition container; positioning, in the deposition container, at least one part of a GaAs crystal growing material and the dopant; heating the deposition container and its vicinity; adjusting, in the deposition container, melt-GaAs in which the dopant is contained; performing seeding; and cooling the deposition container in order to limit the growth of a P-type GaAs single crystal. The method according to claim 12 or 13, wherein Si and Zn, which is a P-type indicative dopant in a GaAs single crystal, are loaded in a deposition container, so that said Si content has an atomic concentration of from 1 x 10 17 to 1 x 10 19 cm -3 , and said Zn has an atomic concentration of from 2 x 10 18 to 6 x 10 19 cm -3 . The method according to any one of claims 12 to 14, wherein the B content has an atomic concentration of from 1 x 10 17 to 1 x 10 20 cm -3 . The method according to any one of claims 12 to 15, wherein the deposition container is a horizontal type boat container. The method according to any one of claims 12 to 15, wherein the deposition container is a vertical type boat container.

Inventors: FUJISAWA HIDEO, KATANO KIZUKU, YAMAMOTO OSAMU, FUJISAWA, HIDEO, KATANO, KIZUKU, YAMAMOTO, OSAMU, Fujisawa, Hideo c/o Mitsubishi Chemical Corp., Katano, Kizuku c/o Mitsubishi Chemical Corp., Yamamoto, Osamu c/o Mitsubishi Chemical Corp.
Applicants: MITSUBISHI CHEM CORP, MITSUBISHI CHEMICAL CORPORATION
Application year: 1999
Main classification: C30B11
IPC codes: C30B11