METHODS OF MAKING SEMICONDUCTOR LIGHT-EMITTING DEVICES AND VAPOUR PHASE GROWTH APPARATUS USED FOR CARRYING OUT THE METHODS

Abstract: A method of making a semiconductor light-emitting device comprises forming by epitaxial growth on a substrate (1) a plurality of layers (61 to 65) of semiconductive compounds consisting of elements of groups III-V of the periodic table. The substrate (1) is heated to a temperature of 580°C to 630°C, and a mixed gas of triethyl compounds of metals of group III and a phosphine gas are separately fed and caused to flow in such a way that the ratio of phosphine to the triethyl com­ pounds of metals of group III is at least 300:1. The gases are mixed immediately upstream of the substrate (1) to form a semiconductive layer of a given composition comprising el­ ements of groups III-V on the substrate (1). The procedure is repeated to form a plurality of semiconductor layers (61 to 65) on the substrate (1), thereby obtaining a semiconductor light-­ emitting device. An apparatus (10) for carrying out the method is also described.

Description: METHODS OF MAKING SEMICONDUCTOR LIGHT-EMITTING DEVICES AND VAPOUR PHASE GROWTH APPARATUS USED FOR CARRYING OUT THE METHODS This invention relates to methods of making semiconductor lightemitting devices and vapour phase growth apparatus used for carrying out the methods. Semiconductive light-emitting devices using semiconductor compounds of elements of groups III-V of the periodic table, for example, double hereto junction-type semiconductor laser diodes, include, as particularly shown in Figure 1 of the accompanying drawings, a substrate 1 of a single crystal semiconductor compound, on which a first clad layer 2, an active layer 3, a second clad layer 4 and a cap layer 5 are epitaxially grown in that order. An insulating layer 6, such as of Si3N4, is formed on the cap layer 5, and has a through-hole in the form of a strip window 6a, through which one electrode 7 passes and is attached to the cap layer 5 in ohmic contact. Another electrode 8 is deposited on the other side of the substrate 1 in ohmic contact. In the light-emitting device using this type of semiconductive compound, it is convenient to use, as the substrate 1, a single crystal of GaAs as it is relatively inexpensive and is widely used. On the other hand, when a mixed crystal of elements of groups III-V, for example AlGaInP, is used as a semiconductor laser diode, lattice matching on the GaAs substrate 1 is possible with the highest direct transition-type band gap, permitting oscillation of light having a short wavelength. Thus, wide utility of the mixed crystal can be expected. However, with the semiconductor AlGaInP compound, epitaxial growth by conventional vapour phase epitaxial growth techniques or liquid phase epitaxial growth techniques is very difficult due to thermodynamic limitations. Formation of the AlGaInP semiconductor layer by the metal organic chemical vapour deposition (MOCVD) method has therefore been proposed. Where the MOCVD method is applied to the formation of AlGaInP compounds of groups III-V, it is common to use gases of organic metals such as triethyl compounds, for example triethylaluminium, triethylgallium and triethylindium (hereinafter referred to simply as TEA1, TEGa and TEIn, respectively) as starting feeds for Al, Ga, and In, which are metals of groups III-V. Moreover, phosphine, PH3, is used as a starting gas for phosphorus. However, TEIn is thermally unstable, whereas PH3 is very thermally stable. When the two gases are mixed at room temperature, a non-volatile intermediate product is formed and deposited on wall surfaces of a reaction furnance, thus making it difficult to form a crystalline epitaxial layer of good quality in a well-controlled manner. In order to suppress the intermediate reaction in the MOCVD method, it is usual to reduce the pressure in the reaction furnance or to feed the PH3 after decomposition. However, the growth under reduced pressure involves not only a complicated apparatus, but also low controllability. The method in which PH3 has been preliminarily decomposed, is undesirable because the feed gas temperature has to be increased to cause the decomposition. When the decomposed gas is combined and mixed, for example, with TEIn, which is thermally unstable as mentioned above, for passage to the substrate surface, TEIn tends to suffer unfavourable decomposition or intermediate reaction. Therefore, an AlGaInP expitaxial layer having good characteristics cannot be obtained in a well-controlled manner. According to the present invention there is provided a method of making a semiconductive light-emitting device by forming, on a substrate by epitaxial growth, a plurality of layers of semiconductive compounds consisting of elements of groups III-V of the periodic table, the method being characterised by the steps of: heating the substrate to a temperature of 5800C to 6300C; separately flowing a mixed gas of triethyl compounds of metals of group III and a gas of phosphine, wherein the ratio of phosphine to the triethyl compounds of metals of group III is at least 300:1; mixing said gases together immediately prior to the substrate, thereby forming a semiconductive layer of a selected composition comprising elements of group III-V on the substrate; and repeating the above procedure so as successively to form a plurality of layers on the substrate, the plurality of layers consisting of semiconductive compounds, each of which are represented by the formula: (AlyGal-y)xInl-xP in which 0 is less than or equal to y is less than or equal to 1 and 0 is less than or equal to x is less than or equal to 1. According to the present invention there is also provided a vapour phase growth apparatus for making a semiconductive light-emitting device by epitaxial growth of semiconductive compounds of elements of groups III-V, the apparatus comprising: an atmospheric reaction furnace; and a substrate mount positioned in said furnace, such that a gas passage having an inlet is established between the substrate mount and an inner side wall of the reaction furnace; characterised by: a first starting gas feed port located at the inlet of the gas passage and through which triethyl compounds of metals of group III of the periodic table are caused to flow; and a second starting gas feed port located between the inlet of the gas passage and the first starting material gas feed port and for the flow of phosphine; the second starting gas feed port being inclined with respect to the first starting gas feed port, the first and second starting gas feed ports having substantially the same shape and size, a mixed gas of the triethyl compounds of metals of group III and the phosphine flowing from the first and second starting gas feed port, respectively, being mixed immediately upstream of a substrate located near the inlet to the gas passage so that the mixed gas flows over and along the substrate surface. The invention will now be described by way of example with reference to the accompanying drawings, throughout which like parts are referred to by like references, and in which: Figure 1 is a schematic, sectional view showing a conventional semiconductive laser diode; Figure 2 is a schematic, enlarged, sectional view of an embodiment of a vapour phase growth apparatus according to the invention; Figures 3 and 4 are sectional views, taken along the lines A-A and B-B respectively of Figure 2; Figure 5 is a graph showing the relation between epitaxial growth rate and distance of a substrate from an inlet end; Figure 6 is a graph showing the relation between luminous intensity and substrate temperature; Figure 7 is a graph showing the relation between luminous intensity and PH3/III; ; Figure 8 is an enlarged, sectional view of a semiconductor laser device obtained by a method according to the invention; and Figures 9 and 10 are, respectively, curves of an output characteristic and an emission spectrum respectively. In Figures 2 to 4, there is shown an embodiment of vapour phase growth apparatus 10. The apparatus 10 includes a reaction furnace 11 made, for example, of a quartz tube. In the furnace 11, there is provided a substrate mounting 13, which is made, for example, from graphite, and on which a substrate 1 is mounted. A plurality of semiconductor layers of AlGaInP compounds are epitaxially grown on the substrate 1. The mounting 13 is heated so that the substrate 1 can be heated to a predetermined temperature. The substrate 1 consists of a GaAs monocrystal wafer. A heater for the mounting 13, and thus for the substrate 1, may be a high frequency inductor heater using a high frequency coil 14 provided around the furnace 11. A temperature detector such as a thermocouple 5 is provided for detecting the temperature of the mounting 13. The mounting 13 is provided in face-to-face relation with one side wall, for example, an upper wall surface 11a, of the furnace 11 to maintain a given space g therebetween, so that a gas passage 16 having a rectangular cross-section with a width W and a height g is established between the upper surface of the mounting 13 and the upper wall surface 11a of the furnace 11 along the longitudinal axis of the furnace 11. In this manner, the surface of the substrate 1 on the mounting 13 is exposed to the passage 16. The substrate 1 is located near an opening forming an inlet end 16a of the passage 16. A first starting gas feed pipe 19 having a first starting gas feed port 17, extends to and faces the inlet end 16a of the passage 16. In other words, the first feed port 17 is arranged almost coaxially with the passage 16, so that gas from the first feed port 17 passes along the axial direction of the passage 16. The first feed port 17 has a width W1 and a height dl, sufficient to cover (that is, at least as large as) the diameter or width of the substrate 1 mounted on the mounting 13. A second starting gas feed pipe 20 is provided which has a second starting gas feed port 18 and an opening between the gas passage 16 and the feed port 17 facing the passage 16. The second feed port 18 is arranged such that the direction of gas flow from the second feed port 18 is inclined (that is, is not parallel) with respect to the axial direction of the first feed port 17 and the passage 16. The direction of the gas flow from the second feed port 18 may be, for example, at right angles to the gas flow from the first feed port 17. The first and second feed ports 17 and 18 are designed to have almost the same shape and size. More particularly, the width W2 and the height d2 of the second feed port 18 are determined, such that W2 is approximately equal to W1 and d2 is approximately equal to dl. The second feed port 18 is so arranged that the width W2 is along the respective widths W and W1 of the inlet end 16a and the first feed port 17, and that the width W2 is coincident with the width W1 of the first feed port 17. A cooling means 21, such as, for example, a cooling tube through which cooling water is passed, is provided along the wall surface which faces the substrate 1 in the furnace 11 to the extent that the passage 16 and part of the first feed tube 19 are covered. In this arrangement, triethyl compounds of metals of group III, for example, TEGa (that is, (C2H5)3Ga), TEAl (that is, (C2H5)3Al) or TEIn (that is, (C2H5)3In), are mixed in given mixing ratios and fed or caused to flow from the first feed pipe 19 by entrainment with an H2 carrier gas in an amount less than 0.1% of the mixture. Phosphine, PH3, is fed from the second feed pipe 20 and entrained in an H2 carrier gas in an amount less than 10%. Thus, the first and second starting gases are combined and mixed downstream of the feed ports 17 and 18 or immediately upstream of the inlet end 16a of the passage 16, and immediately upstream of the substrate 1. The mixed gas flows into the passage 16 and passes along and over the surface of the substrate 1 as shown by an arrow a'. At a position downstream of the feed ports 17 and 18, the second starting gas is uniformly mixed with the first starting gas, whereupon the first starting gas from the first feed port 17 should form a main stream. The mixed gas is passed, without disturbing the main stream, along the surface of the substrate 1 in the passage 16. In the passage 16, the mixed gas flows at a flow rate of 80 cm/second or more in order that the organic metal compounds such as, for example, TEIn, do not decompose or react in the gas phase near the surface of the substrate 1. This gas flow can be achieved not only by the arrangement of the second feed port 18 at an inclined angle, for example, at right angles, with respect to the first feed port 17 and the passage 16, but also with the flow rates of the first and second gases. In practice, the flow rate in the passage 16 is determined to be almost the same as the flow rate at the first feed port 17. Assuming that the sectional areas of the first and second feed ports 17 and 18 are taken as A and B, respectively, with flow rates from the respective feed ports 17 and 18 being taken as a and b, and a sectional area of the gas passage 16 is taken as C, and a flow rate in the passage 16 is taken as c (c = a + b), the following relations should be satisfied in order to assure only a small disturbance of the gas flow: a/A = (a + b)/C = c/C (1) a/A is geater than b/B (2) Now, when A = B = 3 mm x 30 mm and C = 3.5 x 30 mm, the above equations are satisfied when a = 6 litres/minute and b = 1 litre/minute. Based on the above, the feeds of the first and second gases from the first and second feed pipes 19 and 20 are, respectively, selected as 6 litres/minute and 1 litre/minute. In order to permit the first starting gas from the first feed port 17 to flow into the passage 16 as the main stream without creating a disturbance of the stream, it is desirable to make the upper surface level of the mounting 13 or the surface level of the substrate 1 lower than the lower surface of the feed port 17. In this manner, the mixed gas of the triethyl compound TEGa, TEA1 or TEIn and the phosphine, PH3, flows over the surface of the substrate 1, by which AlGaInP semiconductor layers can be epitaxially grown on the substrate 1. During the epitaxial growth, the substrate should be maintained at a temperature of 5800C to 6300C. The mixing ratio of the triethyl compounds and phosphine should be at least 1:300. The cooling means 21 is provided to cool portions other than the substrate 1 in the furnace 11 (which is heated by the heated substrate 1) so that the starting gases are not unstably decomposed and are not involved in side reactions. Using the apparatus 11, (AlyGAl-y)xInl-x semiconductor layers were epitaxially grown on the substrate 1. The results of measurement of the growth rate in relation to the direction of the starting gas flow are shown in Figure 5. In this figure, the abscissa indicates a distance from the inlet end 16a of the passage 16. Curves 51a, 51b and Sic are for semiconductor compositions of the above formula in which y = 0 and x = 0.5. Curve 52 is for a composition of the formula in which y = 1 and x = 0.5, and curve 53 is the case where y = 0.5 and x = 0.5. Curves 54a, 54b and 54c are for comparison in which Al0#3Ga0#7As is epitaxially grown. In Table 1, the growth efficiency is shown in which a number of organic metals are epitaxially grown using the apparatus 11. According to the results of the table, the growth efficiencies of TEIn and TEA1 are close to the efficiencies of other organic metals, revealing that the side reactions can be suppressed. In Table 1, the vapour pressure of each organic metal used for calculation of the growth efficiency is also shown. TABLE 1 Organic Metal Vapour Pressure Growth Efficiency (mmHg) ( ,eLm/minute) TEIn (150C) 0.19 4 x TEGa (-50C) 0.87 3-5 x 103 TEA1 (200C) 0.029 7-9 x 103 TMIn (300C) 3.5 4 x TMGa (-150C) 30 3 x Table 2 shows the results of measurement of the growth efficiency where the flow rate of starting gases in the passage 16 was increased over the flow rate used in Table 1. TABLE 2 Organic Metal Growth Efficiency t {¯m/minute) Metals of Group III/ Metals of Group III/ P (PH3) Compounds As (AsH3) Compounds TEIn 9.5 x 103 TEGa 7.5. x 103 1.1 x 104 TEA1 1.6 x 104 2.2 x 104 In Table 2, the metals of group III and As in the form AsH3 were epitaxially grown and shown for comparison. From the table it will be seen that high growth efficiencies are attained using group III metal/P compounds. With the method and apparatus 11 described, an epitaxial layer of GaO 51In0 49P was formed on the GaAs substrate 1 by feeding H2 gas containing TEGa and TEln gases from the first feed pipe 19, and H2 gas containing PH3 from the second feed pipe 20 and subjected to measurement of photoluminescence. The temperature of the substrate 1 was set at 5800 C to 6300C and the feed ratio (PH3/III) of the phosphine gas to the gases of the triethyl compounds of metals of group III was at least 300:1. Figure 6 shows the relation between luminous intensity and substrate temperature, and Figure 7 shows the relation between luminous intensity and (PH3/III) for a substrate temperature of 6200C. As will be apparent from Figure 6, it is preferable to set the substrate temperature at 5800C to 6300C in order to obtain an epitaxial layer of good characteristics. Within this temperature range, the decomposition rate of PH3 is low, so that PH3 should be fed, in excess, so as to obtain a pressure of phosphorus necessary for growth and sufficient for suppressing decomposition of the grown layer. Figure 7 reveals that PH3/III should be at least 300:1. The semiconductor laser device of Figure 8 was then fabricated. For the fabrication, the substrate temperature was 600 0C and the flow rate of all gases was 6 litres/minute. (a = 6 x 6/7 litres/minute and b = 6 x 1/7 litres/minute.) More particularly, the laser device was fabricated as follows: there were formed, on an n-type GaAs substrate 1 doped with Si, a buffer layer 61, a first clad layer 62, an active layer 63, a second clad layer 64, and a cap layer 65 in this order by epitaxial growth using the MOCVD method. The buffer layer 61 was an n-type GaAs layer doped with Se, the first clad layer 62 was an n-type A10 21Ga0.31I"0.48P layer doped with Se, the active layer 63 was an undoped Ga0#5;ln0#48P layer. The second clad layer-64 was a p-type Ga0#52In0#31In0#48P layer doped with Zn, and the cap layer 65 was a p-type GaO 52In0 48P layer doped with Zn. The layers 61 to 65 were respectively formed by feeding TEGa, TEA1 and TEIn as starting gases for the Ga, Al and In metals of group III from the first feed pipe 19 in mixing ratios corresponding to the respective compositions of the layers 61 to 65, and also feeding As or P of group V, in the form of AsH3 or PH3, from the second feed pipe 20 in amounts corresponding to the compositions of the respective layers 61 to 65. The starting gases for Se and Zn used as the dopants were selenium halide and dimethylzinc, respectively. Selenium halide was fed along with PH3 or AsH3, and dimethylzinc was fed along with TEGa, TEA1 and/or TEIn. The cap layer 65 was covered with an insulating layer 66 consisting of Si3N4, in which an opening was made to form a strip window 66a. An electrode 67 was attached to the cap layer 65 through the window 66a in ohmic contact. Another electrode 68 was formed on the back surface of the substrate 1. The resulting double hetero junction-type semiconductor laser device can be continuously oscillated at 770K. It should be noted that the strip window 66a was designed to have a width of from m and a length of 0 25û,çLm. At 77 K, the threshold current, itch, was 55 mA and the oscillation wavelength was 0.653y m. Figure 9 shows an output characteristic of the laser device and Figure 10 shows an emission spectrum of the device. The semiconductor laser diode described, exhibits the short wave oscillation inherent to semiconductor AlGaInP compounds. As described hereinabove, the vapour phase growth apparatus is designed to have a specific positional relation between feed portions for the respective starting gases and also a specific positional relation between the substrate, on which epitaxial growth is performed, and a gas passage in such a way that starting gas containing metals of group III and a starting gas containing an element of group V are mixed just before reaching the substrate. In addition, the starting gases are fed to the substrate in such a way that the gases containing metals of group III are fed as the main stream without disturbing the stream. In this manner, the elements of groups III and V react with one another, although the starting materials used have different decomposition rates, thereby effectively suppressing formation of side reaction products. In the method described, the substrate temperature and the ratio of the starting gases containing metals of group III and the starting gas containing an element of group V are specifically defined, by which a semiconductor light-emitting device of high quality can be obtained. Although the starting gases of metals of group II used are triethyl compounds and the starting gas of an element of group V is in the form of PH3, formation of intermediate products can be avoided without utilizing any vacuum method. Thus, the apparatus can be simplified and is easy to handle, bringing about a number of advantages.

Claims: CLAIMS 1. A method of making a semiconductive light-emitting device by forming, on a substrate (1) by epitaxial growth, a plurality of layers (61 to 65) of semiconductive compounds consisting of elements of groups III-V of the periodic table, the method being characterised by the steps of: heating the substrate (1) to a temperature of S800C to 6300C; separately flowing a mixed gas of triethyl compounds of metals of group III and a gas of phosphine, wherein the ratio of phosphine to the triethyl compounds of metals of group III is at least 300:1; mixing said gases together immediately prior to the substrate (1), thereby forming a semiconductive layer of a selected composition comprising elements of group III-V on the substrate (1); and repeating the above procedure so as successively to form a plurality of layers (61 to 65) on the substrate (1), the plurality of layers (61 to 65) consisting of semiconductive compounds, each of which are represented by the formula: (AlyGal y)xInl P P in which 0 is less than or equal to y is less than or equal to 1 and 0 is less than or equal to x is less than or equal to 1. 2. A method according to claim 1 wherein selected layers of the plurality of layers (61 to 65) are doped with a dopant of Se or Zn. 3. A method according to claim 1 or claim 2 wherein said mixed gas of triethyl compounds is carried by a hydrogen carrier gas in a concentration less than 0.1%. 4. A method according to claim 1, claim 2 or claim 3 wherein said #hOSrh!fle is carried by a hydrogen carrier gas in a concentration less than 10%. 5. A method according to any one of the preceding claims wherein said mixture of gases flows over the substrate (1) at a flow rate of 80 cm/minute. 6. A vapour phase growth apparatus (10) for making a semiconductive light-emitting device by epitaxial growth of semiconductive compounds of elements of groups III-V, the apparatus (10) comprising: an atmospheric reaction furnace (10); and a substrate mount (13) positioned in said furnace (10), such that a gas passage (16) having an inlet (16a) is established between the substrate mount (13) and an inner side wall (ill) of the reaction furnace (11); characterised by: a first starting gas feed port (17) located at the inlet (16a) of the gas passage (16) and through which triethyl compounds of metals of group III of the periodic table are caused to flow; and a second starting gas feed port (18) located between the inlet (16a) of the gas passage (16) and the first starting material gas feed port (17) and for the flow of phosphine; the second starting gas feed port (18) being inclined with respect to the first starting gas feed port (17), the first and second starting gas feed ports (17, 18) having substantially the same shape and size, and a mixed gas of the triethyl compounds of metals of group III and the phosphine flowing from the first and second starting gas feed port (17, 18), respectively, and being mixed immediately upstream of a substrate (1) located near the inlet (16a) to the gas passage (16) so that the mixed gas flows over and along the substrate surface. 7. An apparatus (10) according to claim 6 further comprising heating means (14) for heating the substrate (1) to a temperature of from 580 C to 630 C. 8. An apparatus (10) according to claim 7 or claim 8 wherein said heating means (14) surrounds said reaction furnace (11) 9. An apparatus (10) according to claim 6, claim 7 or claim 8 wherein the second starting gas feed port (18) is at right angles to the first starting gas feed port (17). 10. An apparatus (10) according to any one of claims 6 to 9 wherein the first and second starting gas feed ports (17, 18) have substantially the same width and height. 11. An apparatus (10) according to any one of claims 6 to 10 wherein said substrate mount 13 and a substrate (1) carried thereon are positioned below the lower surface of the first starting gas feed port (17).

Inventors: IKEDA, MASAO C/O PATENT DIVISION, KAWAI, HIROJI C/O PATENTS DIVISION, MORI, YOSHIFUMI C/O PATENTS DIVISION
Applicants: SONY CORPORATION
Application year: 1985
Main classification: H01L33
IPC codes: H01S5, H01L21, H01L33