JPS58191423A - Vapor growth device for 3-5 semiconductor - Google Patents

Abstract

PURPOSE:To improve the controllability of a composition by mounting a cover sliding on the vessel edge of a II group metal vessel and a device operating the cover from the outside. CONSTITUTION:The cover for the II group metal vessel can be slid to the downstream side so as to cover a II group metal or open the II group metal to a gas current by pushing or pulling solid bar ends 4 of the outside of the device in solid bars 3 made of quartz. A stainless seal 5 and the solid bars 3 are fixed by O rings made of bytown. Grease is applied to the O rings, and the solid bars are pushed and pulled in the axial direction of a reaction pipe 6 made of quartz. In is entered into the II group metal vessel of a support reaction pipe 7, and Ga is entered into the II group metal vessel of a support reaction pipe 3. The controllability of the composition of a II-V mixed crystal is improved by using the device as a result of the measurement of the variation of a composition in the direction of growth of a (In, Ga)As growth layer obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 1-V semiconductor vapor phase growth apparatus using the chloride method, and its effects can be applied to IaxGa, -xAs and nAsy P
This is remarkable in the composition controllability in vapor phase growth of 01-V mixed crystals such as h-y.

The epitaxial layer of the 1-V semiconductor is formed by liquid phase growth, vapor phase growth, single molecular beam epitaxial growth, or the like. Among these, the vapor phase deposition method is gaining superiority in terms of uniform growth over a large area and mass productivity. Jin's vapor phase growth method can be roughly divided into the halogen transport method (which involves reacting group Ⅰ element O chloride vapor with group Ⅰ element vapor to precipitate IV compounds).
Volatile organic compounds of group I metals or l
Metal-organic pyrolysis method (MOVPI), which is based on the thermal decomposition reaction of organic compounds of group metals and coordination metals of compound of group II elements.
There is. Furthermore, the halogen transport method was combined with the chloride method, in which a chloride of a group Ⅰ element and a group I metal are reacted to produce a chloride of a group Ⅰ element and a bulk gas of a group V element, and a reaction between a group Ⅰ metal and aqueous chloride. ■Group element chloride is produced by V group element vapor company v
It can be divided into the hydride method, which is produced by a hydride O layer reaction of group elements. In conclusion, there are three main vapor phase growth methods: chloride method, hydride method, and organometallic thermal decomposition method.

In the discussion, Otori-■ Semiconductor devices require high-purity ■-■ semiconductors such as Gunn diodes, avalanche FT diodes, 2 inverted WMI8) transistors, and the various vapor phase growth methods mentioned above. When comparing the methods from the viewpoint of high purification, simply put, the p-ride method has the original advantage.

The first reason is that, as shown in the 11th DC, the chloride method does not use organic royal metals, hydrogen chloride, or hydrides of group V elements, which are insufficient in terms of purity, and uses high N degree royal metals and group I elements. Second, as is well known in the chloride method, trichloride of #1 can be used to cover the Kll group metal container.
A crust of Ic1-V compounds is formed, and O
n! It is thought that rounding has the effect of trapping impurities or p-type impurities.

Indicates that OFi is used.

However, when crystals ■~v11 are produced by the chloride method, the controllability of the composition is poor, and the composition is still controlled.
FA crystals are not produced by the chloride method. Hitherto, the cause has not been investigated much, and when a l-■ mixed crystal is produced by a vapor phase growth method, a hydride method or an organometallic thermal decomposition method has been used. However, high purity I
- There are no examples of epitaxial growth of Vjl crystals using the hydride method or organometallic method, and there are no examples of epitaxial growth of Vjl crystals using the chloride method.
It is expected that crystals can be grown in a vapor phase.

The present invention was developed in response to these demands, and its purpose is to provide an IV semiconductor vapor phase growth apparatus that can significantly improve the controllability of composition. In the present invention, vapor of a ternary compound of a group element is introduced onto a high-temperature Oto group metal using a carrier gas, and the gas produced by the reaction is introduced onto a substrate at a lower temperature than the above-mentioned Ou group metal to form an IV crystal. A chloride vapor phase growth apparatus for epitaxial growth on the substrate, wherein the Group 1 metal container O
This is a semiconductor vapor phase growth apparatus characterized by a lid that slides over the edge of the container and a device for operating the lid from the outside.

As in Book 11@0, group V bulk trichloride is added to K1 on group I metal.
By using a container made of a group I metal that cannot be passed through with a lid and using a device that absorbs group V elements,
Escape due to evaporation of group (1) elements from group metals is suppressed, and a high-purity composition can be controlled by the chloride method, making it possible to epitaxially grow I-V crystals.

The Honki beak will be described in detail below using examples.

In Example 111(a), the present invention was applied (Inn Ga
) This shows an As vapor phase growth apparatus. ! I I
The upper figure in I (a) is a top view of the growth apparatus. The lower figure in FIG. 1(a) is a side view of the growth apparatus. Parts of the figure are omitted in the figure below.The quartz imperial metal container 1, which is a feature of the present invention, and the quartz lid 2, which slides over the edge. By pushing and pulling the quartz bar 3 at the end 4 of the bar outside the device, the quartz bar 3 can be slid downstream so as to cover the Imperial metal and open the Group I metal to the gas flow. The stainless steel seal 5 and the bar 3 are fixed with a Piton 111 O-ring, and the O-ring is coated with grease so that the bar can be pushed and pulled in the axial direction of the quartz reaction tube 6. In is placed in the group I metal container of the branch reaction tube 7.

Group 1 metal container K of branch reaction tube 8 contains FiGa and is round.

(I, Ga) The implementation process of As vapor phase growth can be blocked as desired.

(1) Slide the quartz lid to the downstream side and I! 1sp
and the can is mK111*t, In and G1 are 800
9. Set the temperature to °C before introducing. IO was changed from hydrogen gas to hydrogen gas with a concentration of aC1°. At this time, substrate 1
1 is not placed on the substrate holder 12.

(After the 21In and GaK arsenic are saturated, slide the quartz holder upstream and place the group I metal container between the two.)

) The introduced gas was changed to hydrogen gas and the temperature inside the reaction tube was lowered to room temperature.

(After chemically etching the P substrate 11, the substrate holder 1
After introducing phosphine 13, the saturated In and As1llllQGa in the metal container were heated at 800°.
= InP substrate was set at 700'C.

(6) At the same time as stopping the introduction of phosphine and moving the quartz lid to the downstream side, the introduced gas was switched to hydrogen gas containing *ct. The introduced gas's CL, intensity and flow rate are Ia and Ll when GaAs is grown on an InP substrate.
l @JMayoK Adjust each circle.

The composition fluctuations in the growth direction of the Inn Ga As dominant layer obtained in this way were measured by scanning Auger spectroscopy of the image polished by 5°, and the results are as follows. It can be seen that the relatives of *(InnGa)mu$ shown in g are constant in the growth direction. For comparison, the 31st EIK shows the results of uniformly determining the compositional fluctuations in the growth direction of the (Ine Ga ) S growth layer when processes from (!) to β) were carried out with the quartz lid placed on the downstream side. It can be seen that in the conventional method (1), as the IAs composition decreases, the composition becomes unstable and the growth rate decreases. These results indicate that the use of the apparatus of the present invention improves the controllability of the composition of the I-■ mixed crystal.

As shown in FIG. 1(b)K, the binding 22 of the I-group metal material 21 of the IV semiconductor vapor phase growth apparatus of the present invention is the group-I metal surface 2.
0 Container rim KFi quartz 11 which is higher than 3
The quartz lid, which is provided with an I-id 25 to prevent the 1124 from falling, has a protrusion 1127 for pushing and pulling with a quartz bar 26. Shape 2 at the tip of the stick
8 can be located 4 m upstream and downstream of the protrusion 27 from the solid bar 011fiK. The upper figure in FIG. 1(b) is a view from above, and the lower figure is a view from the side.

[Brief explanation of the drawing]

Figure 1 (a) shows the present invention applied to jl (In, Ga
) MuS vapor phase growth apparatus is shown. l...Quartz group 111 metal container, 2...Quartz lid, 3
... Solid quartz rod, 4 ... Solid rod end, 5 ... Stainless steel seal, 6 ... Quartz reaction tube, 7, 8 ... Branch reaction tube, 9゜lO ... Introducing gas , 11... InP substrate, 12... substrate holder, 13... 7 male fins. 1g1(b) shows a group 1 metal container according to the present invention, which is equipped with a lid that slides on the container rim and a device for controlling the volume from the outside. 21... Rim of Group I metal container, 22... Rim of Group ■ metal container. 23...Group metal surface, 24...Quartz lid, 25.
...Guide provided on the edge of the group ■ metal container S, 26... Quartz bar, 27... Projection of quartz lid, 28...
The shape of the bar. FIG. 1112 shows the results of obliquely polished scanning Auger spectroscopy of the Inga Slayer by the method of the present invention. Iris 311 was made by the conventional method (Inn Ga)
The obliquely polished image of the MU S growth layer shows the results of scanning Auger spectroscopy. 7・' The Japanese orator Uchihara Tamashii.

Claims (1)

[Claims] The tertiary compound vapor of group V element is converted to high II by using a carrier gas.
The above-mentioned l
A silide method vapor phase growth apparatus is used to epitaxially form a KNI crystal on a substrate with a lower IIO than that of a mgei group metal. 1. A 1-V semiconductor vapor phase growth apparatus comprising an operating apparatus.