JPS58140400A - Vapor growth method of gallium arsenide - Google Patents

Abstract

PURPOSE:To vapor-grow gallium arsenide of n type having low electron concns. with reduced consumption of arsenic compds. by contg. traces of silicon compds. beforehand in either of org. gallium or arsenic compds. and causing the thermal decomposition reaction of the org. gallium and the arsenic compds. CONSTITUTION:Traces of silicon compds. such as tetraethyl silane are beforehand mixed with org. gallium such as trimethyl gallium and the mixture is diluted with gaseous hydrogen and is fed into a reaction chamber. Arsenic compds. such as arsine and impurities such as hydrogen sulfide are diluted respectively with gaseous hydrogen and are introduced into the reaction chamber, where these materials are heated and GaAs is vapor-grown on a GaAs substrate by thermal decomposition reaction. The molar ratio for inversion to low p-n is realized by the addition of traces of silicon compds. according to the above- mentioned method and while the consumption of the arsenic compd. is reduced in this state, the GaAs of the n type growth layer of low electron concns. is grown.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention utilizes a thermal decomposition reaction tube for organic gallic acid and an arsenic compound to produce galicum arsenide (GaAa
) Gallium arsenide vapor phase growth method Kll
do.

(*Technical background of Ming) A type II arsenide gas phase growth layer with an electron concentration of 1θ14 161 degrees and #111 degrees is generally used as an active layer of a Gsxao diode in the 4-200 Hz band. In KFi, which forms the active layer with good reproducibility, first, the carrier concentration in the undoped state is kept sufficiently low, and in this state, for example, group III impurities such as sulfur are added.
By dobindering, an active layer with a desired electron exchange rate is grown to a desired thickness on a gallium arsenide crystal substrate. In this AND-1 state, the concentration of the grown layer is constant as shown in Figure 1. The temperature varies depending on the molar ratio ([Musl/[Ga]) between the arsenic compound and organic gallium that are the starting materials.

It is known that the growth layer exhibits the p-type in the north of the low molar ratio, the p-type in the high molar ratio, and that a high-resistance layer is formed at the intermediate o-molar ratio (p-m inverted molar ratio). Therefore, in order to obtain a low background meeting, [Mu@'3/CGa]
It is necessary to remain near the t p -m inversion molar ratio and to obtain the electron concentration at the cutoff value,! - Good controllability compared to other impurities near 0p-a inversion 4 ratio - Sulfur (8)
[Problems with the background art] As is well known, organic gallium, for example, trimethyl gallium ((CHI)l Gl % TMG'
) and arsine gas (5aHs) as an arsenic compound.
is used, the normal growth temperature is 620-750℃.
The p-n inversion molar ratio reached as high as 10 to 30, and most of the #1 arsenic compound was wasted, and the arsenic dust accumulated in the reactor was lost to the arsine waste gas absorption device. If it is absorbed and the reactor's contaminated tube gets worse, 4. has disadvantages such as having to pay for the exhaust gas collection device. [Purpose] Jin's W14 removes the above disadvantages and makes arsenic compounding effective. The purpose of the present invention is to provide a method for vapor phase growth of gallium arsenide, which is performed by consuming a large amount of gallium arsenide.

[Summary of the invention]

This invention is based on an experimental finding that by incorporating a trace amount of a silicon (S&) compound into an organic gallium or arsenic compound such as arsine gas, the p-inversion molar ratio can be significantly reduced compared to when no silicon is added. The vapor phase growth method of the present invention can be achieved by applying this fact, and by adding a small amount of 8i compound to the organic gallium or arsenic compound in advance. The low furnace inversion molar ratio is 1*, and in this state it has been improved to grow a morphological growth layer with a low electron concentration while reducing the consumption of arsenic compounds. [Example of development Wi4] Below Trimethylgallium (1G) and arsine (MusH@
) using gas and sound, and using the pyrolysis method to generate X-band (100Hz
(B) - Describes an example in which gallium arsenide for combat diodes was grown in a vapor phase. FIG. 2 is a schematic diagram of a vapor phase growth apparatus used in this example. Water for diluting the raw material gas - The gas is diluted through the purification device (1), and a portion of it is filled with trimethyl gallium TMG and kept at 0°C in stainless steel pats (2). Arsine gas is diluted to 10% with hydrogen gas and is then supplied directly from the pressure vessel (3). Similarly, hydrogen sulfide, an impurity source for morphological doping, is supplied directly from the pressure vessel (3). (UtS) is diluted with 10 ppnl fC (with hydrogen gas) and supplied directly from the high pressure vessel (4) filled with G. Flow rate needle (5)
, (L (7), (8) respectively control the flow rate to a predetermined flow rate and guide it to the reaction vessel (9).・These gases are thermally decomposed near the heating architrave heated by high frequency heating, and the heating architrave is heated by high frequency heating. A layer of gallium arsenide doped with sulfur is deposited on a gallium arsenide substrate placed on the 0 (100) plane tilted 2° in the (110) direction.
The growth temperature tj is 650℃, and the total gas flow rate is 1047m.
It was set to

Figure 31%1 shows the dependence of the [Asl/[Ga] molar ratio of the packed carrier concentration in the Andog-like state as a preliminary experiment for the formation of the growth layer for the Gunn diode. The curve (Otori) is when additive-free trimethyl gallium is used, and 11111 (b) is tetraethylsilane ((C,)(,)481,!18) so that 1!1 degree in trimethylgallium becomes aoppm. As is clear from Figure 0, which shows the case with addition, by adding a trace amount of silicon compound, p''?
It can be seen that the value is reduced to about 4K, which is about 1/15 of the 4-inversion cage molar ratio.

Figure 4 shows the relationship between the electron concentration in the growth layer and the amount of hydrogen sulfide added when trimethyl gallium added with tetraethylsilane is added on top of hydrogen sulfide at a p-layer inversion molar ratio.・Electron concentration Fi4X10" to 3X1G"・Hydrogen sulfide flow rate: 33 ml
/win, X-band Gunn diode growth layer,
Electron concentration target value 9±I X 10"/cxx", thickness 1
0J1! Figure 5 shows the variation in electron S degree with respect to the number of growth times when 51g1 was grown for 11 consecutive sessions. - The variation is within the target value range with good reproducibility. - In the above example, trimethyl gallic Although we have described the pyrolytic vapor phase growth of gallium arsenide using arsine and arsine, this phenomenon also occurs when other organic gallium and arsenic compounds are used.
+1 can be applied. Also, the silicon compound is not limited to tetraethylsilane, but other silicon compounds may also be used. ◎You may also add a small amount of silicon compound in argon instead of trimethyl gallium. [Effect of the invention] As stated above, according to this invention, tQj4~10''
In order to grow a gallium arsenide vapor phase epitaxy layer with a low electron concentration of /ys'', it is possible to grow a gallium arsenide vapor phase epitaxy layer with a low electron concentration of
As a result of being able to reduce the inversion ratio, n-type low electron concentration layer gold can be grown with much less consumption of arsine, and [4E
% As shown in Figure 5, the electron concentration in the grown layer is 0, which improves controllability and reproducibility.

[Brief explanation of the drawing]

FIG. 1 is a curve diagram showing the relationship between the carrier concentration of the undoped growth layer and the arsenic compound/organic gallium molar ratio [Musl/(Ga), and FIG. 2 is an example of the vapor phase growth apparatus used in the present invention. The schematic layout diagram shown in FIG. 3 shows the undoped background carrier [A%V
CG m '3 Diagram showing molar ratio dependence, provided that curve m(b
) is an example using trimethyl gallium to which 1I11 degree 30 ppm of tetophethylsilane tm was added according to the method of this invention, track 1/II! A (,) is an example using t\ trimethylgallium without adding tetraethylsilane, and Figure 4 is
A diagram showing the relationship between the growth layer electron concentration and hydrogen sulfide hexagonal,
FIG. 5 is a dot diagram showing the relationship between the growth layer electron concentration and the number of growth times.
jI It(2)...Stainless steel spring (9
)...Reaction container (3)...AsH-gas high pressure container
Matata...Door heating stand (4)...H, 8 gas high pressure container aυ...
...Ga person sj! Board agent Patent attorney Inoue - Male No. 1 Figure 0

Claims (1)

[Claims] When performing vapor phase growth of gallium arsenide (by thermal decomposition reaction between organic gallium and an arsenic compound), organic gallium or an arsenic compound is pre-contained with a trace amount of a silicon compound, and p
Try to keep the m1 inversion molar ratio small 1. Gallium arsenide vapor phase growth method using mold