US3893876A - Method and apparatus of the continuous preparation of epitaxial layers of semiconducting III-V compounds from vapor phase - Google Patents

Method and apparatus of the continuous preparation of epitaxial layers of semiconducting III-V compounds from vapor phase Download PDF

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US3893876A
US3893876A US28537972A US3893876A US 3893876 A US3893876 A US 3893876A US 28537972 A US28537972 A US 28537972A US 3893876 A US3893876 A US 3893876A
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gas
mixture
epitaxial
gaas
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Shin-Ichi Akai
Makoto Hayashi
Shin-Ichi Iguchi
Takashi Shimoda
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Sumitomo Electric Industries Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/301AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00Metal treatment
    • Y10S148/065Gp III-V generic compounds-processing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00Metal treatment
    • Y10S148/067Graded energy gap
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00Metal treatment
    • Y10S148/072Heterojunctions
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00Semiconductor device manufacturing: process
    • Y10S438/936Graded energy gap

Abstract

This invention relates to a method for the continuous preparation of epitaxial layers of semiconducting III-V compounds on suitable substrates of the single crystal from a gas mixture thereof. The plurality of substrates are moved in parallel with the flow of said gas mixture in a reaction furnace which is given a temperature gradient in the same direction as the flow of said gas mixture, the temperature decreasing with distance in the direction of the gas flow. The semiconducting compounds are effectively recovered as epitaxial layers on the substrates, and the composition of the mixed crystal of III-V semiconductors can be changed continuously to result in the graded composition, without timewise changing the composition of said gas mixture. Through the gas mixture entering into the reaction furnace is of constant composition, the composition of the gas mixture is gradually changed downstream of the gas flow in the reaction furnace as a result of effective recovery of the semiconducting compounds on the substrates.

Description

Akai et al.

July s, 1975 METHOD AND APPARATUS OF THE CONTINUOUS PREPARATION OF EPITAXIAL LAYERS OF SEMICONDUCTING III-V COMPOUNDS FROM VAPOR PHASE inventors: Shin-lchi Akai; Makoto Hayashi;

Shin-Ichi Iguchi; Takashi Shimoda, all of Osaka, Japan Sumitomo Electric Industries, Ltd., Osaka, Japan Filed: Aug. 31, 1972 Appl. No.: 285,379

Assignee:

Foreign Application Priority Data Sept. 6, 1971 Japan 46-68658 US. Cl. 148/175; 117/106 A; 117/107.1; l17/107.2; 118/48; 118/49; l18/49.1; 118/49.5; 148/174 Int. Cl. H011 7/36; C230 ll/OO Field of Search 148/174, 175; 117/106 A, ll7/l07.1, 107.2; 118/48, 49, 49.1, 49.5

References Cited UNITED STATES PATENTS OTHER PUBLICATIONS Weinstein et al., Preparation and Properties of GaAs-GaP. Heterojunctions, J. Electrochem. Soc., Vol. 111, No. 6, June 1964, p. 674-682.

Finch et al., Preparation of GaAs P by Vapor Phase Reaction, IBID, Vol. 111, No. 7, July 1964, p. 814-817.

Primary ExaminerL. Dewayne Rutledge Assistant Examiner-W. G. Saba Attorney, Agent, or F irmCarothers and Carothers [5 7] ABSTRACT This invention relates to a method for the continuous preparation of epitaxial layers of semiconducting III-V compounds on suitable substrates of the single crystal from a gas mixture thereof. The plurality of substrates are moved in parallel with the flow of said gas mixture in a reaction furnace which is given a temperature gradient in the same direction as the flow of said gas mixture, the temperature decreasing with distance in the direction of the gas flow. The semiconducting compounds are effectively recovered as epitaxial layers on the substrates, and the composition of the mixed crystal of Ill-V semiconductors can be changed continuously to result in the graded composition, without timewise changing the composition of said gas mixture. Through the gas mixture entering into the reaction furnace is of constant composition, the composition of the gas mixture is gradually changed downstream of the gas flow in the reaction furnace as a result of effective recovery of the semiconducting compounds on the substrates.

4 Claims, 1 Drawing Figure 1 METHOD AND APPARATUS OF THE CONTINUOUS PREPARATION OF EPITAXIAL LAYERS OF SEMICONDUCTING III-V COMPOUNDS FROM VAPOR PHASE BACKGROUND OF THE INVENTION This invention relates to a method of continuously preparing on a lIl-V semiconductor substrate the epitaxial layers of one of the lll-V semiconductors which include Ill-V binary semiconductors consisting of a Ill-B element of the Periodic Table and a VB element (for example, GaAs, GaP, lnP, etc.) and especially their mixed crystals (for example, InAs P GaAs P ln, ,Ga,P, etc. where .r l).

The continuous vapor growth method, particularly the method of continuously growing epitaxial layers on a single crystal stubstrate, was suggested already in the past with respect to Si and Ge. For instance, a method of continuously growing epitaxial layers of Si from a gas mixture of hydrogen and SiCl is described in Japaneses Patent Publication No. SHO-43/5564 by the present applicant. Another patent publication, Japanese Patent Publication No.SHO-43/2l369, reveals a method wherein epitaxial layers of Si are continuously prepared from a gas mixture of hydrogen and SiCl while the continuous growth of the epitaxial layers expedited by the formation of an oxide film on the surface of the epitaxially grown silicon layer from CO gas.

However, not only III-V semiconductors but also other compound semiconductors at large are unlike Si and Ge. They consist of two or more elements. Since control is required to maintain a stoichiometric ratio during the growth of these semiconductors, the continuous growth of the epitaxial layers of these compound semiconductor is very difficult and is seldom accomplished.

The growth of epitaxial layers of llI-V semiconductors is generally carried out by a batch process, which is not continuous. For example, there are the following reports.

I. Japanese Patent Publication No.SHO-40/24704, A Method for the Deposition of Epitaxial Film of Ill-B V-B element compounds," reveals a method of preparing epitaxial layers by flowing a hydrogen gas in the storage of a volatile compound of a Ill-B element and the source of a V-B element or the storage of a volatile compound of a V-B element and bringing the reaction mixture from these two flows in contact with a substrate, the method being applicable not only to Ill-V binary semiconductors but also to 111-V mixed crystal semiconductors. However, all that is mentioned therein refers to a batch process. Nothing is mentioned with respect to the continuous growth of epitaxial layers.

11. Japanese Publication No. SHO-42/7492, A Method of Manufacturing Epitaxial Films, describes a method of depositing an epitaxial film having a graded energy gap of lll-V mixed crystal, wherein a gas mixture similar to that of the above (1) is used and the composition of two kinds of reacting gases of the same group of the Periodic Table is changed timewise by changing the flow rate of the afore-mentioned hydrogen gas or the temperature of the afore-mentioned source or storage tank, to thereby grow an epitaxial film having a graded energy gap. However, the description also refers to a batch process. It is impossible to continuously grow an epitaxial film while changing the composition of the reacting gases timewise by this method. It is inevitable that a batch process must be adopted which is discontinuous or semi-continuous.

111. The method (11) above is described in a more concrete way in John W. Burd: Transactions of the Metallurigcal Society of AIME Vol. 245, March (1969), p. 571. As to gas mixtures, the mixtures of H /HC1/GaAs and P, H /HCl/Ga and AsH /PH and H /AsC13/PCl /Ga are mentioned. However, a batch process only is described.

IV. A method described in Tooru Hara et al: Oyobutsuri, Volume 37, No. 1l( 1968), p. 1064, refers to the gas mixture from Hg/Asclg/ PCl /Ga, that is, the gas mixture from the reaction products of a hydrogen gas saturated with AsCl and PCL; with Ga. It is especially mentioned in this literature that the value ofx in GaAs ,P varies according to the temperature of the substrate. It is also mentioned that if the temperatureof the GaAs substrate is kept at 815C, GaAs P grows having a value ofx equal to the ratio of As and P in the, therefore, the value of can be controlled by the composition of the gas. However, nothing is mentioned in regard to how the value of can be controlled for a continuous epitaxial growth. Furthermore, according to this literature, a decreasing temperature gradient with distance from the Ga source zone to the GaAs substrate zone, i.e., in the direction of the gas flow is provided. Such a system unavoidably has a drawback in that besides the growth of GaAs P, on the GaAs substrate, GaAs P, is also deposited on the inner wall of the reaction tube on the side of the Ga source zone from the GaAs substrate in the aforementioned temperature gradient zone, so that GaAs -P is not effectively recovered on the afore-mentioned substrate. This drawback is common also to the aforementioned (1), (l1) and (111).

V. US. Pat. No. 3,441,453, Method for Making Graded Composition Mixed Compound Semiconductor Materials by R.W. Conrad et al describes a kind of batch process, wherein the composition of the gas mixture is of constant composition and a substrate is moved in the reaction furnace having a decreasing temperature gradient with distance in the direction of gas flow, thereby gradually changing the temperature of said substrate so as to deposit the graded composition compound semiconductor. This process also has a drawback as aforementioned in method (1V). Description of the Invention This invention has for an object epitaxial layers of a Ill-V mixed crystal semi-conductor on a plurality of Ill-V compound semiconductor substrates while at the same time having the composition of the mixed crystal semiconductor (for example, the value of x in GaAs,. P change continuously, without changing timewise the composition of said gas mixture.

A characteristic of this invention is that in the method of growing an epitaxial layer of a 111 V ternary compound semiconductor represented by a general formula AB C on a 111 V binary compound semiconductor from a gas mixture, wherein AB C stands for both A'B" .C" and B' ,C',.A", A' being a Ill-B element, A" a V-B element, B and C" two different V-B elements, 8' and C' two different Ill-B elements and the value of x between 0 and 1, the value of x is continuously changed to result in the graded composition without changing timewise the composition of said gas mixture entering into the reaction furnace, which is given a temperature gradient, decreasing with distance in the direction of the gas flow, by continuously moving the plurality of said lll-V binary compound semiconductor substrates, upstream of said gas flow in the case of the substrate which has a lower melting point, and downstream of said gas flow in the case of the substrate which has a higher melting point than said ternary compound semiconductor, respectively. If the binary compound semiconductor AB has a lower melting point than the semiconductor AC, the composition of the gas mixture in the reaction furnace is richer in the constituent C and poorer in the constituent B in the higher temperature zone and vice versa in the lower temperature zone of the reaction furnace. If the semiconductor AB has a higher melting point than the semiconductor AC, the change of the composition of the gas mixture is reversed.

As AB C compounds in the afore-mentioned characteristics of this invention, there are GaP N, l AlAs l- GaAs P lnAs P (0 l for the foregoing three), Ga Al As P ln Ga As P, (0 1, 0 v 1 for the foregoing two), GaSb ,As lnSb As, (0 l for the foregoing two), InSb Bi (0 x 1),In Ga,N, Ga Al P, In1.I- Al P, In Ga P, Ga B As, Ga Al As, In l-xAl As, In Ga As, Ga AI Sb, In Al Sb, In Ga Sb (0 x 1 for the foregoing eleven), etc.

The gas mixture is produced from various reaction products of many known gas systems such as an H2/AsCl /PCl /Ga, an H2/Asl-1 /PH /HCl/Ga, an

H /AsCl /PCl /GaAs, an H2/AsCl /PCl /GaAs/GaP and so on.

The above and other objects of this invention along with the features and advantages thereof will become more fully apparent as the description proceeds with reference to the accompanying drawing. Some embodiments of the present invention are illustrated in the drawing, but the invention is in no way limited thereto.

The figure is a vertical cross section of an example of the continuous epitaxial growth furnace for lIl-V semiconductors used for the present invention.

The present invention will be described in detail herebelow mainly with respect to GaAs and GaAs P, as examples.

In the figure, 1 denotes the horizontal vapor phase reaction chamber, 2 and 3 the resistance heating furnaces for heating the horizontal vapor phase reaction chamber 1 and giving it a temperature gradient in the horizontal direction, 4 a gas mixture of a carrier gas, at least one volatile compound of a lIl-B element and at least one element or compound selected from among the V-B elements and their volatile compounds, and 5 the exhaust gas.

6 denotes a platinum tape heater for producing a heating and mixing zone 7 to prevent the condensation of the gas mixture 4. In case the gas mixture 4 is, for example, composed of a hydrogen gas, Ga CPI- AsH,-, and PH, to heat the mixing zone 7. 8 and 9 denote a preheater and afterheater respectively. Each of these heating furnaces 2, 3, 8, and 9 is of a split type. 10 denotes a fused quartz reaction tube, 11 a plate of carbon or quartz for the purpose of transporting the substrate 12 for epitaxial growth into the horizontal reaction chamber 1, and 13 and 14 two flows hydrogen gas. Two flows of gas are introduced into the reaction chamber 1 through the slits l5 and 16 above the substrates, and is discharged together with the exhaust gas 5.

17 and 18 denote the slits which serve to separate the flow of hydrogen gas from inert gases 19 and 20 (for example, Ar, N etc.) which are exhausted to the inlet and outlet 21 and 22 respectively through which the substrates are transferred to 23 and 24 into clean benches (not shown in the drawing). The arrow 25 indicates the direction of movement of the plate 11, but the movement may be reversed.

The characteristic features of the continuous epitaxial growth furnace shown in the figure are that the shower of an inert gas (19, 23 and 20, 24) prevents the outer atmosphere from finding its way into the quartz reaction tube 10 and the slits 17 and 18 prevent the hydrogen gas 13, 14 from flowing out to the outlet and inlet 21 and 22 and that the hydrogen gas introduced in through the slits l5 and 16 is exhausted together with the exhaust gas 5, so that the gas mixture 4 flows only in the horizontal vapor phase reaction chamber 1 and does not get in contact with substrates 12-1 being sent into said reaction chamber 1 and substrates 12-2 sent out from said reaction chamber 1. For continuous growth of epitaxial layers of a lll-V semiconductor, especially a Ill-V mixed crystal semi-conductor, it is necessary to effect control such that the resistance furnace 2 shall have a temperature which is about uniform (though the temperature of the left part is slightly higher) and the heating furnace 3 shall have a temperature gradient that the temperature is higher in the left.

In case it is desired to do vapor phase etching as a pretreatment before the subsrate l2 enters the vapor phase reaction chamber 1, a very small quantity of HCl gas may be added to hydrogen gas 14.

This and the next examples are described in order to clarify the characteristic features of the continuous epitaxial growth of llI-V compound semiconductors.

EXAMPLE 1 This example relates to a method of continuously growing epitaxial layers of GaAs.

The continuous epitaxial growth furnace shown in the figure was used. The substrate 12 was used a wafer having a face of the crystallographic plane cut from n-type GaAs grown by the horizontal Bridgeman method. The substrate was doped with Te of approximately 1 X l0 cm and was chemically etched after mirror polishing. The region of the electric furnace 2 was kept at 755C 750C, and the region of the electric furnace 3 at 750C 730C. The region of the electric furnace 3 was given a temperature gradient of 1- 2C per cm. The temperature gradient is decreasing with distance in the direction of the gas flow in the region of the electric furnaces 2 and 3. The gas mixture 4 used was the reaction product of hydrogen saturated with AsCl and Ga placed at 850C. The temperature of the gas mixing zone 7 was controlled at 800 900C. The basic parameters for epitaxial growth, i.e., the proportions of the components in the gas mixtures, the working range of the flow rates of the gas mixtures, the pressures of the various gas streams, etc., were similar to the prior art reference (lV). When the speed of movement of the substrate 12 was about 5 cm/hour in the direction of the arrow 25, the thickness of the epitaxial layer in the epitaxial wafer sent out one after another to the left of the growth furnace shown in the figure was l5p. +l,u.. The electron concentration of the surface layer of the grown layers was approximately I X l0 cm and it changed to approximately 3 X 10 cm as it progressed further into the interior. This may be due to the change of an identified impurity concentration.

What deserves special attention with respect to this Example is that the growth layers of the epitaxial wafer prepared by the continuous epitaxial growth have a uniform thickness and that there is little difference between those on different substrates. If the growth furnace shown in the figure is used and only one piece of substrate l2-3 is placed in the region of the furnace 3 in the reaction chamber 1 to be grown there without moving, other substrates b eingremoved that is to say, if grown by a batch process then GaAs is deposited on the inner wall of the quartz tube between the substrate 12-3 and the mixing zone 7, namely the region of the electric furnace 2 and the region of the electric furnace 3 on the left side of the substrate 12-3. If the gas is then stopped and the substrate 12-3 is taken out, and the next batch, i.e. a fresh substrate l2-3,-is put in and growth effected again, then'growth takes place also on the grains of GaAs deposited-on the inner wall of the quartz tube, with the result that-the quantity deposited on the inner wall increases and consequently the quantity grown on the new substrate 12-3 becomes less than that grown on the preceding substrate, even if the quantity of the gas mixture supplied is kept constant. This means that the batch process has a drawback in that the rate of growth varies depending on the number of times growth has been made. This also means that the gas mixture is lost as a condensation product on the inner wall of the quartz tube. This problem indicates the difficulty of the epitaxial growth of compound semi-conductors.

As described in detail in this Example, GaAs which would have been deposited on the inner wall of the quartz tube as mentioned above is instead effectively recovered on the GaAs substrate 12 by continuous epitaxial growth according to this invention. The aforementioned loss is consequently reduced and besides the rate of growth does not vary timewise. Although the rate of growth somewhat changes depending on the positon of the substrate as it moves on, all the substrates undergo the same growth course in the continuous epitaxial growth, so that epitaxial wafers of little scatter in quality are obtained. It is also permissible to place dummy wafers on the slate 11 at the time the movement is started and recover GaAs on the dummy wafers instead of depositing it on the inner wall of the quartz tube.

EXAMPLE 2 In place of Ga in Example 1, GaAs with an electron concentration of about 1 X lO cm at 300K was used. As the gas mixture 4, the reaction product of hydrogen saturated with AsCl and GaAs held at 850C was used. The other conditions were the same as in Example I. In this case, too, epitaxial layers of the n-type GaAs could be grown continuously without any difficulty.

Epitaxial layers of the p-type GaAs can easily be obtained by using GaAs doped with Zn in place of Ga.

The same result will also be obtained by using a gas mixture of, for example, the reaction product of H /HCl/Ga and a gas mixture of H /AsH or As.

Continuous epitaxial growth of GaAs P, (0 x l can be effected by adding a gas such as P or PH or PCL, in-the gas mixture of the afore-mentioned Examples' l and 2.

EXAMPLE 3 This example relates to a method of continuously growing epitaxial layers of GaAs P on the 111) face of the n-type GaP. The concentration of Te in the sub strates was approximately '5 x 10 cm. direction of movement of the substrates 12 was opposite to the direction of the arrow 25. The region of the electric furnace 2 was kept at 885C 820C, the region of the electric furnace 3 was kept at 820C 815C, the region of the electric furnace was given a temperature gradient of 3 10C per cm. The temperature gradient is decreasing with distance in the direction of the gas flow in the region of the electric furnaces 2 and 3. As thegas mixture 4, the mixture of the reaction product of H ,AsCl /GaAs, the reaction product of H /Pcl /GaP, and the gas mixture of H /H Se was used. The temperatures of the GaAs source and 6a? source were about 800C and 900C, respectively. The temperature of the gas mixing zone was controlled'at 900950C. The speed of movement of substrates 12 was about 10 cm/hour in the opposite direction to the direction of the arrow 25.

The basic parameters for epitaxial growth were similar to the prior art reference (IV). The ratio of As and P in the gas mixture was kept at about 6:4, and the temperature and the flow rate of hydrogen gas were always kept constant. The epitaxial layers obtained consisted ofa layer of about 25p of GaAs P, in which the value of changed continuously from the proximity of l to approximately 0.4 and a layer of about 45p. in which the value of .r was 0.39 i 0.02.Though the gas mixture entering into the reaction furnace is of constant composition, that is, the ratio of As and P in the gas mixture is kept at about 6:4, the composition of the gas mixture in the reaction furnace is richer in the constituents of the binary Ill-V semiconductor of the higher melting point, i.e., P at the higher temperature and poorer at the lower temperature, because the GaAs P, crystal with the value of in the proximity of l is deposited at the higher temperatures such as 885C, that is, the crystal which is much richer in GaP is effectively deposited from the gas mixture wherein the ratio of As and P is about 6:4 in the left part of the furnace 2, and as a result, the content of P is changed at the lower temperature.

The method of continuously growing epitaxial layers of the n-type GaAs and the p-type GaAs has been explained with reference to Examples 1 and 2, and the method of continuously growing epitaxial layers of GaAs ,,.P, was explained with reference to Example 3. In Example 3, epitaxial layers of GaAs P in which the value of x was varied continuously were continuously grown without timewise changing the ratio of As and P in the gas mixture 4 in the figure.

In the afore-mentioned Examples, GaAs was taken up as an example of Ill-V binary semiconductors and GaAs P r as an example of llI-V mixed crystal semiconductors. However, the method of this invention is by no means limited to these lll-V semiconductors. It can continuously grow epitaxial layers of the aforementioned various Ill-V semiconductors on the aforementioned various substrates. That is to say, the combination of the gas mixture 4, temperature gradient of the electric furnace 2 or 3 and the direction of movement of the substrates 12 shown in the figure will make this method easily applicable to the continuous epitaxial growth of many other Ill-V semiconductors. For substrates 12, Ge and Si may also be used instead of Ill-V semiconductors. g f.

1. A method for the continuous preparation of the epitaxial layers of a lII-V temary'compound semiconductor represented by a general formula AB C on a llI-V binary compound semiconductor from a gas mixture, wherein AB C stands for both A CH C" and B', ,.C"' -A", A' and A" being a "1-8 element and a V-B element, respectively, and B' and C' and B" and C" being two different lll-B elements and V-B elements, respectively, and the value of .r being between and 1, wherein said Ill-V ternary compound semiconductor with a graded composition is grown without changing timewise the composition of said gas mixture entering into the reaction furnace. which is given a temperature gradient decreasing with distance in the direction of the gas flow, and by gradually changing the temperature of said Ill-V binary compound semiconductor, and which is characterized by continuously changing the value of to result in the graded composition by continuously moving the plurality of said lll-V binary compound semiconductor substrates, upstream of said gas flow in the situation when the substrate has a lower melting point, and downstream of said gas flow in the situation when the substrate has a higher melting point than said ternary compound semiconductor, respectively, thus effectively growing said epitaxial layers on said substrates thereby gradually decreasing the constituent C and increasing the consituent B in the gas mixture in the reaction furnace downstream of said gas flow in the situation when the compound AB has a lower melting point than the Compound AC and vice versa in the situation when the compound AB has a higher melting point than the compound AC.

2. A method as claimed in claim 1 wherein said lll-V ternary compound semiconductor is GaAs P, and GaP is utilized for said lll-V binary compound semiconductor substrate.

3. A method as claimed in claim 2 which is characterized in that said gas mixture is produced from the reaction products of a hydrogen gas saturated with AsC1 with GaAs and the reaction products of a hydrogen gas saturated with PCI with GaP.

4. A method as claimed in claim 1 which is characterized in that dummy wafers are placed in the reaction furnace before the movement of said substrates is started, thereby effectively depositing said ternary compound semiconductor on said wafers.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,893,876

DATED July 8, 1975 INVENTOMS) Shin-ichi Akai, Makoto Hayashi, Shin-JLchi Iguchi and Takashi Shimoda It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below;

Column 2, line 48, after "object" insert --the oontinuous growth of-- Column 5, line 2, erase "identified" and substitute --unidentified-- I Signed and Scale-d this A ttest:

RUTH C. MASON C. MARSHALL DANN Anefll'ng ff Commissioner uj'Parems and Trademarks PA H..\I M).

OATH.)

IN VRNTOK b) Column Column Column Column Column Column Column [SEAL] (I E RT 1 i I (1 A71" E 0 F CORRECTION July 8,

It rs cerhhed that error appears it the above-identified patent and that said Letters Patent :rre herehy corrected as shown below:

"Through" and substitute --Though line 19, before insert --gas mixture-- line 46, delete "Descrip-" line 47, erase "tion of the Invention" and Substitute --DESCRIPTION OF THE INVENTION-- line line

line

line

before "to" insert -it is necessary-- erase and substitute (CH delete "used" (second occurrence) before "direction" insert --The-- Signed and Scaled this thirtieth D f March 1976 A ttest:

RUTH C. MASON Allcxling Officer C. MARSHALL DANN (mnmissimu'r of Patents and Trademarks UNITED S'IATES PAtt lr T ()FFHJE (fl ti M t t I (l AT E 0 t1" COR RECTION IAI'MI rm. 3, 893, 876

OATH) July 8, 1975 I Shin-ichi Akai, i-iakoto Hayashi, Shin-ichi |\N["\"T0Mb) Igucni and Takashi Shimoda It rs certified that error appears m the ab0veidentitied patent and that said Letters Patent are hereby corrected as shown below;

In the ABSTRACT [57] line 15, erase "Through" and substitute -Though- Column 2,. line 19, before insert -gas mixture- Column 2, line 46, delete "Descrip-" Column 2, line 47, erase "tion of the Invention" and substitute --DI3SCRIPTION OF THE INVENTION-- Column 3, line 57, erase "C' and substitute (CH I H 3,3 33 Column 3, line 58 before "to" insert -it is necessary-- Column 4, line 41, delete "used" (second occurrence) Column 6, line 8, before "direction" insert --The-- Signed and Scaled thisthirtieth D f March 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (mnmissr'mwr uj'Parents and Trademarks

Claims (4)

1. A METHOD FOR THE CONTINUOUS PREPARATION OF THE EPITAXIAL LAYERS OF A III-V TERNARY COMPOUND SEMICONDUCTOR REPRESENTED BY GENERAL FORMULA AB1-XCX ON A III-V BINARY COMPOUND SEMICONDUCTOR FROM A GAS MIXRUE, WHEREIN ABI-XCX STANDS FOR BOTH AIIIBV1-X AND BIII1-XCIIIXAV,AIII AND AV BEING III-B ELEMENT AND A V-B ELEMENT, RESPECTIVELY, AND BIII AND CIIIAND BV AND CV BEING TWO DIFFERENT III-B ELEMENTS AND V-B ELEMENTS, RESPECTIVELY, AND THE VALUE OF X BEING BETWEEN 0 AND 1, WHEREIN SAID III-V TERNARY COMPOUND SEMICONDUCTOR WITH A GRADED COMPOSITION IS GROWN WITHOUT CHANGING TIMEWISE THE COMPOSITION OF SAID GAS MIXTURE ENTERING INTO THE REACTION FURNACE, WHICH IS GIVEN A TEMPERATURE GRADIENT DECREASING WITH DISTANCE IN THE DIRECTION OF THE GAS FLOW, AND BY GRADUALLY CHANGING THE TEMPERATURE OF SAID III-V BINARY COMPOUND SEMICONDUCTOR, AND WHICH IS CHARACTERIZED BY CONTINUOUSLY CHANGING THE VALUE OF X TO RESULT IN THE GRADED COMPOSITION BY CONTINUOUSLY MOVING THE PLURALITY OF SAID III-V BINARY COMPOUND SEMICONDUCTOR SUBSTRATES, UPSTREAM OF SAID GAS FLOW IN THE SITUATION WHEN THE SUBSTRATE HAS A LOWER MELTING POINT, AND DOWNSTREAM OF SAID GAS FLOW IN HE SITUATION WHEN THE SUBSTRATE HAS A HIGHER MELTING POINT THAN SAID TERNARY COMPOUND SEMICONDUCTOR, RESPECTIVELY, THUS EFFECTIVELY ROWING SAID EPITAXIAL LAYERS ON SAID SUBSTRATES THEREBY GRADUALLY DECREASING THE CONSITUENT C AND NCREASING THE CONSITUENT B IN THE GAS MIXTURE IN THE REACTION FURNACE DOWNSTREAM OF SAID GAS FLOW IN THE SITUATION WHEN THE COMPOUND AB HAS A LOWER MELTING POINT THAN THE COMPOUND AC AND VICE VERSA IN THE SITUATION WHEN THE COMPOUND AB HAS A HIGHER MELTING POINT THAM THE COMPOUND AC.
2. A method as claimed in claim 1 wherein said III-V ternary compound semiconductor is GaAs1-xPx and GaP is utilized for said III-V binary compound semiconductor substrate.
3. A method as claimed in claim 2 which is characterized in that said gas mixture is produced from the reaction products of a hydrogen gas saturated with AsC13 with GaAs and the reaction products of a hydrogen gas saturated with PC13 with GaP.
4. A method as claimed in claim 1 which is characterized in that dummy wafers are placed in the reaction furnace before the movement of said substrates is started, thereby effectively depositing said ternary compound semiconductor on said wafers.
US3893876A 1971-09-06 1972-08-31 Method and apparatus of the continuous preparation of epitaxial layers of semiconducting III-V compounds from vapor phase Expired - Lifetime US3893876A (en)

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Cited By (18)

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US4010045A (en) * 1973-12-13 1977-03-01 Ruehrwein Robert A Process for production of III-V compound crystals
US4048955A (en) * 1975-09-02 1977-09-20 Texas Instruments Incorporated Continuous chemical vapor deposition reactor
US4071383A (en) * 1975-05-14 1978-01-31 Matsushita Electric Industrial Co., Ltd. Process for fabrication of dielectric optical waveguide devices
US4116733A (en) * 1977-10-06 1978-09-26 Rca Corporation Vapor phase growth technique of III-V compounds utilizing a preheating step
US4171996A (en) * 1975-08-12 1979-10-23 Gosudarstvenny Nauchno-Issledovatelsky i Proektny Institut Redkonetallicheskoi Promyshlennosti "Giredmet" Fabrication of a heterogeneous semiconductor structure with composition gradient utilizing a gas phase transfer process
US4172756A (en) * 1976-02-06 1979-10-30 U.S. Philips Corporation Method for the accelerated growth from the gaseous phase of crystals, and products obtained in this manner
US4256052A (en) * 1979-10-02 1981-03-17 Rca Corp. Temperature gradient means in reactor tube of vapor deposition apparatus
US4449037A (en) * 1978-10-31 1984-05-15 Fujitsu Limited Method and apparatus for heating semiconductor wafers
US4462332A (en) * 1982-04-29 1984-07-31 Energy Conversion Devices, Inc. Magnetic gas gate
US4479455A (en) * 1983-03-14 1984-10-30 Energy Conversion Devices, Inc. Process gas introduction and channeling system to produce a profiled semiconductor layer
US4483736A (en) * 1981-03-24 1984-11-20 Mitsubishi Monsanto Chemical Co., Ltd. Method for producing a single crystal of a IIIb -Vb compound
US4625678A (en) * 1982-05-28 1986-12-02 Fujitsu Limited Apparatus for plasma chemical vapor deposition
US4699675A (en) * 1985-12-26 1987-10-13 Rca Corporation Vapor phase growth of III-V materials
US5037674A (en) * 1985-05-29 1991-08-06 The Furukawa Electric Co., Ltd. Method of chemically vapor depositing a thin film of GaAs
US5997588A (en) * 1995-10-13 1999-12-07 Advanced Semiconductor Materials America, Inc. Semiconductor processing system with gas curtain
US6010937A (en) * 1995-09-05 2000-01-04 Spire Corporation Reduction of dislocations in a heteroepitaxial semiconductor structure
EP1146140A1 (en) * 2000-04-10 2001-10-17 Air Products And Chemicals, Inc. Process for deposition of oxides and nitrides with compositional gradients
WO2002013245A1 (en) * 2000-08-04 2002-02-14 The Regents Of The University Of California Method of controlling stress in gallium nitride films deposited on substrates

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JPS5624928A (en) * 1979-08-09 1981-03-10 Nippon Telegr & Teleph Corp <Ntt> Electrode forming method of semiconductor
JPS57193025A (en) * 1981-05-25 1982-11-27 Semiconductor Energy Lab Co Ltd Manufacture of film
JPH0369879B2 (en) * 1983-01-10 1991-11-05 Nippon Electric Co

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US2877138A (en) * 1956-05-18 1959-03-10 Ind Rayon Corp Method of heating a filament to produce a metal coating in a decomposable gas plating process
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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4010045A (en) * 1973-12-13 1977-03-01 Ruehrwein Robert A Process for production of III-V compound crystals
US4071383A (en) * 1975-05-14 1978-01-31 Matsushita Electric Industrial Co., Ltd. Process for fabrication of dielectric optical waveguide devices
US4171996A (en) * 1975-08-12 1979-10-23 Gosudarstvenny Nauchno-Issledovatelsky i Proektny Institut Redkonetallicheskoi Promyshlennosti "Giredmet" Fabrication of a heterogeneous semiconductor structure with composition gradient utilizing a gas phase transfer process
US4048955A (en) * 1975-09-02 1977-09-20 Texas Instruments Incorporated Continuous chemical vapor deposition reactor
US4172756A (en) * 1976-02-06 1979-10-30 U.S. Philips Corporation Method for the accelerated growth from the gaseous phase of crystals, and products obtained in this manner
US4116733A (en) * 1977-10-06 1978-09-26 Rca Corporation Vapor phase growth technique of III-V compounds utilizing a preheating step
US4449037A (en) * 1978-10-31 1984-05-15 Fujitsu Limited Method and apparatus for heating semiconductor wafers
US4256052A (en) * 1979-10-02 1981-03-17 Rca Corp. Temperature gradient means in reactor tube of vapor deposition apparatus
US4483736A (en) * 1981-03-24 1984-11-20 Mitsubishi Monsanto Chemical Co., Ltd. Method for producing a single crystal of a IIIb -Vb compound
US4462332A (en) * 1982-04-29 1984-07-31 Energy Conversion Devices, Inc. Magnetic gas gate
US4625678A (en) * 1982-05-28 1986-12-02 Fujitsu Limited Apparatus for plasma chemical vapor deposition
US4479455A (en) * 1983-03-14 1984-10-30 Energy Conversion Devices, Inc. Process gas introduction and channeling system to produce a profiled semiconductor layer
US5037674A (en) * 1985-05-29 1991-08-06 The Furukawa Electric Co., Ltd. Method of chemically vapor depositing a thin film of GaAs
US4699675A (en) * 1985-12-26 1987-10-13 Rca Corporation Vapor phase growth of III-V materials
US6010937A (en) * 1995-09-05 2000-01-04 Spire Corporation Reduction of dislocations in a heteroepitaxial semiconductor structure
US5997588A (en) * 1995-10-13 1999-12-07 Advanced Semiconductor Materials America, Inc. Semiconductor processing system with gas curtain
EP1146140A1 (en) * 2000-04-10 2001-10-17 Air Products And Chemicals, Inc. Process for deposition of oxides and nitrides with compositional gradients
US6537613B1 (en) 2000-04-10 2003-03-25 Air Products And Chemicals, Inc. Process for metal metalloid oxides and nitrides with compositional gradients
WO2002013245A1 (en) * 2000-08-04 2002-02-14 The Regents Of The University Of California Method of controlling stress in gallium nitride films deposited on substrates
US7687888B2 (en) * 2000-08-04 2010-03-30 The Regents Of The University Of California Method of controlling stress in gallium nitride films deposited on substrates
US20110108886A1 (en) * 2000-08-04 2011-05-12 The Regents Of The University Of California Method of controlling stress in group-iii nitride films deposited on substrates
US8525230B2 (en) 2000-08-04 2013-09-03 The Regents Of The University Of California Field-effect transistor with compositionally graded nitride layer on a silicaon substrate
US9129977B2 (en) 2000-08-04 2015-09-08 The Regents Of The University Of California Method of controlling stress in group-III nitride films deposited on substrates
US9691712B2 (en) 2000-08-04 2017-06-27 The Regents Of The University Of California Method of controlling stress in group-III nitride films deposited on substrates

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