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United States Patent (19) (11) 4,237,471 Pommerrenig 45) Dec

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United States Patent (19) (11) 4,237,471 Pommerrenig 45) Dec United States Patent (19) (11) 4,237,471 Pommerrenig 45) Dec. 2, 1980 54 METHOD OF PRODUCING A 58) Field of Search ........................ 357/30, 16, 61, 63 SEMCONDUCTORPHOTODODE OF NDUM ANTMONDE AND DEVICE 56 References Cited THEREOF U.S. PATENT DOCUMENTS 75 Inventor: Dieter H. Pommerrenig, Burke, Va. 3,558,373 1/1971 Moody ................................. 148/171 73 Assignees: Hamamatsu Corporation, Middlesex, Primary Examiner-Martin H. Edlow N.J.; Hamamatsu TV Co., Ltd., Attorney, Agent, or Firm-Moonray Kojima Hamamatsu, Japan 57 ABSTRACT (21 Appl. No.: 51,245 A method of producing semiconductor photodiodes of indium antimonide, by growing an indium antimonide 22 Filed: Jun. 22, 1979 epitaxial layer of one type conductivity onto a substrate of indium antimonide of another type conductivity, Related U.S. Application Data utilizing conventional vapor phase or liquid phase epi 60 Continuation of Ser. No. 879,640, Feb. 21, 1978, aban taxial techniques, wherein the antimony in the epitaxial doned, which is a division of Ser. No. 739,659, Nov. 8, layer is partially replaced by either arsenic or phospho 1976, abandoned. rus, thus resulting in a high performing photoelectric 51 Int. Cl’............................................. H01L 27/14 device. 52 U.S.C. ........................................ 357/30; 357/16; 357/61 6 Claims, 16 Drawing Figures U.S. Patent Dec. 2, 1980 Sheet 1 of 2 4,237,471 A.27, 7 W/W 727.4c /////////////////// XXXXXXXXXXXXXXXXXXXXXXXX A27.4eXXYYXXYYXXXX U.S. Patent Dec. 2, 1980 Sheet 2 of 2 4,237,471 77.5A O 27 PZZZZZZZZZZZZZZZZZZZZ-53 " V ZZZZZZZZZZZZZZZZZZZZZZZ \ \ 22222XXXXXXXXXXXV N Ny.V 4,237,471 2 thereby, and wherein an indium antimonide epitaxial METHOD OF PRODUCING ASEMECONDUCTOR layer of one type conductivity is epitaxially grown onto PHOTODODE OF NEDUMANTMONDE AND an indium antimonide substrate of another type conduc DEVICE THEREOF tivity, with the antimony in the epitaxial layer partially replaced with arsenic or phosphorus, Photodiodes and This is a continuation of application Ser. No. 879,640 other devices are then fabricated therefrom. Preferred Feb. 21, 1978, which is itself a division of Ser. No. epitaxial layers may encompass InAsSb.1-x, wherein x is 739,659 filed Nov. 8, 1976, both of which are aban from 0.01 to 0.50, preferably within the range of 0.01 to doned. 0.05, and most preferably 0.05. The same ratios hold for 10 phosphorus. BACKGROUND OF THE INVENTION A feature of the invention is a method wherein there This invention relates to a method of producing semi is partial substitution of antimony with arsenic or phos conductor photodiodes having an indium antimonide phorus in the indium antimonide epitaxial layer. epitaxial layer of one type conductivity onto an indium A further feature of the invention is the use of an antimonide substrate of another type conductivity, and 15 epitaxial layer of InAsSbi-, wherein x is from 0.01 to more particularly to such a method wherein the anti 0.50, preferably 0.01 to 0.05, and most preferably 0.05. mony in the epitaxial layer is partially replaced by an other element. BRIEF DESCRIPTION OF THE DRAWING Epitaxial growth is a process of growing solid mate FIG. 1 depicts an illustrative apparatus to practice rial from a suitable environment onto a substrate. The 20 the invention wherein vapor phase epitaxial depositing growth is epitaxial when the material grown forms an is accomplished. extension of the crystal structure of the substrate. By FIG. 2 depicts an illustrative apparatus to practice the addition of gases comprising donor or acceptor type the invention wherein liquid phase epitaxial depositing impurities, the epitaxially deposited layer may be of is accomplished. n-type or p-type conductivity as desired. 25 FIG. 3 depicts an illustrative substrate having an It is commonly known that diffusion processes are epitaxial layer grown thereon, with the epitaxial layer used to produce the p-type region of pn-InSb photovol having partial substitution of arsenic or phosphorus for taic detectors. Uniformly n-type doped indium antimon antimony in the indium antimonide. ide crystals are enclosed together with p-type dopants FIGS. 4A-4F depict the step by step production of such as cadmium or zinc in a sealed quartz ampoule. 30 a mesa configuration photocondutive device employing The diffusion will take place at 450-500 C. After re the inventive method and moval of the diffused substrate, the material is further FIGS. 5A-5G depict step by step production of a processed into single or multi-element semiconductor planar configuration photoconductive device employ photodiodes by utilizing standard planar or mesh tech ing the inventive method. nologies. 35 These methods require costly and complicated etch DETALED DESCRIPTION OF PREFERRED ing and optimization processes which greatly aggravate EMBODIMENTS the establishment of reproducible, thin p-layer regions FIG. 1. depicts a typical epitaxial gas or vapor phase and fail completely when extremely thin, uniform thick reactor apparatus for growing epitaxial layers on a sub nesses are required. Therefore, the resulting photoelec strate, comprising a furnace chamber 1, having a tem tric devices suffer in their performance characteristics. perature and heating control system not shown, a re Still another method being utilized is the growth of an movable cap 2, gas inlet 4 and gas exhaust 3. Through epitaxial layer of indium antimonide having the oppo inlet 4 may be supplied different gases for the deposition site conductance type on an indium antimonide mono of or growth of a suitable layer. Within the chamber 1 crystal. This method suffers greatly from the nonstoi 45 may be placed crystal dish 9 on which a substrate 10, chiometric transport properties of both species, the such as of indium antimonide may be placed. Also in indium and antimony, which will result in an epitaxial chamber 1 there may be placed another dish 11 on layer of very low quality. which may be placed solid indium 12, and another dish It was, therefore, necessary to find a method of pro 13, on which may be placed, for example, a dopant 14 ducing indium antimonide single and multi-element 50 such as zinc or cadium for p-type doping and tin or detectors according to the epitaxial growth method, tellurium for n-type doping. From sources 5, 6, 7 and 8, which does not have the deficiency of the conventional there is supplied for example, reagent gases H2, HCl, epitaxial methods. AsH3, or PH3, and SbH3, respectively, with suitable The main demands placed upon the epitaxial process flow control with known type of metering. are restoration of the stoichiometry of the epitaxial 55 In operation of FIG. 1, the dish 9 having indium layer, to assure equivalent and a sufficient partial pres antimonide slice 10, such as of n-type conductivity, sure of all gas species involved and to apply standard thereon is charged through the right end having cap 2 device processing technologies to the production of removed therefrom, and into the chamber 1. Also, the photoelectric indium antimonide diodes. These require containers 11 and 13 having loaded thereon solid in ments can be fulfilled by executing the epitaxial process 60 dium and zinc dopant, respectively, are also charged in an apparatus having the capability of producing epi into the chamber 1, through the open right end. Then taxial layers of the desired composition. cap 2 is used to close chamber 1. Chamber 1 is then purged by supplying hydrogen gas from source 6 SUMMARY OF THE INVENTION through inlet 4. The chamber is then raised in tempera Accordingly, an object of the invention is to elimi 65 ture to a range of about 480 C. to 520C. The tempera nate the above and other deficiencies of the prior art. ture of the indium is raised to about 700 C. and that of These and other objects are attained in the invention zinc 14 is raised to about 380° C. As the temperature of which encompasses a method and devices produced the reaction chamber approaches a constant value, the 4,237,471 3 4. epitaxial growth atmosphere is established in chamber 1 minutes, heat is applied to chamber 21 and raised to a by supplying for example, antimony hydride as an anti temperature of about 500 C. This temperature will mony source from source 5 and arsine as an arsenic produce a uniform melt of the mixture 27 without af. source from source 8, and hydrogen chloride as a trans fecting the characteristics of the indium antimonide port agent for both the indium and zinc, from source 7. monocrystal 29. As the temperature of the chamber The gases are supplied through the single common inlet reaches equilibrium which is about 20 minutes, the 4, or through a plurality of individual inlets. The hydro chamber 21 is tilted in such a way that the liquid melt 27 gen is continuously supplied, serving as a carrier and will roll over slice 29 in a complete manner, such as reducing gas. Zinc is utilized to provide p-type doping shown in FIG. 2. After a suitable time, such as five while the epitaxial layer is being grown. Of course, 10 minutes, has elapsed, the temperature of chamber 21 is cadmium can also be used to provide p-type doping. If sequentially lowered in small increments, in order to n-type doping is desired tin or tellurium may be used. shift the thermodynamic equilibrium of the melt to solid By suitably adjusting the molecular ratio of stibine state, thus resulting in the growth of the epitaxial layer. and arsine, the compositional ratio of epitaxial film can The thickness of the epitaxial layer is a function of the be altered. The mixed crystal InAsSb.
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