US3498894A - Preparation of compound semiconductors by fused salt electrolysis - Google Patents

Preparation of compound semiconductors by fused salt electrolysis Download PDF

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US3498894A
US3498894A US609084A US3498894DA US3498894A US 3498894 A US3498894 A US 3498894A US 609084 A US609084 A US 609084A US 3498894D A US3498894D A US 3498894DA US 3498894 A US3498894 A US 3498894A
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fused salt
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Jerome J Cuomo
Richard J Gambino
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International Business Machines Corp
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Definitions

  • a fused salt solution for the synthesis of gallium phosphide is a single crystal layer of GaP was produced epitaxially i on the l11 face of a silicon single crystal using this composition.
  • Electroluminescent diodes have been produced by selectively doping the GaP layer during deposition.
  • This invention relates generally to preparation of compounds by fused salt electrolysis, and it relates more particularly to both synthesis and epitaxial growth of compound semiconductors thereby.
  • III-V crystalline semiconductor zinc blende compounds including a metal from the group consisting of Ga, Al, and In with a metalloid from the group consisting of P, As, and Sb.
  • IIVI crystalline semiconductor zinc blende compounds including a metal from the group consisting of Zn, Cd, and Hg with a metalloid from the group consisting of S, Se, and Te.
  • IIV crystalline semiconductor compounds including a metal from the group consisting of Zn, Cd, and Hg with a metalloid from the group consisting of P, As, and Sb. It has been generally considered in the prior art that: neither the synthesis of semiconductor compounds could be achieved by fused salt electrolysis, nor that the desirable quality and quantity of crystalline deposits by fused salt electrolysis would be suflicient to permit its use for provision of semiconductor compounds useful for semiconductor devices and especially for semiconductor compounds of the zinc blende structure. I
  • Another advantage obtained by the practice of this invention is the preparation of compound semiconductors without excessive overpressure of the metalloid.
  • Another advantage obtained by the practice of this invention is the preparation of compound semiconductors with uniform doping of the deposited crystals during growth.
  • FIG. 1 is a schematic drawing partially in section illustrating an electrolytic cell useful for obtaining epitaxial growth of a semiconductor compound by fused salt electrolysis according to the practice of this invention.
  • FIGS. 2A and 2B present current-voltage curves for the codeposition of two exemplary elements useful for an understanding of the theory of this invention.
  • this invention provides for both synthesis and epitaxial growth of semiconductor compounds by fused salt electrolysis. More specifically, crystalline deposits of zinc blende structure III-V and II-VI semiconductor compounds and II-V semiconductor compounds are obtained by fused salt electrolysis from a melt containing ions in suificiently electrochemically active form of each of the constituents of the compound.
  • this invention provides crystalline layers of GaP from fused salt melts having a composition including:
  • GaP Ga O and NaPO
  • GaP Gallium phosphide
  • GaP is a specific example of a III-V semiconductor compound which is more generally characterized as one including a metal from the group consisting of Al, Ga, and In with a metalloid from the group consisting of P, As and Sb, i.e., GaP, GaAs, and GaSb; AlP, AlAs, and AlSb; InP, InAs, and InSb, or solid solutions thereof.
  • Crystals with grown in p-n junctions are produced by adding sequentially compound sources of either p-type or n-type dopants to the solution during growth.
  • a layer of p-type material is grown in one fused salt solution, followed by the over-growth of a second layer in a separate fused salt solution which contains an n-type dopant.
  • Junctions can also be produced by solution regrowth through the practice of this invention on a crystalline layer which may be produced by another technique.
  • a layer of GaP doped with Se i.e., n-ty'pe
  • the apparatus shown in FIG. 1 consists of an atmosphere chamber of quartz glass heated by electrical windings 12 in insulation 13. Within the chamber 10 there is placed a graphite anode crucible 14 in which the fused salt solution 16 is established. A single crystal silicon substrate 18 is appended to rod 20 and is immersed in the fused salt melt 16. Current is applied between the anode crucible 14 and the silicon substrate 18 via terminals 22 and 24. Voltage source 26 is 4 connected via variable resistance 28 to terminals 22 and 24 to establish terminal 24 positive and terminal 22 negative. The electrolytic cell voltage is measured between terminals 22 and 24 and cell current is measured by ammeter 25 in the series path.
  • the solution 16 can also be maintained in the molten tate by other conventional techniques such as radio frequency heating or internal resistance heating.
  • Crucible 14 may be of any material that is not attacked by the molten salt solution such as tantalum or quartz coated with pyrolytic graphite.
  • the main function of the atmosphere chamber 10 is to protect the crucible 14 and other graphite parts 20 from oxidation by surrounding them with an inert gas atmosphere.
  • a graphite rod or other inert conductor may be used as a cathode; the silicon or other crystalline substrate is required only if epitaxial crystal growth is desired.
  • the fused salt electrolysis approach of this invention to preparation of semiconductor crystals utilizes readily controlled parameters of voltage and current density which illustratively permits regulation of growth rate, dopant concentration, and deposit location.
  • the solid curve labeled a+b, represents the current-voltage characteristics of the cathode deposition reactions observed in the electrolysis of a solution containing two ions A+ and B+.
  • This curve is interpreted as being essentially a composite of two curves shown in FIG. 2A by the dashed lines labeled a and b, which represent hypothetical currentvoltage characteristics for the independent electrolytic reactions from the same solution A++e A and B++e B.
  • the formation of a binary compound AB by an electrolytic reaction is in some respects similar to the codeposion of two elements.
  • the current-voltage curve for such a reaction may be substantially the same shape as curve a+b in FIGS. 2A or 2B.
  • the voltage V now represents the minimum voltage necessary for the formation of the compound AB. Between V and V in FIG. 2A,
  • the minimum voltage necessary for the deposition of a compound in the practice of this invention depends on the composition of the fused salt melt, the temperature of the electrolytic cell operation, and the composition and surface condition of the cathode. This minimum voltage corresponds to the voltage at which an abrupt change in slope in the current-voltage curve occurs so it is readily determined experimentally.
  • electrode reactions with certain characteristics are advantageous, i.e., both of the constituent elements should deposit at the cathode at approximately the same voltage. It is desirable that at least one of the constituent elements be a volatile element and that the compound be nonvolatile.
  • III-V crystalline semiconductor zinc blende compounds including a metal from the group consisting of Ga, Al, and In with a metalloid from the group consisting of P, As, and Sd.
  • II-VI crystalline semiconductor zinc blende compounds including a metal from the group consisting of Zn, Cd, and Hg with a metalloid from the group consisting of S, Se, and Te.
  • (c) II-V crystalline semiconductor compounds including a metal from the group consisting of Zn, Cd, and Hg With a metalloid from the group consisting of P, As, and Sb.
  • the metal and metalloid elements of a compound must have deposition potentials such that they codeposit cathodically from a fused salt solution or fused salt eutectic solution system.
  • Fused salt solutions for the synthesis and epitaxial crystal growth of compound semiconductors by fused salt electrolysis in the practice of this invention consist of three types of constituents: solvents and solvent modi bombs; sources of metal ions; and sources of metalloid ions.
  • a solution for the synthesis of GaP consists of 2 moles NaPO /2rn0le NaF, and mole Ga O in which NaPO serves both as the solvent and as the source of the metalloid P, NaF is a solvent modifier which lowers the melting point and viscosity of NaPO and Ga O is the source of Ga ions.
  • Other solvents which can be used are fused alkali halides or their mixtures.
  • Other compounds can be used as a source of phosphorous producing ions, e.g. P phosphates other than NaPO or fluoro-phosphates of the alkali metals.
  • the source of gallium ions can also be from one of its halides, or from an alkali metal gallate or from a halogall
  • Fused salt mixture for the practice of this invention should be maintained during the electrolysis at a temperature which is suflicient to melt the solvent and dissolve the metal and metalloid source compounds.
  • the lower temperature limit is determined by the nature of the salt mixture, i.e., the solvents melting point.
  • the solvents melting point is modified by the addition of the solute.
  • a further factor which influences the temperature is the solubility of the solute in the solvent.
  • the upper temperature limitation is determined by the vaporization or the decomposition of any one of the components present in the fused salt solution and also by the stability of and by the dissociation temperature of the semiconductor compound being deposited.
  • the atmosphere over the solution during the fused salt electrolysis desirably should not be reactive with it or with the crucible it is contained in.
  • Inert gases such as argon or helium are suitable as Well as nitrogen, forming gas or air diluted with nitrogen.
  • the electrolytic cell voltage necessary for the synthesis of GaP is the voltage at which the two elements Ga and P codeposit at the cathode.
  • the minimum voltage is approximately 0.4 volt.
  • the upper limit voltage is the deposition potential of the other ions in the solution such as the alkali metals.
  • the solvent in which a fused salt for the practice of this invention is established desirably forms an ionicliquid on melting in which compounds of the desired metals and metalloids are soluble yielding ions which are reduced to the constituent elements at the cathode on electrolysis of the solutionso that they are codeposited.
  • the solvent should not decompose on evaporation at an excessive rate at the temperature of solution in the electrolytic cell.
  • the solvent should not contain any ions other than those desired in the product com pound, which have cathodic deposition potentials lower than or equal to the potential at which the product compound deposits at the cathode of the electrolytic cell.
  • the solution should desirably be electrolyzcd at a cell potential sufficient to codeposit the constituent elements of the resultant compound but low enough that the nonvolatile metal element is not deposited in excess of the stoichiometry of the desired compound or that other undesired elements in the solution are deposited cathodically.
  • a crystalline substrate cathode is provided on which epitaxy can occur.
  • the substrate cathode should desirably have a crystal structure and crystalline orientation such that epitaxy is possible for the crystal structure and lattice constants of the desired product compound.
  • the substrate cathode must be an electrical conductor at the temperature of operation of the electrolytic cell and should desirably be non-reactive with the fused salt solution at the cathodic potential at which the product compound deposits.
  • the temperature of operation of the electrolytic cell should desirably be suflicient to melt the solvent and produce a solution of the compounds which acts as source of the metal ions and metalloid ions.
  • the conductivity of the product com- 7; pound at the temperature of' codepositi'on should 'desirably be such that the potential at the growth surface of the crystal can be maintained at the deposition potential of the compound without inducing electrical breakdown in the product crystal.
  • Another solution suitable for synthesizing GaP in the practice of this invention is an alkali-halide solution of NaCl-l-KCl to which is added a gallium containing compound and a phosphorous containing compound such as .Ga O and NaPO respectively, i.e., v
  • Eutectic solution systems are suitable for the practice of this invention.
  • a suitable eutectic solution for the-preparation of GaP by fused salt electrolysis is KCl+LiCl to which is added a gallium containing compound such as Ga O and a phosphorous containing compound such as NaPO e.g.,
  • doping of crystals during fused salt electrolysis epitaxial growth is readily achieved by addition of the dopant ion to the fused salt solution.
  • the addition of ZnO to a melt of 2NaPO +0.5NaF+0.25Ga O provides crystalline GaP which is uniformly doped p-type.
  • the addition to the fused salt solution of Se ions or Te ions in the form of Na SeO or Na TeO respectively provides crystals of GaP that are doped n-type. By alternately using Zn and Se, a p-n junction is readily produced.
  • EXPERIMENTAL DATA GaP crystals prepared through the practice of this invention by a fused salt electrolysis are epitaxial deposits with color which ranges from yellow to amber.
  • X-ray diffraction analysis indicates a Laue pattern for a single crystal.
  • a dendritic overgrowth on an original epitaxial layer.
  • Exemplary photoluminescence measurements for Zn doped GaP produced by the practice of this invention at both 77 K. and 42 K. provide the characteristic red light of 6840 A. wavelength with relatively high efficiency of energy transformation.
  • Exemplary electroluminescence measurements of the Zn doped GaP produced by the practice of this invention provides red-orange light with somewhat less officiency of energy transformation than the noted photoluminescence measurements.
  • An optimum temperature range for the metaphosphate fused salt solution 2NaPO -l-O.5NaF+0.25 Ga O is 750 C. to 950 C.
  • EXAMPLE 1 The GaP was deposited on a single crystal'silicon cathode (chemically polished 111 orientation disk) at a temperature of 925 C. from a melt consisting of 2NaPO /2NaF, and AGa O at a potential of 1.5 volts and a current density of approximately 100 ma./cm. Theproduct formed as a golden 'yellow single crystal layer to microns thick which was in turn covered by a thicker polycrystalline layer. w p
  • EXAMPLE 2 A mixture of Ga O ,.l IaPO and Na]? was melted in a graphite crucible and the solution was electroplated using the graphite crucible as an anode and a graphite rod as the cathode. Apolycrystalline deposit of GaP formed the c ode.
  • EX E 3 A mixture 'with the composition l6NaPO 4NaF, and 1621 0 was heated to 850 C. in; a resistance furnace. A potential of -5 volts-was applied to thecell with a current of 5 amperes for 1 hour. GaP deposited .as yellow microcrystals at thecathode. The product was identified by X- ray diffraction analysis. The lattice constant was found to be 5.47 A. as compared to 5.45 A. reported in the literature. i 1
  • EXAMPLE 4 In this example, a sodium metaphosphate electrolyte was used with melt composition of: gallium to phosphorous ratio 0.125 to 0.25 and molality of Ga O solute in 2NaPO /2NaF solvent equals 0.05 to 0.1.
  • the temperature range was, 800 C. to 1050 C.; and the electrical conditions were 0.40 to 6.0 volts, current equals. to 5000 milliamperes with current density range of 12.5 to 625 ma./cm. for an electrode area of 8 cm.
  • the electrodes were polycrystalline graphite; single crystalline 100 and 111 Si, single crystalline 1,11 'Ge,.and polycrystalline Ge.
  • the optimum results were obtained using a substrate of single crystalline 111 Si with melt temperature of 800 0, cell voltage of 1.5 volts and current density of 50 ma./cm. After a time of 20 hours, a single crystal layer of 100 microns was obtained.
  • EXAMPLE 5 This example provided GaP dendritic crystals and oriented triangles as evidence of epitaxial growth.
  • An electrolyte alkali-halide system of sodium chloride was used.
  • the composition of the melt was 1 molar NaCl, 1 molar KCl, 1 to 0.33 molar ratio Ga/P.
  • Current density was 12 mat/cm. for-voltage of 1.2 volts to 1.8 volts.
  • EXAMPLE 6 The following are exemplary data on the synthesis of All, whichis a III- V, zinc blen'de compound semiconductor.
  • a solution with the composition 2NaPO 0.5NaF, and 025181 03 was electrolyz'ed at 900 C. with an applied potential of 0.6 volt.
  • the cathode product was insoluble in water, but dis solved slowly in" acid yielding phosphine gas and a solution containing aluminum-ions. These reactions confirm the presence of AIF in the cathode product.
  • EXAMPLE 8 The following are exemplary data on ZnSe which is a II-VI zinc blendeflcpmpound semiconductor.
  • a solution with the composition 43 mole percentKCl, 57 mole percent LiCl to which was added a 1:1 molar ratio mixture ,of SeCl; and ZnCl The solution was operated at 500 C.
  • The'cell voltage was 0.96 viand the current was ma.
  • EXAMPLE 9 The dopant zinc was added to sodium metaphosphate electrolyte as ZnO in a concentration of 2.5 X molar. A deposit of uniformly doped p-type GaP of 100 microns thickness was obtained after hours on a substrate of single crystalline 111 Si. The operational parameters were temperature of 800 C., cell voltage 0.9 volt, and current density of 50 ma./cm. The total surface area of the crystal was 8 cm. with areas up to 0.5 cm. free of cracks.
  • EXAMPLE 10 With dopants ZnO and -Na SeO in a sodium metaphosphate electrolyte, there resulted a thickness of GaP of microns after 20 hours on a substrate of single crystalline 111 Si.
  • the operational parameters were temperature 805 C., cell voltage of 0.9 volt, and current density of 62 ma./cm.
  • the resultant layer of GaP was doped by both Zn and Se as revealed by photoluminescence.
  • EXAMPLE 11 The following is a description of an exemplary procedure for growing p-n junctions in a compound semiconductor in the practice of this invention. Two fused salt melts were used. A single crystal of p-type GaP was grown from a solution containing ZnO as the source of Zn bearing ions by electrolysis at a cell voltage of 0.9 volt for 20 hours. After this period of time, the cathode was withdrawn from the p-type dopant solution and transferred to the n-type dopant solution which contained Na SeO as a source of selenium bearing ions. A layer of n-type GaP was deposited over the p-type layer by further electrolysis for 2 hours. The p-n junction thus formed was suitable for electroluminescent diodes and emitted red light on the passage of an electric current.
  • Method of synthesizing binary compound GaP comprising the steps of:
  • Method of depositing a layer of a semiconductor compound including a metal from the group consisting of Ga, Al, and In and a metalloid from the group consisting of P, As, and Sb comprising the steps of:
  • Method of depositing a layer of a semiconductor compound including a metal from the group consisting of Zn, Cd, and Hg and a metalloid from the group consisting of S. Se, and Te comprising the steps of:
  • Method of depositing a layer of a semiconductor compound including a metal from the group consisting of Zn, Cd, and Hg and a metalloid from the group consisting of P, As, and Sb comprising the steps of:
  • Method of growing epitaxially a crystalline layer of GaP comprising the steps of:
  • Method of epitaxially growing a p-n junction in a crystalline region comprising the steps of:

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  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Led Devices (AREA)
US609084A 1967-01-13 1967-01-13 Preparation of compound semiconductors by fused salt electrolysis Expired - Lifetime US3498894A (en)

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Publication number Priority date Publication date Assignee Title
WO1993004221A1 (en) * 1991-08-16 1993-03-04 University Of Georgia Research Foundation Method and apparatus for the electrodeposition of bismuth based materials and superconductors
US6086745A (en) * 1997-07-03 2000-07-11 Tsirelnikov; Viatcheslav I. Allotropic modification of zirconium and hafnium metals and method of preparing same
US20080295991A1 (en) * 2005-08-02 2008-12-04 Leibnz-Institu Fuer Festkoerpe-Und Werkstofforschu E.V. Helmholtzstrasse 20 Process for Producing Metal-Containing Castings, and Associated Apparatus
US8360002B2 (en) * 2006-07-14 2013-01-29 Georgia Tech Research Corporation In-situ flux measurement devices, methods, and systems

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2810605C2 (de) * 1978-03-11 1980-03-13 Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt Elektrolytisches Abscheideverfahren zur Herstellung von großflächigen Halbleiterbauelementen
EP0080844A1 (en) * 1981-11-25 1983-06-08 The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and The preparation of adducts which may be used in the preparation of compound semiconductor materials

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US3086925A (en) * 1960-10-19 1963-04-23 Union Carbide Corp Preparation of refractory sulfides
US3105800A (en) * 1960-02-15 1963-10-01 Watanabe Toshio Method of manufacturing a negative temperature coefficient resistance element
US3382161A (en) * 1965-05-03 1968-05-07 Atomic Energy Commission Usa Electrolytic separation of transition metal oxide crystals
US3440153A (en) * 1964-04-24 1969-04-22 United Aircraft Corp Electrolytic method of producing highly oriented crystalline structures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3105800A (en) * 1960-02-15 1963-10-01 Watanabe Toshio Method of manufacturing a negative temperature coefficient resistance element
US3086925A (en) * 1960-10-19 1963-04-23 Union Carbide Corp Preparation of refractory sulfides
US3440153A (en) * 1964-04-24 1969-04-22 United Aircraft Corp Electrolytic method of producing highly oriented crystalline structures
US3382161A (en) * 1965-05-03 1968-05-07 Atomic Energy Commission Usa Electrolytic separation of transition metal oxide crystals

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004221A1 (en) * 1991-08-16 1993-03-04 University Of Georgia Research Foundation Method and apparatus for the electrodeposition of bismuth based materials and superconductors
US5256260A (en) * 1991-08-16 1993-10-26 University Of Georgia Research Foundation Method and apparatus for the electrodeposition of bismuth based materials and superconductors
US6086745A (en) * 1997-07-03 2000-07-11 Tsirelnikov; Viatcheslav I. Allotropic modification of zirconium and hafnium metals and method of preparing same
US20080295991A1 (en) * 2005-08-02 2008-12-04 Leibnz-Institu Fuer Festkoerpe-Und Werkstofforschu E.V. Helmholtzstrasse 20 Process for Producing Metal-Containing Castings, and Associated Apparatus
US8002014B2 (en) 2005-08-02 2011-08-23 Leibniz-Institut Fuer Festkoerper-Und Werkstofforschung Dresden E.V. Process for producing metal-containing castings, and associated apparatus
US8360002B2 (en) * 2006-07-14 2013-01-29 Georgia Tech Research Corporation In-situ flux measurement devices, methods, and systems
US8377518B2 (en) * 2006-07-14 2013-02-19 Georgia Tech Research Corporation In-situ flux measurement devices, methods, and systems

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DE1719496B2 (de) 1980-02-14
SE337580B (en]) 1971-08-16
DE1719496C3 (de) 1980-10-09
CH500763A (de) 1970-12-31
NL6717359A (en]) 1968-07-15
GB1173939A (en) 1969-12-10
FR1552289A (en]) 1969-01-03
BE707014A (en]) 1968-04-01
DE1719496A1 (de) 1971-08-26

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