CA1209452A - Heterostructure comprising a heteroepitaxial multiconstituent material - Google Patents

Heterostructure comprising a heteroepitaxial multiconstituent material

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Publication number
CA1209452A
CA1209452A CA000435166A CA435166A CA1209452A CA 1209452 A CA1209452 A CA 1209452A CA 000435166 A CA000435166 A CA 000435166A CA 435166 A CA435166 A CA 435166A CA 1209452 A CA1209452 A CA 1209452A
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substrate
template
epitaxial
layer
temperature
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French (fr)
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John M. Gibson
Raymond T. Tung
John M. Poate
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AT&T Corp
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Western Electric Co Inc
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/28518Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System the conductive layers comprising silicides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/0237Materials
    • H01L21/02373Group 14 semiconducting materials
    • H01L21/02381Silicon, silicon germanium, germanium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02436Intermediate layers between substrates and deposited layers
    • H01L21/02439Materials
    • H01L21/02491Conductive materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02518Deposited layers
    • H01L21/02521Materials
    • H01L21/02524Group 14 semiconducting materials
    • H01L21/02532Silicon, silicon germanium, germanium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02656Special treatments
    • H01L21/02658Pretreatments

Abstract

A HETEROSTRUCTURE COMPRISING A HETEROEPITAXIAL
MULTICONSTITUENT MATERIAL

Abstract The method for producing a heterostructure comprising a heteroepitaxial multiconstituent material on a substrate comprises deposition on the substrate surface at a relatively low deposition temperature of a thin disordered layer of a "template-forming" material, i.e., material containing at least one constituent of the multiconstituent material to be grown, and differing in chemical composition from at least the substrate material, raising the substrate temperature to an intermediate transformation temperature, thereby causing the template-forming material to undergo a reaction that results in formation of "template" material, typically material having substantially the same composition as the multiconstituent material to be grown. Onto the thus formed template layer is then deposited the material for the epitaxial multiconstituent layer. The inventive method has wide applicability, and permits, inter alia, growth of essentially perfect epitaxial CoSi2 or NiSi2 on Si(100).
Material grown by the method can be in form of an essentially continuous layer or a patterned layer, and can serve as the substrate for the growth thereon of further epitaxial material of different chemical composition.

Description

12Q~4~

A HETEROSTRUCTURE COMPRISING A HETEROEPITAXIAL
MULTICONSTITUENT MATERIAL

F-ield-of-the Invention This invention pertains to a method of producing a heterostructure by epitaxial growth of crystalline multiconstituent material on a substrate.
sackground--of-the Invention Heteroepitaxy, i.e., the epitaxial growth of a layer of material on a substrate that differs in chemical composition from the epitaxial layer, has been a field of active research for some time. These efforts have led to some technologically important applications. For instance, III-V or II-VI semiconductors have been combined with ternary materials in heteroepitaxial systems. Exemplary of this application is the system GaAs/AlxGal_xAs that is widely used in optoelectronic devices. Patterned monocrystalline layers of III-V compounds have also been grown on III-V substrates (U.S. Patent 3,928,092, issued December 23, 1975 to W. C. Ballamy et al). Semiconductor layers are also being grown epitaxially on insulators. An example of such a heteroepitaxial system of technological importance is silicon on sapphire. Similarly, compound semiconductors, especially the III-V compounds, have been grown on sapphire substrates. For a general review, see, for instance, ~eteroepi~axial Semiconductors for ElectEonic Devices, G. W. Cullen and C. C. Wang, editors, Springer-Verlag, New York (1978).
Despite the efforts of the last years, the number of heteroepitaxial systems that have been developed sufficiently to permit device application is small. In particular, the number of demonstrated heteroepitaxial structures comprising an epitaxial metal layer is at present very limited. However, such systems not only are necessary for making three-dimensional integrated circuits, but would permit the realization of novel device ~Z~452 structures, e.g., a metal-base transistor. Chief among the reported heterostructures containing an epitaxial metal layer are CoSi2 on Si, and NiSi2 on Si.
When CoSi2 or NiSi2 epitaxial films are grown on Si(lll) by one of the techniques that have been employed successfully to date, e.g., by low temperature metal deposition and high temperature reaction, or by molecular-beam epitaxy, it has been found that the epitaxial material formed often contains two types of crystallites. Both types share the surface normal [111] direction with the substrate, but one has an orientation that is rotated by 180 degrees about the normal, as compared to the substrate, and the other has an orientation that is identical to that of the substrate. The former will be referred to herein as "type B", and the latter as "type A". When grains of both orientations are present in epitaxial material then the total amounts of each are often similar. The grains, of course, are separated by high-angle grain boundaries, which contribute significantly to electron scattering in the material, thus reducing the usefulness of such material as contact material in Very Large Scale Integration ~VLSI) semiconductor devices. Furthermore, a silicide layer containing both A and B type crystallites is typically unsuitable to serve as substrate layer for the growth of subsequent device-quality heteroepitaxial material, e.g., a further Si layer, as would be required in the manufacture of three-dimensional integrated circuits.
Although epitaxial layers of CoSi2 and NiSi2 have recently been grown on Si(lll), single crystal NiSi2 could not be grown on Si(100), due to [111] faceting of the NiSi2/Si interface. K. C. Chiu et al, Applied Physic6 ~e~ters, Vol. 38, pp. 988-990, (1981). Epitaxial growth of high quality single crystal metal silicide on Si(100) is, however, of great technological interest since current silicon technology uses almost exclusively (100)-oriented material.

lZ~45Z

Silicide-silicon heterostructures and a technique for preparing these structures have been disclosed by J.C. Bean et al in a U.S. patent no. 4,492,971 issued on Jan. 8, 1985. The technique disclosed therein comprises exposing a single-crystal silicon substrate to a vapor comprising a silicide-forming metal, while maintaining the substrate at an appropriate temperature at which the metal reacts, in situ, with the silicon to form a metal silicide single crystal. The heteroepitaxial silicide layers formed by this technique typically are of high perfection, as determined by Rutherford _ackscattering spectroscopy (RBS) and channeling, and by transmission electron microscopy.
Because of the great technological promise of heteroepitaxially grown layers of material of device quality, and because of the limited number of systems in which such growth has been achieved so far, a broadly applicable method for growing such layers is of substan-tial interest. In particular, a method for growing substantially perfect metal silicide on silicon is of great interest to the semiconductor industry. And furthermore, a growth technique that permits control of the orientation of the epitaxial material formed is of added technological and scientific significance.
Definitions:
A "multiconstituent" material herein is a material consisting substantially of material of nominal chemical composition AXByCz...., where A, B, ....
are arbitrary chemical elements, and at least x and y are different from zero.
nEpitaxial" material is crystalline material grown on a single crystal substrate, with the epitaxial material having at least one crystallographic axis in common with the substrate.
A "heteroepitaxial" material is an epitaxial `~

material, with the concentration of at least one chemical element being substantially different in the substrate material from that in the epitaxial material.
A "template layer" is a thin layer of material formed on a substrate for the purpose of influencing the crystallography of material, typically multiconstituent material, epitaxially grown thereon. The chemical compo-sition of the template layer is typically substantially the same as that of the epitaxial material to be grown thereon.
"Template-forming" (T-F) matérial is material deposited on the substrate in substantially disordered form, which can undergo a transformation to form the template layer. The transformation typically comprises a transformation from the disordered to the crystalline state, and can further comprise a reaction with a chem-ical element whose concentration in the T-F material is substantially different from its concentration in the substrate. T-F material comprises at least one of the chemical constituents of the epitaxial material to be grown thereon, and differs in chemical composition from the substrate material.
By ~transport element" we mean an element that is present in greater than trace amounts in both the substrate material and the heteroepitaxial multicon-stituent material formed thereon, and that can react with T-F material to form, under appropriate reaction conditions, template material.
Summary of the Invention According to the invention there is provided a method for producing a heterostructure comprising epitaxial multiconstituent first material on a substrate comprising a second material, with the second material differing in chemical composition from the first material, the method comprising: (a) growing on at least a part of the substrate, at a growth temperature, epitaxial first ~!

~ZQ~452 - 4a -material comprising material deposited on the substrate, characterized in that the method further comprises: (b) depositing, prior to (a), substantially spatially uniformly on at least the part of the substrate, an effective amount of matter, to be referred to as template-forming material, the template-forming material comprising at least one of the chemical constituents of the first material and dif-fering in chemical composition from at least the second material, the substrate being during deposition of the template-forming material at a deposition temperature that is substantially lower than à transformation temperature, whereby the template-forming material deposit is in sub-stantially disordered form, and (c) raising, subsequent to (b) but still prior to (a), the temperature of the substrate with the template-forming material thereon to a transformation temperature, the transformation tempera-ture being lower than the growth temperature, whereby a template material is formed on the substrate, the thus produced composite forming the substrate referred to in (a).
We are describing herein a method for producing a heterostructure comprising an epitaxial multiconstituent material on a substrate. The method comprises depositing, substantially spatially uniformly, a thin layer of T-F
material, typically less than about 10 nanometers (100 A) thick, onto the substantially atomically clean substrate, or onto part thereof, with the substrate at a relatively low deposition temperature, resulting typically in a substantially disordered deposit. The method further comprises raising the temerature of the substrate, with ~a ~2~4S;~:

the thin layer of T-F material deposited thereon, to an appropriate transformation temperature at which the deposited material undergoes a transformation, typically forming ordered, epitaxial material. Onto this transformed material, referred to herein generally as the "template"
layer, is then deposited material for growing the epitaxial layer, with epitaxial crystal growth taking place if the substrate is maintained at an appropriate, typically higher, growth temperature, and with the crystallography of the epitaxial layer being controlled by the template layer.
The inventive method for heteroepitaxial formation of multiconstituent materials is considered to be of broad applicability. In particular, it is considered to apply to the growth of multiconstituent epitaxial material, either in unpatterned or patterned layer form, on multiconstituent substrates as well as on monoconstituent substrates. Exemplary of systems considered suitable for application of the inventive method are epitaxial metallic or insulating layers on Si, Ge, III-V and II-VI
semiconductors. Preferred systems are the metal silicides and germinates on Si and Ge, respectively, including silicides of other than (111) orientation, e.g., CoSi2 or NiSi2 of (100) orientation on (100) Si substrates. Obvious variations of the method, e.g. growth on the template layer of epitaxial material differing in chemical composition from the template layer, are also contemplated.
The inventive method typically permits use of lower epitaxial growth temperatures and of shorter growth times than prior art reaction methods. This is of obvious commercial interest. Furthermore, the method permits growth of truly monocrystalline material, e.g., NiSi2, results in substantially smooth interfaces in systems subject to faceting by prior art methods, e.g., (100) NiSi2, and typically yields pinhole-free material of device-grade quality.

~Z~452 Brief Description of the Drawings FIG. 1 schematically depicts a thin layer of as-deposited material on a substrate;
FIG. 2 schematically shows the substrate with a template layer formed thereon;
FIG. 3 schematically shows the substrate with an epitaxial layer grown thereon;
FIG. 4 schematically depicts a heteroepitaxial structure comprising a substrate, an epitaxial layer grown thereon, and a further epitaxial layer grown on the first epitaxial layer, FIG. 5 schematically shows patterned epitaxial material on a masked substrate, and FIG. 6 shows experimentally determined relationships between the thickness of a nickel layer deposited onto a Si (111) substrate and the orientation of the epitaxial NiSi2 grown on the template layer formed therefrom.
~etailed--Description An important aspect of the inventive method is the formation of a thin template layer. This is accomplished by depositing an appropriate thickness of T-F material on the substrate, and transforming the T-F material, in a subsequent transformation which can comprise a reaction with one or more transport elements, into the template layer.
The T-F material is deposited while the substrate is at an appropriate low deposition temperature, e.g., at room temperature. As a consequence of this low-temperature deposition, the (as-deposited) T-F material is typically in a disordered state.
Subsequent to the deposition of the T-F material the substrate temperature is raised to an appropriate transformation temperature, typically lower than the growth temperature of the epitaxial material to be grown, at which the deposited material undergoes a transformation to form the template layer. The transformation typically comprises 12~2452 an ordering transformation which results in appearance of long range order in previously disordered material, and may comprise a reaction in which the T-F material and one or more transport elements derived from the substrate react to form template material. An example of the former is the formation of single crystal NiSi2 template material from co-deposited disordered stoichiometric Ni and Si, and an example of the latter is the formation of such template material from Ni deposited onto a Si substrate.
Formation of a template layer is schematically shown in FIGS. 1 and 2. FIG. 1 shows a layer 11 of T-F
material on substrate 10, and FIG. 2 shows template layer 21, formed by a T-F transformation at the transformation temperature, on substrate 10.
A further aspect of the invention is the possibility of controlling, in appropriate heteroepitaxial systems, the crystalline orientation of the epitaxial layer through control of some parameter, typically the thickness, of the template layer. In such systems it is typically necessary to closely control the thickness of the deposited T-F material, taking account of the fact that reaction of the T-F material with the transport element (or elements) typically produces material of different specific density than the starting deposit.
After formation of the template layer on the original substrate, sufficient amounts of at least some of the constituents of the epitaxial material are to be deposited thereon, and epitaxial material of the appropriate chemical composition and crystalline orientation and perfection grown under appropriately chosen conditions. This entails maintaining the substrate at an appropriate growth temperature that is typically higher than the T-F transformation temperature for a period of time during and/or after deposition. Furthermore, it may impose limits on the deposition rate, as well as on the chemical composition of the deposits. In this step of the inventive process, for instance, all of the chemical lZQ~452 constituents of the epitaxial material can be deposited substantially simultaneously and in the appropriate stoichiometric ratio, or one or more of the chemical constituents of the epitaxial material may be substantially absent from the flux, to be derived from the substrate material. Furthermore, the constituents can be deposited in a one-step or in a multistep procedure. The former refers to procedures in which the epitaxial layer is grown to final thickness in a substantially continuous manner, and the latter to procedures in which the layer is built up to final thickness in a sequence of deposition/growth steps.
FIG. 3 schematically depicts heteroepitaxial layer 31 grown on substrate 10 by the inventive process.
It is to be noted that typically the template layer cannot be separately identified at this stage (or at later stages) of the heterostructure-producing process, since the template material typically becomes part of the epitaxial material. However, this is not necessarily the case, and we also contemplate practice of the inventive process resulting in epitaxial material grown on a later identifiable template layer.
FIG. 4 schematically shows a double-heterostructure, namely a first epitaxial layer 31, e.g., a metal silicide layer grown by the inventive process on substrate 10, and a second epitaxial layer 40, e.g., a silicon layer, grown on layer 31. Such a double-heterostructure is illustrative of structures grown by means of the inventive process that are useful, inter alia, in three dimensional semiconductor devices, e.g., metal-base transistors. Growth of layer 40 is typically by conventional epitaxy methods.
FIG. 5 illustrates schematically patterned multiconstituent epitaxial material on a substrate as produced by the inventive method. On substrate 10 a patterned masking layer 50 is formed, e.g., a SiO2 layer, formed and patterned by conventional techniques on Si.

12~~5:~
g Onto the thus masked substrate T-F material is deposited, for instance, about 1.8 nm (18 R) of Ni. By heating the composite to an appropriate transformation temperature, a template layer is formed in the bared substrate regions, e.g., by reaction with the substrate material. Onto the substrate is then deposited further material, e.g., Ni, from which epitaxial material 51 is formed in the previously bare regions of the substrate, e.g., single crystal NiSi2, whereas the material deposited onto the masking material (52) does not form epitaxial material, e.g., remains Ni. Typically there exist etches in which material 51 etches slower than material 52, therefore it is possible to remove the latter without removing all of the former, resulting in patterned heteroepitaxial material on a partially masked substrate.
An important aspect of this invention is a requirement for a high degree of cleanliness throughout the practice of the inventive process. This typically implies operation under UHV conditions, typically vacuum pressures lower than about 1.3 x 10 6 Pa (10 8 Torr), and substrate surface preparation, e.g., sputtering or heat treatment, that results in removal of contaminants.
Any deposition method, for either the T-F
material or the epitaxial-layer-forming material, that is compatible with the above-indicated cleanliness requirement is potentially useful in the practice of the invention.
Such methods include evaporation, molecular beam epitaxy, and sputtering.
As has been mentioned above, single crystal epitaxial metal silicides on silicon are of considerable interest for semiconductor device applications. The inventive method can advantageously be applied to the growth of these heterostructures, espscially to the growth of structures comprising CoSi2 on Si or NiSi2 on Si, and growth of metal silicides on silicon is a preferred application of the inventive method. We will now discuss this application.

12~!~4S2 In order for the inventive method to yield high quality epitaxial single crystal metal silicide, the Si substrate surface has to be atomically clean, and be substantially damage free, prior to deposition thereon of T-F material.
Onto the substrate surface the T-F material, e.g., Co or Ni, with or without Si, is deposited by any appropriate technique, e.g., by MBE or by evaporation. The deposition rate is typically between about 0.01 nm/sec (0.1 R/sec) and about 1 nm/sec (10 R/sec) and during deposition the substrate is to be maintained at a relatively low temperature, typically at less than about 200C, preferably less than about 100C. As a consequence of the low deposition temperature, the T-F material is in a disordered state, i.e., a state such that no long-range order is detectable by, e.g., LEED.
The thickness of the layer of T-F material deposited determines the thickness of the template layer formed therefrom, and the thickness of the template layer can have an effect on the growth of epitaxial material thereon. For instance, we have found that the thickness of the T-F nickel layer can determine the orientation of the epitaxial NiSi2 grown on the template layer formed from the deposited Ni by means of a reaction on a Si(lll) substrate.
This is exemplified by FIG. 6, which presents the experimentally determined relationship between the average thickness of the ~as-deposited) T-F nickel layer and the percentage of NiSi2 with A-orientation in a 100 nm (1000 ~) thick layer of epitaxial NiSi2 grown thereon, as it exists under a typical set of experimental conditions used by us.
As can be seen from curve 60 of FIG. 6, there exists a thickness regime in which growth of B-type epitaxial material is strongly favored [Ni average thickness less than about 0.7 nm (7 R)], a regime in which the epitaxial material is a mixture of A-type and B-type crystallites lNi average thickness between about 0.7 nm (7 R) and about 1.5 nm (15 R)], a regime in which the ..

~2~45Z

growth of A-type epitaxial material is strongly favored [Ni average thickness between about 1.5 nm (15 R) and about
2.1 nm (21 R)], and finally a further regime in which the epitaxial material is a mixture of A-type and B-type crystallites. Since the epitaxial material contained only A- and/or B-type material, curve 61, which shows the percentage of s-type NiSi2, is the mirror image about the 50 percent line of curve 60.
Subsequent to the low temperature deposition of the T-F material, a layer of template material is formed by raising the substrate temperature to the appropriate transformation temperature. The transformation temperature depends, inter alia, on the chemical composition of the epitaxial material to be formed. For instance, for NiSi2 on Si(lll), we have found that transformation temperatures between about 400 degrees C and about 600 degrees C
typically yield template material according to the invention, and for CoSi2 on Si(lll) this is the case for transformation temperatures between about 400C and about 700C. It is generally advantageous to raise the temperature relatively rapidly to the transformation temperature. For instance, in NiSi2 on Si(lll), we have found that raising the temperature in about 15 seconds from room temperature to the transformation temperature produces better quality epitaxial material than raising it in about 5 minutes. The time at the transformation temperature required for substantial completion of the transformation is generally short, typically less than about 5 minutes.
LEED observation of transformed material, i.e., template material, typically shows patterns characteristic of crystalline material.
The T-F material in metal silicide/Si systems advantageously consists essentially of the metal. For instance, in the CoSi2/Si and NiSi2/Si systems, the preferred T-F materials are Co and Ni, respectively. In these systems, the transport element is Si. At the transformation temperature, Si from the substrate reacts ~2~5Z

chemically with the T-F metal to form ordered epitaxial template material that typically has a chemical composition similar to that of the epitaxial material to be grown thereon.
The template layer formed by reacting a layer of T-F metal with Si is typically of different thickness than the original layer of T-F metal. For instance, Ni of average thickness x forms, after reacting with Si, NiSi2 of about 3.65 ~ average thickness.
Following the formation of the template layer by heating of the substrate with T-F metal deposited thereon, the growth of epitaxial silicide on the composite substrate formed by the template-covered original Si substrate can be accomplished by any appropriate technique, typically at temperatures above about 600C. It requires deposition of an appropriate amount of metal, or metal and Si, on the composite substrate. Exemplary deposition methods are evaporation, MBE, and sputtering. The overall chemical composition of the deposit can be either substantially that of the epitaxial silicide to be formed (e.g., by co-deposition of metal and Si), or it can contain a substantially lower concentration of Si (e.g., by deposition of metal only).
A variety of deposition and growth procedures can be employed in this step of the inventive method. For instance, the material can be deposited while maintaining the composite substrate at a temperature at which epitaxial growth does occur. This is exemplified by the growth of NiSi2 on Si(lll) by deposition, typically at a rate between about 0.01 and 1 nm/sec (.1 and 10 ~/sec), of Ni onto the composite substrate maintained at a temperature between 700 and 850C.
A different possible deposition and growth procedure comprises co-depositing metal and Si in approximately stoichiometric proportion, with the composite substrate being maintained at an appropriate elevated temperature and the deposition rates adjusted such that 12~$452 epitaxial growth can occur simultaneously with material deposition. For instance, epitaxial CoSi2 films can be grown by co-depositing Si and Co in approximately 2:1 atomic ratio on the surface of a composite Si(lll) substrate according to the invention, i.e., a template-covered Si(lll) substrate, maintained at about 600-650C.
Very thin templates, e.g., those that favor formation of s-type NiSi2, advantageously are kept a minimum of time at temperatures substantially higher than the highest transformation temperatures for the system in question. Eor instance, templates formed by depositing less than about 0.7 nm (7 R) Ni onto Si(lll) are best not kept at temperatures above about 650C for periods longer than a few minutes. Such templates can, however, be "stabilized" by appropriately increasing the thickness of the transformed layer subsequent to the T-F transformation.
In the Si(lll)/NiSi2 system, this can, for instance, be done by deposition of Ni [e.g., 2 nm (20 R thick)l at about 650C, or by a multiplicity of low temperature Ni deposition/transformation cycles.
Other deposition and growth procedures for epitaxial material that can be employed in the practice of the inventive method are either well known to those skilled in the art or can be readily devised by them, and we consider the scope of the invention not to depend on the method or procedure used for growing the epitaxial material on a composite substrate according to the invention.
Example I: A Si(lll) substrate was degreased and dipped in HF, then placed into a vacuum chamber. After UHV conditions were reached [base pressure about 1.3 x 10 8 Pa 10 10Torr)], the substrate was sputtered by 1.5 KeV argon and annealed to about 850C. Just prior to deposition of T-F metal the substrate was heated to about 1100C for about 2 minutes and allowed to cool down slowly.
The surface produced the sharp 7 x 7 LEED pattern that is characteristic of a clean Si(lll) surface, and contained no impurities except a negligible amount of carbon. A Ni ~2Q~452 layer of about 1.8 nm (18 R) average thickness was deposited on the clean substrate surface maintained at room temperature [by electron gun evaporation at a rate of about 0.1 nm/sec (1 A/sec)], followed by rapidly heating the substrate to the transformation temperature of about 500C
and maintaining it at that temperature for about 4 minutes.
After raising the substrate temperature to about 775C and maintaining it there, about 25 nm (250 R) of Ni was deposited by e-gun evaporation, at a rate of about 0.2 nm/sec (2 R/sec). This resulted in concurrent growth of a layer of NiSi2, of about 100 nm (1000 R) thickness, consisting exclusively of A-type single crystalline material, as determined by RBS and TEM, with conventionally determined channeling xmin less than about 3%.
Example II: After preparing a Si(100) substrate substantially as described in Example I, a Ni layer of about 1 nm (10 R) average thickness was deposited thereon at about 0.1 nm/sec (1 R/sec), with the substrate approximately at room temperature. After rapidly raising the substrate temperature to about 550C for about 4 min.
and further raising the temperature to about 650C, 20 nm (200 8) of Ni were deposited. The resulting, about 80 nm (800 R) thick, (100) oriented single crystalline NiSi2 layer was continuous and had Xmin less than 5%. Moreover, the Si/NiSi2 interface was found to be flat within the resolution of RBS. This is to be contrasted with analogous prior art (100) films which have grossly faceted interfaces, and typically Xmin of no less than about 12~.
Example III: A Si(100) substrate is prepared substantially as described above, a Co layer of about 0.5 nm (5 R) average thickness is deposited at about 0.1 nm (1 ~/sec), while the substrate is at about room temperature. Then the substrate temperature is raised to about 600C for about 4 minutes, followed by deposition of 20 nm (200 R) of Co at about 700C, at a rate of about 0.02 nm/sec (0.2 R/sec), resulting in formation of a single crystal epitaxial CoSi2 film of about 74 nm (740 R) ~2(~52 thickness.
Example IV: On a Si(lll) surface a 0.3 ~m thick SiO2 layer is grown by thermal oxidation. After etching windows through the layer by standard photolithography and plasma etch techniques, and heating, in UHV, the masked substrate to about 900C for about 10 minutes to remove native oxide from the window regions of the substrate, a patterned layer of epitaxial single crystal NiSi2 is formed in the window regions by a technique substantially as described in Example I. After epitaxial growth of the material by reaction with Si from the substrate, a layer of Ni remains on the sio2. This is removed by chemical etching in 150 parts CH3COOH, 50 parts HNO3 and 3 parts HCl at 50C.
Example V: Patterned (100) NiSi2 is formed on a Si(100) surface by a procedure substantially as described in Example IV.
Example VI: Patterned (100) NiSi2 is formed as in Example V, followed by growth thereon of epitaxial (100)-oriented single crystal Si by conventional MBE
deposition of Si at a rate of about 0.5 nm/sec (5 ~/sec), at a substrate temperature of about 500C.

Claims (26)

Claims:
1. A method for producing a heterostructure comprising epitaxial multiconstituent first material on a substrate comprising a second material, with the second material differing in chemical composition from the first material, the method comprising:
(a) growing on at least a part of the substrate, at a growth temperature, epitaxial first material compris-ing material deposited on the substrate, CHARACTERIZED IN THAT
the method further comprises:
(b) depositing, prior to (a), substantially spa-tially uniformly on at least the part of the substrate, an effective amount of matter, to be referred to as template-forming material, the template-forming material comprising at least one of the chemical constituents of the first material and differing in chemical composition from at least the second material, the substrate being during deposition of the template-forming material at a depo-sition temperature that is substantially lower than a transformation temperature, whereby the template-forming material deposit is in substantially disordered form, and (c) raising, subsequent to (b) but still prior to (a), the temperature of the substrate with the template-forming material thereon to a transformation temperature, the transformation temperature being lower than the growth temperature, whereby a template material is formed on the substrate, the thus produced composite forming the sub-strate referred to in (a).
2. Method of claim 1, wherein at least part of the substrate is covered by a patterned masking layer.
3. Method of claim 1, wherein the average thickness of the template-forming material is less than about 100.ANG..
4. Method of claim l, wherein the second material consists of a material selected from the group consisting of silicon, germanium, the III-V semiconductors, and the II-VI semiconductors.
5. Method of claim 4, wherein the first material consists of a material selected from the group consisting substantially of multiconstituent metallic materials and multiconstituent insulating materials.
6. Method of claim 5, wherein the second material consists essentially of material selected from the group consisting of silicon and germanium, and the first material consists substantially of a material selected from the group consisting of the metal silicides and the metal germaninates.
7. Method of claim 6, wherein the second material consists essentially of silicon, and the first material of a metal silicide.
8. Method of claim 7, wherein the template-forming material consists substantially of a metal.
9. Method of claim 8, wherein the first material consists substantially of a material selected from the group consisting of CoSi2 and NiSi2.
10. Method of claim 9, wherein the deposition temperature is less than about 200°C.
11. Method of claim 9, wherein the transformation temperature is between about 400°C and about 700°C.
12. Method of claim 9, wherein the growth temperature is greater than 600°C.
13. Method of claim 7, wherein the crystallographic orientation of the substrate substantially is a (111) or a (100) orientation.
14. Method of claim 9, wherein the effective thickness of the template-forming material is less than about 21.ANG..
15. Method of claim 7, wherein the material deposited in step a) contains the constituents of the first material in substantially the same proportions as the first material.
16. Method of claim 15, wherein the material in step a) is deposited by co-deposition.
17, Method of claim 16, wherein the material deposited in step a) contains silicon and a material selected from the group consisting of Co and Ni, in substantially 2:1 atomic proportions.
18. Method of claim 7, wherein the material deposited in step a) does not contain Si in an effective amount for forming the layer of first material.
19. Method of claim 18, wherein formation of the first material comprises a chemical reaction with Si derived from the substrate.
20. Method of claim 19, wherein the material deposited in step a) is selected from the group consisting of Co and Ni.
21. Method of claim 20, wherein step a) is carried out more than once.
22. Article comprising a heterostructure produced by the method of claim 1.
23. Article of claim 22, wherein the second material consists substantially of silicon, and the first material is a patterned metal silicide.
24. Article of claim 23, wherein the metal silicide consists substantially of CoSi2 or NiSi2, and the crystallographic orientation of the substrate sub-stantially is a (111) or a (100) orientation.
25. Article of claim 22, wherein the hetero-structure comprises a second epitaxial material grown on the epitaxial first material, with the second epitaxial material differing in chemical composition from the first material.
26. Method for producing a heterostructure comprising epitaxial first material on an epitaxial substrate layer overlying a monocrystalline second material substrate, with the substrate layer material differing in chemical composition from the first material and the second material, the method comprising:
a) growing, on at least a part of the sub-strate layer, at a growth temperature, epitaxial first material comprising material deposited on the substrate layer, CHARACTERIZED IN THAT the method further comprises b) depositing, prior to a), substantially spa-tially uniformly on at least part of the monocrystalline second material substrate, a layer of material no more than about 100.ANG. thick, the material to be referred to as template-forming material, the template-forming material differing in chemical composition from at least the second material, the second material substrate being during depo-sition of the template-forming material at a deposition temperature that is substantially lower than a transfor-mation temperature, whereby the template-forming material deposit is in substantially disordered form, and c) raising, subsequent to b), but still prior to a), the temperature of the second material substrate with the template-forming material thereon to a trans-formation temperature, whereby the epitaxial substrate layer is formed on the second material substrate.
CA000435166A 1982-09-30 1983-08-23 Heterostructure comprising a heteroepitaxial multiconstituent material Expired CA1209452A (en)

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JPS5983997A (en) 1984-05-15
FR2534068A1 (en) 1984-04-06
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US4477308A (en) 1984-10-16
FR2534068B1 (en) 1985-04-19

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