CA1216133A - Compositionally varied materials and method for synthesizing the materials - Google Patents

Abstract

ABSTRACT

Designed tailormade nonequilibrium synthetic disordered materials are provided containing non-periodically distributed local environments whose position and type are controlled to obtain specif-ic properties which can be coupled or decoupled one from another and collectively from the con straints implied by an ordered structure. Atoms or groups of atoms can be placed in the matrix in specific designed positions to compensate the spins to obtain unusual physical and chemical properties. The compositional variation which produces the required nonequilibrium "multi-dis-ordered" materials is accomplished by selectively depositing desired atoms and groups of atoms into designed locations to permit the construction of a true three-dimensionally engineered material.
Where order is an engineering need, it can be de-signed in a local scale or interspersed in varying amounts including layers through the material to create new material functions.
The materials encompass materials which can include non-epitaxial crystalline layers A and B, homogeneous in the x and y directions, but which are randomly or nonperiodically but specifically spaced in the z direction. Further, the materials include any combination of layers in a non-epi-taxial, non-superlattice structure, such as poly-crystalline or amorphous layers interleaved with crystalline or noncrystalline layers. Further, included are non-epitaxially grown material struc-tures containing columns or groups of atoms which can be arranged periodically and isotropically.
Many deposition techniques can be utilized singu-larly or in combination with a variety of activa-tion techniques to construct the materials, which include sputtering, electrochemical, laser, ion beam, thermal evaporation, chemical vapor deposi-tion or glow discharge (plasma) techniques. Other excitation processes also can be combined with the above techniques.

Description

2~6~33 582 This invention relates to a method of Cynthia-sizing a new class of materials by varying the composition throughout the bulk to attain kirk-teristics tailor made for desired applications.
The compositions and configurations of the first few coordination spheres of the constituents of a material are controlled to distribute a variety of local environments throughout the material. These synthetic materials are free from the constraints of crystalline symmetries and therefore can yield new types of non equilibrium disordered structures of varying complexity. The invention enables the production of improved materials which have a wide range of applications in substantially all fields of utilization, for example, in photo responsive applications, such as solar cells; in superconduc-tivity; in catalysis; in thermoelectricity; in magnetism; as well as in the development of en-tiredly new materials having properties which can make possible entirely new applications.
Numerous attempts to construct both natural and new crystalline analog materials have been made with the aim of extending the range of mate-fiat properties heretofore limited by the avail-ability of natural crystalline materials. one such attempt is compositional modulation by mole-ular beam epitaxy (ME) deposition on single cry-tat substrates. For example, in Dangle et at., So Patent No. 4,261,771, the fabrication of monolayer semiconductors by one ME technique is described. These modulated prior art structures are typically called "super lattices." Superlat-tires are developed on the concept of layers of materials forming a one-dimensional periodic pox tential by a periodic variation of alloy compost-Allah lion or of impurity density. Typically, the largest period in these super lattices is on the order of a few hundred Angstroms; however, monk atomic layered structures have also been con-strutted. The super lattices can be characterized by the format of several layers of A (such as Gays) followed by several layers of B (such as Alas), in a repetitive manner; formed on a single crystal substrate. The desired super lattice is a single crystal synthetic material with good cry-Tulane quality and long range order. The convent tonal super lattice concepts have been utilized for special electronic and optical effects.
In addition to super lattices, Dangle disk closes quasi-superlattices and non-superlattice structures. The former are comprised of opt-axially grown islands of a foreign material in an otherwise homogeneous layered background Metro-at. Non-superlattice structures are an extension of quasi-superlattice materials in that the islands are grown into columns extending vertical-lye through the homogeneous layered background ma-tonal. These super lattice type structures suffer from the same problems that plague homogeneous crystalline materials. There is very little van-anion possible in the range of constituents and in the type of super lattices constructed, because of the requirements that the spacing between the layers be approximately the same as that of the equilibrium crystalline constituents. These super lattices are restricted to a very small number of relatively low melting point crystalline materials and the growth rates are constrained by the ME technique.

~Z~6133 In addition to the ME type of super lattice construction techniques, other researchers have developed layered synthetic micro structures Utah-living different forms of vapor deposition, in-eluding diode and magnetron sputtering and stank dart multi source evaporation. The layer dime-sons are controlled by shutters or by moving the substrates relative to the material sources or controlling reactive gas partial pressure or with combinations of shutters and relative motion. The materials reported have been formed from crystal-line layers, noncrystalline layers and mixtures thereof; however, each of the efforts so far no-ported is directed at the synthesis of superlat-tice-type structures by precisely reproducing the deposition conditions on a periodically reoccur-in basis. These materials can be thought of as synthetic crystals or crystal analogies in which it is crucial that the long range periodicity, repetition of a particular combination of layers or grading of layer spacing be maintained. These structures are both structurally and chemically homogeneous in the x-y plane, but are periodic in the third (z) direction. These construction apt preaches can utilize a greater variety of Metro-also but as previously reported, they have not produced as great a variety of structures as have been demonstrated by ME techniques.
The previous works of the undersigned, as described for example in US. Patent Nos.
4,177,473, 4,177,474 and 4,342,044, describe form-in various types of matrices and dispersing non-equilibrium configurations therein. The prince-pies of layering and compositional modulation in the prior work is dependent upon the amounts of 6:~33 material distributed on an atomic and molecular scale throughout the material. For example, as described in the prior work, very small amounts of material were added to a matrix to increase the bulk resistance properties of the resulting mate-fiat. The addition of larger amounts of material to the matrix decreases the bulk resistance prop-reties. The principles are utilized to modify a range of materials from metallic to dielectric ma-trials. These techniques provide a distribution of material configurations on an atomic and mole-ular scale from microscopic to macroscopic con fig-unctions in the matrix material. The distribution of compositional changes of a primarily nonequi-librium nature lead from individual atoms or groups of atoms to layering when sufficient amounts of material are introduced into the ma-trip. These techniques provide significant con-trot of material properties such as thermal and electrical conductivity and other parameters by introducing atoms and alloys into materials which bond in a manner not previously described.
We have found that the above limitations and disadvantages can be overcome with the present in-mention which allows for the first time even more fundamental control of material properties. The invention frees materials not only from crystal-line symmetry, but also from the periodic local order required in previous amorphous and disk ordered materials. By the principles and methods disclosed herein, spatial and orientation Al place-mint of similar or dissimilar atoms or groups of atoms is possible with such increased precision and control of the local configurations to result in qualitatively new phenomena. The atoms need SLY

not be restricted to "d band" and "f band" atoms, but can be any atom in which the controlled as-poets of the interaction with the local environ-mint plays a significant role physically, elect tribally or chemically so as to affect the physic eel properties and hence the functions of the ma-trials. This results in means of synthesizing new materials which are disordered is several dip-fervent senses simultaneously. Such structures can be referred to as "multi-disordered".
The invention provides the means for design-in materials containing sequentially or nose-quentially three-dimensionally distributed local environments including non equilibrium disordered environments. These environments can possess local order even in one or two as well as three dimensions. This order can be of a periodic nature and its proximity and type can be con-trolled to obtain specific properties which can be coupled or decoupled from one another as well as from the constraints implied by either crystalline ordered or disordered structures. In contrast to the prior art, the invention discards the full strictures of a super lattice, epitaxy of layers, islands or columns, periodicity of compositional and structural variations, stoichiometry and home-junta of the constructed materials. The combo-sessional variation which produces the required non equilibrium disordered materials is accom-polished by independently controlling and select lively depositing desired atoms or groups of atoms into specific locations to permit the construction of a completely three-dimensionally engineered ma-tonal.

:~2::L6~;~3 The invention also provides for precisely varying the spatial and energetic orbital rota-tionships of atoms and groups of atoms, such that local environments can be produced which are dip sectionally oriented without regard to the sun-rounding matrix material. The resulting density of electronic states then can vary with position as well as with energy. The purpose of this apt preach can be understood, for example, in terms of active sites. For example, in hydrogen storage work, varied active sites for disassociation and storage can be placed by design in the bulk as well as on the surface of the material. Atoms or groups of atoms, with various orbital configure-lions that allow for weak bonding or completing, such as those with d-band configurations, or even more localized f-band configurations, can be disk pursed to allow for spaces between sites to pro-vise designed diffusion lengths and sites of a unique nature due to the atoms utilized and the local environments designed for them.
While layers of similar or dissimilar inter-aspersed atoms can be one embodiment, another would be the consequential placement of layers of dip-fervent compositions modulated in amorphous or disk ordered form. The most sophisticated and possibly the ultimate version of the invention is the placement of single atoms or groups of atoms some in excited states, not in layered form, but in specific sites in the three-dimensional solid, which could not be accomplished using conventional plasma or vacuum deposition techniques. In this manner, an atom or group of atoms can be placed in three-dimensional space in ways that have not been possible previously. For example, electrical and thermal conductivity and optical band gaps can be dramatically altered. There can be unusual doping effects and the materials can be designed to con-trot catalytic activity rather than leave it to the result of random effects. Desired thermoelec-trig effects can be designed in these materials since the photon scattering can be drastically aft footed. Various materials including optical mate-fiats can be specifically designed to include non-equilibrium configurations and can be made by co-deposition and by means of individual excitation so that unique nearest neighbor configurations can be made. Therefore, even in an amorphous material disorder disappears as a single parameter; since there is a designed atomic order which does not depend on periodicity or on any kind of spatial or energetic arrangement except as necessary for the design of the material properties for the material functions desired.
Many deposition techniques can be utilized singularly or in combination to construct the ma-trials of the invention. These include sputter-in, electrochemical, thermal or laser evapora-lion, chemical vapor deposition or any type of plasma techniques, especially those which promote the generation of free radicals. Atoms or groups of atoms also can be placed in designed locations in a material constructed by ion beam or beams of neutral atomic or molecular species. These tech-piques allow a material to be constructed which can be changed throughout (i.e., each layer can be different) or which can not only be sequential in nature or any combination thereof to produce mate-fiats with properties unlike those resulting from construction utilizing the prior art synthesis SLY

techniques. the deposition process can not only be automated by these techniques, but independent excitation of selected species prior or during deposition can produce unusual atomic and Milwaukee-far configurations. For example, laser tuning can be utilized to produce the selective excitation of the species during the deposition process to no-suit in materials that have unusual chemical and orbital relationships and can exist in a layered or compositional modulated form.
Fig. 1 is an essentially three dimensional schematic representation of the concept of a come positional varied material; and Fig. 2 is a partial diagrammatic represent-lion of one embodiment of deposition system for depositing the compositional varied materials of the invention.
Referring to Fig. 1, there is shown a sake-matte representation of a portion of a compost-tonally modulated material 10. In terms of the schematic, the prior art can be thought of as a crystalline analog material 10 having layers, typically A and B, homogeneous in the x and y dip reactions (or any plane) with the spacing "d" of the layers being periodic in the z direction (nor-met to the plane). The thickness of each layer A
and each layer B is uniformly repeated, but may not be equal in thickness to one another. A mod-ligation of this scheme, restricted to epitaxially grown materials, US. Patent No. 4,261,771, intro-dupes islands and columns of foreign material grown from a single crystal substrate and embedded in a homogeneous layered matrix also epitaxially grown from the same substrate.

1~6133 g In contrast, the materials of the present in-mention encompass materials which can include non-epitaxial crystalline layers A and B, home-generous in the x and y directions, but which are selectively or randomly spaced in the z direct lion. Further, the materials of the present in-mention include any combination of layers in a non-epitaxial, non-superlattice structure, such as polycrystalline or amorphous layers interleaved with crystalline or noncrystalline layers.
Further, the invention includes non-epitaxially grown material structures containing columns or groups which can be arranged periodically. Add-tonally, any of the non-epitaxially grown prior art material structures can be incorporated as primary construction elements in combination with the materials of the present invention.
The invention allows the formation of entire-lye new non equilibrium materials, which are come posed of regular or non regular patterns of new types of disordered structures of varying complex-fly. Homogeneous amorphous materials have been utilized to overcome some of the inherent con-straits imposed by crystalline structures of the prior art. The prior art is designed to achieve homogeneous materials, whereas the instant invent lion is directed at controlled in homogeneous mate-fiats, through differing local environment con-figurations, placement and chemical composition.
However, the materials of this invention surpass the advantages presented by homogeneous amorphous materials by the control of local atomic species and environments and their nearest neighbor inter-action using the placement and coordination of the primary structural elements as well as placing 1;216~33 --1 o--deviant orbital relationships in new and unique positions. Their arrangement is such that their proximity to one another does not encourage us-wanted fluctuations that are sometimes present in homogeneous amorphous material, or the coupling and modification of properties by force of the periodic potentials inherent in the super lattice structures of the prior art. For example, doping on a more substitutional level can be achieved.
The materials do involve the design of coupling or decoupling of properties where desired, such as the electron, magnetic and photon interactions.
This allows separate and different relationships to be designed into the material without the disk advantages and restrictions of the prior art.
The structures of the materials of the invent lion utilize layers and individual atoms or groups of atoms which need not follow a sequential pat-tern from layer to layer. These layers can be deliberately designed so that they are not go-metrically regular in spatial separation and sub-sequent layers can be entirely different from the proceeding layers, for example an elemental layer or an alloy layer, which can be amorphous or cry-Tulane. ME is one specialized technique of the prior art which provides a method for producing precisely layered crystalline materials for some optical and electronic applications. The present invention which includes plasma techniques, no-moves the crystalline lattice symmetry constraints as well as problems which can be caused by mist matches in amorphous materials. Even in amorphous materials, layering can produce a heterojunction effect if they are of thicknesses thicker than or comparable to the depletion or screening width.

I ~6~3~

One of the basic problems in any kind of solid state device is to avoid not only inter-facial effects but heterojunction effects as one changes materials, adds materials or layers mate-fiats. The invention provides a technique for the first time of controlling the interracial, strain and stress effects inherent in amorphous Metro-also which can be eliminated or minimized. Unlike previous techniques, each layer can be designed to produce chemical effects with the next layer, which is in contrast to the deposition of a typic eel prior homogeneous amorphous film where the initial layer can vary from the following layers by accident. In other words, there can be a de-signed chemical interaction between different layers and groups of atoms in the compositional modulated form of the invention. The procedure allows layered structures to be made where the layers are of a thickness such that the material can appear to be electronically homogeneous and in that way avoids heterojunction effects. By making these kinds of layered structures a new material is achieved which has, for example, the desirable electrical properties of one of the constituents while retaining the optical properties of the two constituents.
Differing atoms with different an isotropic effects can be placed in not only regular duster-button, but in planned "irregular" distribution throughout the material. This provides complete freedom of energy positions, spatial positions, spin compensations, chemical relativities, mug-netic and electronic effects. In superconductive-try, the need is to be able to add selected eye-mints to form new materials to enable the control lZ~L6~ 33 of specific properties such as the formation of Cooper pairs, the mass and polarizability of the elements, the Deb temperature, the density of states at the Fermi energy, and the strength of the electron-phonon interactions. All of these properties can be affected by placement of atoms in specific positions on overall structures such as chains or groups. The placement of groups or atoms, for example, in disordered materials can improve JO and umklapp scattering which previously could not be done. ASP Conference Proceedings No. 4, Cohen, p. 26, 1972. For example, to affect the electrical conductivity of the composite ma-tonal, the groups can be either designed so that they can be within tunneling distances, or, by varying the intergroup distance one can design avalanche effects. The atoms and groups of atoms then become specific random or non random impure-ties.
Amorphous materials are presently utilized in a manner to take advantage of the great variety of interactions between constituent atoms or mole-cures in contrast to the restricted number and kinds of interactions imposed by a crystalline lattice. In the present invention, the advantages or crystalline and amorphous properties can be combined for those devices and applications in which periodicity is essential to the physics.
Periodicity can be placed in an amorphous matrix through the utilization of these compositional modulation and layering concepts. The material can include spatially repeating compositional units, atoms, groups of atoms or layers without the overall bulk inhibition of crystalline period-lClty .

ISLE

Also, individual atoms or groups of atoms inverse configurations can be provided, which can be combined with other atoms or groups of atoms and be disbursed throughout the material. As stated, the individual atoms or groups of atoms, in these materials need not be in a regular pat-tern, but can have a varying spatial pattern, such as briny graded or consequential throughout the material. By the proper choice of atoms or groups of atoms, their orbital and isolated configure-lions, an isotropic effects not permitted in any prior type of material can be produced.
These procedures provide varying geometrical environments for the same atom or a variety of atoms, so that these atoms can bond with other surrounding atoms in different coordination con-figurations as well as unusual nonbinding rota-tionships resulting in entirely new chemical en-vironments. The procedures provide means for en-ranging different chemical environments which canoe distributed and located throughout the material in the spatial pattern desired. For example, one part or portion of a material can have entirely different local environments from other portions.
The varying electronic states resulting from the various spatial patterns which are formed and the various chemical environments which can be de-signed, can be reflected in many parameters as a type of density of states or change of states in the energy gap of a semiconductor except that this density of states can be spatially arranged.
In essence, the material of the invention is a compositional modulated material utilizing the very concept of irregularity, inhomogeniety, "disk-order" or localized order which have been avoided 12~1G~33 in the prior art, to achieve benefits which have not been exhibited in prior materials. The local environments need not be repeated throughout the material in a periodic manner as in the layered or compositional modulated materials of the prior art. Further, because of the above-described of-feats the specific types of disorder and their en-rangement in a spatial pattern, the materials as described by this invention cannot be thought of as truly amorphous materials as typically produced by the prior art since the material is more than a random placement of atoms. The placement of atoms and orbital of a specific type that can either interact with their local environment or with one another depending upon their spacing throughout an amorphous material and an amorphous matrix can be achieved. The composite material appears to be homogeneous, but the positions of the orbital of the atoms can have relationships designed to emphasize a particular parameter, such as spin compensation or decompensation. The materials thus formed give a new meaning to disorder based on not only nearest neighbor relationships, but "disorder" among functional groups, which can be layers or groups, on a distance scale which can be as small as a single atomic diameter. Hence, a totally new class of "synthetic non equilibrium multi-disordered" materials have been made avail-able.
For example, these local chemical environ-mints can provide a spatial pattern of different catalytically active sites throughout the Metro-at. In designing catalytically active materials, the local chemical environments are spatially con-trolled to provide desired catalytically active sites while other sites can be designed into the 12~133 material to deactivator poisonous species which inhibit catalytic activity. Various sites can be separated by design so that, for example, the splitting of a molecule can take place at one point in the material and the storage of its con-stiluent atoms at another, while nearby sites can inactivate the undesirable reaction products. The invention provides designed diffusion lengths, controlled pore type activity and specially shaped configurations. These structures and properties are normally created (if at all) by accident on the surfaces of the prior materials. In contrast, the structures and properties are designed in de-sired locations in the present materials as a bulk phenomena and in orders of magnitude greater in numbers than those of the prior materials.
The materials of the present invention can be formed in a variety of methods, such as by sputa toning, plasma deposition or combinations thereof as set forth above. One illustrative deposition system 12 is partially shown in Fig. 2. The depot session system 12 includes a housing 14 which is evacuated in a conventional manner to the pressure desired. The system 12 includes a plurality of ion beam sources 16, 18, 20, 22 and 24 mounted on the housing 14. Each of the sources can direct respective beams 26, 28, 30, 32 and 34 of atoms or groups of atoms from one or more selected elements onto a substrate 36. The temperature of the sub-striate 36 can be controlled by a heater 38, swishes an infrared lamp or array of lamps, which can be mounted inside a substrate holder 40.
Each of the ion beam sources 16, 18, 20, 22 and 24 can include a deflector plate to direct the atoms or groups of atoms onto the substrate 36 in a desired pattern. Each of the sources also in-~Z~6~33 ~16-eludes a neutralizer grid to remove excess charge from the ions.
Each of the ion sources 16, 18, 20, 22 and 24 also includes respective power leads 42, 44, 46, 48 and 50 and gas inlets 52, 54, 56, 58 and 60.
The sources can be turned on or off and the beams can be directed as desired onto the substrate 36 by controlling the internal deflector plates and/or moving the substrate 36. Also, the beams 26, 28, 30, 32 and 34 can be directed through no-spective shutters 62, 64, 66, 68 and 70 mounted on a shutter barrier 72. The shutters can be of an electronic type for ease and speed of operation.
The number of ion beam sources illustrated is not critical and can be selected as desired. The type and configuration of the substrate and its orientation with the ion beams also can be so-looted as desired. Further, the one or more ion beams can be combined with a plasma, sputtering or other type of deposition parameters to insert atoms into the material as it is being deposited in a timed sequence. The materials of the invent lion produced by the system can thus be engineered in a truly three-dimensional design to select the properties desired without regard to long-range periodicity or other crystalline lattice con-straits. Free radicals also can be deposited and the atoms and radicals can be independently ox-cited as they are deposited and "frozen into" and interact with the matrix.
A comparison of properties of some represent-alive materials produced by the techniques of the present invention to homogeneous and super lattice type materials are illustrated in Tables I-V.
Each of the materials was deposited utilizing substantially the same deposition conditions.

I

Table I illustrates properties of some repro-tentative homogeneous materials which provide a basis for comparison to the properties of some representative materials of the present invention illustrated in Table III-V.
Table II illustrates properties of some rep-resentative super lattice type materials.
The layer spacing (d) of the three materials is respectively 13, 53 and 88 Angstroms. The properties change substantially uniformly with a change in layer spacing d.
Table III illustrates some representative ox-apples of the present invention in the format of ABC ABC, eta, with different layer spacings. The layer spacings of the two examples are respective-lye 64 and 20 Angstroms.
The power of decoupling the material proper-ties by use of the techniques of the present in-mention is illustrated by comparing the properties of the three component layered structures with those of the homogeneous and super lattice Metro-awls in Tables I and II. The homogeneous materials exhibit substantially no change in their proper-ties without a change in composition. The super-lattice materials of Table II are of interest in that they exhibit a continuous variation in prop-reties with varying layer thicknesses of materials having substantially the same composition. It should be noted that all the properties are coupled in that each property changes in direct proportion to the layer spacing, i.e. all the properties are continuously increasing or degrees-in with the variation in layer thickness.
In marked contrast, the material properties in Table III are decoupled as shown by the in-12~ 33 crease in p and To with decrease in layer thick-news, while both HC2 and dHC2/dT decrease in value. Furthermore, these properties are signify scantly different than those exhibited by sub Stan-tidally the same homogeneous composition.
Table IV illustrates the property changes due to introduction of groups of atoms in the come posit material. The first material, while con-twining substantially the identical atomic combo-session of silicon as the second material, incl~desthe silicon in groups substantially at the inter-face between succeeding sets of Mohawk layers. The layer spacing of the above two examples is respect lively 11 and 80 Angstroms. Further, although the Mohawk compositions are somewhat different, as shown by the homogeneous materials in Table 1, numbers 3 and 4, the properties do not vary significantly in this Mohawk compositional range. The first material with groups of atoms has properties which are both decoupled and dramatically different from those of the second layered material.
Table V shows the properties of an illustra-live material with varying layer spacing, which shows a further dramatic decoupling of the proper-ties from the previous materials. The properties of this material can be compared to those of the last example in Table I.
This material consists of five sets of ten layers of the four materials. The composition shown is the overall composition as identified by Auger analysis. The layer spacing of each of the 10 layers in each set is respectively 11, 17, 7, 43, 21, 9, 12, 8, 11 and 38 Angstroms. This mate-fiat has both local disorder, random spacing and grouping of atoms in each set with the sets repeated in a periodic fashion.

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o ~LZ16~33 As disclosed above, a material can be put down in accordance with the invention by utilizing alternating layers of materials A and B; however, an atom or group of atoms, can be inserted as de-sired within the various layers A and B to de-couple and control the desired parameters in the material. These groups can be formed from one type of atom or various types of atoms and can be compositional different throughout the bulk.
These atoms or groups of atoms can be inserted in a time sequence manner and can include laser anti-ration to change local sites throughout the mate-fiat as it is deposited. Further, the groups can be inserted in a material which is formed only of a material A without layering. Also, the layer structure of the materials can be much more eon-placated than that described above and can be for example A, B, C, B, D, A, C, E, etc.
The techniques of the invention can be Utah-lived as a new way of doping photovoltaic Metro-awls or changing the band gap as desired within the photovoltaic material, controlling the phcnon and electron relationships in a thermoelectric Metro-at to provide the desired thermal and electrical conductivity properties, in catalysis to provide the sites desired and in superconductivity to pro-vise the desired critical temperature, critical current and critical field properties. The optical properties can be changed without chanting the electronic properties. Other unique anise-tropic effects can be produced by the unique anti-voted bonding by various atoms, free radicals or clusters thereof. Atoms or groups of atoms can be placed into the matrix throughout a composite ma-tonal which depends upon periodicity. The mate-

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fiat can be produced by many means where timing of the release of the atoms or groups of atoms is a controllable parameter.
Numerous modifications and variations of the present invention are possible in light of the above techniques. The substrate holder 40 can be festered with respect to the ion beams 26, 28, 30, 32 and 34 to deposit the atoms in the desired lo-cation on the substrate 36. The choice of atoms and groups of atoms is not limited by the examples and can be any combination of atoms desired.
Further, the gases input to the ion sources can be atomic gases or molecular compounds and background gases can be utilized in the system if desired.
It is therefore to be understood that within the scope of the appended claims the invention can be practiced otherwise than as specifically de-scribed.

Claims (98)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compositional varied material comprising:
a matrix formed from at least a first type of atom having at least one physical property, said matrix having a preselected spatial pattern therein, said spatial pattern including at least a second type of atom or atoms or groups of said second type of atom or atoms at predetermined locations in said pattern to form the material, at least some of said second type of atom or atoms or groups thereof forming non-equilibrium disordered local environments, said second type of atom or atoms and said locations including means to couple or decouple at least a second physical property with said matrix physical property to produce one or more functions of said material.

2. The material of claim 1 wherein:
said matrix is formed in a periodic repeating spatial pattern and said second type of atom or groups of atoms are placed in said matrix in non-periodic locations.

3. The material of claim 1 wherein:
said matrix is formed in a periodic repeating spatial pattern and said second type of atom or group of atoms are placed in said matrix in periodic locations.

4. The material of claim 1 wherein:
said matrix is formed in a periodic repeating spatial pattern and said disordered local environments are placed in said matrix in nonperiodic locations.

5. The material of claim 1 wherein:
said matrix is formed in a periodic repeating spatial pattern and said disordered local environments are placed in said matrix in periodic locations.

6. The material of claim 1 wherein:
said matrix is formed in a nonperiodic repeating spatial pattern and said second type of atom or groups of atoms are placed in said matrix in non-periodic locations.

7. The material of claim 1 wherein:
said matrix is formed in a nonperiodic repeating spatial pattern and said second type of atom or group of atoms are placed in said matrix in periodic locations.

8. The material of claim 1 wherein:
said matrix is formed in a nonperiodic repeating spatial pattern and said disordered local environments are placed in said matrix in nonperiodic locations.

9. The material of claim 1 wherein:
said matrix is formed in a nonperiodic repeating spatial pattern and said disordered local environments are placed in said matrix in periodic locations.

10. The material of claim 1 wherein:
said matrix is disordered on an atomic scale and periodic on a marcroscopic scale.

11. The material of claim 1 wherein:
said matrix and said second type of atom or group of atoms is disordered on an atomic scale and periodic on a macroscopic scale.

12. The material of claim 1 wherein:
said matrix is periodic on an atomic scale and disordered on a macroscopic scale.

13. The material of claim 1 wherein:
said matrix and said second type of atom or group of atoms is periodic on an atomic scale and disordered on a macroscopic scale.

14. The material of claim 1 wherein:
said second type of atom or group of atoms is disordered on an atomic scale and periodic on a macroscopic scale throughout said matrix.

15. The material of claim 1 wherein:
the locations of said second type of atom or group of atoms are within tunneling distance of one another.

16. The material of claim 1 wherein:
said second type of atom or group of atoms are bonded in different configurations in different locations throughout at least a portion of said matrix.

17. The material of claim 1 wherein:
said second type of atom or group of atoms include excited species frozen into at least some locations.

18. The material of claim 1 wherein:
said second type of atoms or groups of atoms include directionally oriented local environments in at least some locations different than in other locations.

19. The material of claim 1 wherein:
said second type of atom or groups of atoms include free radicals frozen into at least some locations.

20. The material of claim 1 further including:
at least a third type of atom or groups of atoms.

21. The material of claim 1 wherein:
said matrix includes at least a third type of atom interleaved in layers with said first type of atom, said second type of atom or groups of atoms being disposed in at least some of the layers of said first type of atom to form different atomic layers.

22. The material of claim 21 wherein:
said different atomic layers are patterned with a non-periodic spacing.

23. The material of claim 21 wherein:
said matrix includes at least three different compositional type layers repeated in a predetermined order.

24. The material of claim 21 wherein:
at least some of said layers are non-epitaxial crystalline layers.

25. The material of claim 21 wherein:
at least a first set of said layers are polycrystalline interleaved with at least a second set of crystalline layers.

26. The material of claim 21 wherein:
at least a first set of said layers are polycrystalline interleaved with at least a second set of polycrystalline layers.

27. The material of claim 21 wherein:
at least a first set of said layers are polycrystalline interleaved with at least a second set of amorphous layers.

28. The material of claim 21 wherein:
at least a first set of said layers are crystalline interleaved with at least a second set of amorphous layers.

29. The material of claim 21 wherein:
at least a first set of said layers are amorphous interleaved with at least a second set of amorphous layers.

30. The material of claim 21 wherein:
said layers are interleaved in a graded order from periodic to non-periodic throughout the material.

31. The material of claim 21 wherein:
said layers are spaced to form an electronically homogeneous material with at least one other physical property being coupled or decoupled from said electronic property.

32. The material of claim 21 wherein:
said layers are disordered on an atomic scale and periodic on a macroscopic scale.

33. The material of claim 21 wherein:
said layers are periodic on an atomic scale and disordered on a macroscopic scale.

34. The material of claim 21 wherein:
said layers of said third type of atom include at least a fourth type of atom of group of atoms in at least some of the layers.

35. The material of claim 1 wherein:
said material is homogeneous in two dimensions and non-homogeneous in the third dimension.

36. The material of claim 1 wherein:
said material is homogeneous in one dimension and non-homogeneous in two dimensions.

37. The material of claim 1 wherein:
said material is non-homogeneous in all three dimensions.

38. The material of claim 1 wherein:
said properties include one or more electrical, optical, mechanical, magnetic or thermal characteristics.

39. A method of preparing a compositionally varied material comprising:
forming a matrix from at least a first type of atom having at least one physical property, arranging a spatial pattern in said matrix, including at least a second type of atom or atoms or groups of said second type of atom or atoms at predetermined locations in said spatial pattern to form the material, forming nonequilibrium disordered local environ-ments with at least some of said second type of atom or atoms or groups thereof and coupling or decoupling at least a second physical property of said second type of atom or atoms and said locations with said matrix physical property to produce one or more functions of said material.

40. The method of claim 39 including:
forming said matrix in a periodic repeating spatial pattern and placing said second type of atom or groups of atoms in said matrix in nonperiodic locations.

41. The method of claim 39 including:
forming said matrix in a periodic repeating spatial pattern and placing said second type of atom or group of atoms in said matrix in periodic locations.

42. The method of claim 39 including:
forming said matrix in a periodic repeating spatial pattern and placing said disordered local environments in said matrix in nonperiodic locations.

43. The method of claim 39 including:
forming said matrix in a periodic repeating spatial pattern and placing said disordered local environments in said matrix in periodic locations.

44. The method of claim 39 including:
forming said matrix in a nonperiodic repeating spatial pattern and placing said second type of atom or groups of atoms in said matrix in nonperiodic locations.

45. The method of claim 39 including:
forming said matrix in a nonperiodic repeating spatial pattern and placing said second type of atom or group of atoms in said matrix in periodic locations.

46. The method of claim 39 including:
forming said matrix in a nonperiodic repeating spatial pattern and placing said disordered local environments in said matrix in nonperiodic locations.

47. The method of claim 39 including:
forming said matrix in a nonperiodic repeating spatial pattern and placing said disordered local environments in said matrix in periodic locations.

48. The method of claim 39 including:
forming said matrix from at least a third type of atom and said first type of atom in a disordered atomic scale and in a periodic macroscopic scale.

49. The method of claim 39 including:
forming said matrix and said second type of atom or group of atoms in a disordered atomic scale and in a periodic macroscopic scale.

50. The method of claim 39 including:
forming said matrix from at least a third type of atom and said first type of atom in a periodic atomic scale and in a disordered macroscopic scale.

51. The method of claim 39 including:
forming said matrix and said second type of atom or group of atoms in a periodic atomic scale and in a disordered macroscopic scale.

52. The method of claim 39 including:
forming said second type of atom or group of atoms in a disordered atomic scale and in a periodic macroscopic scale throughout said matrix.

53. The method of claim 39 including:
placing the locations of said second type of atom or group of atoms within tunneling distance of one another.

54. The method of claim 39 including:
forming said second type of atom or group of atoms in different configurations in different locations throughout at least a portion of said matrix.

55. The method of claim 39, including:
freezing excited species of said second type of atom or group of atoms into at least some locations.

56. The method of claim 39 including:
directionally orienting local environments of said second type of atoms or groups of atoms in at least some locations different than in other locations.

57. The method of claim 39 including:
freezing free radicals of said second type of atom or groups of atoms into at least some locations.

58. The method of claim 39 further including:
forming at least a third type of atom or groups of atoms in said material.

59. The method of claim 39 including:
forming said material homogeneous in two dimensions and non-homogeneous in the third dimension.

60. The method of claim 39 including:
forming said material homogeneous in one dimension and non-homogeneous in two dimensions.

61. The method of claim 39 including:
forming said material non-homogeneous in all three dimensions.

62. The method of claim 39 wherein:
coupling or decoupling said properties include one or more electrical, optical, mechanical, magnetic or thermal functions.

63. A method of preparing a compositionally varied material comprising:
forming a matrix from at least a first type of atom having at least one physical property and a second type of atom having at least a second physical property, said matrix including a plurality of layers of at least said first and second types of atom, arranging a spatial pattern in said matrix, including at least a third type of atom or atoms or groups of said third type of atom or atoms at predetermined locations in said spatial pattern to form the material, said locations being at least in some of said plurality of layers or between succeeding ones of some of said plurality of layers, forming nonequilibrium disordered local environments with at least some of said third type of atom or atoms or groups thereof and coupling or decoupling at least a third physical property of said third type of atom or atoms and said locations with said matrix physical property to produce one or more functions of said material.

64. The method of claim 63 including:
forming said matrix in a periodic repeating spatial pattern and placing said third type of atom or groups of atoms in said matrix in nonperiodic locations.

65. The method of claim 63 including:
forming said matrix in a periodic repeating spatial pattern and placing said third type of atom or group of atoms in said matrix in periodic locations.

66. The method of claim 63 including:
forming said matrix in a periodic repeating spatial pattern and placing said disordered local environments in said matrix in nonperiodic locations.

67. The method of claim 63 including:
forming said matrix in a periodic repeating spatial pattern and placing said disordered local environments in said matrix in periodic locations.

68. The method of claim 63 including:
forming said matrix in a nonperiodic repeating spatial pattern and placing said third type of atom or groups of atoms in said matrix in nonperiodic locations.

69. The method of claim 63 including:
forming said matrix in a nonperiodic repeating spatial pattern and placing said third type of atom or group of atoms in said matrix in periodic locations.

70. The method of claim 63 including:
forming said matrix in a nonperiodic repeating spatial pattern and placing said disordered local environments in said matrix in nonperiodic locations.

71. The method of claim 63 including:
forming said matrix in a non periodic repeating spatial pattern and placing said disordered local environments in said matrix in periodic locations.

72. The method of claim 63 including:
forming said matrix in a disordered atomic scale and in a periodic macroscopic scale.

73. The method of claim 63 including:
forming said matrix and said third type of atom or group of atoms in a disordered atomic scale and in a periodic macroscopic scale.

74. The method of claim 63 including:
forming said matrix in a periodic atomic scale and in a disordered macroscopic scale.

75. The method of claim 63 including:
forming said matrix and said third type of atom of group of atoms in a periodic atomic scale and in a disordered macroscopic scale.

76. The method of claim 63 including:
forming said third type of atom or group of atoms in a disordered atomic scale and in a periodic macroscopic scale throughout said matrix.

77. The method of claim 63 including:
placing the locations of said third type of atom or group of atoms within tunneling distance of one another.

78. The method of claim 63 including:
forming said third type of atom or group of atoms in different configurations in different locations throughout at least a portion of said matrix.

79. The method of claim 63 including:
freezing excited species of said third type of atom or group of atoms into at least some locations.

80. The method of claim 63 including:
directionally orienting local environments of said third type of atoms or groups of atoms in at least some locations different than in other locations.

81. The method of claim 63 including:
freezing free radicals of said third type of atom or groups of atoms into at least some locations.

82. The method of claim 63 including:
forming said material homogeneous in two dimensions and non-homogeneous in the third dimension.

83. The method of claim 63 including:
forming said material homogeneous in one dimension and non-homogeneous in two dimensions.

84. The method of claim 63 including:
forming said material non-homogeneous in all three dimensions.

85. The method of claim 63 wherein:
coupling or decoupling said properties include one or more electrical, optical, mechanical, magnetic or thermal functions.

86. A method of preparing a compositionally varied material comprising:
forming a matrix from at least a first type of atom having at least one physical property, said matrix including a plurality of layers of at least said first type of atom, arranging a spatial pattern in said matrix, including at least a second and a third type of atom interleaved in a plurality of layers of at least said second type of atom and a plurality of layers of at least said third type of atom at predetermined locations in said spatial pattern to form the material, forming nonequilibrium disordered local environments with at least some of said second or third type of atoms and coupling or decoupling at least a second physical property of said second type of atom or at least a third physical property of said third type of atom and said locations with said matrix physical property to produce one or more functions of said material.

87. The method of claim 86 including:
forming said different atomic layers in a non-periodic spacing pattern.

88. The method of claim 86 including:
forming said matrix with at least three different compositional type layers and repeating said layers in a predetermined order.

89. The method of claim 86 including:
forming at least some non-epitaxial crystalline layers.

90. The method of claim 86 including:
forming at least a first set of polycrystalline layers interleaved with at least a second set of crystalline layers.

91. The method of claim 86 including:
forming at least a first set of polycrystalline layers interleaved with at least a second set of polycrystalline layers.

92. The method of claim 86 including-forming at least a first set of polycrystalline layers interleaved with at least a second set of amorphous layers.

93. The method of claim 86 including:
forming at least a first set of crystalline layers inter-leaved with at least a second set of amorphous layers.

94. The method of claim 86 including:
forming at least a first set of amorphous layers inter-leaved with at least a second set of amorphous layers.

95. The method of claim 86 including:
spacing said layers to form an electronically homogeneous material with at least one other physical property being coupled or decoupled from said electronic property.

96. The method of claim 86 including:
forming said layers in a disordered atomic scale and in a periodic macroscopic scale.

97. The method of claim 86 including:
forming said layers in a periodic atomic scale and a dis-ordered macroscopic scale.

98. The method of claim 86 including:
forming said layers of said third type of atom with at least a fourth type of atom or group of atoms in at least some of the layers.