WO2014202796A1 - Iii-v or ii-vi compound semiconductor films on graphitic substrates - Google Patents

Abstract

A composition of matter comprising a film on a graphitic substrate, said film having been grown epitaxially on said substrate, wherein said film comprises at least one group III-V compound or at least one group II-VI compound.

Description

lll-V OR ll-VI COMPOUND SEMICONDUCTOR FILMS ON GRAPHITIC SUBSTRATES

This invention concerns a process for growing thin films epitaxially on graphitic substrates. In particular, the invention employs molecular beam epitaxy techniques to grow semiconducting thin films epitaxially on graphitic substrates. The resulting graphite supported semiconducting films form a further aspect of the invention. The films are preferably semiconductor materials and have wide ranging applications in, for example, the electronics industry or in solar cell applications.

Over recent years, the interest in semiconductors has intensified as nanotechnology becomes an important engineering discipline. Semiconductor technology has found important applications in a variety of electrical devices such as sensors, solar cells and LED's.

Many different types of semiconductors are known, some in film form. Conventionally, semiconductor films have been grown on a substrate identical to the semiconductor itself (homoepitaxial growth) Thus, GaAs was grown on GaAs, Si on Si etc. This, of course, ensures that there is a lattice match between the crystal structure of the substrate and the crystal structure of the growing semiconductor. Both substrate and semiconductor can have identical crystal structures.

Using the same material as a substrate is, however, also highly limiting. Also, the necessary substrate materials may be expensive. It is also normal to require the substrate to be cut to expose a particular plane within the crystal structure of the substrate such as the (001) plane or the (111) plane. That can be difficult and adds to the expense of the substrate.

However, with the introduction of ternary semiconductors, a lattice match on binary substrates such as GaAs, GaSb and InP could be achieved by tuning the composition of the ternary, quaternary, etc semiconductor. This therefore represents heteroepitaxial growth as the substrate and the growing film are different.

Also the growth of pseudomorphic epilayers is known. In the

pseudomorphic epilayer there is a small strain (of the order of 1%) in the epilayer due to a lattice mismatch (of the order of 1%) between the epilayer and substrate. Pseudomorphic epilayers can only be grown defect free up to a certain thickness, called the "critical thickness", above which the pseudomorphic epilayer starts to "relax". During relaxation, dislocations are introduced in the epilayer in order to reduce the strain energy in the layer. These dislocation rich layers are of limited interest as semiconductors.

One way of compensating for the strain in the epilayer has been to grow "strained- layer superlattices". These strained- layer superlattices comprise alternating epilayers of two or more materials with different equilibrium lattice constants which compensate each others strain. Thus, layers with alternating compressive and tensile strain can be grown. In certain cases, these strained- layer superlattices can be grown very thick since the average lattice constant of the superlattice as a whole can be tailored to match the lattice constant of the substrate.

However, the necessary substrate materials for heteroepitaxial growth may not be readily available and they may again be expensive.

The present inventors therefore sought other substrate materials on which to grow semiconductor thin films, in particular, cheap substrates that are economically viable on an industrial scale. The present inventors sought to use graphitic substrates to carry semiconductor thin films, in particular graphene.

Perfect graphene is a one-atom-thick planar sheet of sp²-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The crystalline or "flake" form of graphite consists of many graphene sheets stacked together.

Graphene has attracted a lot of interest recently due to its advantageous properties. It is light, transparent and yet very strong and electrically conducting. Its use as a support for a semiconducting thin film would therefore be very attractive.

In Jiang et al. Physical Review Letters 10 Feb 2012, Sb₂Te₃ thin films on graphene are taught. These films are grown by molecular beam epitaxy and are semiconductors due to intrinsic defects within the film or from inherited dopants from the graphene substrate.

The present inventors, however, sought the formation of group (III)/(V) or (II)/(VI) semiconductors of completely different structure to Sb₂Te₃. Sb₂Te₃ has no lone pairs so has no interlayer adhesion. Like graphite therefore, it is flaky and with only very weak van der Waals forces holding one layer of the crystal structure to the next layer. It is a "2-dimensional" material. Carrying a thin film of Sb₂Te₃ offers very different challenges to depositing a thin film of a semiconductor of this invention which have lone pairs available for interlayer bonding and for interacting with the substrate. The semiconductors of the present invention are therefore "3- dimensional".

The present invention relates to "3 -dimensional" materials as the semi- conductors of the present invention have free lone pairs and interatomic bonding.

When growing a "3 -dimensional" crystal film on a substrate, it is essential for there to be a lattice match between the substrate and the semiconductor in order to form a single crystal film of high structural, electronic and optical quality suitable for applications. Without this lattice match, a useful film does not form. For the present invention therefore lattice matching is essential where for Sb₂Te₃ it is irrevelant.

Since graphitic substrates have no lone pairs at the surface and very short atomic bond length compared with typical semiconductors like silicon and GaAs, there is no reason to anticipate nucleation and epitaxial growth of films thereon. As surprisingly noted below, the present inventors have realized that there is an excellent lattice match possible between a graphitic substrate and some

semiconductors depending on how the semiconductor atoms are positioned on the surface of graphene. Alternatively, there is a close lattice match possible between a suitable group (II), (III), (V) or (VI) elements and the graphitic substrate.

With a lattice match present, the use of molecular beam epitaxy offers excellent results in terms of film growth. The inventors have surprisingly found that certain group (III/V) or (II/VI) semi-conductors have excellent lattice match to graphene. Alternatively, a lattice matching base layer can be used to start the thin film growth process to therefore allow the formation of thin films on a graphitic substrate.

Summary of Invention

Thus, viewed from one aspect the invention provides a composition of matter comprising a film on a graphitic substrate, said film having been grown epitaxially on said substrate, wherein said film comprises at least one group III-V compound or at least one group II-VI compound or a group IV compound, preferably at least one group III-V compound or at least one group II-VI compound.

Viewed from another aspect the invention provides a process for preparing a film grown epitaxially on a graphitic substrate comprising the steps of:

(I) providing group II-VI elements or group III-V elements or group IV elements or group IV elements to the surface of said graphitic substrate, preferably via a molecular beam; and

(II) epitaxially growing a group III-V or group II-VI film on the surface of the graphitic substrate or a group IV compound.

Viewed from another aspect the invention provides a process for growing a film on a graphitic substrate comprising the steps of:

(I) providing a base layer film on said substrate, wherein said base layer film comprises an element or compound having a lattice mismatch of 2.5% or less, preferably 1% or less to that of graphene;

(II) contacting said base layer film with group II-VI elements or group III-V elements preferably via a molecular beam so as to grow a group III-V or group II-VI film.

Viewed from another aspect the invention provides a composition of matter comprising a film on a graphitic substrate wherein said composition comprises, in the following order,

(a) a graphitic substrate,

(b) a base layer film comprising an element or compound having a lattice mismatch of 2.5% or less, 1% or less to that of graphene; and

(c) a film comprising a group III-V compound or group II-VI compound or a group IV compound, preferably a group III-V compound or a group II-VI compound.

Viewed from another aspect the invention provides a composition of matter comprising a film on a graphitic substrate wherein said composition comprises, in the following order,

(a) a graphitic substrate, (b) a base layer film comprising GaSb, InAs, AsSb, GaN, SbBi, AlAs, AlSb, CdSe or Sb, preferably GaSb, InAs, AsSb, GaN, SbBi or Sb; and

(c) a film comprising a group III-V compound or group II- VI compound or a group IV compound, preferably a group III-V compound or a group II- VI compound.

Optionally, the surface of the graphitic substrate can be chemically/ physically modified to enhance the epitaxial growth of films.

Viewed from another aspect the invention provides a device, such as an electronic device, comprising a composition as hereinbefore defined, e.g. a solar cell.

Viewed from another aspect the invention provides the use of molecular beam epitaxy to grow at least one film as hereinbefore defined on a graphitic substrate. Definitions

By a group III-V compound is meant one comprising at least one ion from group III and at least one ion from group V. Similarly, a group II- VI compound is one comprising at least one group II ion and at least one group VI ion. In this application the term group (II) covers both classic group (Ila) and (lib) periods, i.e. the alkaline earth series and the Zn series of elements. There may be more than one ion present from each group, e.g. InGaAs (i.e. a ternary compound) and so on. Quaternary compounds may also be present and so on.

A group IV compound is one comprising two or more elements from group IV, preferably i.e. C, Si, or Ge, such as SiC. In all embodiments, the film is preferably one comprising a group III-V compound or group II-VI compound.

Graphitic substrates are substrates composed of single or multiple layers of graphene or its derivatives. The term graphene refers to a planar sheet of sp²-bonded carbon atoms in a honeycomb crystal structure. Derivatives of graphene are those with surface modification. For example, hydrogenatoms can be attached to the graphene surface to form graphane. Another option is chlorographene. Graphene with oxygen atoms attached to the surface along with carbon and hydrogen atoms is called as graphene oxide. The surface modification can be also possible by chemical doping or oxygen/hydrogen plasma treatment.

The term epitaxy comes from the Greek roots epi, meaning "above", and taxis, meaning "in ordered manner". The atomic arrangement of the film is based on the crystallographic structure of the substrate. It is a term well used in this art.

Epitaxially growth means herein the growth on the substrate of a film that mimics the orientation of the substrate.

Molecular beam epitaxy (MBE) is a method of forming depositions on crystalline substrates. The MBE process is performed by heating a crystalline substrate in a vacuum so as to energize the substrate's lattice structure. Then, an atomic or molecular mass beam(s) is directed onto the substrate's surface. The term element used above is intended to cover application of atoms, molecules or ions of that element. When the directed atoms or molecules arrive at the substrate's surface, the directed atoms or molecules encounter the substrate's energized lattice structure. An MBE process is described in detail below. Over time, the oncoming atoms form a film.

The film which forms on the substrate is preferably continuous. It cannot therefore be regarded as a series of discreet plaques rather the film forms over a portion of the substrate surface such as at least 50% of the substrate surface.

However, as discussed further below, the film can also be deposited in the holes of a mask.

The amount of lattice mismatch is measured against any lattice constant of graphene with any lattice constant of the semi-conductor as explained below. If a semiconductor compound or element has a lattice constant that is within 1% of one of the lattice constants of graphene, then the semiconductor is suitable for use as a base layer herein and may also be deposited directly onto the graphitic substrate.

We regard a close lattice mismatch to be up to 1% mismatch, an almost perfect lattice match is up to 0.1% mismatch. Detailed Description of Invention This invention concerns the epitaxial growth of thin films on a graphitic substrate. The composition of the invention comprises both the substrate and the films grown thereon and optionally the carrier.

Having a film grown epitaxially provides homogeneity to the formed material which may enhance various end properties, e.g. mechanical, optical or electrical properties.

Epitaxial films may be grown from gaseous or liquid precursors. Because the substrate acts as a seed crystal, the deposited precursors can take on a lattice structure and orientation identical to those of the substrate. This is different from other thin- film deposition methods which deposit polycrystalline or amorphous films, even on single-crystal substrates.

In the present invention, the substrate is a graphitic substrate, more especially it is graphene. As used herein, the term graphene refers to a planar sheet of sp²-bonded carbon atoms that are densely packed in a honeycomb (hexagonal) crystal lattice. This graphene substrate should contain no more than 10 layers of graphene or its derivatives, preferably no more than 5 layers (which is called as a few-layered graphene). Especially preferably, it is a one-atom-thick planar sheet of graphene.

The crystalline or "flake" form of graphite consists of many graphene sheets stacked together (i.e. more than 10 sheets). By graphitic substrate therefore, is meant one formed from one or a plurality of graphene sheets.

It is preferred if the substrate is 20 nm in thickness or less. Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm. The substrate preferably comprises only a few such layers and may ideally be less than 10 nm in thickness. Even more preferably, it may be 5 nm or less in thickness. The area of the substrate is not limited. This might be as much as 0.5 mm² or more, e.g. up to 5 mm² or more such as up to 10 cm². The area of the substrate is thus only limited by practicalities.

It will be clear that the graphitic substrate may need to be supported in order to allow growth of the films thereon. The graphene sheet can be supported on any kind of materials including conventional semiconductor substrates, metals and transparent glasses. Thus glass or metal foil can be used. The use of silica is especially preferred or a compound of Si such as SiC. The use of SiC is a particularly preferred embodiment.

The support must be inert. It is also possible to grow the graphitic substrate directly on a metallic film deposited on an oxidized silicon wafer or directly on metal foils. Then the graphitic substrates can be detached from the metal by etching and easily transferred on to any materials.

In a highly preferred embodiment, the graphitic substrate is a laminated substrate exfoliated from a Kish graphite, or is a highly ordered pyro lytic graphite (HOPG). Alternatively, it could be a chemical vapour deposition (CVD)-grown graphene substrate on metallic films or foils made of e.g. Cu, Ni or Pt.

Whilst it is preferred if the graphitic substrate is used without modification, the surface of the graphitic substrate can be modified. For example, it can be treated with plasma of hydrogen, oxygen, N0₂ or their combinations. Treatment with nitrogen is also possible. Oxidation of the substrate might enhance film nucleation. It may also be preferable to pretreat the substrate, for example, to ensure purity before film growth. Treatment with a strong acid such as HF or BOE is an option. Substrates might be washed with iso-propanol, acetone, or n-methyl-2-pyrrolidone to eliminate surface impurities.

The cleaned graphitic surface can be further modified by doping. A solution of FeCl₃, AuCl₃ or GaCl₃ could be used in a doping step. Ideally, the graphitic substrate used should be a good conductor. Any impurities in the substrate can be extracted into the forming semiconductor film and that might not be preferred. This process is avoided if the substrate is free of impurities.

As the present invention targets thin films, it will also be important that the graphitic substrate is smooth. It should be free of grain boundaries and preferably only one type of the possible A, B or C type stacked graphene layers at the surface will be present. If more than one of the A, B or C type stacked graphene layers is present at the surface, then different sections of the growing film may not be in registry and will thus cause defects in the forming film.

Highly smooth graphene support structures are taught in the literature, e.g. in

Virojanadara, C; Yakimova, R.; Zakharov, A. A.; Johansson, L. I., Large homogeneous mono -/bi- layer graphene on 6H-SiC(0001) and buffer layer elimination. J. Phys. D: Appl. Phys. 2010, 43, 374010. Carriers such as SiC and Si are preferred.

The use of graphitic substrates, ideally thin graphitic substrates, is highly advantageous in the present invention as these are thin but very strong, light and flexible, highly electrically conducting and thermally conducting. They are transparent at the low thicknesses preferably employed herein, they are impermeable and inert.

Semiconductor films

In order to prepare thin films of commercial importance, it is essential that these grow epitaxially on the substrate. This is achieved herein by ensuring an excellent lattice match between the graphene substrate and the thin film, or optionally via a lattice match of a base layer film as described in detail below.

It is ideal if growth of the film occurs in the [1 1 1] (for cubic crystal structure) or [0001] (for hexagonal crystal structure) direction. As noted above, there is no guarantee that this is possible with a particular substrate where that substrate material is different from the film being grown. The present inventors have determined, however, that epitaxial growth on graphitic substrates is possible by determining a possible lattice match between the atoms in the semiconductor film and the carbon atoms in the graphene sheet.

The carbon-carbon bond length in graphene layers is about 0.142 nm.

Graphene has hexagonal crystal geometry. The present inventors have surprisingly realised that graphitic substrates can provide a substrate on which semiconductor films can be grown as the lattice mismatch between the growing film material and the graphitic substrate can be very low.

The inventors have realised that due to the hexagonal symmetry of the graphitic substrate and the hexagonal symmetry of the semiconductor atoms in the (1 1 1) planes of a film growing in the [11 1] direction with a cubic crystal structure (or in the (0001) planes of a film growing in the [0001] direction with a hexagonal crystal structure), a lattice match can be achieved between the growing films and the substrate. Figures la- Id show four different hexagonal structural configurations of the semiconductor atoms in the (111) (or (0001)) planes of a semiconductor film on top of the hexagonal lattice of carbon atoms in the graphene layer, placed in such a way that no lattice mismatch will occur. As possible semiconductor adsorption sites on top of graphene, we consider 1) above the center of the hexagonal carbon rings of graphene (H-site) and 2) above the bridge between carbon atoms (B-site), as indicated by arrows in figure la.

The figures show an idealised lattice-matched arrangement of the

semiconductor atoms in the (111) planes of a cubic crystal ((0001) planes for hexagonal crystal) when the atoms are placed on 1) H- and B-sites (figures la, lb and Id), and 2) H- or B-sites (figure lc). Dashed lines emphasize the hexagonal symmetry of the lattice of semiconductor atoms in the (111) plane. The relative rotations of these hexagons for each atomic arrangement are written on the top of each figure. For (figure la) and (figure Id), two relative orientations are possible, ±10.9° and ±16.1°, respectively (only the + rotations are shown in the images).

Figure le shows artificial lattice-matched lattice constants for the atomic arrangements in (a), (b) , (c) and (d). Dashed and solid lines correspond to the hexagonal (ai) and cubic (a = ai X 2) crystal phases of these lattices, respectively. The square (■ ) and the hexagon represent the cubic and the hexagonal phases, respectively, for Si, ZnO, and binary III-V semiconductors.

If the semiconductor atoms are placed above alternating H- and B-sites as in figure la, an exact lattice match can be achieved if the lattice constant, a, of a cubic semiconductor crystal (the lattice constant, a, is defined as the side length of the cubic unit cell) is equal to: 4.607 A. A few binary cubic semiconductors exist with lattice constants close to this value, with the closest being A1N (a = 4.40 A) and GaN (a = 4.51 A). For hexagonal semiconductor crystals, exact lattice matches will be achieved if the lattice constant, a_ls is equal to: 3.258 A. A few binary hexagonal semiconductors exist with lattice constants close to this value, with the closest being SiC (ai = 3.07 A), A1N (aj = 3.11 A), GaN (ai = 3.19 A) and ZnO (ai = 3.25 A) crystals.

If the semiconductor atoms are placed above alternating H- and B-sites as in figure lb, an exact lattice match can be achieved if the lattice constant, a, of a cubic semiconductor crystal is equal to: 1.422 A x 3/2 x sqr(6) = 5.225 A. This is close to the lattice constant of GaP (a = 5.45 A), A1P (a = 5.45 A), InN (a = 4.98 A) and ZnS (a = 5.42 A). For hexagonal semiconductor crystals exact lattice matches will be achieved if the lattice constant, a_ls is equal to: 1.422 A x 3/2 x sqr(3) = 3.694 A. This is close to the ai lattice constants of the hexagonal forms of InN (ai = 3.54 A) and ZnS (ai = 3.82 A) crystals.

For the atomic configuration as in figure lc, an exact lattice match can be achieved if the lattice constant, a, of a cubic semiconductor crystal is equal to: 1.422 A (carbon atom distance) x 3 x sqr(2) = 6.033 A. This is close to the lattice constant of group III-V compounds such as InAs, GaAs, InP, GaSb, AlSb and AlAs, and II- VI compounds such as MgSe, ZnTe, CdSe, and ZnSe semiconductor crystals. In particular, this is close to the lattice constant of group III-V compounds such as InAs (a = 6.058 A), GaSb (a = 6.096 A) and AlSb (a = 6.136 A), and II-VI compounds such as ZnTe (a = 6.103 A) and CdSe (a = 6.052 A) semiconductor crystals.

For hexagonal semiconductor crystals, exact lattice matches will be achieved if the lattice constant, a_ls is equal to: 1.422 A (carbon atom distance) x 3 = 4.266 A. This is close to the ai lattice constants of the hexagonal forms of the II-VI materials CdS (ai = 4.160 A) and CdSe (ai = 4.30 A) crystals which means that the ternary semiconductor CdSSe can provide a perfect lattice match for a certain molar fraction of S.

If the semiconductor atoms are placed above alternating H- and B-sites as in figure Id, an exact lattice match can be achieved if the lattice constant, a, of a cubic semiconductor crystal is equal to: 6.28 A. This is close to the lattice constant of InSb (a = 6.479 A), MgTe (a = 6.42 A) and CdTe (a = 6.48 A).

Certain ternary compounds like e.g. InGaSb, InAsSb and AllnSb can provide a perfect lattice match, as can some quaternary compounds like InGaAsSb and AlInAsSb. For hexagonal semiconductor crystals, exact lattice matches will be achieved if the lattice constant, a_ls is equal to: 4.44 A. This is close to the ai lattice constants of the hexagonal forms of InSb (ai = 4.58 A), MgTe (ai = 4.54 A) and CdTe (ai = 4.58 A) crystals.

Without wishing to be limited by theory, due to the hexagonal symmetry of the carbon atoms in graphitic layers, and the hexagonal symmetry of the atoms of cubic or hexagonal semiconductors in the [111] and [0001] crystal direction, respectively, a close lattice match between the graphitic substrate and semiconductor can be achieved when the semiconductor atoms are placed above the carbon atoms of the graphitic substrate, ideally in a hexagonal pattern. This is a new and surprising finding and can enable the epitaxial growth of films on graphitic substrates.

The four different hexagonal arrangements of the semiconductor atoms as described above, can enable semiconductor films of such materials to be grown.

Whilst it is ideal that there is no lattice mismatch between a growing film and the substrate, small lattice mismatches are possible. The films of the invention ideally have a lattice mismatch of up to about 1% with the substrate. More preferably, lattice mismatches should be 0.5% or less, e.g. 0.25%> or less. These values apply to any film thickness. Lattice match values can be calculated based on a knowledge of the crystal structure of the semiconductor in question and the information provided above. If a semiconductor can grow in a form with a lattice constant that matches any of the atomic arrangements depicted in figure la- Id for its (111) plane in case of cubic crystal or for its (0001) plane in case of hexagonal crystal, then an appropriate lattice match is present. For the avoidance of doubt, the lattice match should be calculated for the whole of the film present on the substrate.

Note however, that the success of the process of the invention depends, to an extent, on the thickness of the film. Thus, average strain for a total film thickness of 100 nm should typically be less than 0.5%. Average strain for a total film thickness of 0.5 μιη should typically be less than 0.2%. Average strain for a total thickness of 1 μιη should typically be less than 0.15%. Average strain for a total thickness of 5 μιη should typically be less than 0.1%. In order to avoid defects in thicker films therefore, it is preferred if the lattice mismatch is as small as possible.

For some binary semiconductors like cubic InAs (a = 6.058 A), cubic GaSb (a = 6.093 A), cubic CdSe (a = 6.052 A), and hexagonal CdSe (ai= 4.30 A), the lattice mismatch is so small (< ~1%) that excellent growth of these binary semiconductors can be expected for film thicknesses up to several tens of nm.

However, as the film grows thicker strain compensating growth techniques may need to be employed in order to reduce the strain energy and avoid crystal defects like dislocations. In essence therefore, film thickness up to the critical thickness can be achieved without defect risk. This will be of order 30 nm for 1.0% lattice mismatch and of order 100 nm for 0.5% misfit. Thus, beyond the critical thickness superlattice techniques may be needed or different semiconductor materials such as ternary or quaternary semiconductors.

Of course, due to their nature, the lattice constants of ternary, quaternary etc compounds can be manipulated by changing the relative amount of each element present. The lattice constants of these compounds can be tuned to a certain value by tuning the composition of these compounds. The use therefore, of ternary and quaternary semiconductor compounds is preferred when thicker films, such as more than 100 nm, are desired. Devices may require a total film thickness of the order of 5 μιη, typically from 1 to 10 μιη.

It is within the scope of the invention for the film being grown on the substrate to comprise multiple layers of different group (III)(V) or (II)(VI) compounds. Thus, a ternary or quaternary semiconductor might be grown on a binary semiconductor.

Other multiple layer films might result from the use of compensating growth techniques such as strained superlattices. If the film contains superlattices, each layer of the superlattice could have more than 1% strain if strain compensation is used such that the average lattice constant of the superlattice as a whole is lattice- matched to the graphitic substrate.

Such compensating growth techniques would be known to the skilled man.

It will be appreciated, however, that for certain semiconductor combinations there might be too large mismatch between the lattice constant of the semiconductor and the lattice constant of graphene for successful film growth. In such

circumstances, it may not be possible to grow such a semiconductor directly onto the graphitic substrate.

Base Layer

In order to allow other semiconductor films to be present and maximise the possibilities here, the inventors propose the use of an intermediate layer or base layer between a semiconductor thin film and the substrate. This method is preferably used where the semiconductor cannot be lattice matched with the graphitic substrate or that the particular semiconductor for some reason does not form a thin film directly on the graphitic surface, e.g. because none of its

constituents have enough surfactant behaviour to cover the graphitic surface.

This intermediate layer is one which is lattice-matched and therefore forms a kind of surfactant between a thin film semiconductor layer and the graphitic substrate. The base layer material, which can be an element or compound has a lattice mismatch of 2.5% or less, preferably 1% or less with graphene. For example, the lattice mismatch between (111) oriented Sb (rhombohedral A7) and graphene is 1.0% when Sb atoms are positioned above H sites only, B sites only or T sites only. GaSb also has 1.0% lattice mismatch with graphene. InAs has 0.43% lattice mismatch with graphene. This base layer need only be a few atomic layers thick.

By using a base layer that itself is "3 -dimensional", this layer provides lone pairs through which a semiconductor layer can start to grow. The adhesion to the "2-dimensional" substrate is achieved via the use of the base layer.

The base layer is preferably a group V element or alloy of a group III-V compound such as GaSb, InAs, AsSb, SbBi or Sb. AlSb might also be used. The alloy As(0.077)-Sb(0.923) should be perfectly lattice-matched to graphene, in the configuration of Fig. 1(c). (Where 0.077 is the As molar fraction in the alloy.)

Likewise an Sb-Bi alloy can be lattice-matched to the configuration in Fig. 1 (d).

Another option is a ternary lattice-matched base layer, such as those based on AlAsSb, AllnSb, In GaSb or AlInAs. A further option is a combination of base layers, such as an elemental layer of Sb followed by a ternary layer as described above. The Sb layer could be as little as one atom thick although more likely the layer might be a two or three atoms thick.

A further option for the base layer might be CdSe or CdSSe. In one embodiment CdSSe might be grown on a layer of CdSe to form the base layer.

The use of Sb is most preferred as the base layer. The (11 l)-oriented bilayers of rhombohedral, A7, Sb has a close lattice match to graphene (1.0% mismatch). The base layer can be deposited on the substrate using the techniques discussed in detail below in connection with the deposition of the semiconductor. However, when the base layer is Sb, it is preferred if this is deposited under mild conditions, such as less than 200°C, preferably 100 to 135°C, or such as less than 325°C, preferably 200 to 300°C, dependent on the flux intensity of Sb₄ or Sb₂ that is used during deposition, the latter conditions being ideal for Sb₂.

As noted above, only a few atomic layers (perhaps only one atomic layer or two atomic layers) of the base layer is required. In case of Sb, the minimum would be a (11 l)-oriented Sb bilayer. It should be considered that laying down one Sb atomic layer with the next layer being Ga is the same as a GaSb base layer and hence the same as growing the GaSb directly on graphene. Once the base layer is present, the semiconductor film can be deposited. Where a base layer is used, it may be that the initial growth of semiconductor film takes place at a lower temperature similar as was used for the deposition of group V element (or group V alloy etc). A third step can then involve the deposition of III- V film(s) at higher temperature typical for normal epitaxial growth of the III-V compound in question. The second step above is preferred to avoid desorption of group V element (or group V alloy) during the third step.

It may be that to grow a superlattice on a graphitic substrate where each layer of the superlattice has too much strain for it to be possibly grown directly on graphene that a base layer is required, e.g. of Sb, GaSb or InAs. It may also be possible to use AlSb (lattice mismatch 1.7%).

The base layer may also be a "superlattice" with alternating atomic layers [(11 l)-planes] of Sb and Bi. This superlattice would make a close lattice match to the "d" in Fig. 1(e) and thus provide a substrate with a lattice constant where there are no binary substrates available today.

Semiconductors

The semiconductor films of the invention are formed from at least one III-V compound or at least one II- VI compound or a group IV compound such as SiC.

Group II elements are Be, Mg, Ca, Zn, Cd, and Hg. Preferred options here are Zn and Cd. Group III options are B, Al, Ga, In, and Tl. Preferred options here are Ga, Al and In.

Group V options are N, P, As, Sb. All are preferred.

Group VI options include O, S, Se and Te. The use of O, Se and Te is preferred.

The manufacture of a group III-V film is preferred. It will be appreciated that any compound which forms during film growth need not be completely stoichiometric as the possibility of doping exists, as discussed below.

Preferred binary compounds for film manufacture include InAs, GaAs, AlAs, InP, GaP, AlP, InSb, GaSb, AlSb, ZnTe, CdSe and ZnSe. It is within the scope of the invention to grow alternating thin layers (of order 1 nm or a few nm thick) of binary semiconductors such that the electronic properties and average lattice constant of the thin film as a whole is matched with the substrate. The use of GaSb or InAs is highly preferred. Other options include ZnO and AlSb It is preferred in the film is not A1N.

Whilst the use of binary materials is possible, the growth of ternary or quaternary films or even quintinary films is preferred. Especially preferred options are InGaAs, InAlAs, InAsP, InPSb, InAsN, InPN, InSbN, GalnSb, GaAsN, GaInN, GaPN, GaSbN, AlInSb,AlAsSb, AlSbP, AlInN, A1PN, AlAsN,AlSbN, InGaAsSb, AlGaAsSb, and InGaAsN as these can be grown perfectly lattice-matched to graphene, and are suitable for a number of devices. It will be appreciated that in ternary, quaternary etc materials the relative amounts of each ion can vary.

The ternary compounds may therefore be of formula XYZ wherein X is a group III element, Y is a group III or V element different from X and Z and Z is a group V element. The X to Y or Y to Z molar ratio in XYZ is preferably 0.2 to 0.8, i.e. the formula is preferably X_xYi__xZ (or XYi__xZ_x) where subscript x is 0.2 to 0.8. Quaternary systems may be represented by the formula A_xBi__xC_yDi__y where A and B are group III elements and C and D are group V elements. Again subscripts x and y are typically 0.2 to 0.8. Other options will be clear to the skilled man.

It is within the scope of the invention for the films to be doped. Doping typically involves the introduction of impurity ions into the film. These can be

19 3 18 3

introduced at a level of up to 10 /cm , preferably up to 10 /cm . The films can be undoped, p-doped or n-doped as desired. Doped semiconductors are extrinsic conductors whereas undoped ones are intrinsic.

Extrinsic semiconductors with a larger electron concentration than hole concentration are known as n-type semiconductors. In n-type semiconductors, electrons are the majority carriers and holes are the minority carriers. N-type semiconductors are created by doping an intrinsic semiconductor with donor impurities. Suitable donors for III-V compounds can be e.g. Si and Te. Suitable donors for group IV semiconductors can be e.g. P and As.

The p-type semiconductors have a larger hole concentration than electron concentration. The phrase 'p-type' refers to the positive charge of the hole. In p-type semiconductors, holes are the majority carriers and electrons are the minority carriers. P-type semiconductors are created by doping an intrinsic semiconductor with acceptor impurities. Suitable acceptors for III-V compounds can be e.g. Be and Zn. Suitable acceptors for group IV semiconductors can be e.g. B. It will be appreciated that whether an impurity will act as a donor or acceptor in a III-V compound will in some cases depend on the orientation of the growing surface and the growth conditions. Dopants can be introduced during the growth process or by ion implantation of the films after their formation. Doping may also be effected by allowing impurities from the substrate to enter the semi-conductor film.

Preferred films of the invention will contain dopants.

Once the film growth has been established on the graphene substrate, there is no real limit to the manipulations that can be carried out. Different film layers can be added simply by changing the nature of the atoms present. For example, a film is established, it would also be possible to grow a top film layer in which there was a "p-i-n" or "n-i-p" structure by use of appropriate doping techniques. Thus, initially the film might be p-doped before an undoped intrinsic layer is applied and an n- doped layer is introduced (or vice versa).

It will be appreciated that doping only part/parts of the film is possible, e.g. using ion implantation for specific components. Doping may therefore occur processing after growth.

Films The films grown in the present invention may be from 250 nm to several microns in thickness, e.g. 0.5 to 10 microns, more preferably 1 to 5 microns. The surface area of the films is limited only by the apparatus used to deposit the films and the size of the substrate. The surface area may also be dictated by the size of the holes in which the film is grown, as described further below.

The thickness of the films is often controlled by the length of time for which the growing process runs. A longer process typically leads to a thicker film.

The base layer when present may be one or two atomic thicknesses, e.g. 2 A or more up to 10's of nanometres depending on the nature of the base layer and the nature of the thin film grown upon that base layer.

Film/Base layer deposition/growth We deal firstly with the direct deposition of films of the invention on a graphitic substrate. The films of the invention grow epitaxially on the substrate or base layer. They attach to the underlying graphitic substrate through covalent, ionic or quasi van der Waals binding. Accordingly, at the junction of the substrate and the film, crystal planes are formed epitaxially. These build up, one upon another, in the same crystallographic direction thus allowing the epitaxial growth of the film.

The films of the invention should preferably grow in the [111] direction for films with cubic crystal structure and [0001] direction for films with hexagonal crystal structure. Planes (111) and (0001) both represent the same (hexagonal) plane of the film, it is just that the nomenclature of the plane varies depending on the crystal structure of the growing film.

The films are preferably grown by molecular beam epitaxy (MBE). Whilst it is within the scope of the invention for vapour deposition to be used, e.g. a CVD especially a metal organic CVD (MOCVD) or metal organic vapour phase epitaxy (MOVPE) method, the use of MBE is highly preferred.

In this method, the substrate is provided with a molecular beam of each reactant, e.g. a group III element and a group V element preferably supplied simultaneously. It may, however, be advantageous to begin the deposition process using one reactant at a time. Thus a first layer might involve deposition of Sb followed by the application of Ga. A first layer might involve deposition of In followed by As or vice versa. The deposition might involve growth of AlSb, preferably Sb then Al. Once both reactants are present and each has formed an atomic layer, a compound of these two will form. This alternating deposition may or may not be repeated one or more times. Thereafter, both ions can be supplied simultaneously and a film will continue to grow. The substrate temperature may need to be raised before growing in conventional MBE mode with group III-V elements.

A higher degree of control of the nucleation and growth of the films on the graphitic substrate might be achieved with the MBE technique by using migration- enhanced epitaxy (MEE) where group (III) (V) elements are supplied alternately with no time in between or atomic-layer MBE (ALMBE) where e.g. the group III and V elements can be supplied alternately with a delay in between.

A preferred technique is solid-source MBE, in which very pure elements such as gallium and antimony are heated in separate effusion cells, until they begin to slowly evaporate (e.g. gallium) or sublimate (e.g. antimony). The gaseous elements then condense on the substrate, where they may react with each other. In the example of gallium and antimony, single-crystal gallium antimonide is formed. The use of the term "beam" implies that evaporated atoms (e.g. gallium) or molecules (e.g. Sb₄ or Sb₂) do not interact with each other or vacuum chamber gases until they reach the substrate.

Doping ions can also be introduced easily using MBE. Figure 2 is a possible set up of an MBE process.

Molecular beam epitaxy (MBE) takes place in ultra high vacuum, with a background pressure of typically around 10^"10 to 10^"9 Torr. Films are typically grown slowly, such as at a speed of up to a few, such as about 2, im per hour. This allows films to grow epitaxially and maximises structural performance.

The growth temperature may be in the range 300 to 700°C for a conventional II-VI or III-V semiconductor film. Much lower temperatures are needed for base layer growth which is typically around 130°C. The temperature employed is, however, specific to the nature of the material in the film, the surface orientation, and fluxes of III and V elements used. For GaAs growth on GaAs(OOl) surface, a preferred temperature is 580 to 630°C, e.g. 590°C. For GaAs growth on GaAs(l 11) surface, such as the GaAs(l 11)B surface a higher temperature is preferred, e.g. 530°C or higher such as 610°C or higher. For InAs and GaSb the range is lower, for example 430 to 540°C, such as 450°C for InAs growth on InAs (001) surface and

465°C for GaSb growth on GaSb(l 11) surface. GaSb growth on GaSb(OOl) surface may occur at 490 °C. Appropriate temperatures will be found by the skilled person.

Film growth can be initiated by opening the shutter of the Ga/In effusion cell and the shutter and/or valve of counter ion effusion cell (e.g. arsenic or antimony), simultaneously (continuous (analog or digital) MBE growth) or alternating (MEE, ALMBE).

The temperature of the effusion cells can be used to control growth rate. Convenient growth rates are 0.05 to 2 im per hour, e.g. 1 im per hour.

The beam equivalent pressure (flux) of the molecular beams can also be adjusted depending on the nature of the film being grown. Suitable levels for beam equivalent pressures are between 1 x 10^"8 and 1 x 10^"5 Torr.

The beam flux ratio between reactants (e.g. group III atoms and group V molecules) can be varied, the preferred flux ratio being dependent on other growth parameters and on the nature of the film being grown.

A significant benefit of MBE is that the growing film can be analysed in situ, for instance by using reflection high-energy electron diffraction (RHEED). RHEED is a technique typically used to characterize the surface of crystalline materials. This technology cannot be applied so readily where films are formed by other techniques such as MOVPE.

As noted above, the films of the invention preferably grow as cubic (zinc blende) or hexagonal (wurtzite) structures. It is also within the scope of the invention for the nature of the material forming the film to be changed during the growing process. Thus, by changing the nature of the molecular beams, a portion of different structure would be introduced into a film. An initial GaAs film could be extended with an InAs film section for example by changing from a Ga feed to an In feed. The GaAs/InAs film could then be extended with a GaAs film section by changing back to a Ga feed and so on. It is also within the scope of the invention to include nanostructures in the film during the growing process, e.g. InAs or GaSb quantum dots in GaAs matrix. The growth of such nanostructures will be known to the skilled man. Again, by developing different structures with differing electrical properties, the inventors offer films with interesting and manipulable electronic properties which can be tailored by the manufacturer towards all manner of end applications.

Where a base layer is present, the base layer is preferably deposited using one of the techniques described above, e.g. ALMBE. Thereafter, semi-conductor formation follows the instructions above.

In one embodiment, after an initial elemental base layer film is deposited, often an Sb layer, a second elemental layer, typically of a different material can be deposited such as a Ga layer. It may be worthwhile to lay down alternate atomic layers such as of Sb and Ga before starting to grow a desired semiconductor but preferably only one atomic layer of Ga is laid down and this marks the start of the GaSb layer, on top of which e.g. InAs or a ternary or a quaternary compounds could be grown.

It may also be useful, initially to apply a flux of the components of the semiconductor separately. Thus a flux of element (III) is applied and then element (V), or alternatively in the reverse order, before a joint simultaneous flux can be used to grow the film.

If a base layer is used which is heat sensitive, such as an Sb base layer, once III-V film growth is established, temperature can be increased to conventional epitaxial deposit temperatures. The semiconductor film grown need not be the same as the base layer or contain the element(s) of the base layer.

The base layer or main film can be doped. Once semiconductor film growth has started doping can be initiated. If present, doping should be begun a few atomic layers into film formation. This will ideally introduce an ohmic contact into the film. A preferred dopant is Si or Te. Alternatively, the dopant can be Be, or Mg. Mg is used as a preferred dopant for p-type nitrides. Be is used as preferred dopant for p-type arsenides and antimonides. Si is used as preferred dopant for n-type arsenides and nitrides, whereas Te is used as preferred dopant for n-type

antimonides. It will be appreciated that doping only part/parts of the film is possible, e.g. using ion implantation for specific components. Doping may therefore occur processing after growth.

In one embodiment, the film can be grown on a substrate provided with a mask. The mask protects the substrate but defines a pattern of holes in which film growth is intended. For example, a silicon dioxide or alumina mask can be applied on a graphitic substrate with a pattern of holes in the mask through which film growth occurs. Once film deposition has taken place, the mask can be left in place, partially removed or completely removed, e.g. by etching, to leave a series of thin films on the substrate corresponding to the position of the holes in the mask.

Applications

The films of the invention have wide ranging utility. They are semi- conductors so can be expected to offer applications in any field where

semiconductor technology is useful. They are primarily of use in electronics and optoelectronic applications, e.g. in solar cells, photodetectors, light-emitting diodes (LEDs), waveguides and lasers.

An ideal device for their deployment might be a thin film solar cell. Such solar cell has the potential to be efficient, cheap and lightweight at the same time. This is a rapidly developing field and further applications on these valuable materials will be found in the next years.

The invention will now be further discussed in relation to the following non limiting examples and figures.

Brief Description of the Figures

Figure la-d shows the atomic arrangements when semiconductor atoms are placed above 1) H- and B- sites (Figure la, b, and d), and 2) H- or B-sites (Figure lc) on graphene. In Figure le the bandgap energies of the III-V semiconductors (as well as Si and ZnO) are plotted against their lattice constants. Vertical solid (dashed) coloured lines depict the lattice constant of an ideal crystal that would give perfect lattice match with graphene for a cubic (hexagonal) crystal with the four different atomic arrangements (Figure la-d) with respect to graphene. In the case of some binary semiconductors, the lattice mismatch with graphene is very small (e.g. InAs, GaSb, and ZnO) for one suggested atomic configuration. For other binary semiconductors like GaAs, the lattice mismatch is quite large and in-between two different atomic configurations (as in Figure lb or Figure lc). It can be realized from the figure that many ternary, quaternary and quintinary semiconductors can be perfectly lattice-matched to graphene.

Figure 2 shows an MBE experimental set up.

Figure 3 is a theoretical side view of a support, graphene layer, base layer and top semiconductive layer.

Figure 4 shows a thin film of GaSb grown directly on a Kish graphite surface.

Figure 5 shows that for SbGpl3, triangle-like shaped GaSb platelets confirm the epitaxial relation with graphite substrate.

Experimental procedure:

Thin film is grown in a Varian Gen II Modular molecular beam epitaxy (MBE) system equipped with a regular Al filament cell, a Ga dual filament cell, an In SUMO dual filament cell, an As valved cracker cell, and an Sb valved cracker cell allowing to fix the proportion of dimers and tetramers. In the present study, the major species of arsenic are As₂, and antimony are Sb₂.

Growth of thin film is performed either on a Kish graphite flake or on a graphene film (1 to 7 monolayers thick, preferably only one monolayer thick) grown either by a chemical vapor deposition (CVD) technique directly on a metal film such as Cu, Ni, and Pt, or grown on SiC substrates by using a high-temperature sublimation technique. The graphene film samples are purchased from external suppliers. The CVD graphene films are purchased from "Graphene Supermarket", USA.

The CVD graphene film samples are cleaned by isopropanol followed by a blow dry with nitrogen, and then indium-bonded to a silicon wafer. The graphene/SiC substrates are blow dried with nitrogen, and then indium-bonded to a silicon wafer.

The samples are then loaded into the MBE system for the thin film growth. The samples are annealed at a substrate temperature of 550 °C (or higher) for a duration of 10 minutes to get rid of any oxide residues on the substrate. The deposition of III- V film is typically done by a three-step (if a base layer is used) or a two-step growth method. In case a base layer is used, the first step involves the deposition of a group V element (or of an alloy of group V elements) on the graphitic layers at lower substrate temperatures as described below. The second step involves the growth of III-V film at a lower substrate temperature similar as was used for the deposition of group V element (or group V alloy). The third step involves the deposition of III-V film(s) at higher temperature typical for normal epitaxial growth of the III-V compound in question. The second step above is preferred to avoid desorption of group V element (or group V alloy) during the third step.

Example 1:

After annealing the graphene substrate at 550 °C, the substrate temperature is then decreased to typically between 200 °C and 300 °C for Sb deposition. Sb flux is first supplied to the surface during a time interval typically in the range 5 s to 1 minute, dependent on Sb flux and substrate temperature. A few nm, preferably less than a few tens of nm, of Sb are then grown, preferably by MEE or ALMBE. Then, the substrate temperature is increased to a temperature suitable for GaSb thin film growth: i.e. around 450°C. The temperature of the Ga effusion cell is preset to yield a nominal planar growth rate of 0.3 μιη per hour. The Sb₂ flux is set to 1 x 10^"6 Torr to grow the GaSb thin film at this temperature. The GaSb thin film is doped to a level appropriate for which device structure will be grown on top of this thin film template structure.

Example 2: After annealing the graphene substrate at 550 °C, the substrate temperature is decreased to between 15 °C and 80 °C for As deposition, the temperature being dependent on which deposition rate is wanted. As flux is first supplied to the surface during a time interval typically in the range 5 s to 1 minute. A few nm, preferably less than a few tens of nm, InAs are then grown, preferably by MEE or ALMBE. Then, the substrate temperature is increased to a temperature suitable for InAs thin film growth: i.e. around 450°C. The temperature of the In effusion cell is preset to yield a nominal planar growth rate of up to 0.7 μιη per hour. The As₂ flux is set to 6^X 10^"6 Torr to form the InAs thin film at this temperature. The InAs thin film is doped to a level appropriate for which device structure will be grown on top of this thin film template structure.

The substrates prepared in examples 1 and 2 hereby called as III-V/GP thin film substrate can be used as a template for the fabrication of various optoelectronic or electronic devices, and solar cells.

In Examples 3-4 below, we describe the deposition of 1) p-i-n doped ho mo junction GaSb thin film on III-V/GP thin film substrate, and 2) p-n doped heterostructure GaSb/InGaAsSb thin film on III-V/ GP thin film substrate. These thin film structures are intended to use for applications such as light emitting diodes and photo detectors.

Example 3: p-i-n doped homo junction GaSb thin film is further grown on III-V/GP thin film substrate of example 1 to use it as a photodetector. The thickness of each of the p-doped, n-doped, and intrinsic III-V epilayer is typically kept between 0.5 and 3 μιη. For p-type doping, Be is used. Te is used as an n-dopant. The Be cell temperature is set to 990°C which gives a nominal p-type doping concentration of 3 x 10¹⁸ cm^"3. The Te cell temperature is set to 440 °C which gives a nominal n-type doping concentration of 1 x 10¹⁸ cm^"3. The deposition temperature for all the layers is set to 450 °C. The temperature of the Ga effusion cell is preset to yield a nominal planar growth rate of 0.7 μιη per hour, and the Sb₂ flux is set to 1 x 10^"6 Torr to grow the GaSb thin film. Example 4: p-type_GaSb / intrinsic GalnAsSb / n-type_GaSb thin film is further grown on III-V/GP thin film substrate. The composition of the intrinsic GalnAsSb is tailored such that it is lattice-matched to GaSb. The thickness of each these three epilayers is typically kept between 0.5 and 3 μιη. For p-type doping, Be is used. Te is used as an n-dopant for the GalnAsSb epilayer. The Be cell temperature is set to 990 °C which gives a nominal p-type doping concentration of 3 x 10¹⁸ cm^"3. The Te cell temperature is set to 440 °C which gives a nominal n-type doping concentration of 1 10¹⁸ cm^"3.

Example 5: n-type GaSb / n+ GalnAsSb / p-GalnAsSb / p+ GalnAsSb thin film is further grown on III-V/GP thin film substrate to use it as a photodetector. The composition of the GalnAsSb is tailored such that it is lattice-matched to GaSb. The thickness of each of these epilayers is typically kept between 0.5 and 3 μιη.

For p-type doping, Be is used. Te is used as an n-dopant for the GalnAsSb epilayer. The Be cell temperature is set to 990 °C which gives a nominal p+ type doping concentration of 1 ^x 10¹⁸ cm^"3, and the Be cell temperature is set to 940 °C which gives a nominal p-type doping concentration of 9 x 10¹⁶ cm^"3 The Te cell temperature is set to 440 °C which gives a nominal n-type doping concentration of 1 x 10¹⁸ cm^"3.

Example 6:

A series of thin films were grown directly on a Kish graphite. The conditions of growth are summarised in table 1. After annealing the sample at 550 °C, the substrate temperature is reduced to the temperature shown in column 2which the thin film is grown. The SEM images in figure 4 show that we have grown GaSb crystal material on Kish graphite. Nucleation: Samples SbGpl3, SbGp 22 and SbGp 17 show that GaSb nucleates on Kish graphite and forms triangle-like shaped GaSb platelets due to epitaxial relation with the graphitic surface. Nucleation can be achieved with regular MBE at 300°C and with MEE (Migration-Enhanced Epitaxy method in MBE) at 200°C and at 300°C. The material deposited on the Kish graphite is the equivalent of 3 monolayers (ML) of GaSb in each case.

Thin film: Samples SbGp24/26/27/31 show that an almost continuous film of GaSb with nominal thickness 100 nm can be grown on Kish graphite using a two- step growth method (MEE nucleation step at 300°C + MBE growth at 300-520°C).

The samples SbGp26/27/31 are grown according to such two-step method (MEE step at low temp + MBE step at higher temp), i.e. Sb base layer was not used for these samples.

1 Sample

I Number Growth details i Short description of the sample

( SbGp 13 GaSb thin film: 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.7MLs-l, Tc=300°C. I 3 ML GaSb dep at Tc=300C

Sb flux predep= 1χ10^Λ-6, 5 min at Tc=400 °C.

SbGp 14 GaSb thin film: 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.7MLs-l, Tc=300°C. ! 1

GaSb thin film: MEE 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.7MLs-l, Tc=300

SbGp 15 °C. [Open Sb 1.4 sec + Open Ga 1.4 sec + wait 2]x3 times 3 ML MEE GaSb dep at Tc=300C

SbGp 16 GaSb thin film: 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.7MLs-l, Tc=350°C. I 3 ML GaSb dep at Tc=350C I

GaSb thin film: MEE 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.3MLs-l, I 3 ML MEE GaSb dep at Tc=300C, Ga 0.3

SbGp 17 Tc=300°C. [Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x3 times MLs- 1

GaSb thin film: MEE 5 sec (3 ML), Sb flux=6xlO^A-7, Ga=0.3MLs-l, 3 ML MEE GaSb dep at Tc=300C, Ga 0.3 I

SbGp 18 Tc=300°C. [Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x3 times MLs-1, LOW Sb flux

GaSb thin film: MEE 5 sec (3 ML), Sb flux=1.5xlO^A-6, Ga=0.3MLs-l, 3 ML MEE GaSb dep at Tc=300C, Ga 0.3

SbGp 19 Tc=300°C. [Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x3 times MLs-1, High Sb flux

GaSb thin film: Two temp MEE, Sb flux=lxlO^A-6, Ga=0.3MLs-l, Tc=300°C. Two temp MEE: 1 ML at 300C and 2 MLs

SbGp 20 [Open Sb 1.7 sec + Open Ga 1.7 sec + wait 2]x2 times + Tc=400°C. [Open at 400C

1 Sample

I Number i Growth details Short description of the sample j I Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x2 times

1 GaSb thin film: Two temp MEE, Sb flux=lxlO^A-6, Ga=0.3MLs-l, Tc=300°C.

j [Open Sb 1.7 sec + Open Ga 1.7 sec + wait 2]x2 times + Tc=375°C. [Open Two temp MEE: 1 ML at 300C and 2 MLs

SbGp 21 Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x2 times at 375C

GaSb thin film: MEE 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.3MLs-l, 3 ML MEE GaSb dep at Tc=200C, Ga=0.3

SbGp 22 Tc=200°C. [Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x3 times VII.s- 1

GaSb thin film: MEE 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.3MLs-l, 3 ML MEE GaSb dep at Tc=325C, Ga=0.3

SbGp 23 Tc=325°C. [Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x3 times VII.s- 1

GaSb thin film: 100 nm thick, Sb flux=lxlO^A-6, Ga=0.3MLs-l, Tc=300°C. 100 nm GaSb dep at Tc=300C, Ga=0.3

SbGp 24 [Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x20 times + GaSb 980 sec. Vll.s- l

GaSb thin film: MEE 5 sec (3 ML), Sb flux=8xlO^A-7, Ga=0.1MLs-l, 3 ML MEE GaSb dep at Tc=300C, Ga=0.1

SbGp 25 Tc=300°C. [Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x9 times Vll.s- l

GaSb thin film: 100 nm thick, Sb flux=lxlO^A-6, Ga=0.3MLs-l, Tc=300°C.

[Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x30 times + GaSb 980 sec at 100 nm GaSb dep: 3 nm at Tc=300C, 98

SbGp 26 Tc=450C. nm at Tc=450C

Sample

Number Growth details i Short description of the sample

GaSb thin film: 100 nm thick, Sb flux=lxlO^A-6, Ga=0.3MLs-l, Tc=300°C.

[Open Sb 3.4 sec + Open Ga 3.4 sec + wait 2]x30 times + 100 sec at 100 nm GaSb dep: 3 nm MEE + 10 nm at

SbGp 27 Tc=300C+ GaSb 800 sec at Tc=450 °C. Tc=300C, 80 nm at Tc=450C

GaSb Te thin film: MEE 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.3MLs-l,

GaTe=600C, Tc=300°C. [Open Sb 3.4 sec + Open Ga and GaTe 3.4 sec +

SbGp 28 wait 2]x3 times j j

GaSb Te thin film: MEE 5 sec (3 ML), Sb flux=lxlO^A-6, Ga=0.3MLs-l,

GaTe=550C, Tc=300°C. [Open Sb 3.4 sec + Open Ga and GaTe 3.4 sec +

SbGp 29 wait 2]x3 times | I

Claims

Claims

1. A composition of matter comprising a film on a graphitic substrate wherein said composition comprises, in the following order,

(a) a graphitic substrate,

(b) a base layer film comprising an element or compound having a lattice mismatch of 2.5% or less, preferably 1% or less to that of graphene; and

(c) a film of a group III-V compound or group II- VI compound or a group IV compound.

2. A composition of matter comprising a film on a graphitic substrate wherein said composition comprises, in the following order,

(a) a graphitic substrate,

(b) a base layer film comprising GaSb, InAs, AsSb, GaN, SbBi, AlAs, AlSb, CdSe or Sb; and

(c) a film comprising a group III-V compound or group II- VI compound or a group IV compound.

3. A composition of matter comprising a film on a graphitic substrate, said film having been grown epitaxially on said substrate,

wherein said film comprises at least one group III-V compound or at least one group II-VI compound or a group IV compound.

4. A composition as claimed in any preceding claim in which film growth occurs in the holes of a mask present on the substrate.

5. A composition as claimed in any preceding claim in which the film or part of the film of group III-V compound or group II-VI compound is doped.

6. A composition as claimed in any preceding claim in which the graphitic substrate is carried on a support.

7. A composition as claimed in any preceding claim in which the graphitic substrate is free of grain boundaries.

8. A composition as claimed in any preceding claim in which the film does not comprise A1N.

9. A composition as claimed in any preceding claim in which the base layer is GaSb, InAs, CdSe, AlSb, AlAs, AsSb (e.g. Aso.osSbo.92), SbBi (e.g. Sbo.45Bio.55), GaN,or Sb, preferably GaSb, InAs, AsSb (e.g. Aso.osSbo.92), SbBi (e.g. Sbo.45Bio.55), or Sb.

10. A composition as claimed in any preceding claim in which the base layer and/or the film is grown using migration-enhanced epitaxy (MEE) and/or atomic layer molecular beam epitaxy (ALMBE).

11. A composition as claimed in any preceding claim in which the film is a group (III)(V) film.

12. A composition as claimed in any preceding claim in which the film is ternary, quaternary, or quintinary group III-V film.

13. A composition as claimed in any preceding claim in which the thickness of the base layer, if present, and film is at least 250 nm.

14. A composition as claimed in any preceding claim in which the film comprises a plurality of group (III)(V) compounds in different layers.

15. A composition as claimed in any preceding claim wherein the lattice mismatch of the film comprising at least one group III-V compound or at least one group II-VI compound is 2.5% or less, preferably 1% or less to that of graphene.

16. A process for preparing a film grown epitaxially on a graphitic substrate comprising the steps of:

(I) providing group II-VI elements or group III-V elements or group IV elements to the surface of said graphitic substrate, preferably via a molecular beam; and

(II) epitaxially growing said film from the surface of the graphitic substrate.

17. A process for growing a film on a graphitic substrate comprising the steps of:

(I) providing a base layer film on said substrate, wherein said base layer film comprises an element or compound having a lattice mismatch of 2.5% or less to that of graphene;

(II) contacting said base layer film with group II-VI elements or group III-V elements preferably via a molecular beam so as to grow a film of a group III-V compound or a plurality of group III-V compounds in different layers or a film of a group II-VI compound or a plurality of group II-VI compounds in different layers.

18. A process as claimed in claim 16 or 17 wherein deposition of the base layi film or formation of the film grown epitaxially on a graphitic substrate involves migration-enhanced epitaxy (MEE) followed by atomic layer molecular beam epitaxy (ALMBE), preferably in that order.