Patent Description:
The possibility to assemble organic molecules on two-dimensional materials (2D materials), such as for example graphene has recently been proposed to provide enhanced electronic properties of 2D materials. The assembly of molecules on 2D materials may also provide means for creating novel 2D materials with properties which are not available in bare 2D crystals.

It appears that the organization and conformation of molecules on the 2D crystal may influence the electronic structure of the 2D material by interplay of interactions between the 2D material and deposited molecules. However, it is of importance that the molecules form a layer on the 2D material and not form closely packed islands. <NPL>) discloses a review of growth, characterization, transfer doping and hydrogen intercalation of epitaxial graphene.

Traditionally, molecules are deposited onto the 2D material in ultra high vacuum (UHV) conditions. However, the molecule-2D material complex prepared by sublimation of molecules onto the 2D material in UHV conditionsis chemically unstable and deteriorates upon exposure to ambient conditions, and this complicates the use of the molecule-2D material for some implementations, such as implementations employing doped 2D-materials, where the doping may be achieved by assembly of dopant molecules on the surface of the 2D material.

Accordingly, there is room for improvements in processes for preparing composites of 2D material having a molecular layer on the 2D material surface. There also appears to be a need for such composites with improved chemical stability.

In view of the above-mentioned and other drawbacks of the prior art, it is an object of the present invention to provide a method which allows for the preparation of composites comprising a molecule layer on a 2D material that are chemically stable not only in ultra high vacuum and at cryogenic temperatures, but also at higher temperature and pressure conditions such as ambient conditions.

According to a first aspect of the present invention, it is therefore provided a method for assembling molecules on the surface of a two-dimensional material formed on a substrate, the method comprises: forming a spacer layer comprising at least one of an electrically insulating compound or a semiconductor compound on the surface of the two-dimensional material, depositing molecules on the spacer layer, annealing the substrate with spacer layer and the molecules at an elevated temperature for an annealing time duration, wherein the temperature and annealing time are such that at least a portion of the molecules are allowed to diffuse through the spacer layer towards the surface of the two-dimensional material to assemble on the surface of the two-dimensional material.

The present invention is based on the realization to allow the molecules to diffuse through a spacer layer for assembling on the surface of the two-dimensional material. Accordingly, the molecules are not directly deposited onto the surface of the 2D material; instead, a spacer layer is first formed on the 2D material. Next, the molecules are deposited on the spacer layer and diffuse through the spacer layer towards the surface of the 2D material during an annealing process in a predetermined temperature for a predetermined time duration.

With the inventive concept, there is no need for ultra-high-vacuum when depositing the molecules. Furthermore, the spacer layer provides for embedding the molecules which are assembled on the surface of the 2D material, which is at least partly responsible for providing the chemical stability of the molecule assembly on the surface of the 2D material.

A 2D material in accordance with the present inventive concept preferably only comprises a single atomic layer or only a few atomic layers of one or more atomic species.

The electrically insulating compound or semiconductor compound forming the spacer layer may be any such compound which allows the diffusion of molecules through the compound during an annealing process. The spacer layer is preferably a solid spacer layer.

The semiconductor compound may be a wide bandgap semiconductor in some possible implementations. A wide bandgap semiconductor may have a bandgap larger than <NUM> eV.

That the annealing temperature is at an elevated temperature should be interpreted broadly but is preferably above room temperature. The annealing time and temperature may be based on several factors, such as the characteristics of the compound of the spacer layer. Generally, the interplay between the compound of the spacer layer and the annealing time and temperatures should be such that the molecules are allowed to diffuse through the spacer layer during the annealing.

In some embodiments, the spacer layer is encapsulated with at least one encapsulating layer comprising an electrically insulating compound after the molecules have been deposited on the spacer layer. Accordingly, the molecules deposited on the spacer layer are provided with encapsulation which advantageously provides further improved chemical stability of the molecular assembly on the 2D material. The encapsulating layer(s) may comprise the same compound as the spacer layer.

According to further embodiments, at least one metal layer may be deposited on the encapsulating layer(s). The metal layer(s) impede escape of the molecules from the surface of the 2D material, and also from the spacer layer, in particular when the spacer layer is a polymer matrix and thereby provide further improved stability.

In some possible embodiments, the electrically insulating compound in the spacer layer may comprise a polymer, wherein the annealing temperature is above the glass transition temperature of the electrically insulating polymer. Annealing above the glass transition temperature advantageously allows for faster diffusion of the molecules through the spacer layer.

According to the invention, the molecules are molecular dopants, wherein the molecular dopants diffuse through the spacer layer towards the surface of the two-dimensional material to assemble on the surface of the two-dimensional material to thereby dope the two-dimensional material. Accordingly, there is provided a method for doping a two-dimensional material in a stable manner at ambient conditions. In this manner, high mobility and stable 2D materials may be provided.

The annealing time and annealing temperature may be based on a desired degree of doping of the two-dimensional layer.

The forming of the spacer layer may be performed in various ways. In one implementation, forming the spacer layer comprises: coating the layer of two-dimensional material with a liquid comprising an electrically insulating polymer, and annealing the coated substrate comprising the two-dimensional material for a second time duration at a temperature above the glass transition temperature of the electrically insulating polymer to form the spacer layer on the two-dimensional material. Thereby, a relatively simple method for forming the spacer layer is provided.

The liquid comprising electrically insulating polymer may for example be spin-coated onto the two-dimensional material on the substrate. However, the liquid comprising electrically insulating polymer may also be applied by dipping the substrate into the liquid or by spraying the liquid onto the 2D material. Spin-coating provides a simple and reliable method for coating the two-dimensional material with the liquid.

According to other possible implementations, the spacer layer may be formed by depositing the electrically insulating polymer by at least one of physical vapor deposition or chemical vapor deposition. Depositing molecules on the spacer layer may comprise coating the spacer layer with a liquid solution comprising an electrically insulating polymer and the molecules. This allows for relatively simple preparation for molecule deposition on the spacer layer. Furthermore, it allows for spin-coating the spacer layer with the liquid solution comprising the electrically insulating polymer and the molecular dopant, in a similar manner as with the spacer layer. In addition, the chemical stability in air is further improved by embedding the molecule into a suitable polymer matrix, to form a polymer blend dopant layer.

The concentration of the molecule in the liquid solution is chosen based on their molecular mass and density. For example, the concentration by weight of the molecular dopant in the liquid solution may be at least <NUM>%, such as <NUM>%, <NUM>%, <NUM>%, or <NUM>%.

The spacer layer may advantageously encapsulate the two-dimensional material on the substrate. Thereby, the molecules assembled on the surface of the 2D material are more reliably maintained on the surface.

The thickness of the spacer layer is at least <NUM>. For example, the spacer layer may be about <NUM>, <NUM>, or even <NUM>, <NUM>, or <NUM> micrometer.

At least one of the electrically insulating polymers comprises PMMA or copolymers of PMMA.

The two-dimensional material may be any two dimensional material exfoliated from its parent material.

In possible implementations, the two-dimensional material is epitaxial graphene. The graphene may be produced by chemical vapor deposition.

The substrate is preferably Silicon-carbide, in particular when the two-dimensional material is epitaxial graphene.

Various types of molecular dopants may be used and is within the scope of the claims, however, in one possible implementation the molecular dopant is at least one of Tetrafluoro-tetracyanoquinodimethane (F4TCNQ) and tetracyanoquinodimethane (TCNQ).

According to a second aspect of the present invention, there is provided an electronic device comprising: a substrate; a two-dimensional material formed on the substrate; a spacer layer comprising at least one of an electrically insulating compound or a semiconductor compound on the surface of the two-dimensional material a layer of electrically insulating compound and molecules formed on the space layer; an encapsulation layer comprising at least one of an electrically insulating compound or a semiconductor compound formed on the layer comprising the molecules; a metal layer formed on the encapsulation layer, wherein a layer of molecules of the same species as the molecules in the layer on the spacer layer is assembled on the layer of the two-dimensional material.

The molecules are molecular dopants, whereby the molecular dopants on the spacer layer thereby causes doping of the two-dimensional material. The molecular dopants advantageously cause an increase of the mobility of the two-dimensional material. When the molecular dopants have diffused through the spacer layer, they are advantageously arranged on the surface of the two-dimensional material, which causes so-called modulation doping.

Furthermore, if the encapsulation layer is removed from an electronic device according to embodiments of the second aspect of the inventive concept, then it may be observed that the electronic mobility of the two-dimensional material is reduced. This might be caused by desorption of the molecular dopants away from the surface of the two-dimensional layer or by chemical degradation due to the removal of the encapsulation.

According to further embodiments of the inventive concept, the electronic device may comprise at least four connection pads connected to the two-dimensional material, wherein two of the connection pads are arranged as input ports for providing an electric current to the two-dimensional material, and wherein the other two connection pads are arranged as output ports for sensing a voltage across the two-dimensional material in response to an input signal acting on the two-dimensional material. Accordingly, the electronic device may be functional as a Hall bar, the input signal may be a magnetic field applied perpendicular to the surface of the two-dimensional material.

In addition, the electronic device may be a quantum resistance standard.

The metal layer may advantageously be configured as a gate for providing electrostatic gating of the doped two-dimensional material. In this way, the mobility and carrier density of the two-dimensional material may be tuned.

Further embodiments of, and effects obtained through this second aspect of the present invention are largely analogous to those described above for the first aspect of the invention.

According to a third aspect of the invention, there is provided use of an electronic device according to any one of the embodiments of the second aspect, as a quantum resistance standard.

In the present detailed description, various embodiments of the inventive concept is mainly described with reference to a two-dimensional material in the form of graphene and molecular dopants in the form of F4TCNQ. However, it should be noted that this by no means limits the scope of the present invention, which equally well applicable to any two dimensional material exfoliated from its parent material, and to any dopant molecule which can diffuse through a suitable spacer layer.

<FIG> schematically illustrates a method for assembling molecules on the surface of a two-dimensional material. <FIG> will be described in conjunction with the flow-chart of method steps illustrated in <FIG>.

<FIG> illustrates a substrate <NUM> having thereon a layer of a two-dimensional material <NUM>. The two-dimensional material may be any two dimensional material exfoliated from its parent material. In one preferred implementation, the two-dimensional material <NUM> is epitaxial graphene produced by chemical vapor deposition on a silicon-carbide substrate <NUM>. The epitaxial graphene may be wafer scale graphene grown on the silicon-carbide substrate <NUM>.

<FIG> illustrates a spacer layer <NUM> that has been formed (step S102, <FIG>) on the two-dimensional material <NUM>. The spacer layer comprises an electrically insulating compound, or a semiconductor compound. The spacer layer <NUM> may be produced in various ways, for example, by coating the two-dimensional material <NUM> with a liquid comprising an electrically insulating polymer, and subsequently annealing the substrate with the liquid solution above the glass transition temperature of the electrically insulating polymer. Alternatively, the spacer layer <NUM> may be produced by physical vapor deposition (PVD) or chemical vapor deposition (CVD). The fabrication process (e.g. coating with a liquid, PVD, CVD) depends at least partly on the type of electrically insulating compound, or type of semiconductor compound. PVD and CVD are standard micro-fabrication processes known to the skilled person. The thickness of the spacer layer <NUM> depends on the type of spacer layer material but is preferably at least <NUM> thick, but it may be up to even <NUM> thick.

Now turning to <FIG> illustrating molecules <NUM> being deposited (step S104, <FIG>) on the surface of the spacer layer <NUM>. Only one of the molecules <NUM> is numbered to avoid cluttering the drawings. There are various ways of depositing the molecules on the spacer layer, one which will be described with reference to subsequent drawings. Example methods include evaporation processes, deposition from solution, and spray coating.

The substrate with the spacer layer and the molecules deposited on the spacer layer are annealed (step S106, <FIG>) at an elevated temperature for a predetermined time duration. The elevated temperature is above room temperature and is generally determined based on the material of the spacer layer <NUM> and the properties of the molecule <NUM>. The annealing temperature and the annealing time are selected such that the molecules <NUM> are allowed to diffuse through the spacer layer <NUM> towards the two-dimensional material <NUM>. As conceptually illustrated in <FIG>, the molecules <NUM> assemble on the surface of the two-dimensional material <NUM> after havening diffused through the spacer layer <NUM> during annealing.

Now turning to <FIG> which schematically illustrate a method for assembling molecules on the surface of a two-dimensional material. <FIG> will be described in conjunction with the flow-chart of method steps illustrated in <FIG>.

Similar to <FIG>, <FIG> illustrates a substrate <NUM> having thereon a layer of a two-dimensional material <NUM>. The two-dimensional material <NUM> may be any two dimensional material exfoliated from its parent material. In one possible implementation, the two-dimensional material <NUM> is epitaxial graphene produced by chemical vapor deposition on a silicon-carbide substrate <NUM>. The epitaxial graphene may be wafer scale graphene grown on the on the silicon-carbide substrate <NUM>.

A spacer layer <NUM> as illustrated in <FIG> may be formed by first coating the layer of two-dimensional material <NUM> with a liquid comprising an electrically insulating polymer as is also indicated by step S202 in <FIG>. The substrate <NUM> with the two dimensional material <NUM> coated with the liquid solution is annealed (step S204, <FIG>) for a time duration at an elevated temperature above the glass transition temperature of the electrically insulating polymer. In this way, the spacer layer <NUM> is formed in this presently described example embodiment. Coating the layer of two-dimensional material <NUM> with the liquid comprising the electrically insulating polymer may be performed by spin-coating methods known per se to the skilled person.

In one possible implementation the electrically insulating polymer is poly(methyl methacrylate) (PMMA). In case of using PMMA in the spacer layer <NUM>, the PMMA is typically dissolved in a suitable solvent and the annealing temperature should be sufficiently high so that the glass transition temperature (which depends on the molecular weight of PMMA) is exceeded. For example, the annealing time duration may be about <NUM> and the annealing temperature about <NUM>, such that a solid spacer layer is formed.

<FIG> illustrates that the spacer layer <NUM> has been coated with a liquid solution (step S206) comprising an electrically insulating polymer <NUM> and molecules <NUM>. The coating may be performed by spin coating methods.

The substrate <NUM> with spacer layer <NUM> and the liquid solution comprising the molecules <NUM> and the electrically insulating polymer <NUM> is annealed (step S208, <FIG>) for a time duration at an elevated temperature above the glass transition temperature of the electrically insulating polymer <NUM>. Also this electrically insulating polymer may be PMMA or MMA, or copolymers of PMMA.

The annealing temperature and the annealing time are selected such that the molecules <NUM> are allowed to diffuse through the spacer layer <NUM> towards the surface two-dimensional material <NUM>. As conceptually illustrated in <FIG>, the molecules <NUM> assemble on the surface of the two-dimensional material <NUM> after having diffused through the spacer layer <NUM> during annealing. However, there are often some molecules left in the annealed molecule layer <NUM> comprising the electrically insulating polymer <NUM> and molecules <NUM>.

Now with reference to <FIG>and to the flow-chart in <FIG>. In further embodiments, an encapsulating layer <NUM> is formed on the annealed molecule layer <NUM> (step S210, <FIG>) as schematically shown in <FIG>. The encapsulating layer <NUM> may comprise of an electrically insulating compound such as a polymer (e.g. PMMA or MMA, or copolymers of PMMA). The production of the encapsulating layer <NUM> may be performed in the same way as the above described layers comprising electrically insulating compounds (i.e. coating and annealing). The encapsulation layer improves the chemical stability of the assembled molecules <NUM> on the two-dimensional material <NUM>. In particular, the encapsulation layer at least partly prevents drift in carrier concentration caused by exposure to ambient dopants.

Further, and as schematically illustrate in <FIG>, a metal layer <NUM> may be deposited on the encapsulating layer <NUM> (step S212, <FIG>). The metal layer <NUM> may comprise e.g. gold or aluminum, and may be deposited using known processes such as sputtering, physical vapor deposition, chemical vapor deposition, etc. The metal layer <NUM> shields the molecules <NUM> assembled on the two-dimensional material <NUM> such that the chemical stability is further improved. In addition, the metal layer <NUM> may serve as a gate in embodiments where the molecules are molecular dopants. The metal gate may then be used for providing electrostatic gating of the doped two-dimensional material.

In some embodiments, the two-dimensional material is epitaxial graphene <NUM> grown on a silicon-carbide substrate <NUM>. Further, the electrically insulating compound of the spacer layer <NUM> may be PMMA, as well as the electrically insulating compound in the annealed molecule layer <NUM> and the encapsulating layer <NUM>. The molecules <NUM> may be Tetrafluoro-tetracyanoquinodimethane (F4TCNQ), although other molecules are also applicable, such as e.g. tetracyanoquinodimethane (TCNQ).

Spin-coating and annealing methods are known per se to the skilled person, as well as chemical vapor deposition and physical vapor deposition.

<FIG> each illustrates a cross-section of a respective test device used for comparing carrier density and electron mobility of an electronic device manufactured according to the inventive concept (<FIG>) with other test devices.

<FIG> shows a cross section of first test device <NUM> comprising a silicon-carbide substrate <NUM> having thereon a layer of graphene <NUM> and a layer of PMMA <NUM>, which may correspond to a spacer layer <NUM>.

<FIG> illustrates a cross section of second test device <NUM> comprising a silicon-carbide substrate <NUM> having thereon an annealed layer <NUM> of PMMA <NUM> and molecular dopants <NUM> (only one is numbered), in this case the molecular dopant is F4TCNQ.

<FIG> shows a cross section of a third test device <NUM> comprising a graphene layer <NUM> on a silicon-carbide substrate <NUM>, a PMMA spacer layer <NUM>, an annealed molecule layer <NUM> comprising PMMA <NUM>, and an encapsulating layer <NUM> comprising PMMA.

All devices shown in <FIG>comprises gold contacts <NUM> electrically connected to the graphene layer <NUM> for enabling Hall measurements to extract carrier density and mobility of the graphene layer <NUM>. Accordingly, the devices are patterned as a Hall bar although only one portion of the devices are shown in the cross-sections in <FIG>.

<FIG> shows carrier concentration as a function of temperature extracted from Hall measurements for pristine epitaxial graphene ("As-grown") and the test devices (<NUM>, <NUM>, <NUM>) shown in <FIG>. Both PMMA (test device <NUM>) and the F4TCNQ (test device <NUM>) act independently as a p-dopant which can be seen from the lower carrier concentration in the curves for the test devices <NUM> and <NUM> compared to as-grown graphene, with the former being a weaker p-dopant. When deposited directly onto graphene, it is only when the PMMA spacer layer <NUM> is included between graphene and the F4TCNQ layer <NUM> (test device <NUM>) that the carrier density of the epitaxial graphene decreases by three orders of magnitude, from <NUM><NUM> to <NUM><NUM> cm-<NUM> at T=<NUM> (almost <NUM> orders of magnitude at room temperature).

<FIG> shows Hall carrier mobility as a function of temperature for measurements for pristine epitaxial graphene and the test devices (<NUM>, <NUM>, <NUM>) shown in <FIG>. The carrier mobility for the test devices in <FIG> (<NUM>) and <FIG> (<NUM>) do not exceed <NUM>,<NUM><NUM>/Vs. However, for the third test device <NUM> schematically shown in <FIG> which has molecular dopant layer <NUM> on the spacer layer <NUM> the carrier mobility exceeds <NUM>,<NUM><NUM>/Vs.

Accordingly, as may be understood from the above, the molecule deposited on the spacer layer may be a molecular dopant such as F4TCNQ or TCNQ. Thereby, an air-stable functionalization of graphene with a molecular dopant is achieved which enables high mobility epitaxial graphene.

The thickness of the spacer layer <NUM> appears to not affect the improvement in carrier density and carrier mobility, at least not in the range of <NUM> to <NUM> which suggests that the diffusion of F4TCNQ molecules through the polymer is relatively quick. The spacer layer is preferably at least <NUM> thick.

The chemical composition of a manufactured electronic device has been investigated using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) depth profiling. <FIG> schematically illustrates a cross-section of the device <NUM> which was investigated and which was produced using a method according to the inventive concept. The cross-section in <FIG> illustrates a graphene layer <NUM> on a silicon-carbide substrate <NUM>, a PMMA spacer layer <NUM> (about <NUM> thick) directly in contact with the substrate <NUM> and the graphene layer <NUM>, an annealed molecule layer <NUM> comprising a PMMA-F4TCNQ blend (about <NUM> thick, molecules not shown), an encapsulating PMMA layer (about <NUM> thick) <NUM>, and a gold pad <NUM> on the substrate <NUM> embedded by the spacer layer <NUM>.

The results from the ToF-SIMS investigation is presented in <FIG>and show that F4TCNQ species diffuse through the PMMA spacer layer <NUM> to reach the graphene <NUM> surface, presumably form a charge-transfer complex with the graphene <NUM>, and accumulate at the graphene/spacer interface as can be understood from <FIG> shows the chemical profile in the vertical axis with respect to the substrate, with ion intensity plotted as a function of sputter time, of the trilayer polymer stack along the direction normal to the surface of the graphene <NUM> indicated by the arrow 601a in <FIG>. The ion intensity is shown for flour (F) and the cyanogroup (CN) which both represent the dopant F4TCNQ. The ion intensity for silicon (Si) is also included in <FIG>.

In <FIG>, it can be seen that the intensity of the F4TCNQ counts indicated by the line <NUM> (CN) and <NUM> (F) has a small increase in the annealed molecule layer <NUM> indicating that there are still some F4TCNQ molecules left in the annealed molecule layer <NUM>. At the interface between the graphene layer <NUM> and the PMMA spacer layer <NUM>, there is a larger increase indicated by the peak <NUM> (curve for CN, see also the peak in F-intensity in curve <NUM>), indicative of the accumulation of F4TCNQ molecules at the surface of the graphene layer <NUM>.

<FIG> shows a comparison of the chemical profile in the vertical axis, with ion intensity plotted as a function of sputter time, of the trilayer polymer stack along the direction normal to the surface of the substrate at three different sites on the substrate: graphene (at arrow 601a in <FIG>), bare SiC (at arrow 601b in <FIG>), and thin Au film on graphene (at arrow 601c in <FIG>). The legend in <FIG> represents the site (e.g. at arrows 601a-c) at which the chemical profile was obtained on the device <NUM>.

<FIG> illustrates the chemical signatures arising from the molecular dopant F4TCNQ (i.e. a CN signal as described with reference to <FIG>) at the site (601a) of the graphene, on SiC (601b), and on Au (601b). The signatures acquired at SiC or Au serves as an indicator of the polymer spacer layer substrate interface (seen at about <NUM> sputter seconds, also seen in <FIG>). Note that the thickness of each layer as estimated from SIMS is approximate since the rate of etching is different depending on material. Inhomogeneous sputtering, e.g. due to surface roughness, will also smear and broaden the interfaces, such as the F4TCNQ accumulation layer near graphene.

ToF-SIMS reveals not only that F4TCNQ is found at the annealed molecule layer <NUM> and the PMMA spacer layer <NUM>, suggesting a rapid diffusion of F4TCNQ from the intermediate dopant layer <NUM> comprising F4TCNQ and PMMA, but also that dopants (F4TCNQ) reach the substrate <NUM> surface and accumulate at the conductive surfaces of graphene <NUM> and gold <NUM> (<FIG> and <FIG>).

Accordingly, F4TCNQ is mobile in polymer thin films and its diffusion depends on a number of parameters of the host polymer matrix (e.g. PMMA, MMA, or copolymers of PMMA), notably on the polarity and the glass transition temperature (Tg). Given the polarity of PMMA and the thermal annealing step of the described process above the glass transition temperature of the polymer (Tg ~ <NUM>), a conservative estimate for the lower bound of the flux of F4TCNQ at the substrate surface is <MAT> 5x10-<NUM>mol. cm-<NUM>s-<NUM>, which means that initially an amount of F4TCNQ equivalent to a <NUM> thick solid layer reaches the spacer/substrate interface per second. Here we have used D ~ <NUM>-<NUM> cm<NUM> s-<NUM> measured for diffusion of neutral F4TCNQ in nonpolar P3HT at about <NUM> (see e.g. <NPL>. ), Δc = <NUM> ·<NUM>-<NUM> mol cm-<NUM> the initial F4TCNQ concentration gradient between the molecule layer <NUM> and spacer layer <NUM> (density of F4TCNQ ρ ~ <NUM> cm-<NUM>; molar mass M ~ <NUM> mol-<NUM>), and Δx = <NUM> is the thickness of the spacer layer <NUM>.

The observed p-doping effect on graphene (see <FIG> and above discussion) and the accumulation of F4TCNQ at the graphene <NUM> and gold surfaces <NUM>, signaled by spike in CN-species followed by the appearance of either Si-signal or Au-signal (<FIG> and <FIG>), may be explained by the formation of a charge transfer complex that yields a F4TCNQ anion, which must remain at the graphene interface to preserve overall charge neutrality. In addition, slower diffusion of the F4TCNQ anion in polymer matrix has been observed in poly(<NUM>-hexylthiophene) (P3HT):F4TCNQ blends, in which the diffusion coefficient of neutral F4TCNQ is <NUM>-<NUM> cm<NUM> s-<NUM> decreases by two orders of magnitude for the F4TCNQ- anion (see e.g. <NPL>. When using PMMA as a host matrix for the F4TCNQ, the F4TCNQ remains neutral both in the doping layer and as it diffuses through PMMA spacer layers. It is only when it comes to contact with an electron donor, such as graphene, that charge transfer may take place.

With further reference to <FIG>, there appears to be virtually no accumulation of F4TCNQ at the polymer spacer/SiC interface as indicated by the relatively low peak <NUM> in CN-signal (at SiC, 601c) in the vertical axis towards the SiC substrate <NUM>, the intensity of the CN- signal is roughly <NUM>% greater at the graphene/PMMA spacer interface indicated by peak <NUM> (<NUM>-fold higher at gold/PMMA, see peak <NUM>) compared to the signal measured at the dopant layer (<NUM> x <NUM><NUM> ions cm-<NUM>). From the SIMS measurements an estimate of the fraction of molecules which reach graphene <NUM> can be calculated through the area under the ion intensity curves <NUM> (SiC, at arrow 601c), <NUM> (graphene, at arrow 601a in <FIG>), <NUM> (gold, at arrow 601b) in <FIG>. The total amount of available molecular dopants (F4TCNQ molecules) is calculated using the known densities of PMMA, anisole solvent in which the PMMA is initially dissolved, F4TCNQ molecule and the thickness of the F4TCNQ dopant layer after spin coating (presumed to be a slab of PMMA and F4TCNQ molecules only). Finally, this leads to the estimated number of F4TCNQ on the graphene surface to be roughly ~7x10<NUM> molecules/cm<NUM>.

<FIG> schematically illustrates a cross-section of an electronic device <NUM> according to embodiments of the invention. The electronic device comprises a substrate <NUM> and a two-dimensional material <NUM> formed on the substrate. The substrate <NUM> may be a silicon-carbide substrate and the two-dimensional material may be epitaxial graphene <NUM> grown on the substrate <NUM>. There is further a spacer layer <NUM> comprising at least one of an electrically insulating compound or a semiconductor compound on the surface of the two-dimensional material <NUM>. The spacer layer <NUM> may for example comprise an electrically insulating compound in form of PMMA or MMA, or a combination thereof. On the spacer layer <NUM> there is a layer <NUM> of electrically insulating compound and molecules <NUM>. Also the electrically insulating compound in layer <NUM> may comprise PMMA or MMA, or a combination thereof.

An encapsulation layer <NUM> comprising at least one of an electrically insulating compound (e.g. PMMA or MMA, or a combination thereof) or a semiconductor compound has been formed on the layer <NUM> comprising the molecules <NUM>. There is further a metal layer <NUM> formed on the encapsulation layer <NUM>. A layer of molecules <NUM> of the same species as the molecules in the layer <NUM> on the spacer layer <NUM> is assembled on the layer of the two-dimensional material <NUM>.

In some embodiments, the molecules are molecular dopants in the form of e.g. Tetrafluoro-tetracyanoquinodimethane (F4TCNQ) and/or tetracyanoquinodimethane (TCNQ). Molecular dopants allow doping of the two-dimensional material <NUM>. The metal layer <NUM> may serve to further improve the chemical stability of the device in ambient conditions by preventing the desorption of molecular dopants from the polymer matrix into the surrounding environment.

Further, the metal layer <NUM> may serve as a gate for tuning the carrier concentration in the two-dimensional material <NUM>.

<FIG> is a schematic top view of an example conceptual electronic device <NUM>. The cross-section shown in <FIG> is indicated in <FIG> by lines A-A. The electronic device is here illustrated as a Hall bar <NUM> which may be used as an embodiment or realization of a quantum resistance standard by using the quantum Hall effect in the device.

The electronic device <NUM> may be fabricated using conventional lithography using e.g. electron beam lithography and/or photolithography, which are per se known to the skilled person.

The electronic device <NUM> comprises at least four connection pads connected to the two-dimensional material <NUM> (see <FIG>). Two connection pads <NUM>, <NUM> are arranged for enabling a current (I) to be passed through the two dimensional material in the x-direction, a longitudinal direction of the Hall bar <NUM>. The two connection pads <NUM>, <NUM> are arranged as output ports for measuring transverse voltage (Vxy) when the current (I) is passed through the two-dimensional material in the device <NUM> in the longitudinal direction (x). The two connection pads <NUM>, <NUM> are spatially separated in the transverse direction (y). Furthermore, a longitudinal voltage (Vxx) may be measured between connection pad <NUM> and an additional connection pad <NUM> spatially separated from the connection pad <NUM> in the longitudinal direction. The size of a hall bar <NUM> may for example be: w= <NUM> x L=<NUM>, w= <NUM> x L=<NUM>, W=<NUM> x L= <NUM>.

The doping homogeneity of a two-dimensional material may serve to establish that the molecular dopants are homogenously spread on the surface of the two-dimensional material. The doping homogeneity of the Hall bar <NUM> was assessed using magneto-transport measurements at low temperatures (e.g. <NUM> Kelvin) and showed that the chemical doping of graphene <NUM> in the device <NUM> is significantly conformal over the entire hall bar <NUM> only when the spacer layer <NUM> is included between graphene <NUM> and the dopant layer <NUM>. The doping homogeneity assessment will now be described with reference to <FIG>.

<FIG> is a graph showing the longitudinal resistance (Rxx) measured between connection pads <NUM> and <NUM> of the Hall bar <NUM> in <FIG>, and also the transverse resistance (Rxy1, Rxy2) measured between connection pads <NUM> and <NUM>. For the chemically doped devices such as the hall bar <NUM>, magneto-transport measurements at T=<NUM> in the Hall bar (W=<NUM> x L=<NUM>) device <NUM> comprising the spacer layer <NUM> and molecular doping layer <NUM> show a linear transversal resistance (Rxy1, Rxy2) for magnetic fields |B| < <NUM> mT, after which quantum Hall plateaus <NUM>, <NUM> start to develop and acquire their exactly quantized value Rxy=h/2e<NUM> at |B| > <NUM> mT (h is the Planck's constant). The magnetic field is applied perpendicular to the plane of the Hall bar <NUM>.

With further reference to <FIG> which additionally shows the longitudinal resistance Rxx as a function of applied magnetic field (B). An additional test of charge carrier homogeneity within the measured regions of the Hall bar <NUM> is the observation of fully developed quantum Hall effect (indicated by plateaus <NUM>, <NUM>), with the simultaneous observation of Rxx=<NUM> and quantized plateau in Rxy=h/2e2. Under quantizing conditions, observation of finite Rxx is in fact determined by the magnitude of disorder in the sample, which can manifest as oscillations in Rxx once the Rxy plateaus are reached (see e.g. "<NPL>, or "<NPL>).

Accordingly, the aforementioned magneto-transport characteristics indicate that chemically doped samples with PMMA spacer and F4TCNQ dopant layer behave as systems with a single electronic band and spatially homogenous carrier density across the two-dimensional material <NUM>.

Claim 1:
A method for assembling dopant molecules (<NUM>) on the surface of a two-dimensional material (<NUM>) formed on a substrate (<NUM>), the method comprises:
- forming a spacer layer (<NUM>) comprising at least one of an electrically insulating compound or a semiconductor compound on the surface of the two-dimensional material, the compound of the spacer layer is adapted to allow for the diffusion of dopant molecules through the compound during an annealing process,
- depositing dopant molecules on the spacer layer,
- annealing the substrate with spacer layer and the molecules at an elevated temperature above room temperature for an annealing time duration, wherein the elevated temperature and annealing time duration depend on the compound of the spacer layer and properties of the dopant molecules, and are such that at least a portion of the dopant molecules diffuse through the spacer layer towards the surface of the two-dimensional material during the annealing time duration to assemble on the surface of the two-dimensional material to thereby dope the two-dimensional material and cause an increase of the mobility of the two-dimensional material.