Novel carbon nano-structures for energy generation applications

Abstract

This relates to a device for detecting or converting light or heat energy, the device comprising: a Graphene sheet formed into a scroll such as to provide a monolayer structure in which the radius of curvature of the graphene sheet increases on increasing distance from the longitudinal axis of the scroll.

Claims

1. A bulk heterojunction organic solar ink comprising scrolls and an electron acceptor, wherein each scroll comprises a graphene sheet formed into the scroll such as to provide a structure in which the radius of curvature of the graphene sheet increases on increasing distance from the longitudinal axis of the scroll.

2. The bulk heterojunction organic solar ink according to claim 1, wherein each scroll substantially consists of the graphene sheet.

3. The bulk heterojunction organic solar ink according to claim 1, wherein each scroll has an inner diameter of less than or equal to 5 nm.

4. The bulk heterojunction organic solar ink according to claim 3, wherein each scroll has an inner diameter of 0.3 to 0.5 nm.

5. The bulk heterojunction organic solar ink according to claim 1, wherein each scroll has an outer diameter of less than or equal to 5 nm.

6. The bulk heterojunction organic solar ink according to claim 1, wherein each scroll has a single layer.

7. The bulk heterojunction organic solar ink according to claim 1, wherein each scroll has multiple layers.

8. The bulk heterojunction organic solar ink according to claim 7, wherein the multiple layers in each scroll each have an edge, and the edges of the multiple layers are aligned between the multiple layers.

9. The bulk heterojunction organic solar ink according to claim 1, wherein the graphene sheet is diagonally rolled at a chirality.

10. The bulk heterojunction organic solar ink according to claim 1, wherein the Graphene used for the preparation of the scroll is free from contamination and defects.

11. The bulk heterojunction organic solar ink according to claim 1, wherein graphene platelets used in preparation of the scroll have a length which is at least 25 nm

12. The bulk heterojunction organic solar ink according to claim 1, wherein the electron acceptor is a mix of PCBM and polymers.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0039] FIG. 1 illustrates a comparison of the absorption spectrum from varying diameter semiconducting SWCNTs with bandgap energies for Multi-junction solar cells showing that a range of SWCNTs with varying curvature can achieve the same bandgap energies as that found in Multi-junction solar cells.

[0040] FIG. 2 illustrates that strain exists due to the curvature of the carbon bonds resulting in different bond angles and lengths.

[0041] FIG. 3(a) illustrates a plot of normalised bond lengths as a function of tube diameter for zigzag SWNTs.

[0042] FIG. 3(b) illustrates a plot of bond angles α and β as a function of tube diameter for zigzag SWNTs.

[0043] FIG. 4 illustrates a plot of carbon nanotube diameters against energy separation and carbon-carbon bond angles highlighting a correlation with carbon-carbon bond angles induced by surface tension.

[0044] FIG. 5 illustrates a schematic of a typical small dimension single coiled scroll showing the layer offset achieved in the scroll's Graphene layers due to rotation or twist.

[0045] FIG. 6 illustrates the cross-sectional view of a multiple layer single coiled Graphene scroll showing dimensions.

[0046] FIG. 7(a) illustrates a plot of normalised bond lengths as a function of distance (nm) from the centre of a single coiled Graphene scroll.

[0047] FIG. 7(b) illustrates a plot of bond angles α and β as a function of distance (nm) from the centre of a single coiled Graphene scroll.

[0048] FIG. 8 illustrates the cross-sectional view of a multiple layer single coiled Graphene scroll showing that a curvature gradient is present with increasingly larger bond angles of carbon atoms from the inner core to the outer periphery of the scroll.

[0049] FIG. 9 illustrates the different absorption energies at each surface layer of the scroll and illustrates how each layer is transparent to the remaining wavelengths of energy passing through it.

[0050] FIG. 10 illustrates how Graphene's Photoexcitiation cascade via hot-carrier generation establishes a photothermoelectric effect in the single coiled scroll.

[0051] FIG. 11(a) illustrates single coil scrolled topology that could be achieved with a single platelet of Graphene.

[0052] FIG. 11(b) & FIG. 11(c) illustrate a dual coiled scroll achievable from a single platelet of Graphene.

[0053] FIG. 11(d) illustrates a double coiled ‘s’ shape scroll topology that could be achieved with a single continuous monolayer of carbon atoms.

[0054] FIG. 12 illustrates a representation of typical single layer Graphene platelets prior to scrolling.

[0055] FIG. 13 presents a table showing typical scroll dimensions achievable with varying Graphene platelet dimensions.

[0056] FIG. 14 illustrates the steps involved in method one to produce scrolls using chemical and microwave irradiation processes.

[0057] FIG. 15 illustrates the steps involved in method two to produce scrolls using chemical and microwave irradiation processes.

[0058] FIG. 16 illustrates an ink blend of single coiled scrolls as the electron donor and mix of PCBM & polymers as the electron acceptor acting as the active layer in solution-processable thin film photovoltaics (TFPVs), that can be interfaced with carrier-selective contacts.

[0059] FIG. 17 illustrates the proposed cell configuration. The configuration of the present cells consists of single coiled scrolls/polymer blends as the active layer sandwiched between electron and hole transport layers (ETL and HTL, respectively) and carrier selected electrical contacts.

[0060] FIG. 18 illustrates a next generation solar cell architecture utilising double coiled scrolls as the active layer sandwiched between 2 electrical contacts.

DETAILED DESCRIPTION

[0061] The disclosure provides carbon-based nano-structures for applications in energy generation technologies.

[0062] Solar Absorption

[0063] The disclosure provides graphene-based nano-structures with broadband optical absorption and conversion properties.

[0064] FIG. 5 illustrates a schematic of a small dimension single coiled graphene scroll such as to provide a monolayer structure. The radius of curvature of the graphene sheet increases on increasing distance from the longitudinal axis of the scroll. This illustrates the layer offset achieved in the scroll's Graphene layers. The ABC layering of the scroll keeps the scroll from forming a graphite structure. Instead the Graphene sheet keeps its monolayer structure even in scrolled form. By arranging the layers into an ABC stacking order this significantly increases the amount of solar energy the graphene scroll absorbs in selective wavelength ranges. The scroll is tightly wound so that the inner core is as small as possible.

[0065] Embodiments of the present invention take advantage of the tight curvature which exists in small diameter (0.3 nm inner diameter-5.0 nm outer diameter) nano-scrolls. This tight curvature is reflected in the variation of the carbon-carbon bond angles and lengths, which only vary in carbon nano-scrolls with an outer diameter of less than 5 nm. To clarify, the scroll can have any number of layers, however, the ideal scroll should be most tightly wound in its core with reducing tightness due to reduced tension towards the periphery of the scroll. Indeed, the inner scroll diameter should be something similar to that of a single wall carbon nanotube (SWNT), in the order of 0.3-0.5 nm. With an outer scroll diameter of 5 nm this establishes a curvature gradient reflected by the varying carbon-carbon bond angles and lengths along the surface towards the core of the scroll.

[0066] FIG. 6 illustrates the cross-sectional view of a multiple layer single coiled carbon scroll showing dimensions. The ideal scroll should have an inner diameter (Di) of around 0.3 nm and an outer diameter (Do) of approximately 5 nm. The thickness (T) of a graphene sheet is 0.335 nm with an interlayer spacing (S) of 0.34 nm.

[0067] Unlike multi-junction solar cells where different materials are doped to tune their energy bandgaps to match different regions of the solar spectrum, the present invention takes advantage of the varying carbon-carbon bond angles and lengths which are present in the tightly scrolled single nano-structures. Carbon nano-scrolls that consist of layers of very low diameters (<5.0 nm) are expected to exhibit a strain in the carbon atoms similar to that found in small diameter carbon nanotubes, due to the bending of the carbon bonds resulting in different bond lengths and bond angles, shown graphically in FIG. 7(a) and FIG. 7(b) respectively. FIG. 8 illustrates the cross-sectional view of a multiple layer single coiled carbon scroll showing that a curvature gradient is present with increasingly larger bond angles of carbon atoms from the inner core to the outer periphery of the scroll.

[0068] An important aspect of a scrolled sheet of graphene is that the layers effectively decouple and act independently due to the offset of the carbon atoms in the two layers. This feature presents the potential to access both the positive and negative curvature on both sides of the sheet. Effectively the carbon nano-scroll presents a way to suspend a sheet of graphene.

[0069] Embodiments of the present invention capture a larger range of photon energies more efficiently by taking advantage of the way that layers are stacked in a single scrolled graphene sheet allowing for light to be absorbed from any angle incident on the scroll's surface. Top layers absorb lower-energy photons while transmitting higher-energy photons, which are then absorbed by lower layers of the scroll. The absorption bandwidth at any point throughout the scroll is directly related to the carbon-carbon bond angle and carbon-carbon bond length at that point. FIG. 9 illustrates the different absorption energies at each layer of the scroll and illustrates how each layer is transparent to the remaining wavelengths of energy passing through it. Low energy infrared wavelengths are absorbed on the outer layer 1 with surface carbon atoms having carbon-carbon bond angles of 120° whereas higher energy ultraviolet wavelengths are transmitted through the layers of the scroll to layer 4 where carbon atoms have carbon-carbon bond angles of 110°. All visible wavelengths are absorbed in layers 2-3.

[0070] Additional turns of the scroll form larger diameters and correspond to the potential for greater absorption of lower energy photons in the near to mid infrared range. This is reflected in the Kataura plot of FIG. 1 by extending the range of diameters of SWCNTs to cover larger diameters. This is advantageous as it presents the possibility of 24 hr energy absorption, i.e. including night time energy absorption in the absence of sunlight.

[0071] Some embodiments of the scroll include the graphene layers sitting on top of each other so that the edges are aligned. In other embodiments, the sheet is diagonally rolled at any chirality. The chirality of the rolled graphene sheet is a key consideration because chirality is an important factor in the absorption of different energy wavelengths. Therefore, scrolling diagonally at different chiral angles provides alternative embodiments of the structure for multi bandwidth solar absorption.

[0072] Solar Conversion

[0073] Each point along the surface of the carbon nano-scroll absorbs a different bandwidth of light. Effectively, each layer of the scroll is electrically connected in series. The layers are also in optical series such that layer 1 which absorbs in the infrared range of the solar spectrum is on top (facing the sun) and the other layers are in order so as to match ascending photon energy absorption. Hence, in the top layer 1 only the photons with the lowest energy are absorbed. Photons with a higher energy are transmitted to the layer 2 beneath, and so on. In this way the carbon scroll divides the broad solar spectrum into wavelength bands, each of which can be more efficiently absorbed by the individual layer than in a flat sheet of Graphene. In particular, photons with higher energy contribute with a larger photo-voltage than those with lower energy.

[0074] FIG. 10 illustrates how the photon absorption discussed in FIG. 9 can generate a thermoelectric effect around the scroll from the inner most layer 4 to the periphery layer 1. When the scroll absorbs photons, the electrons in the material heat up, and remain hot, while the underlying carbon lattice separating each layer remains cool. The electrons in the excited graphene cannot cool down easily because they couple poorly to the carbon lattice and so cannot transfer their heat to it. Therefore the heat has to move from electron to electron around the scrolled layers instead of being transmitted through them.

[0075] It is predicted that in carbon nano-scrolls that the number of secondary hot electrons will scale linearly with i) the number of absorbed photons, as well as with ii) the energy of individual photon's energy. Increasing the photon energy leads to an increased number of electron-electron scattering events during the relaxation cascade and thus a hotter carrier distribution. It is expected that a high energy photon of wavelength 400 nm would result in the production of 3 further electron-hole pairs, a 600 nm wavelength would result in the production of 2 further electron-hole pairs and a 800 nm wavelength would result in the production of 1 further electron-hole pair. As the scroll embodied in the present invention is designed to absorb higher energy photons at the core of the structure and is tight at the core, it is expected that this will setup a photo-cascade effect driving currents towards the periphery layer of the scroll.

[0076] The ability of the device to convert light energy into an electrical signal also allows the device to function as a photodetector with sensitivity across a range of light frequencies dependent on the dimensions of the scroll.

[0077] The present invention can be achieved with different topologies of scrolled graphene whilst maintaining tight curvature to cover all variations in carbon-carbon bond angles and carbon-carbon bond lengths for broadband light absorption. FIG. 11(a) illustrates a typical single coil scrolled topology that could be achieved with a single platelet of Graphene. FIG. 11(b) & FIG. 11(c) illustrate a dual coiled scroll achievable from a single platelet of graphene. FIG. 11(d) illustrates a double coiled ‘s’ shape scroll topology.

[0078] Preparing Graphene Nano-Scrolls

[0079] Graphene nano-scrolls can be made in any suitable way. Repeatable and reproducible methods of preparation will now be described.

[0080] It has been reported that Graphene samples that are only one layer thick, and are relatively defect and contaminant free are more likely to curl than those that do not meet these standards. Additionally, Graphene shows a tendency to scroll along long smooth edges compared to ragged or shorter edges. For these reasons it is advantageous that the Graphene used for the preparation of Graphene nano-scrolls is of well-defined shape and free from contamination and defects.

[0081] FIG. 6 illustrates the particular dimensions of a scrolled Graphene monolayer which are required to determine the lateral size of the graphene flakes. These dimensions include the inner diameter of the scroll (Di) which is fixed at 0.3 nm, the thickness of the graphene layer (W) which is fixed at 0.34 nm and the interlayer gap (S) which is fixed at 0.34 nm.

[0082] FIG. 12 illustrates a representation of typical single layer Graphene flakes prior to Scrolling showing the range of lateral dimensions required to produce a mechanically stable Graphene nano-scroll. The platelets illustrated have regular dimensions but can potentially have any shape.

[0083] The length (L) of the platelets can be approximated by using the formula

L=πn(Di+(W+S)(n−1)).

[0084] The outer diameter (Do) can be calculated using the formula

Do=2nW+2(n−1)S+Di.

[0085] FIG. 13 sets out in table form the variable parameters for the number of layers (n), the outer diameter (Do) of the scroll and the lateral length (L) of the Graphene flake. In order to achieve mechanical stability in a carbon nano-scroll the length of the Graphene platelets should be no less than 25 nm. From the table the optimised length of the scroll to encompass all carbon-carbon bond angle and length variations would be 29.4 nm, this would provide a tightly scrolled structure with 4 layers and an outer diameter of around 5 nm. In this scroll the layers would be stacked on top of each other as tight as possible with minimal space at the centre of the scroll. This would also provide for greater mechanical stability.

[0086] Importantly, due to the thermoelectric gradient which is possible to achieve in the scroll it is likely that the hot carrier multiplication effect could potentially drive currents in scrolls with more layers and larger outer diameters.

[0087] Top Down Approach: Chemical Exfoliation/Sonication and Microwave Irradiation

[0088] Individual manipulation of Graphene to form Graphene nano-scrolls has previously been achieved by Xu Xie et al., Nature Chemistry Vol. 7, September 2016, 730-736, whereby Isopropyl Alcohol solution was used to roll up monolayer Graphene predefined on SiO.sub.2/Si substrates. If tight scrolling could be achieved using this technique on graphene platelets <100 nm in lateral length then this would be ideal for individual production of Graphene nano-scrolls as characterisation could be carried out directly on the Graphene nano-scrolls in situ on the substrates. However, it is unlikely that this technique will produce tight scrolling but would result in the loose curling up of the graphene sheets as the Xu Xie et al paper stated that their Graphene nano-scrolls had hollow cores and 40 plus layers, implying that they were formed from significantly larger sheets. It is also believed that the ethanol used as a solvent in the experiments carried out by Viculis et al.: Science Vol. 299 28 Feb. 2003, 1361 could also be the reason for inducing scrolling in these Graphene pieces.

[0089] In order to achieve tight scrolling in the Graphene sheets we can look at the reason why placing Isopropyl Alcohol on one side of a graphene sheet induced scrolling. Similar to the original experiments by Bacon in which scrolled structures were found on the surface of graphite electrodes, it is believed that the Graphene scrolls up to reduce its surface area due to a chemical/temperature imbalance on either side of the Graphene sheet. To achieve tighter scrolls with this mechanism we can find a way to control it, that is, make the difference on either side of a Graphene sheet greater so that the graphene continuously tries to reduce its surface area. This can be achieved with a large temperature difference as has been demonstrated by Zheng at al., Adv. Matter. 2011, 23, 2460-2463, in which high quality Graphene nano-scrolls have been produced with microwave spark assistance in liquid nitrogen as the microwaves are not absorbed by the liquid nitrogen when passing through. Effectively, the graphene planes within the graphite structure expand with microwave absorption while simultaneously the 2 surfaces (top and bottom of graphite) in contact with the liquid nitrogen are being cooled. This causes the Graphene sheets to curl up into tighter scrolled structures. It is possible that this mechanism might be even more effective with bilayer Graphene samples as both Graphene planes would have an imbalance across their sides, one side facing the other Graphene layer while the other side exposed is to the liquid nitrogen.

[0090] Once in scrolled form within the liquid nitrogen it may then be possible to further reduce the temperature of the liquid nitrogen and then microwave the already formed carbon nano-scrolls on low power to stimulate further tightening. Liquid nitrogen does not absorb microwaves. In order to understand this we need to think of a carbon nano-scroll immersed in liquid nitrogen at −273 degrees Celcius (0 Kelvin) and then passing low microwaves through the Graphene. The internal layering of the Graphene scroll would cause the graphene to expand. The very outer and innermost layer of the Graphene nano-scroll will be simultaneously cooled and cause further scrolling inwards to reduce its surface exposure to the liquid nitrogen, resulting in a tighter scroll.

[0091] Based on the background previously discussed it is likely that a combination of chemical exfoliation/sonication and microwave irradiation techniques could be employed to achieve tight scrolling of Graphene sheets with small dimensions. The following two methods provide steps to achieve this using bilayer Graphene.

[0092] FIG. 14 illustrates the steps involved in method one to produce scrolls using chemical and microwave irradiation processes. Method one uses the microwave irradiation experiment from Zheng at al. to produce scrolls, this effectively is using short high powered microwaves to induce bilayer separation and simultaneous scrolling.

[0093] FIG. 15 illustrates the steps involved in method two to produce scrolls using chemical and microwave irradiation processes. Method two uses a stage two graphite intercalation compound (GIC2) to produce bilayer Graphene pieces that can be used in conjunction with the Viculus et al experiments to produce loosely scrolled Graphene nano-scrolls. The final step is to microwave the loosely scrolled structures in liquid nitrogen to tighten the scrolls. It should be noted that for both methods the ionic liquids used in intercalation are also able to absorb microwaves. It should also be noted that the Viculus experiments use potassium (KC24) to intercalate the graphite between every plane. KC48 is also a stage two graphite intercalation compound that could be considered, although thorough cleaning would be required prior to microwaving and characterisation.

[0094] Applications

[0095] Bulk Heteroiuction Organic Solar Inks

[0096] Organic solar cells are printable, portable, wearable, disposable, biocompatible and attachable to curved surfaces and utilise bulk heterojunctions as the active layer. These bulk heretojunction inks are based on blends of electron doners and electron accepting elements. FIG. 16 illustrates an ink blend of carbon nano-scrolls 5 as the electron donor and PCBM/polymers 6 as the electron acceptor which acts as the active layer in solution-processable thin film photovoltaics (TFPVs), that can be interfaced with carrier-selective contacts, for effective charge carrier separation 7. Carbon nano-scrolls offer a significant advantage over the use of SWNT's as the electron donor in bulk heterojunctions due to the large number of edge reaction sites at the ends of the scroll and along the outer layer.

[0097] Thin-film photovoltaic (TFPV) technologies focus on producing efficient solar cells with materials amenable to low-cost processing techniques. The present invention proposes to implement solar cells based on carbon nano-scrolls as an avenue toward solution processable photovoltaics that utilize components with broad spectral absorption and high carrier mobility, as well as thermal, chemical, and optical stability.

[0098] FIG. 17 illustrates the proposed cell configuration. The configuration of the present cells consists of coiled Graphene scrolls/PCBM-polymer blends as the active layer 10 sandwiched between electron 9 and hole 11 transport layers (ETL and HTL, respectively) and electrical contacts 8 and 12.

[0099] FIG. 18 illustrates a next generation solar cell architecture utilising double coiled Graphene scrolls as the active layer 12 sandwiched between two electrical contacts 13 and 15.