EP3129518A1

EP3129518A1 - Process for producing a graphene film

Info

Publication number: EP3129518A1
Application number: EP15714579.8A
Authority: EP
Inventors: Jean Dijon; Anastasia TYURNINA
Original assignee: Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Current assignee: Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date: 2014-03-07
Filing date: 2015-03-06
Publication date: 2017-02-15
Also published as: US10337102B2; KR20160130485A; FR3018282A1; US20170016111A1; WO2015132537A1

Abstract

A process for producing a graphene film, comprising the following successive steps: - placing a substrate (1) and a solid carbon source (2) in a reaction chamber (3), which has a gas inlet (4), - heating the solid carbon source (2) by passing a current through said source, under a gas stream, the gas being free of hydrocarbon, so as to convert at least one part of the solid carbon source (2) into a graphene film on the substrate (1).

Description

Process for producing a graphene film

Technical field of the invention

The invention relates to a method of producing a graphene film and also relates to a device configured to produce a graphene film.

State of the art

Thanks to its exceptional properties, graphene has generated a growing interest in the scientific and industrial sectors. Graphene is indeed a promising candidate for many applications: energy storage, elaboration of transparent electrodes, super capacitors, etc. One of the current challenges is to produce good quality graphene, ie a continuous film with low defect densities and uniform thickness, at low cost, reproducibly and on a large scale. Of the methods for forming graphene films, chemical vapor deposition (CVD) is one of the most promising techniques. CVD processes are very attractive because they make it possible to obtain thin carbonaceous layers of high quality. The process of forming graphene on a substrate by CVD takes place in two stages. Firstly, pyrolysis is carried out on a gas containing carbon atoms, generally it is a hydrocarbon. Pyrolysis dissociates the gas and forms carbon radicals. In a second step, the graphene film is formed on the substrate from the carbon radicals. Many hydrocarbons can be used to synthesize graphene. The article by K. Wassei et al. (Small 8 (2012), No. 9, 1415-1422) describes, for example, the use of methane, ethane or propane. The substrate is copper, it has a thickness of 25μιη. The temperature used during the deposition process is 1000 ° C and the pressures are between 250 and 1000mTorr.

Methane is most often used because it allows to form graphene films of better qualities.

The article "A review of chemical vapor deposition of graphene on copper" (J. Mater Chem 21 (201 1), 3324-3334) lists various parameter values, described in the literature, for synthesizing graphene by CVD on copper substrates with methane. Most copper foils have a thickness in the order of 25-50 μm. The temperatures are generally of the order of 1000 ° C.

Graphene can also be deposited on ruthenium crystals Ru (00001) and iridium Ir (1 1 1) using as a carbon source of ethylene gas (New Journal of Physics 1 1 (2009) 063046), or on platinum substrates 200 μm thick from methane, the substrate being heated to above 1000 ° C (Nature Communications 3: 699, DOI 10.1038).

Most CVD deposits are made at high temperatures (1000-1100 ° C) to dissociate hydrocarbons and form graphene.

Nevertheless, such temperatures remain incompatible with processes using metal thin films as the substrate. Indeed, when the thin metallic layers are heated at high temperature, dewetting phenomena may appear. The phenomenon is all the more marked as the thickness of metal is fine. Recently, a study has shown that the graphene synthesis temperature on a nickel substrate 25μιη thick, in the presence of C ₂ H ₂ , could to be reduced to 700 ° C using an infra-red lamp (Carbon, 50 (2012), pages 668-673). The pressure is 10 ^"2 Torr However, graphene film thus obtained is not uniform. It is composed of several graphene films overlapping in places.

Object of the invention

The object of the invention is to overcome the drawbacks of the prior art and, in particular, to propose a production method for depositing a graphene film on thin metallic layers.

This object is approached by the appended claims.

Brief description of the drawings

Other advantages and features will emerge more clearly from the following description of particular embodiments of the invention given by way of non-limiting example and represented in the accompanying drawings, in which:

- Figures 1 to 4 show, schematically, in section, the device of the method of producing a graphene film according to different embodiments,

FIG. 5 represents a photograph obtained by transmission electron microscopy of a graphene film produced according to the production method; FIG. 6 represents a Raman spectrum of 1 ^st and 2 ^nd orders of the graphene film of FIG. . Description of a preferred embodiment of the invention

The process for producing a graphene film comprises the following successive steps:

placing a substrate 1 and a carbon source 2 in a reaction chamber 3, provided with a gas inlet 4,

heating the carbon source 2, under a stream of gas, so as to convert at least a portion of the carbon source 2 into a graphene film on the substrate.

The carbon source 2 is a source of solid carbon.

The gas is hydrocarbon-free.

Preferably, the carbon source 2 is formed of at least one carbon filament. The filament is disposed between the substrate and the gas inlet.

Filament means an element of fine and elongated shape, such as a wire. The filament is electrically conductive.

As shown in FIG. 1, the carbon source 2 can comprise several filaments. The filaments advantageously form a plane parallel to the surface of the substrate.

They are, advantageously, both all arranged at the same distance from the surface of the substrate and parallel to each other, so as to form a homogeneous deposit. In Figure 2, the filaments are shown in section.

Preferably, the filaments are equidistant from one another.

According to a preferred embodiment, the filaments are crisscrossed and parallel to the surface of the substrate so as to form a grid. The surface of the substrate is covered more evenly by the filaments. The grid preferably defines a plane parallel to the surface of the substrate. Preferably, the heating of the carbon source 2 is achieved by passing a current in said source. It could also be heated by induction heating, by laser.

Preferably, the filaments are heated by Joule effect. When heated, the carbon filaments form carbon radicals, necessary for the formation of graphene. The amount of carbon radicals formed is relatively small, which makes it possible to form a graphene film in a controlled manner. The carbon source 2 is a solid element comprising at least 98% by mass of carbon.

The carbon source 2 is, preferably, graphite. By "graphite" is meant that the carbon source comprises at least 98% by weight of graphite, and preferably at least 99.5% by mass of graphite. According to another embodiment, the carbon source 2 may be further formed of carbon nanotubes.

In conventional CVD processes, the filaments are often made of tungsten. However, the carbon of the hydrocarbons reacts with the tungsten, forming parasitic tungsten carbide, which contaminates the reaction chamber.

The use of carbon filaments, and in particular graphite, avoids this pollution.

JP2003206196 also discloses a CVD device not using tungsten. The filaments are carbon based. The CVD device is used to obtain high quality diamonds on silicon wafers.

The filaments are produced from a resin and a powder of carbonaceous particles. The filaments are heated to a temperature of 2050 ° C under a methanol-charged atmosphere. The methanol is then decomposed, carbon radicals are produced and diamond particles are formed. The temperature of the substrate is 900 ° C. The temperature of the substrate is nevertheless still too high. The process, even if it is adapted to form diamond particles, does not make it possible to form graphene on thin layers. Unlike conventional methods, the process for forming the graphene film does not require the use of high temperatures because the carbon radicals come from the graphite filaments and not the gas.

The high temperature of the process is limited to the carbon source.

During the process, and more particularly, during the heating step, the temperature of the substrate is less than or equal to 800 ° C, and preferably less than or equal to 700 ° C.

The method enables graphene to be deposited on substrates that can not be used with conventional CVD processes: substrates with thin metal layers, substrates that deteriorate at high temperatures.

The gas introduced into the reaction chamber 3 via the gas inlet 4, to form the gas flow, is hydrocarbon-free.

More particularly, the gas is devoid of organic carbon molecules. By carbon organic molecule is meant an organic molecule having a carbon chain comprising at least one carbon atom. Alcohols and hydrocarbons are, for example, organic carbon molecules.

By no means is meant that the gas contains less than a few parts per million (ppm) of hydrocarbons and / or carbon species.

Preferably, the gas used is dihydrogen H ₂ .

By "East of dihydrogen" is meant that the gas comprises at least 90% by volume of dihydrogen, and preferably at least 98% of dihydrogen. According to another alternative, a mixture of H ₂ + H ₂ O with a low water concentration could be used. The presence of dihydrogen may allow, in the graphene growth process, to partially etch the carbonaceous deposit and / or to help remove any impurities present on the surface of the substrate.

The increase in temperature would create hydrogen radicals favoring the formation and / or growth of the graphene film.

Advantageously, heating a carbon filament in the presence of dihydrogen makes it possible to create graphene of very good quality. The hydrogen pressure in the reaction chamber 3 is between 10 Torr and 10 Torr, and preferably between 6 Torr and 8 Torr.

The use of such a pressure makes it possible to minimize the amount of carbon radicals formed. Graphene grows slowly and few nucleation sites are formed. Since there are few nucleation sites, the graphene monolayers formed have larger sizes and the graphene film is more homogeneous.

A rise in pressure, up to ambient pressure, for example, would speed up the growth process but would also lead to the formation of several graphene monolayers that can be superimposed on each other.

The closer the pressure is to ambient pressure, the faster the growth of graphene and the more difficult it is to control the number of graphene layers deposited and the uniformity of the film. In the process, the substrate is heated to a maximum temperature of 800 ° C, and preferably at a maximum temperature of 700 ° C.

The maximum temperature is maintained for a period ranging from 5 minutes to 5 hours. Preferably, the duration of the temperature step is between 5 minutes and 180 minutes, and even more preferably between 60 minutes and 120 minutes. The duration of the bearing makes it possible to control the size of the graphene grains composing the continuous film of graphene which can vary from 1 -2 nm to several tens of micrometers. Whatever the duration of the plateau, it has been observed that the graphene film is always continuous, uniform without defects.

According to one embodiment, the substrate is heated solely by the carbon source: the substrate 1 is heated solely by virtue of the heat radiated by the filaments. The carbon source 2 forms a first source of heat for the substrate 1.

When the filaments are heated, they radiate a lot of heat and help to increase the surface temperature of the substrate.

The filaments can be heated at temperatures up to 1700-1800 ° C: the temperature of the surface of the substrate 1, where the formation of graphene takes place, can rise to temperatures up to 700 ° C. By surface of the substrate is meant a thickness of several tens of nanometers from the free face of the substrate, exposed to the carbon source, towards the interior of the substrate, perpendicular to the free face of the substrate.

In general, the temperature of the substrate 1, at the surface and at depth, is lower than the temperature of the carbon source 2 during the heating step.

The temperature of the substrate is, for example, less than 400 ° C., or even lower than 800 ° C., at the temperature of the carbon source 2.

The substrate does not need to be heated to very high temperature, which makes it possible to use a wide range of equipment for heating the device. The reaction chamber is less polluted and many materials can be used as a substrate.

According to another embodiment, the substrate 1 is heated both by the filaments and both via a second heat source 6. The second heat source 6 is disposed under the substrate, at the same time. opposite of the carbon source 2, which is disposed above the substrate 1. The second heat source 6 may be, for example, by a radio frequency power supply (RF) connected to the support 5 of the substrate 1. The support 5 of the substrate 1 is also called a sample holder.

The second heat source 6 may be a heating plate or the reaction chamber may be arranged in an oven. Those skilled in the art will be able to choose any second heat source 6 adapted to the process.

Increasing the heat emitted by the filaments makes it possible to reduce the temperature at which the substrate 1 is heated by the second heat source while maintaining the temperature of the surface of the substrate 1 constant.

The heat radiated by the filaments can be increased by increasing the power used to heat the filaments. The power of the power unit can be increased up to 1000W, which reduces the temperature at which the substrate 1 is heated by the second heat source 6 to a value below 450 ° C.

By modulating the calories emitted by the carbon source and the calories emitted by the second heat source, it is possible to control the temperature of the substrate surface within a predefined temperature range.

The diameter of the filaments can also be increased to intensify the heat emitted by irradiation.

The filaments have a diameter ranging from 0.2 mm to 0.8 mm, and preferably a diameter of 0.5 mm ± 1 mm.

These dimensions make it possible both to sufficiently heat the substrate 1, by irradiation, and at the same time to limit the degassing of parasitic species during the evacuation of the reaction chamber 3.

Advantageously, a vacuuming step is performed. The evacuation step is, for example, carried out at 5 × 10 ^-6 Torr. Degassing occurs at the carbon source when the filaments are energized. Substrate 1 can be contaminated by stray carbon particles leading to the formation of an amorphous carbon film. A decrease in the surface of the carbon source makes it possible to limit this phenomenon.

It has been observed that for filaments having a diameter of less than or equal to 0.4 mm, the parasitic carbon contamination is negligible. The number of filaments used can also be decreased. The carbon source 2 is disposed above the surface of the substrate 1, at a distance of between 0.5 cm and 2.5 cm, and preferably between 0.8 cm and 1.2 cm. Preferably, the carbon source is at a distance greater than or equal to the distance between the filaments to have a uniform heating. The distance between the filaments and the surface of the substrate 1 can also be configured to play on the life of the radical species.

In another embodiment, the substrate may be cooled to stabilize the temperature or to make a graphene film with small grains.

According to a particular embodiment, as represented in FIG. 2, a metal gate 7 is disposed between the substrate 1 and the carbon source 2. The gate 7 makes it possible to reduce the number of parasitic particles reaching the sample during degassing. The parasitic carbon species, arriving at the level of the grid 7, will be absorbed by the metal of the grid.

The metal grid 7 is, for example, nickel. The dissolution of carbon in nickel is relatively high: a nickel grid forms an effective trap for carbonaceous particles.

The metal grid 7 also makes it possible to control the rate of formation of the graphene film. By playing on the dimensions of the openings of the grid 7, it It is possible to increase or decrease the amount of carbon radicals arriving at the substrate 1.

According to another embodiment, the grid 7 could be formed of an optically transparent material, such as for example quartz.

According to another particular embodiment, as shown in Figure 3, a shutter 8 is disposed between the substrate 1 and the carbon source 2. The shutter 8 is produced from an optically transparent material. It is for example, made of quartz.

The shutter 8 is closed during the rise in temperature. Even if the shutter 8 is closed, the heat emitted by the filaments is transmitted to the surface of the substrate 1 by irradiation through the shutter transparent to the wavelength of the irradiation.

The shutter 8 makes it possible to heat the sample, while avoiding the deposit of parasitic carbon on the sample during the pumping and the rise in temperature. The shutter 8 is open when the maximum temperature is reached and during the temperature plateau.

At this time, the kinetic energy of the carbon species will be sufficient to form a single layer of well-structured graphene.

According to another embodiment, the shutter 8 is disposed between the substrate 1 and the carbon source 2 and is closed during the rise in temperature and during the temperature step. It is kept closed when the maximum temperature is reached. The shutter 8 is held in the same position throughout the process. The shutter 8 may be a full screen. The formation speed of the graphene film is thus reduced and the film is more homogeneous. The use of a gate 7 and / or a shutter 8 have a filtering role and allow precise control of the amount of carbon species arriving on the substrate 1, thus improving the quality of the graphene film. The various embodiments described above can be carried out alone or in combination with each other.

Preferably, the substrate 1 is formed of a solid material covered with a thin metal layer. Preferably, the metal is a transition metal, such as Cu, Pt, Fe, Ni, Au, Ir, Ru, etc.

Advantageously, the transition metals have a catalytic effect during the formation of graphene.

The thin metal layer has a thickness between 100 nm and 400 nm, and preferably between 100 nm and 300 nm.

Preferably, the thin layer is a transition metal selected from platinum, copper, titanium or nickel. It may also be an alloy of these metals, such as, for example, a platinum alloy containing from 0.5% to 10% iridium. Even more preferentially:

the solid material is made of silicon,

the thin metallic layer is platinum,

- A chromium layer, having a thickness of 20 nm ± 5 nm, is disposed between the silicon and the thin metal layer.

The solid silicon material may be formed of a silicon film coated with a thin layer of SiO ₂ silicon oxide.

Platinum has several advantages for uniform graphene film growth. Platinum has a very high melting temperature (1768 ° C) and a relatively low coefficient of thermal expansion (less than 9 ym / mK). During the process of forming the graphene film, and in particular during heat treatment, the platinum thin film will be less subject to mechanical stress than another metal layer. Graphene film will have fewer defects.

In addition, the platinum is very difficult, or not at all oxidized, even during climbs / descents in temperature. The roughness of the surface of the platinum thin layer remains low.

The use of platinum also makes it possible, subsequently, to easily transfer the graphene film to another medium, for example by electrochemistry.

Once the graphene film is removed, the substrate can be used for another deposit. The presence of the chromium layer allows better adhesion between platinum and silicon.

The process is not limited to thin substrates, and especially wafers. According to other embodiments, the substrate could be a solid substrate, for example a platinum strip.

The device configured to produce a graphene film on a substrate 1 comprises:

a reaction chamber 3 provided with a carbon source 2 and a support 5, said support 5 being intended to maintain a substrate 1,

a gas inlet 4 configured to form a flow of gas directed from the gas inlet 4 to the carbon source 2,

a heating device configured to heat the solid carbon source; the carbon source is a source of solid carbon. The gas flowing into the reaction chamber is hydrocarbon-free. The gas arriving in the reaction chamber is devoid of organic carbon molecules. The carbon source 2 is preferably formed of at least one filament. Preferably, the carbon source 2 comprises several filaments parallel to the surface of the substrate.

Preferably, the gas flow is perpendicular to the surface of the substrate 1 and the plane formed by the carbon filaments.

Preferably, the carbon source 2 is graphite.

The carbon source is disposed in the reaction chamber so as to be above the surface of the substrate, at a distance of between 0.5 cm and 1.5 cm, and preferably between 0.8 cm and 1.2 cm.

Since a tiny portion of the carbon source 2 is used for each graphene deposit, the carbon source 2 has a relatively long life.

The process will now be described by means of the following example, given, of course, by way of illustration and not limitation. Figure 4 shows schematically and in section the device configured to develop a graphene film. For a better visualization, the various elements of the device are not to scale.

The device makes it possible to grow graphene by CVD at low temperature. The reaction chamber 3 is a quartz bell. The lower part of the reaction chamber 3 comprises the sample holder 5.

The reaction chamber 3 can be arranged in a closed chamber 9.

The walls between the inside of the enclosure and the outside of the enclosure 9 are double walls 10 in which a cooling liquid circulates.

The chamber 9 is provided with a gas inlet 1 1 and a gas outlet 12. The device comprises a pumping system for putting the reaction chamber under vacuum. The pumping system is arranged, for example, at the gas inlet 1 1 of the chamber 9. The reaction chamber 3 can be heated by means of heating coils 13.

The coils are arranged against the outer walls of the reaction chamber 3.

Thermal screens 14 may also be arranged outside the reaction chamber 3, between the heating coils 13 and the inside of the chamber 1 1, to thermally isolate the reaction chamber 3 of the chamber 1 1 .

Thermal screens 10 are thermal insulators. The sample holder 5 may also be heated by heating coils 13 '.

In this example, the filaments are graphite. They have a length of 1 10mm long and a diameter of 0.5mm.

The filaments are 1 cm from the substrate 1. They are parallel to the surface of the substrate 1. The space between each filament is 1 cm.

The filaments cover the substrate on a surface of 10cmx10cm.

The sample holder 5 is made of silicon. The substrate 1 is formed of a stack comprising successively:

- a silicon wafer 0.5mm thick,

a thin layer of SiO ₂ covering the silicon wafer, the thin layer of SiO ₂ has a thickness of 500 nm,

a thin chromium layer 20 nm thick,

a thin layer made of platinum having a thickness of 200 nm. The platinum thin film was deposited by electron beam evaporation on the silicon wafer. The platinum thin film thus produced is polycrystalline.

The reaction chamber 3 is, initially, cleaned with an oxygen plasma so as to remove any carbon parasitic element. The filaments are then placed in the reaction chamber.

The filaments are heated by a power supply delivering a power of 800W, under a stream of hydrogen, which allows them to be cleaned and degassed.

The substrate 1 is placed in the reaction chamber 3, on the sample holder 5.

The sample holder 5 is heated to 700 ° C. The rise in temperature from room temperature to 700 ° C lasts 10 minutes.

The hydrogen pressure is 7 Torr for a flow of 100cm ³ / min (or 100 sccm for standard cubic centimeter per minute).

The temperature plateau is maintained for a period ranging from 5 minutes to 60 minutes, this stage allows the synthesis of graphene.

Then the reaction chamber 3 is cooled to room temperature.

The pressure of hydrogen can be identical during the rise in temperature and during the temperature step.

Alternatively, a first pressure can be used during the rise in temperature and a second pressure can be used during the temperature step.

The Raman spectrum and the image obtained by Transmission Electron Microscopy, made on the obtained graphene sample, and represented respectively in FIGS. 5 and 6, confirm that the graphene sample is in the form of a single graphene film (or SLG for Single Layer Graphene). The film is uniform with very few defects.

The process, described above, is carried out at a sufficiently high temperature to activate the hydrogen, but low enough to avoid both dewetting phenomena. In addition, with such a temperature, a small amount of carbon radicals is generated, promoting the formation of a homogeneous and continuous graphene film.

The thermal gradient allows activation of the carbon while ensuring a good physicochemical behavior of the graphene layer.

The method makes it possible to form a graphene film formed of a carbon monolayer at low temperature on thin metal films. In particular, the size of graphite crystallites is continuously monitored. Continuous graphene films without holes are obtained irrespective of the size of the crystallites.

Graphene films are particularly interesting for many applications, and particularly for microelectronics, spin electronics, or for applications requiring transparent conductive films.

Claims

claims

1. A process for producing a graphene film comprising the following successive steps:

placing a substrate (1) and a source of solid carbon (2) in a reaction chamber (3) provided with a gas inlet (4),

- heating the solid carbon source (2), by passing a current in said source, under a gas flow, the gas being free of hydrocarbon, so as to convert at least a portion of the solid carbon source ( 2) in a graphene film on the substrate (1).

2. Method according to claim 1, characterized in that during the heating step, the temperature of the substrate (1) is less than or equal to 800 ° C, and preferably less than or equal to 700 ° C.

3. Method according to one of claims 1 and 2, characterized in that the gas is dihydrogen.

4. Method according to any one of claims 1 to 3, characterized in that the substrate is heated only by the carbon source.

5. Method according to any one of claims 1 to 4, characterized in that the solid carbon source (2) is formed of at least one filament, the filament being disposed between the substrate (1) and the inlet of gas (4).

6. Method according to claim 5, characterized in that the solid carbon source (2) comprises a plurality of filaments forming a plane parallel to the surface of the substrate.

7. Method according to any one of claims 1 to 6, characterized in that the solid carbon source (2) is graphite.

8. Method according to any one of claims 1 to 7, characterized in that the solid carbon source (2) is disposed above the surface of the substrate (1) at a distance of between 0.5 cm and 2 cm. , 5cm, and preferably between 0.8cm and 1.2cm.

9. Method according to any one of claims 1 to 8, characterized in that the substrate (1) is formed of a solid material covered with a thin metal layer, said thin metal layer having a thickness between 100nm and 400nm .

10. The method of claim 9, characterized in that the thin metal layer is platinum, copper, titanium or nickel or formed of a platinum alloy containing from 0.5% to 10% iridium.

11. Process according to claims 9 and 10, characterized in that:

the solid material is made of silicon,

the thin metallic layer is platinum,

12. Method according to any one of claims 1 to 1 1, characterized in that a grid (7) is disposed between the substrate (1) and the solid carbon source (2).

13. The method of claim 12, characterized in that the gate (7) is nickel.

14. Method according to any one of claims 1 to 13, characterized in that a shutter (8) is disposed between the substrate (1) and the source of solid carbon (2), the shutter (8) being closed during the rise in temperature and the shutter (8) being open during the temperature step.

15. Method according to any one of claims 1 to 13, characterized in that a shutter (8) is disposed between the substrate (1) and the solid carbon source (2), the shutter (8) being closed during the rise in temperature and during the temperature step.

A device configured to develop a graphene film on a substrate (1) comprising:

a reaction chamber (3) provided with:

o a solid carbon source (2), the solid carbon source

(2) being formed of at least one filament, and

a support (5), said support (5) being intended to hold a substrate (1),

a gas inlet (4) configured to form a flow of gas directed from the gas inlet (4) to the solid carbon source (2), the gas being free of hydrocarbon,

a heating device configured to heat the solid carbon source.

17. Device according to claim 16, characterized in that the gas is dihydrogen.

18. Device according to one of claims 16 to 17, characterized in that the solid carbon source (2) is graphite.