Patent Application
20110265918
The present invention relates to a graphene-coated member that has a graphene film on a surface of a metallic base of a desired shape, and to a process for producing such graphene-coated members.
One of the notable physical characteristics of graphene is the carrier mobility as high as 200,000 cm2/Vs, in excess of those of metals and carbon nanotubes. Some of the other reported characteristics include:
(1) the ability to greatly suppress the characteristic 1/f noise of nano devices;
(2) negative refractive index; and
(3) the behavior of the electrons on graphene as if they had a zero mass.
There are also reports that graphene has a number of unique characteristics that fall between metals and semiconductors, attracting growing interests in the wide variety of graphene characteristics.
One known technique of forming graphene is the high-temperature vapor-deposition decomposition of gas molecules as described in Non-Patent Document 1.
Specifically, this literature describes a graphene forming method in which benzene gas is deposited on an iridium surface while high temperature is maintained.
However, because this method relies on the vapor deposition reaction of benzene molecules, only the surface of the iridium substrate can be coated. The high-temperature vapor-deposition decomposition of gas molecules also has the following problems.
The present invention has been completed under these circumstances, and an object of the invention is to provide a graphene-coated member of a novel structure that gets over the conventional problems, and a process for producing same.
A graphene-coated member according to a first invention is a graphene-coated member that includes a graphene film on a surface of a metallic base of a desired shape, wherein the base forms a solid solution with carbon, and wherein the graphene film is formed from solid-solution carbon precipitated at the base surface.
A second invention is a graphene-coated member according to the graphene-coated member of the first invention, wherein the base is free of the graphene film in a portion of the base surface.
A third invention is a process for producing the graphene-coated member of the first invention, the process including:
heating the carbon solid-solution metallic base of a desired shape in a vacuum at 600° C. to 950° C. (here and below, in 50° C. units) to precipitate the carbon at the metallic base surface and form graphene; and
subsequently rapidly cooling the metallic base to 400° C. or less at a cooling rate of 2×10° C./s to 20×10° C./s to integrate the resulting graphene film into the base.
A fourth invention is a process for producing the graphene-coated member of the second invention according to the process of the third invention, wherein the graphene-coated member is formed by heating only a desired graphene-uncoated portion to a temperature above the graphene-forming temperature during the graphene formation, so as to make the graphene-uncoated portion free of the graphene film.
According to the first and second inventions, the solid-solution carbon graphene film is formed in an orderly fashion without being affected by disturbance such as a flow of steam components as might occur in the high-temperature vapor-deposition decomposition. The inventions can therefore provide a member, conventionally unavailable, whose base is coated with a homogeneous graphene film.
The graphene coating can impart new functions to the member, including, for example, oxidation resistance, low-gas absorbability, low-gas releasability, and low secondary electron releasability.
The third invention enables reliable and effective production of such members. The invention also enables creation of not only monolayer graphene but multilayer, for example, bilayer graphene. This is possible with a temperature setting immediately below the temperature that enables the creation of monolayer graphene, and in the vicinity of the bulk solid-solution limit temperature.
The high-temperature-range temperature that forms monolayer graphene, and multilayer, for example, bilayer graphene can be found by high-temperature in situ measurement using surface electron spectroscopy, Monolayer graphene can be created with good reproducibility by a heat treatment that incorporates surface analysis functions.
The monolayer graphene coating can stabilize the surface, and can impart functions, particularly such as oxidation resistance, low-gas adsorbability, low-gas releasability, and low secondary electron releasability to the surface of metals, such as palladium, platinum, iridium, rhodium, nickel, and cobalt, and alloys thereof, forming a solid solution with carbon.
Further, a detached monolayer graphene coating can be restored by performing the heat treatment again.
Further, the monolayer graphene can be extracted by the wet etching of the base metal.
Further, because a region free of the graphene film can be formed anywhere as desired according to the fourth invention, the various characteristics of the graphene film to be exploited can be controlled by the shape of the graphene film.
Any metallic base is usable in the present invention as long as it can form a solid solution with carbon, and an alloy of more than one metal element can be used as the metallic base. Specifically, with the use of metal elements (such as nickel, platinum, palladium, rhodium, iridium, and cobalt) that have prominent carbon solubility in a metal element-carbon binary phase diagram, the solid-solution carbon can reversibly precipitate out to the surface and dissolve into the bulk in thermal equilibrium in response to temperature.
Thus, controlling the vacuum heat-treatment temperature enables the surface coverage by graphene and the number of graphene layers to be controlled. Further, the graphene coating layer can be completely removed by maintaining high temperature, as required.
It is known that the surface monolayer graphene phase can stably exist at high temperatures. For example, a graphene coating layer can be fixed by rapid cooling after a solid solution of carbon in nickel or platinum which is subjected to a high-temperature heat treatment to precipitate monolayer graphene at the surface, as will be described in Example below. It can thus be said by analogy that the same advantage also can be obtained by the substitution using cobalt, palladium, rhodium, sod iridium having similar equilibrium binary phase diagrams, or using alloys of these metals.
The precipitation heat temperature ranges from 600° C. to 950° C., preferably 700° C. to 900° C., more preferably 750° C. to 850° C.
Above the upper limit temperature 950° C., the surface graphene coating layer disappears, and a clean surface can be formed. In the absence of a graphene coating, reactions such as oxidation and adsorption may occur in an atmospheric environment.
Below the lower limit temperature 600° C., the diffusion rate of the solid-solution carbon is low, and a sufficiently long heat-treatment is needed. Further, depending on carbon concentration, the growth of multilayer graphene dominates over monolayer graphene growth.
The rate of rapid cooling is 2×10° C./s to 20×10° C./s, preferably 5×10° C./s to 20×10° C./s, more preferably 10×10° C./s to 20×10° C./s.
No problem is caused above the upper limit; however, such high rates require the use of an apparatus for rapidly cooling the sample, and restrict the sample thickness.
Below the lower limit, the formation of multilayer graphene coating may dominate.
The temperature after the rapid cooling is preferably from ordinary temperature (generally in a range of from 15° C. to 25° C.) to 400° C.
Above the upper limit, the growth of multilayer graphene may occur.
No problem is caused below the lower limit; however, cooling below room temperature additionally requires a sample cooling apparatus.
It was found that graphene formation does not occur in a specific portion heated and not rapidly cooled during the rapid cooling process.
This heat effect can be utilized to avoid graphene formation in particular areas of the target member, or to form a graphene film only in a specific portion, depending on intended use.
Specifically, a product that does not have graphene formation in a desired portion of the base can be produced by, for example, heating a specific portion of the base in a vacuum chamber using an external laser, or by heating a specific portion of the base with a heater installed at a specific part of a base supporting structure.
The present invention also enables formation of multilayer graphene, for example, such as bilayer graphene, in addition to monolayer graphene.
This is possible with a temperature setting immediately below the temperature that enables the creation of monolayer graphene, and in the vicinity of the bulk solid-solution limit temperature.
The high-temperature-range temperature that forms monolayer graphene, and multilayer, for example, bilayer graphene can be found by high-temperature in situ measurement using surface electron spectroscopy. Monolayer graphene can be created with good reproducibility by a heat treatment that incorporates surface analysis functions.
The monolayer graphene coating can stabilize the surface, and can impart functions, particularly such as oxidation resistance, low-gas adsorbability, low-gas releasability, and low secondary electron releasability to the surface of metals, such as palladium, platinum, iridium, rhodium, nickel, and cobalt, and alloys thereof, forming a solid solution with carbon.
Further, a detached monolayer graphene coating can be restored by performing the heat treatment again.
Example of the present invention is described below.
(1) The nickel, cobalt, palladium, rhodium, platinum, iridium metals that can form a solid solution with carbon, and alloys containing these elements as the primary components are doped with carbon to a predetermined solid-solution concentration using an apparatus (system) illustrated in
Specifically, bases of the metals presented in Table 1 below (width, 10 mm; length, 10 mm; thickness, 0.1 mm) were used as metal samples.
Specifically, the bases presented in Table 1 below were subjected to a vacuum solid-phase diffusion method under the conditions of Table 1.
The contact between the high-purity carbon powder and a metal substrate sample is very important in a vacuum solid-phase diffusion method. Thus, it is recommended to use a high-purity graphite fine powder, and a graphite vessel for the high-purity graphite fine powder. Containers configured from materials that do not involve impurity mixing even at high temperatures (for example, high-melting-point metals such as BN, zirconia, and molybdenum) also can be used.
In a vacuum solid-phase diffusion method, the carbon concentration cart be obtained by estimating the solid-solution concentration as an equilibrium carbon solid-solution concentration from the heat-treatment temperature. The equilibrium carbon solubility can be found from the binary phase diagram.
In this Example, the solid-solution carbon concentration was calculated as an equilibrium concentration derived from the binary phase diagram. The results are presented in Table 1.
The formed carbon solid-solution base was used to form a graphene coating film (see
The figure represents a flowchart of synthesizing a graphene coating layer on a carbon solid-solution metal substrate surface.
First, a metal substrate molded into a shape of a thin sheet (the base containing the carbon in a solid-solution state, obtained as above) was surface-smoothed, washed, and optionally further molded. In this Example, the surface was smoothed by mechanical polishing, and mirror-finished by buffing using a 0.05 micron-diameter alumina particle suspension. Ultrasonic washing using ethanol and acetone was performed for washing.
By the heat treatment I of the carbon solid-solution metal substrate material using an ultrahigh vacuum apparatus after the smoothing and washing surface treatment, a monolayer or bilayer graphene coating can be created by surface precipitation. A sample heater designed to provide a sufficiently uniform sample temperature is used.
The state of the graphene monolayer or bilayer is checked by the in situ measurement of the carbon concentration on a sample surface. The in situ measurement is performed using a surface-sensitive analytical technique such as Auger electron spectrometry, X-ray photoelectric spectrometry.
The sample is rapidly cooled to fix the surface graphene-coated state. (heat treatment II)
Specific conditions are as presented in Table 2.
The sample temperature can be monitored using a thermocouple or infrared thermometer.
The surface smoothing for mirror-finishing can be performed by techniques such as electrolytic polishing, electro chemical buffing, and buffing.
Carbon was dissolved in a polycrystalline, high-purity platinum thin plate to form a solid solution, and the sample was maintained at high temperature (1,373 K, 10 min) after surface smoothing to sufficiently dissolve the carbon in the bulk. The sample was then maintained at a predetermined temperature (1,223 K), and rapidly cooled (cooling rate of up to 100 K/s) after forming a monolayer graphene coating on the surface. The surface was then measured with a scanning Auger electron microscope.
The SEM image appears raised at the central portion. This is a region uncoated with graphene, as can be seen in the Auger image (carbon: C KLL, platinum: Pt NOO). The whole surface is coated with the monolayer graphene. The whole surface can be coated with the monolayer graphene by setting the temperature uniform.
The graphene uncoated region can be formed by creating local temperature nonuniformity (higher temperature region). A particular region can be maintained at a relatively high temperature by localized irradiation of, for example, an electron beam or a laser beam, and a clean surface is formed in such regions.
A bilayer graphene coating can be formed preferentially by controlling the maintained temperature of heat treatment I.
The same result was also obtained for carbon solid-solution nickel samples.
The metallic member coated with monolayer or bilayer graphene according to the present invention has a number of potential applications, as follows.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2008-261875 | Oct 2008 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2009/067516 | 10/7/2009 | WO | 00 | 6/9/2011 |
