The embodiments discussed herein relate to a sheet-like structure with linear carbon chains and a fabrication method thereof, as well as electronic equipment using the sheet-like structure.
In recent years, miniaturization of semiconductor devices has been accelerated to improve the performance of electronic equipment used for central processing units (CPUs) of servers or personal computers. The rate of heat generation per unit area is increasing more and more and heat dissipation from electronic equipment is a serious problem. In general, a heat spreader made of a high thermal conductivity material (such as copper) is provided onto a semiconductor device with a thermal interface material (TIM) inserted between the heat spreader and the semiconductor device.
It is desired for thermal interface materials to have a property of good physical contact with the uneven and rough surfaces of the heat source and the heat spreader over a wide area, in addition to its own high thermal conductivity.
Under these circumstances, a thermally conductive sheet using linear carbon chains such as carbon nanotubes or carbon nanowires has been attracting attention for applications to TIMs. Carbon nanotubes have high flexibility and sufficient heat resistance, as well as high thermal conductivity (1500 W/m*K). These characteristics give carbon nanotubes potential in applications to heat dissipation materials.
As an application of CNTs, a thermal conductive sheet using bundles of CNTs grown oriented and embedded in a resin is proposed. See, for example, Japanese Patent Application Laid-open Publication No. 2009-164552 (Patent Document 1). A structure for deforming the end portions of CNTs for the purpose of improving the connectivity at the interface of a heat dissipation sheet using CNTs is also known. See, for example, Japanese Patent Application Laid-open Publication No. 2011-204749 (Patent Document 2). Another known technique is to perform surface treatment and coating on CNTs to provide mechanical strength to the CNTs. See, for example, Japanese Patent Application Laid-open Publication No. 2012-199335 (Patent Document 3).
The conventional thermal conductive sheets described above do not sufficiently make use of high thermal conductivity of CNTs. With the structure of bending the end portions of vertically oriented CNTs in a direction parallel to the sheet surface in Patent Document 2, the phase change material (i.e., the resin) remains on the sheet surface when the load applied during reflow is insufficient. On the other hand, with an excess amount of load, the CNT heat transfer sheet becomes thin and it cannot absorb warp or curved deformation of a heat source device. In either case, satisfactory heat transfer ability cannot be achieved.
In Patent Document 3, vertically oriented CNTs are coated with a coating material and adjacent CNTs are bound by the coating material. The apparent aspect ratio becomes smaller and the buckling stress is enhanced. However, freedom of deformation is limited in CNTs due to the binding of CNTs using coating treatment, and contact between the CNTs and the heat source device and between the CNTs and a heat sink (or a heat spreader) is disturbed. As the number of CNTs in contact with both the heat source device and the heat sink (or heat spreader) is restricted, the thermal conductivity is degraded and sufficient heat dissipation or heat transfer cannot be achieved.
Still another known technique is to immerse portions of CNTs into a resin containing an organic solvent and volatilize the organic solvent to make the CNT growing ends denser than the CNT root end. See, for example, PCT International Publication WO 2007/111107 (Patent Document 4).
According to an aspect of the embodiments, a sheet-like structure includes
According to another aspect of the embodiments, a sheet-like structure fabrication method includes
The object and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not restrictive to the invention as claimed.
Observing carbon nanotubes (CNTs) grown on a substrate, the length of carbon nanotubes varies at their growing ends (hereinafter called “tip ends”) and the carbon nanotubes are curly-entangled with each other at the tip ends. The inventors found a technical problem in that when compressively deforming a CNT heat transfer sheet by applying a load in the orienting direction of carbon nanotubes, anisotropic deformation occurs in the CNTs. The inventors also found that, under the load in the orienting direction, deformation occurs at the root ends of the carbon nanotubes dominantly, and the tip ends of the carbon nanotubes do not deform easily.
In order to achieve a high heat transfer rate in a thermal conductive sheet using carbon nanotubes, the following factors are useful. Namely, providing mechanical strength to the carbon nanotubes in the direction of their vertical orientation while maintaining freedom of deformation at each of the carbon nanotube; and increasing the area contacting a heat source by dominantly deforming the tip ends of the carbon nanotubes with varied length, compared with root ends.
To achieve a sheet-like structure with mechanical strength and improved thermal contacting property, the tip ends of the carbon nanotubes with variation in length are consolidated by a phase change material, while the root ends with a uniform length are aggregated outside the phase change material.
By inserting this sheet-like structure between a heat source and a heat sink (or heat spreader) such that the tip ends of the carbon nanotubes come into contact with the heat source, electronic equipment with high heat transfer rate is realized. When bonding the sheet-like structure, the phase change material melts and the tip ends of the carbon nanotubes come into close contact with the heat source along its uneven and rough surface. On the other hand, the aggregated root ends of the carbon nanotubes have a buckling stress greater than the tip ends and they can support the heat sink or heat spreader securely. The structure and a fabrication method of such a sheet-like structure using carbon nanotubes are described in more detail below.
The linear carbon chains 11 are, for example, vertically oriented single-walled or multi-walled carbon nanotubes. In the embodiment, the linear carbon chains 11 may be called “carbon nanotubes 11.” In place of coaxial nanotubes, carbon nanowires with a carbon chain inside the innermost tube or carbon nanorods may be used.
The growing ends, that is, the tip ends 14 of the carbon nanotubes 11 are embedded in a phase change material 15. The phase change material 15 undergoes reversible phase transition between liquid and solid states upon external stimulus such as heat or light. The phase change material 15 may be, example, a thermoplastic resin such as an acrylic resin, a polyethylene resin, a polystyrene resin, or polycarbonate, a B-stage resin, or a metal material.
The carbon nanotubes 11 form aggregates 13 at their root ends, each aggregate being formed of a bundle 12 of carbon nanotubes 11 of a certain area. The aggregates 13 may be, for example, a honeycomb-shaped network as represented in
The buckling stress of the aggregates 13 is greater than the of the CNT tip ends 14, as will be explained in more detail below. Accordingly, upon application of a load onto the sheet-like structure 10 with melting phase change material 15, the tip ends 14 of the carbon nanotubes 11 deform dominantly, following the uneven and/or rough surface shape of a heat source (not illustrated in
First, in
Any suitable substrate may be used as the substrate 51, including a semiconductor substrate such as silicon substrate, an alumina or sapphire substrate, a magnesium oxide (MgO) substrate, a glass substrate, and a substrate on which a thin film is deposited. For example, a silicon substrate with a silicon oxide film of about 300 nm thick thereon may be used.
The substrate 51 is removed after the carbon nanotubes 11 have grown. It is preferable for the substrate 51 to be stable in quality and property at a growth temperature of the carbon nanotubes 11. It is also desired for the substrate 51 that at least the CNT growing surface is made of a material easily separated from the carbon nanotubes or selectively etched leaving the carbon nanotubes 11 as they are.
To form carbon nanotubes 11, a catalyst layer (not illustrated) such as an iron (Fe) layer with a thickness of 2.5 nm is formed on the substrate 51 by sputtering. The pattern layout of the catalyst metal layer is determined depending on use of the carbon nanotubes 11. For the catalyst metal, cobalt (Co), nickel (Ni), gold (Au), silver (Ag), platinum (Pt) or an alloy containing at least one of these metals may be used in place of or together with Fe.
Carbon nanotubes 11 are grown on the catalyst metal layer over the substrate 51 by hot filament chemical vapor deposition (CVD), thermal CVD, remote plasma-enhanced CVD, or other suitable methods. The source gas is, for example, a mixture of acetylene and argon (at the ratio of partial pressures one to nine). As the carbon source, a hydrocarbon such as methane or ethylene, as well as alcohol such as ethanol or methanol, may be used other than acetylene. By controlling the total gas pressure in the film deposition chamber, hot filament temperature and growth time, single-walled or multi-walled carbon nanotubes with a desired length can be grown.
In the example of
Then in
Then in
Then in
Aggregates in this context represent gatherings of carbon nanotubes, which gatherings are distributed in a plane of the root ends with less localization or more regularity compared with the tip ends 14 of the carbon nanotubes 11 held in the phase change material 15.
The solvent for aggregating the carbon nanotubes 11 is not limited as long as it does not cause denaturation or dissolution of the phase change material 14 applied to the tip ends 14 of the carbon nanotubes 11. Other than water described above, alcohol, ketone-based solution, aromatic solvent, or a mixture thereof may be used. Instead of being immersed in the solvent, the sheet-like structure 10 of the carbon nanotubes 11 may be exposed to solvent vapor. Through dew condensation and drying, carbon nanotube aggregate structures can be acquired. The carbon nanotubes 11 are pushed aside by water drops generated by surface tension of water molecules or droplets generated by dew condensation of solvent vapor and they form aggregates 13.
The aggregates 13 are preferably honeycomb-shaped, but they are not limited to this example. Because the root ends of the carbon nanotubes 11 have little variation in length, aggregates 13 with a uniform height can be formed through self-assembled aggregation. The buckling stress of the aggregates 13 is greater than that of the tip ends 14.
Because the buckling stress of the aggregates 13 of the CNT bundles 12 is greater than that of the tip ends 14, the tip ends 14 touching the heat source 20 deform dominantly while following the surface shape of the heat source 20. Consequently, the sheet-like structure 10 can securely cover the hot spots on the heat source 20. On the opposite side, the aggregates 13 with a uniform height come into contact with the heat spreader 30 over the entire interface area.
For example, the sheet-like structure 10 is assembled into the electronic equipment 1 under the conditions of 200° C., 0.2 MPa and 10 minutes. The viscosity of the phase change material (e.g., thermoplastic resin) 15 used in the embodiment decreases to 10 Pa*s at 200° C. with increased fluidity. The melting phase change material 15 percolates through the carbon nanotubes 11 forming aggregates 13, and excess resin is pushed aside toward the periphery. Since the melting phase change material (thermoplastic resin) 15 with reduced viscosity has a low resistance against the load, the carbon nanotubes 11 receive almost all the load applied.
In estimating a buckling stress for the sheet-like structure 10 with aggregates 13, the estimation value is 0.04 MPa at the tip ends 14 of the carbon nanotubes 11, and 0.26 MPa at the root ends (i.e., at the aggregates 13). When carrying out the assembling at pressure of 0.2 MPa, the tip ends 14 of the carbon nanotubes 11 plastically deform along the bonded interface absorbing the variation in length of the carbon nanotubes 11. At this moment, the root ends of the carbon nanotubes 11 maintain elastic deformability and deform following the surface shape of the bonded interface. After the assembling, the electronic equipment is cooled still under the load, the phase change material (thermoplastic resin) 15 solidifies again.
Through this re-solidification, adhesiveness is exhibited at the interface between the sheet-like structure 10 and the heat source 20 and the interface between the sheet-like structure 10 and the heat spreader 30. The sheet-like structure 10 is fixed while maintaining the deformation of the carbon nanotubes 11 subjected during the assembling.
In the above-described embodiment, the phase change material (thermoplastic resin) 15 originally filling in between the tip ends 14 of the carbon nanotubes 11 is used to fill the gap between the carbon nanotubes 11 of the aggregates 13. However, a second phase change material may be used to fill the gap between carbon nanotubes of the aggregates 13 projecting from the first phase change material 15 for the assembling.
In either case, freedom of deformation of carbon nanotubes 11 is guaranteed at the tip ends 14, and the tip ends 14 can deform sufficiently to make tight contact with the heat source 20 regardless of the variation in length. At the root ends, the aggregates 13 have a buckling stress higher than the tip ends, which confers mechanical strength and satisfactory load tolerance to the sheet-like structure 10 as a whole.
In
In contrast, in
In the structure of
As indicated in
Concerning the thermal resistance, the conventional structure has 0.08 K/W thermal resistance. In contrast, the thermal resistance of the sheet-like structure of the embodiment is reduced to 0.05 K/W. It is understood that the heat transfer rate is improved in the structure of the embodiment.
Buckling stress σcr is expressed by Euler's formula (1).
σcr=Cπ2E/λ2 (1)
where C denotes terminal condition coefficient, E denotes Young's modulus, and λ denotes aspect ratio. With the sheet-like structure 10 fabricated in the embodiment, the Young's modulus E is 1000 GPa, and the terminal condition coefficient C is 0.25 (C=0.25).
The aspect ratio λ1 at the tip ends is 20 μm to 15 nm. Assuming that the area occupancy of the carbon nanotubes 111 is 3%, the buckling stress of the sheet-like structure 10 at the tip ends becomes 0.04 MPa from formula (1).
When an aggregate 13 is formed by 4,444 carbon nanotubes, the diameter or the width of the aggregate 13 is 1 μm at the end part. The aspect ratio λ2 of the aggregate 13 is estimated as 80 μm to 1 μm. From formula (1), the buckling stress of one aggregate 13 is 385 MPa. Assuming that the area occupancy of the aggregates 13 is 6.75×10−4%, the buckling stress of the sheet-like structure 10 at the root ends becomes 0.26 MPa.
For comparison, the buckling stress of untreated carbon nanotubes is estimated. The aspect ratio of the untreated carbon nanotubes is 100 μm to 15 nm, the area occupancy is 3%, the Young's modulus of the carbon nanotube is 1000 GPa, and the terminal condition coefficient C is 0.25. Under these conditions, the buckling stress of the untreated carbon nanotube becomes 0.0017 MPa.
From the foregoing examples, it is understood that the sheet-like structure 10 of the embodiment has a greater buckling stress at the root ends than at the tip ends. The tip ends 14 of the carbon nanotubes 11 are brought into contact with the heat source 20, and the aggregates 13 formed at the root ends are connected to the heat spreader 30. By selecting an appropriate level of bonding load, the contact area at the interface between the sheet-like structure 10 and the heat source 20 can be maximized, while maintaining the thickness of the sheet-like structure 10.
All examples and conditional language provided herein are intended for the pedagogical purpose of aiding the reader in understanding the invention and the concepts contributed by the inventor to further the art, and are not to be construed as limitations to such specifically recited examples and conditions, nor does the organization of such examples in the specification relate to a showing of superiority or inferiority of the invention. Although one or more embodiments of the present invention have been described in detail, it should be understood that the various changes, substitutions, and alterations could be made hereto without departing from the spirit and scope of the invention.
This application is a continuation application filed under 35 U.S.C. 111(a) claiming benefit of priority of PCT International Application No. PCT/JP2013/085155 filed Dec. 27, 2013 and designating the United States, which is incorporated herein by reference in its entirety.
Number | Date | Country | |
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Parent | PCT/JP2013/085155 | Dec 2013 | US |
Child | 15166696 | US |