JP2564589B2 - Method for forming carbon film on solid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Application of the Invention" The present invention has an optical bandwidth of 1.0 eV or more, particularly 1.5 to 5.5 eV.
By coating the carbon-containing or carbon-based coating on the solid film-forming surface temporarily attached to the tape-shaped carrier, it is possible to obtain a reinforcing material for the surface of these solids or a protective material against mechanical stress. Regarding the complex.

“Prior Art” Regarding the coating of carbon film, a patent application “Composite having carbon coating and method for producing the same” filed by the present inventor (Japanese Patent Application No. 56-146936, filed September 17, 1981) is known. Has been. However, these are formed on a tape-shaped carrier whose formation temperature is 150 ° C. or lower, preferably +100 to −100 ° C., and are substantially cooled, and the surface to be formed is mainly composed of an organic resin having heat resistance at these temperatures. No example is given of the case of forming into a solid.

"Conventional problem" In the conventional example, it is said that the carbon film can be obtained only at a high temperature of 200 to 1000 ° C, and depending on the condition of the carbon film, the surface of the carbon film is heated to about 150 ° C at room temperature. )
Alternatively, there is no description that a sufficient hardness can be obtained even by a manufacturing method at a temperature lower than that.

"Means for Solving the Problem" The present invention coats carbon or a coating film containing carbon as a main component on a solid temporarily applied on a tape-shaped carrier, and improves mechanical strength such as abrasion resistance on the surface. It is intended to reinforce, and to introduce hydrocarbon gas such as ethylene and methane into the atmosphere in which plasma is generated by direct current or high frequency, especially high frequency electric field with positive direct current bias added to the solid side, and decompose it. C-C bond is formed by the above, and as a result, non-translucent conductive or poorly conductive carbon such as graphite is not formed, but the optical energy bandwidth (Eg) required by the manufacturing conditions is 1.0. It is characterized by the formation of insulative carbon similar to diamond with eV or higher, preferably 1.5 to 5.5 eV. Further, the carbon of the present invention has a Vickers hardness of 2000 Kg / mm ² or more, and preferably 4500 Kg / mm ² or more,
Ideally, carbon having a diamond-like hardness of 6500 Kg / mm ² (amorphous) or semi-amorphous (semi-amorphous) structure having microcrystallinity of 5 to 200Å or this carbon. Carbon mainly composed of so-called carbon (hereinafter referred to as “main”) in which hydrogen and halogen elements are contained in an amount of 25 atomic% or less or III- or V-valent impurities are 5 atomic% or less, and nitrogen is added in a concentration of N / C ≦ 0.05. In the present invention, a composite body in which (hereinafter simply referred to as carbon) is provided on a solid is provided.

The present invention further provides a solid surface on which this carbon is formed.
0 ° C or less, preferably -100 to 100 ° C
Another feature is that it was formed experimentally at a temperature as low as 500 to 1500 ° C as compared with the method, and that it is possible to coat even an organic resin film having no heat resistance.

In the present invention, boron, which is a trivalent impurity, is added to this carbon at a concentration of 0.1 to 5 atomic%, P-type carbon is provided, and phosphorus and nitrogen, which are V-valent impurities, are similarly added to 0.1 to 5 atomic%.
Another feature is that the carbon on the upper surface of the substrate is made conductive by adding N-type carbon at a concentration of 5 atomic%.

Further, the present invention uses an organic resin substrate such as PET (polyethylene terephthalate), PES, PMMA, Teflon, epoxy, polyimide or the like, or a material that can be used as a metal mesh carrier or a tape carrier such as paper as a substrate. Then, in particular, the solid is temporarily attached or arranged on the tape-shaped carrier, and the carbon film is not formed on the surface of the solid on the tape-shaped carrier while moving in a roll to roll (RTR) system. It is what

INDUSTRIAL APPLICABILITY The present invention is particularly effective for an electric component which is a wear resistant material and requires slip resistance on its surface.

The method for producing the composite used in the present invention will be described below with reference to the drawings.

Example 1 FIG. 1 shows an outline of an RTR-type plasma CVD apparatus for forming a carbon or a film containing carbon as a main component of the present invention.

In the drawing, in the doping system (10), hydrogen as a carrier gas is supplied from (11), a hydrocarbon gas as a reactive gas such as methane and ethylene is supplied from (12), and diborane as a trivalent impurity (diluted with hydrogen to 1%). ) (13), V-valent impurity ammonia or foshin (diluted to 1% with hydrogen) is introduced from (14) through valve (28) and flow meter (29) into reaction system (30) through nozzle (25). To be done. Before reaching the nozzle, it is effective to add microwave energy (26) to excite the reactive gas to activate it in advance.

In the reaction system (30), it moves from the first roll (4) to the second roll (5) via the auxiliary rolls (6) and (7).

This auxiliary roll (7) gives a certain tension (tension) so that the tape-shaped carrier does not have slack,
It is equipped with a spring (27). Between the auxiliary rolls, a first electrode (2), a tape-shaped carrier (1) having a surface to be formed,
It has a second electrode (3), and electric energy is applied between the pair of electrodes (2) and (3) from the high-frequency electrode (15), the matching transformer (16), and the DC bias power supply (17) to generate plasma. (40) occurs. The exhaust system (20) exhausts unnecessary gas through the pressure control valve (25), the turbo molecular pump (22), and the rotary pump (23).

These reactive gases are 0.01 to 0.3t in the reaction space (40).
Orr is, for example, 0.1 torr, and energy of 0.1 to 5 KW can be added by electromagnetic energy due to high frequency. DC bias is
-200 ~ 600V (substantially -400 ~ + 400V) on the surface to be formed
Add. This is because when the DC bias is zero, the self-bias has -200 V (the second electrode is at the ground level). The reactive gas was, for example, methane: hydrogen = 1: 1. The first electrode has cooling means (9),
Enter the cooling liquid from (8) and discharge it to (8 ').
Keep at -100 ° C. Thus, the carbon having an amorphous structure or a microcrystalline structure having a Vickers hardness of 2000 kg / mm ² or more on the surface to be formed by plasma and having a large number of C—C bonds having a thermal conductivity of 2.5 W / cm deg or more is formed. Was generated. Further, this electromagnetic energy was supplied from 50 W to 1 KW, and plasma energy of 0.03 to 3 W / cm ² was applied per unit area. When the plasma density was high, or when the reactive gas had been excited in advance by microwaves, carbon having a semi-amorphous structure having microcrystallinity of 5 to 200 ° could be generated. Deposition rate is 100-1000A / min, especially surface temperature is -50-1
When the temperature is 50 ° C and the DC bias is +100 to 300V, the film forming rate is 100 to 200A / min (when using methane and no microwave), 500 to 1000A / min (when using methane and microwave) Or using microwaves with ethylene). All of these have Vickers hardness
Only the condition of 2000Kg / mm ² or more is acceptable.

Of course, if graphite is the main component (50% or more), it is very soft, black and completely different from the present invention.

The reaction product is formed as a film on the upper surface of the substrate (1) cooled by the cooling medium (9). The impurities after the reaction are exhausted from the exhaust system (20) via a turbo molecular pump and a rotary pump. The reaction system is maintained at 0.001 to 10 torr, typically 0.01 to 0.5 torr, and a plasma state (40) is generated in the reaction system by microwave (26) and high-frequency energy (15). Especially when the excitation source is 1GHz or more,
For example, at a frequency of 2.45 GHz, hydrogen is separated from C—H bonds, and the frequency source is 0.1 to 50 MHz, for example, 13.56 MHz.
At the frequency of, C-C bond, C = C bond are decomposed to form C-C bond or -C-C- bond, and carbon unpaired bonds are made to collide with each other to covalently bond, The structure may have a stable diamond structure locally.

Thus, solids such as semiconductors (silicon wafers), ceramics, magnetic materials, metals or electric parts are temporarily attached or arranged on a tape-shaped substrate, and carbon is contained on the surface of the solid, in particular 25% by mole or less of hydrogen is contained in the carbon. It was possible to form a film containing carbon as a main component or carbon having a P, I or N conductivity type.

Example 2 FIG. 2 is an example of a carbon-coated solid composite obtained by the production method of Example 1. That is, a solid electric component (45) (the shape of this solid is arbitrarily determined by the material to be coated) and the like are temporarily attached (46) on the tape-shaped carrier. This is the RTR in Figure 1.
In this method, carbon (50) is provided on this upper surface in a thickness of 0.1 to 3 μm. After further coating these carbon films (50), these solids (45) are tape-shaped carriers (41).
The pieces were separated and separated as shown in FIG. 2 (C-2).

Examples of such electric parts include a magnetic head and a thermal head. Also, as other solids,
Nuts, gears, especially organic resin frames, gears are raised.

[Example 3] In the present invention, the roll shown in Fig. 1 is turned upside down and the solid (45) is placed on the upper surface of the tape-shaped carrier as shown in Figs. 3 (A) and 3 (B). Flow-coating a carbon film onto a solid is also effective. In that case, the step of temporarily attaching to a solid tape-shaped carrier is not always necessary.

Also in this case, it is effective to coat the carbon film on the back surface of the semiconductor wafer (45), for example, a silicon wafer, as an example of the solid. Then, this carbon film has a thermal conductivity of 2.5 W / cm deg or more, typically 4.0 to 6.0 W / cm.
Since it has deg, it is possible to uniformly dissipate local heat generation such as the power transistor portion in the semiconductor integrated circuit. When formed on the back surface of the wafer (upper side in FIG. 3B), the carbon film was formed to a thickness of 0.5 to 5 μm, for example, 1 μm. It is preferable that this thickness is as large as possible without impairing the adhesion.

After this coating, a probe test of the wafer is performed, and in order to make each IC chip, through a scribe and break process, the structure in which each semiconductor chip is coated with a carbon film on the back surface is die bonded and wire bonded and completed. Let

Example 4 In this example, a carbon film was formed on the upper surface of a silicon wafer on which a semiconductor integrated circuit was previously formed, as shown in FIG. 3 (A). In this case, a carbon film was formed on the upper surface of the silicon wafer as shown in FIG. 3 (A) and then separated from the tape-shaped carrier to obtain FIG. 3 (B). Then, carbon only in the bonding pad portion was removed by ashing with oxygen plasma.

That is, after forming the aluminum pad and the wiring on the upper surface of the silicon wafer, the entire surface of them is filled with silicon oxide.
It was formed to a thickness of 3-1 μm. Further, a carbon film of the present invention was formed thereon with a thickness of 0.1 to 1 μm, for example 0.3 μm. Further, a selective removal resist was selectively coated, and the carbon film was removed only by the bonding pad portion by plasma etching with an oxide gas. Further thereafter, the silicon oxide underneath was removed by using the resist and the carbon film as a mask to expose the aluminum pad. Further, the photoresist was removed. Then, a carbon film was formed as a final coat film on the upper surface of the IC chip.

By doing so, the local heating could be spread more quickly to the whole by a power transistor or the like.

In addition, blocking against sodium ions became possible. Of course, this carbon film may have another silicon oxide film or the like left between aluminum wirings or on the carbon film.

"Effect" The method of the present invention is extremely effective for an electric member in which a magnetic material such as a magnetic head is rubbed on its surface and run. In particular, this carbon film has a thermal conductivity of 2.5 W / cm deg or more, typically 4.0 to 6.0 W / cm deg and 60 W / cm deg of diamond.
Since it is close to, the heat generated by high-speed tape carrier running can be uniformly dissipated to the whole, and local temperature rise and accompanying characteristic deterioration of the magnetic head can be prevented, resulting in wear resistance, high thermal conductivity, and carbon film. Many properties such as unique high smoothness are used effectively in combination.

As is clear from the above description, the present invention constitutes an organic resin or a glass compounded therewith, a magnetic material, a metal or a ceramic, a semiconductor or a composite thereof,
The surface of these solids is coated with carbon or a film containing carbon as a main component. The application of this composite is immeasurable as seen in many other examples. In particular, while this carbon can be formed at a low temperature of 150 ° C or lower, its hardness and adhesion to a substrate are extremely excellent. The feature is that

The ceramic in the present invention is alumina, zirconia,
Oxide superconducting materials known as carborundum and YBCO are effective. Further, the magnetic substance may be a rare earth magnet such as samarium or cobalt, an amorphous magnetic substance, iron oxide or an anisotropically shaped magnetic substance obtained by coating nickel oxide, chromium or the like.

[Brief description of drawings]

FIG. 1 shows an outline of a roll-to-roll type manufacturing apparatus for forming carbon or a coating film containing carbon as a main component on the surface to be formed of the present invention. 2 and 3 show an embodiment of the composite of the present invention.

Claims (2)

(57) [Claims] 1. A step of temporarily attaching or arranging a solid on the surface of a tape-shaped carrier, and moving the solid and the tape-shaped carrier from a first roll to a second roll while the tape-shaped carrier is provided between the rolls. Direct current or high-frequency voltage is applied between the first electrode arranged on the back side of the tape and the second electrode arranged on the surface side of the tape-shaped carrier facing the electrode to generate plasma. Then, it is generated and decomposed with a hydrocarbon gas or an additive gas in addition to this to form a carbon film or a film containing an additive-added carbon as a main component on the tape-shaped carrier and the solid. A method for forming a carbon film on a solid, which comprises the steps of: and thereafter separating the solid from the tape-shaped carrier. 2. The method for forming a carbon film on a solid according to claim 1, wherein the solid is an electric component.