Method of producing a carbon-based film

Abstract: Carbonaceous films are coated on a surface by chemical vapor reaction. In advance of the deposition of carbonaceous film, a silicon nitride film is coated on the surface to prevent interdiffusion between the carbonaceous film and the underlying surface.

Description: BACKGROUND OF THE INVENTION The present invention relates to an improved plasma processing method and products thereof. More particularly, but not exclusively, it relates to a method of adhering a protective film of carbonaceous material to comparatively soft substrates in order to provide a transparent electrically insulating coating thereon. Hard, thin films of diamondlike carbon have been deposited on substrates in a number of ways. By "diamondlike carbon" is meant carbon with exceptional hardness, e.g. which can neither be cut with a razor blade nor scratched by rubbing with steel wool. The chemical bonding of such diamondlike carbon appears to be dominated by sp³ tetrahedral diamondlike bonding as opposed to the sp² triagonal bonding of graphite. Diamondlike carbon films may or may not give evidence of crystallinity under x-ray analysis. EP-A-0175980 describes a diamond like carbon coating in which a fluorocarbon gas may optionally be present during the carbon deposition. EP-A-0166708 describes deposition of a carbon layer over an intermediate layer, which may be a noble metal or alternatively a carbide, nitride, oxide or other ceramic. Japanese Patent Application No. Sho 56-146936 describes a process in which carbon deposition is carried out with the deposited carbon material being subjected to attack by accelerated ions at the same time so that soft portions of the deposited material are selectively removed to leave comparatively hard material. This technique is excellent for increasing the hardness of the carbon film thus deposited. The carbon being deposited, however, tends to penetrate into the underlying substrate. Figs. 1(A) and 1(B) of the accompanying drawings show an example. A carbon film 2 was deposited on a Si substrate 3 by chemical vapor reaction. The substrate was then subjected to Auger analysis in order to investigate the distribution of carbon atoms and Si atoms in the depth direction and it was found that a mixture of silicon and carbon was formed at the interface between the substrate 3 and the carbon film 2 as shown in Fig. 1(B). The silicon carbon mixture is relatively soft and tends to increase the likelihood of the carbon film coming off the underlying substrate, particularly when the carbon film is relatively thick. Furthermore, when fluorine is desired to be introduced into carbon films in order to control their transparency and/or resistivity, the underlying surface to be coated has traditionally been exposed to caustic fluorine gas during the deposition process and may consequently be damaged. SUMMARY OF THE INVENTION The present invention proposes that a nitride film, such as a silicon nitride film for example, be deposited on the underlying surface to be coated in advance of the deposition of a carbonaceous film which includes fluorine. The provisions first of a silicon nitride film functions to protect the underlying surface from undesirable caustic action of fluorine during deposition of the carbonaceous film. The use of a fluorine compound gas together with a carbonaceous gas in the deposition of a carbonaceous film by a CVD process is provided in one embodiment. This is particularly desirable when for example the external surfaces of the windows of a vehicle are required to be coated with abrasion-proof hard carbonaceous films. In accordance with another aspect of the present invention, carbonaceous films can be selectively deposited on a predetermined surface portion by pretreatment of the predetermined portion. The pretreatment is to form a number of fine scratches on the surface portion. Diamond can then be selectively grown on the scratched surface. Scratching can be performed, for example, by coating areas of the substrate that are not to be treated with a mask, then dipping the substrate in a fluid in which there are dispersed hard fine particles such as diamond particles or carborundum particles, and applying ultrasonic vibrations to the dispersion. Further features of the invention are set forth in the appended claims and, together with the features abovementioned, will become clearly understood from consideration of the following detailed description of exemplary embodiments that is given with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figs. 1(A) and 1(B) are graphical showings of the depth of penetration of carbon atoms into an underlying silicon substrate in a prior art deposition process; Fig. 2 is a schematic cross-sectional diagram showing a plasma CVD apparatus in accordance with one embodiment of the present invention; Fig. 3 is a graphical diagram showing the penetration of carbon atoms into an underlying silicon substrate in accordance with the present invention; Figs 4(A) and 4(B) are cross-sectional views showing a printing drum for a copying machine which has been coated with a carbonaceous protective film in accordance with the present invention; Figs. 5(A) and 5(B) are vertical and horizontal cross-sectional views showing a window glass for motor cars which has been coated with a carbonaceous protective film in accordance with the present invention; and Fig. 5(C) is a schematic cross-sectional view showing a modification of the embodiment shown in Figs. 5(A) and 5(B); Fig. 6 is a schematic cross-sectional diagram showing a microwave assisted CVD apparatus in accordance with one embodiment of the present invention; and Figs. 7(A) through 7(C) are cross-sectional views showing a process in accordance with the present invention for forming a carbonaceous film coating on a tool bit. DETAILED DESCRIPTION OF THE EMBODIMENTS Referring now to Fig. 2, a chemical vapor deposition apparatus is illustrated. The apparatus comprises a vacuum chamber 7 defining a deposition space therein, an evacuation system 25 comprising a rotary pump 23 and a turbo molecular pump 22 which are connected to the chamber 7 through a valve 21, a gas supply system 30 comprising six gas feeding lines, each being provided with a flow meter 29 and a valve 28 connected to the reaction chamber 7, a pair of mesh electrodes 3-1 and 3-2 made of aluminium and located at upper and lower positions inside of the deposition space, a power supply 40 for supplying energy to the mesh electrodes 3-1 and 3-2, a plurality of substrate holders 20 for holding substrates 1, the holders 20 being connected to the chamber 7 through capacitors 19, a plurality of A1 mesh electrodes 50 (13-n, 13'-n) interposed between adjacent substrates and outside of the first and last substrates, and a bias voltage applying means 17 for applying an AC voltage between adjacent ones of the electrodes 50. The reaction chamber 7 is provided with a gate valve 9 through which substrates to be coated may be disposed in the chamber. The energy supply 40 comprises a first power source 15-1 which supplies an AC voltage to the mesh electrode 3-1 through a matching device 16-1 comprising an LCR circuit, a second power source 15-2 which supplies an AC voltage to the mesh electrode 3-2 through a matching device 16-2 comprising an LCR circuit, and a phase adjuster 26 connected between the first and second power sources 15-1 and 15-2. Both the first and second power sources are grounded at terminals 5-1 and 5-2. The bias applying device 17 is provided with first and second AC voltage sources 17-1 and 17-2, which supply AC voltages between adjacent electrodes 13-n and 13'-n. One terminal of each of the voltage sources 17-1 and 17-2 is grounded at 5-3. In operation, after evacuating the chamber 7, a reactive gas is introduced into the deposition space 8 at a pressure of from 0.133 to 133 Pa (from 0.001 to 1 Torr) in order to deposit silicon nitride film on the substrate. For example, the reactive gas may consist of a silane such as disilane (Si₂H₆) and NH₃ in the ratio of from 1:10 to 10:1, preferably from 1:10 to 3:10 and may be introduced so that the total pressure in the reaction chamber 7 becomes from 0.133 to 133 Pa (from 0.001 Torr to 1.0 Torr), e.g. 6.65 Pa (0.05 Torr). The temperature in the deposition space is no higher than 150°C, e.g. room temperature without heating. High frequency alternating voltages of from 1 MHz to 100 MHz, e.g. 13.56 MHz, are applied to the mesh electrodes 3-1 and 3-2 from the first and second power sources 15-1 and 15-2. The phase difference between these high frequency voltages is adjusted to be 180° +- 30° by means of the phase adjuster 26. Alternatively, the frequency of one of these voltages may be adjusted to be an integral multiple of that of the other. By virtue of the injection of such high frequency electric energy into the plasma chamber, the reactive gas is converted into a plasma state and silicon nitride (Si₃N 4-x ; 0<_x<4) is deposited onto the substrates. The thickness of the deposited films may be from 0.01 to 0.1 micrometers. Optionally, at the same time, an AC voltage may be applied between adjacent electrodes 13-n and 13'-n in order to induce an electric field normal to each substrate. The frequency of the AC voltage between the electrodes 13-n and 13-n' is selected to be in the range of from 10 Hz to 100 kHz, e.g., 50 Hz. At such comparatively low frequencies, plasma ions can follow the electric field and bombard the substrate surfaces on which carbon deposition is being carried out. This low frequency AC voltage causes a self-bias voltage of from -50V to -600V. Next, after the completion of the silicon nitride deposition, a carbon compound gas is introduced into the deposition space 8 at a pressure of from 0.133 to 133 Pa (from 0.001 to 1 Torr). For example, the carbon compound gas consists of C₂F₆ and C₂H₄ in the ratio of from 1:4 to 4:1, e.g. 1:1, and may be introduced so that the pressure in the reaction chamber 7 becomes 66.5 Pa (0.5 Torr). The transparency and resistivity of the carbon material that is deposited can be controlled by changing the amount of fluorine contained in the carbon material through adjustment of the introduction rate of C₂F₆ relative to C₂H₄. The temperature in the deposition space is no higher than 150°C. High frequency alternating voltages of from 1 MHz to 100 MHz, e.g. 13.56 Mhz, are applied to the mesh electrodes 3-1 and 3-2 from the first and second power sources 15-1 and 15-2. The phase difference between these high frequency voltages is adjusted to be 180° +_ 30° by means of the phase adjuster 26. By virtue of the injection of such high frequency electric energy into the plasma chamber, the carbon compound gas is converted into a plasma state and carbon deposition onto the substrates occurs. The deposition rate is from 10 to 100 nm/min (100 to 1000Å/min). The thickness of the deposited carbon films may be from 0.1 to 8 micrometers on flat surfaces and from 1 to 3 micrometers on uneven surfaces. At the same time, an AC voltage is applied between adjacent electrodes 13-n and 13'-n in order to induce an electric field normal to each substrate. The frequency of the AC voltage between the electrodes 13-n and 13-n' is selected to be in the range of from 10 Hz to 100 kHz, e.g., 50 Hz. At such comparatively low frequencies, plasma ions can follow the electric field and bombard the substrate surfaces on which carbon deposition is being carried out. As a result, softer deposited materials are removed so that the hardness of the carbon material that remains is relatively high, e.g. 700 to 5000 kg/mm². The resistivity of the carbon is for example from 1 x 10⁸ to 5 x 10¹⁵ ohm meter (1 x 10⁶ to 5 x 10¹³ ohm centimetre) typically from 1 x 10⁹ to 1 x 10¹³ ohm meter (1 x 10⁷ to 1 x 10¹¹ ohm centimetre). The optical energy band gap is no narrower than 1.0 eV, typically 1.5 to 5.5 eV. The carbon material is called diamond like carbon. The carbon material may include hydrogen at 30 atom% or less. It includes fluorine, for example at 0.3 to 10 atom%. Other examples of carbon compound gases are ethylene, methane, acetylene, and carbon fluorides such as C₂F₆ and C₃F₈, CHF₃ and CH₂F₂. Auger analysis was performed in order to investigate the composition in the thickness direction of silicon nitrogen and carbonaceous films deposited in accordance with the present invention. As a result, a graphical diagram shown in Fig. 3 was obtained. As may be seen from the diagram, carbon atoms have substantially not penetrated into the underlying silicon substrate by virtue of the first deposited silicon nitride film. Carbonaceous films containing fluorine in accordance with the present invention were coated on several substrates. Figs. 4(A) and 4(B) are horizontal and vertical cross-sectional views showing a printing drum for a copying machine. Numeral 1 designates an A1 drum coated with an OPC (organic photosensitive conductor) film. A silicon nitride film 45-1 was deposited on the external surface of the drum to a thickness of from 0.01 to 0.1 micrometer in the same manner as explained above. A carbonaceous film containing fluorine 45-2 was next deposited on the silicon nitride film 45-1 also in the same manner as explained above. Optionally, 0.3 atom % to 10 atom % of boron or nitrogen may be introduced into the carbonaceous film by making use of B₂H₆ or NH₃ during carbon deposition. Also, instead of a uniform carbonaceous film containing fluorine, a dual film can be deposited by first deposition of 10 to 200nm (100 to 2000Å) by use of ethylene alone, followed by deposition by use of a reactive gas comprising carbon and fluorine as described in the above. Figs. 5(A) and 5(B) are horizontal and vertical cross sectional views showing a curved glass or plastic pane 1 to be fitted in the front window of a motor car, the pane 1 being coated with a silicon nitride film 45-1 and a carbonaceous film containing fluorine 45-2 of from 0.1 to 8 micrometers in accordance with the present invention. The whole surface of the glass pane 1 would be coated with carbon film in accordance with the present invention. This film can be coated on only one side of the pane. In this case, the panes treated in the apparatus shown in Fig. 2 are disposed in parallel with each other in order to make pairs as illustrated in Fig. 5C. The deposition chamber may be cleaned after deposition by introducing an etchant gas such as oxygen or NF₃ instead of the reactive gas. Unnecessary carbonaceous films and nitrogen films can be removed by inputting electric energy in the same manner as the deposition process to preform plasma etching. It is possible to coat only a selected surface portion of a substrate. In this case, the selected surface is given a number of scratches which attract species. Referring to Fig. 6 and to Figs. 7(A) to 7(C), a method of selective deposition of diamond film (which may also be employed with carbonaceous films containing fluorine according to the present invention) will be illustrated. A microwave assisted CVD apparatus comprising a vacuum chamber 56, a vacuum pump 59, a substrate holder 63 for supporting thereon a substrate to be coated, the holder being provided with a temperature control device therein (not shown), a substrate location adjustment mechanism 62, a microwave generator 58 connected to the vacuum chamber 56 through an insulator 66 and a quartz window 65, Helmholtz coils 57 surrounding the end of the vacuum chamber 56, and a gas feeding system 61. Steel tool bits 54, for example, are placed on the holder 63. The distance between the surfaces of the bits 54 and the window 65 is adjusted to be 150-250 mm by means of the adjustment mechanism 62. After evacuation, a reactive gas consisting of Si₂H₆ and HN₃ is introduced into the vacuum chamber at from 100 Pa to 10⁻² Pa. The strength of the magnetic field at the surface to be coated is adjusted to 0.22T (2.2 K Gauss). Microwave energy is then injected into the chamber from the generator 58 at 50W to deposit silicon nitride films 55 on the bits to a thickness of from 0.01 micrometer to 0.1 micrometer. The temperature is maintained at a temperature not lower than 350°C, preferably not lower than 800°C. Higher adhesivity can be expected at a higher temperature. After completing the silicon nitride deposition, the bits are removed from the chamber and coated with a mask 60 made from a photoresist, the mask covering only selected surface portions as shown in Fig. 6(B). The bits are then dipped in an alcohol in which diamond powder comprising fine particles of 1 micrometer average diameter is dispersed. Ultrasonic vibrations are applied to the dispersion in order to form a number of scratches on the surface portions of the bits that are free of the masks. The masks are then removed and the bits are disposed again in the chamber. Then, a vaporized alcohol is inputted into the chamber at 10² to 10⁻² Pa, e.g. 10 Pa, and decomposed by microwave energy in the same manner in order to grow diamond film to a thickness of 3 micrometers at 90nm/min (900 Å/min) on the scratched surfaces as shown in Fig. 6(C). The alcohol is for example ethyl alcohol, methyl alcohol or propyl alcohol. The hardness of the diamond film can be expected to be not lower than 5000 kg/mm². The deviation in film thickness is within +_10% in a circular area of 100 mm diameter. In accordance with experiments using ethyl alcohol introduced at 40 SCCM together with hydrogen (100 SCCM) in order that the total pressure in the reaction chamber was 13 Pa, it was confirmed that the carbon structure is diamond structure by Raman spectra having a sharp peak at 133,100m⁻¹(1331 cm⁻¹). The diamond film did not come off the underlying surface even after undergoing reliability tests involving thermal shock between -10°C and 150°C. The experiment was repeated using a reactive gas consisting of methyl aluminium and ammonia in order to deposit an aluminium nitride film. The nitride film then was subjected to thermal annealing at about 400°C. While several embodiments have been specifically described by way of example, it is to be appreciated that the present invention is not limited to the particular examples described and that modifications and variations can be made without departing from the scope of the invention as defined by the appended claims. For example, the present invention is useful when front, side or rear windows or side mirrors are coated with carbon protective films. Although in the above embodiment a silicon nitride film is formed underlying the carbonaceous film containing fluorine, other nitride films can be used instead. For example, titanium nitride film can be made from aluminium nitride, titanium nitride or boron nitride.

Claims: A method of depositing a carbonaceous film containing Fluorine onto a substrate, in which a nitride film is first deposited onto the substrate. A method according to claim 1 comprising the steps of: disposing said substrate in a reaction chamber; introducing a first reactive gas comprising nitrogen and capable of producing a nitride by chemical vapor reaction; inputting energy to said first reactive gas in order to deposit said nitride film on said substrate through said chemical vapor reaction; introducing a second reactive gas comprising Carbon and Fluorine; and inputting energy to said second reactive gas in order to deposit said carbonaceous film containing fluorine on said nitride film. The method of claim 2 wherein said first reactive gas comprises nitrogen and silicon and is capable of producing silicon nitride through chemical vapor reaction. The method of claim 3 wherein said first reactive gas consists of a silane and ammonia. The method of claim 4 wherein said silane is disilane. The method of any preceding claim wherein said second reactive gas consists of a hydrocarbon and a carbon fluoride. The method of any preceding claim wherein the thickness of said nitride film is from 0.01 micrometer to 0.1 micrometer. The method of any preceding claim wherein said carbonaceous film is composed of a diamondlike carbon film. The method of any preceding claim wherein said substrate is a transparent pane for windows of a vehicle. The method of any preceding claim wherein said substrate is of glass. The method of any preceding claim, wherein the carbonaceous film contains Nitrogen. The method of claim 11, appended to claim 2, in which the second reactive gas further comprises Nitrogen. The method of claim 6 wherein said carbon fluoride is C₂F₆, C₃F₈, CHF₃, or CH₂F₂. The method of any preceding claim wherein said nitride is silicon nitride, titanium nitride, aluminium nitride or boron nitride. The method according to any preceding claim further comprising, after the deposition of the nitride film and before the deposition of the carbonaceous film, the steps of: coating a mask on said substrate; scratching the surface of said substrate wherein it has not been covered with said mask; and removing said mask. The method of any preceding claim wherein said carbonaceous film is grown at a temperature not lower than 350°C. The method of claim 15 wherein said scratching step is carried out by dipping said substrate in a fluid in which a number of hard particles are dispersed and applying ultrasonic vibration. The method of claim 17 wherein said hard particles are diamond particles. An article having a protective film coated on a surface to provide abrasion-proof properties to said surface, said protective film comprising a nitride film directly deposited on said surface and a carbonaceous film deposited on said nitride film and containing fluorine. The article of claim 19 wherein said nitride film is composed of silicon nitride. The article of claim 19 or claim 20 wherein said carbonaceous film further contains Nitrogen. The article of any of claims 19 or 21 in which said nitride is titanium nitride, aluminium nitride or boron nitride.

Inventors: HAYASHI SHIGENORI, ISHIDA NORIYA, ITOU KENJI, KADONO MASAYA, KOJIMA MASAHIRO, SASAKI MARI, TAKEYAMA JUNICHI, YAMAZAKI SHUNPEI, HAYASHI, SHIGENORI, ISHIDA, NORIYA, ITOU, KENJI, KADONO, MASAYA, KOJIMA, MASAHIRO, SASAKI, MARI, TAKEYAMA, JUNICHI, YAMAZAKI, SHUNPEI
Applicants: SEMICONDUCTOR ENERGY LAB, SEMICONDUCTOR ENERGY LABORATORY CO., LTD.
Application year: 1989
Main classification: C23C16
IPC codes: C23C16