Procedure for forming, on a solid substrate, a film with properties similar to those of diamonds, the solid bodies so coated and the self-sustained film so obtained

Abstract: The main goal of this invention patent is a procedure for forming an amorphous carbon film over a solid, which film has physical and chemical properties similar to those of diamond. Its ancillary objects are the solid bodies so coated and the self-sustained film obtained in a subsequent stage of dissolution of said substrate. The application field is quite wide, and we cite: tools, shafts and bushings of certain mechanisms, surgical prostheses, lens protection and other optical devices, etc. The inventive idea consists of generating a highly accelerated beam of carbon-hydrogenated ions, which is made to impact with sufficiently high energy on the surface of the substrate. The beam is concentrated by electrostatic lenses and homogenized by a magnetic mass separator. The main objectives of this invention are: a procedure for forming, on a solid substrate, a film with properties similar to those of diamond: high hardness, high chemical stability, transparency, high heat conductivity and high electric resistivity; obtainable at ambient temperature, simpler than known procedures; able to produce a smooth film, regardless of the electrical qualities of said substrate and of its geometry, and with such a degree of adherence that it does not allow separation of this film other than by destructive means.

Description: INTRODUCTION - FIELD OF APPLICATION The main goal of this invention patent is a procedure for forming an amorphous carbon film over a solid, which film has physical and chemical properties similar to those of diamond. Another object of this invention are the solid bodies so coated by applying this procedure. Finally, another ancillary object is the self-sustaining film obtained by applying this procedure on a solid substrate, continuing with a dissolution stage of said substrate. Diamond is one of the crystalline forms of carbon, the least stable, whose properties are very well known. Outstanding among them are its hardness, its transparency, high refraction index, good thermal stability, high electrical resistivity, high thermal conductivity and the fact that it is chemically inert. Another crystalline form of carbon, more stable, is that of graphite, but its properties differ from those of diamond. Numerous industrial activities require parts whose superficial characteristics are the same as those of diamond. Thus appeared the idea of covering parts made of other materials with films having these properties, e.g. for tool manufacture. They are not only more economic than natural diamond (which is expensive and difficult to process, especially when the parts are large), but said superficial properties can also be combined with the desired volumetric properties of the materials of the parts. If, in addition, as is the case with this procedure, the films formed are smooth, without waviness, even smoothing out the small imperfections of the substrate, the application field is quite wide. Thus, the coated bodies can obtain their hardness and smoothness in order to be integrated in friction mechanisms such as, for example, shafts and/or bushing mechanisms with a high degree of precision, performance and/or reliability. The same properties, combined with chemical inertness, can be used in the field of surgical prostheses. For example, if the prosthetic knee-cap, which replaces the head of a femur, is made of a material which is sensitive to the biological substances present, it corrodes and, when losing its smoothness, starts acting as an abrasive of the cotyloid cavity of the iliac bone, which is partly cartilaginous; the same happens if it loses its smoothness because the material is soft; and all of the above is accelerated if the surface is wavy from the beginning. On the other hand, with this type of coating, the abrasion of the cavity does not take place. Another application field, which can take advantage of the aforementioned properties along with transparency, is in the coating of lenses and other optical devices. A very fine coating of amorphous carbon, e.g. of approximately one micron, with a high degree of hardness, smoothness, chemical inertness and transparency, will protect costly lensed equipment against dust, sand, the action of acid traces etc. As will be seen below, it is possible to obtain a self-sustaining amorphous carbon film, free from the solid on which it was formed (by diluting or melting the substrate). This film, duly sustained, has a few special applications, such as for example serving as stripper in certain types of particle accelerators, through which, when a highly accelerated atom passes, it completely loses its electrons. STATE OF THE ART In addition to covering surfaces with very small diamonds using glues, with results quite far from current requirements, it has already been attempted, by other procedures, to cover parts with a film with properties similar to those of diamond. Among a multitude of more or less successful attempts, there are currently two procedures (with some variations) which are industrially feasible. One of these procedures is the so-called CVD (Carbon Vapor Deposition), which consists in generating a plasma of a hydrocarbon (generally methane), diluted in hydrogen, and depositing plasma ions over a substrate brought to a temperature on the order of 800° C, through an electric field. The limitations of this method arise, on one hand, from the need to heat the substrate, which limits the variety of materials that can be used and, on the other hand, from the geometry of the part to be covered. It is limited by the fact that the surface of said part must be an equipotential surface forming the electric field. The second procedure consists in making deposits at ambient temperature, using carbon ion beams. To avoid graphitization of the deposit, it is simultaneously bombarded with an argon beam. The energy of both beams is of the order of 1 KeV. The shortcoming of this method is that it requires two simultaneous ion beams, which makes it complicated and more expensive. A third procedure is diclosed in Applied Physics Letters, Vol. 50 (1987), pages 132 to 134 (A Anttila, J. Koskinen, R. Lappalainen, J.-Pl Hirvonen; "Comparison of diamondlike coatings deposited with C + and various hydrocarbon ion beams"). This procedure consists in generating a mass-separated beam of hydrocarbon ions of a single type having an ion collection energy of 0,5 keV or 1keV and depositing the ions on a WC-CO hard metal substrate at a maximum current density of 100 µ A/cm 2 in a vacuum of 100 µPa (10 -9 bar). The films generated with hydrocarbon ions under this conditions are brittle and have a weak adhesion to the substrate. JP-A-61 270 370 and This Solid Films, vol.167, no. 2, pages 211-218, both disclose ion implantation of hydrocarbon ions with on energy of about 30 keV. The procedure of this invention overcomes the limitations and shortcomings of the known methods. SHORT DESCRIPTION OF THE INVENTION The procedure for forming, on a solid substrate, a film with properties similar to those of diamond, is characterized as including the following stages: a) cleaning and degreasing the outer surfaces of the solid substrate; b) introducing the substrate in a first chamber, which is substantially at ground potential, with a layout which also includes an ion source at high positive voltage as compared to the ground, and a path between the ion source and the first chamber in which are found, at least, one set of electrostatic lenses and one magnetic mass separator; creating a vacuum in the layout; c) generating a first ion beam of C + , CH n + (n<5) in the ion source, at a high positive voltage as compared to the ground; d) forming and concentrating the first ion beam with the set of electrostatic lenses; e) homogenizing the first beam with the magnetic mass separator, capable of deviating the undesired ions, obtaining a second ion beam with carbon-hydrogenated ions of a single type, having an energy of the order of 30 keV, arising from the acceleration caused by the high positive voltage as compared to ground; f) applying the second ion beam, by concentrating and homogenizing it in the mass separator, on the surface of the substrate at approximately 2µA for about 10 hours, such that it is covered with an amorphous carbon diamondlike film, including SP2 and SP3 carbon with properties similar to those of diamond, the ion source used in stage d) being preferably located in a second chamber, at high positive voltage as compared to the ground, in which there is a thermo-emitting hot filament, negative as compared to the walls of the second chamber, capable of providing electrons; the second chamber, equipped with a needle valve through which methane enters in a controlled manner; thus establishing an arc between the filament and the walls, which ionizes and fragments the methane molecules, producing C + , CH 3 + and CH 4 + plasmas which, since they are positive, are strongly repelled and accelerated by the positive potential of the second chamber towards potentials closer to that of the grounds. Since this is an innovative process as compared to the previous art, the main differences are explained below, with the clarification that there are other, unlisted, differences. 1) None of the known procedures for forming diamondlike coatings includes projection of an ion beam on a substrate in a chamber substantially at ground potential, thus allowing the substrate to be made of any material, electric conducting or insulating, not depending on the geometry of the substrate in order to generate the accelerating electric field. More homogeneous coatings are thus obtained. 2) None of the known procedures for forming diamondlike coatings includes generation of an ion beam at energies higher than 1 KeV in a vacuum less than 10 -9 bar, without using a simultaneous rare gas beam. Furthermore, since ions have so much energy, some of them penetrate the substrate, forming an interpenetration or interface area, with an estimated thickness between 50 and 300 Å, which makes the carbon film adhere quite well to the substrate, its separation by mechanical means being impossible, except by destruction of the superficial layer (abrasion with diamond paste). There are other methods, less preferable, for generating the first ion beams (e.g., made of another material, such as ethane, or with another energy source, such as radio frequency). GOALS OF THE PRESENT INVENTION Therefore, one goal of the present invention is a procedure for forming, on a solid substrate, a film with properties similar to those of diamond: high hardness, high chemical and thermal stability, transparency, high heat conductivity and high electric resistivity. Another goal of the present invention is a procedure for forming, on a solid substrate, a film with properties similar to those of diamond, obtainable at ambient temperature, simpler than known procedures. Another goal of the present invention is a procedure for forming, on a solid substrate, a film with properties similar to those of diamond, which is smooth and, furthermore, tends to smooth the small superficial imperfections of the solid substrates used. Another goal of the present invention is a procedure for forming, on a solid substrate, a homogeneous film with properties similar to those of diamond, regardless of the electric qualities of the substrate and its geometry, and with a degree of adherence such as not to allow separation of such film except by destructive means. A subsequent goal of the present invention are the solid bodies formed from any solid substrates coated according to the present procedure. The last goal of the present invention is the self-sustaining amorphous carbon film obtained by covering a solid substrate according to the present procedure, and then dissolving or melting the substrate. DETAILED DESCRIPTION OF THE INVENTION USING AN EXAMPLE To make clear the advantages summarily presented herein, to which users and specialists may add many more, and in order to facilitate understanding of the characteristics of the invented procedure, we describe below, as an example, an experiment conducted, having a purely explanatory intention concerning the basic conception of the invention. This experiment was obtained from an isotope separator at the National Commission for Atomic Energy of the Republic of Argentina. A silicon crystal with (1,1,1) crystallographic orientation was polished to mirror quality and washed with degreasing substances under ultrasound. This substrate was placed in a vacuum chamber in which the coating was performed. In another chamber, elevated to positive voltage as compared to the ground (variable between 1 and 70 keV), methane was introduced through a needle valve; with a hot filament (electronic thermo-emitter) at lower voltage, an arc was created between the filament and the walls of the chamber, which ionized and fragmented the methane molecules, generating a C + , CH n + plasma (n<5). The ion beam was formed and concentrated through a system of electrostatic lenses, and was introduced in a double-focus Scandinavian-type mass separator, allowing high resolution separation of a specific ion among others. Thus, a new CH 3 + ion beam was homogenized, which, at energy level between 1 and 30 keV, was applied onto one face of the sample at a current on the order of 2µA for 10 hours. After obtaining the coating, it was analyzed. The material with the properties closest to those of diamond appeared to be that obtained at energies of 30 KeV; the data obtained for this case are presented below. By ellipsometric methods and ERDA (Elastic Recoil Detection Analysis), a thickness of .3µ and a refraction index of 2.2 were measured, at a wave length of 5500 nm. With these data, resistivity could be measured, and appeared to be 10 12 Ω cm. Hardness was determined on the Mohs scale, by an attempt to scratch the film formed with materials of known hardness; a value of 9 was obtained. It must be noted that other hardness measurements, based on impact, do not apply, due to the reduced thickness of the film formed. By Raman spectroscopy (using the 5145 Å line of an argon LASER, the dispersed light was analyzed in a 90 degree geometry, with a Jarrell-ASH 25-300 spectrometer). It was determined that the film is amorphous, with a mix of SP2 and SP3 bonds. These measurements were repeated after the sample was brought to a temperature of 700 ° C in a nitrogen atmosphere, for 30 minutes. Graphite was found to appear. The surface was subjected to the action of hydrochloric, sulfhydric, sulfuric and nitric acids, as well as sodium hydroxide, with negative reaction. It was observed that, as with diamond, the surface could be oxidized with potassium bichromate and sulfuric acid at 200 ° C. By direct observation with the electronic microscope, it was seen that the coating "copies" the substrate, attenuating its waviness. Adherence was optimal, and could only be eliminated with diamond paste. The experience described Was repeated with other substrates: copper, steel, glass and a sodium chloride crystal. It was verified that the characteristics obtained were substantially independent of the substrate used. In the case of sodium chloride, after obtaining the coating, the substrate was dissolved in water, obtaining a self-sustaining film. By rotating the substrate during the application of the procedure, the entire surface thereof can be coated. SPECTROMETRIC CHARACTERISTICS OF THE FILMS OBTAINED It is interesting to have an in-depth look into Raman spectroscopy. The first order Raman spectrum of graphite (characterized by trigonal SP2 bonds) presents a sole acute peak at 1580 cm -1 . Diamond (characterized by tetrahedral SP3 bonds) also has a sole acute Raman active first order band at 1332 cm -1 . When graphite becomes amorphous, its band goes down in frequency (up to 1500 cm -1 approximately) and widens considerably, obtaining a spectrum more similar to state density calculated for an amorphous material made up of SP2 bonds. The Raman spectrum of amorphous diamond is unknown. State density calculations, supposing SP3 bonds in an amorphous structure, also indicate a widened band between 1200 and 1300 cm -1 . On the other hand, microcrystalline graphite presents, besides the 1580 cm -1 band, a band of approximately 1350 cm -1 (depending on the size of the granule). Raman spectroscopy thus appears to be a sensitive tool, both for the crystalline and amorphous character of the sample, as well as for its composition in terms of SP2 or SP3 bonds. In the samples obtained by application of the present procedure (including the self-sustaining film), a peak was obtained at 1295 cm -1 , which corresponded to the structure of amorphous diamond. To investigate this topic further, certain experiments were conducted, applying on appropriate (1,1,1) silicon substrates ion beams of C + and CH 3 + with various energies. Ions were selected with the magnetic separator. With C + alone, and low energies (1 KeV), a sole peak was obtained, widened at 1545 cm -1 . When energy was increased to 10 KeV, a slight shoulder was formed, located at lower frequencies. In exchange, with CH 3 + alone, already at 1 KeV a peak was formed at 1520 cm -1 , as well as a shoulder (swelling in the scale corresponding to lower frequencies) which, when analyzed, corresponded to a second peak (of lower amplitude) at 1330 cm -1 . At 10 keV the shoulder was bigger, with the peak at 1500 cm -1 , and the second peak at 1300 cm -1 . Finally, at 30 keV, the first peak is at less than 1500 cm -1 , and the second peak at 1295 cm -1 . In summary, in the case of the deposit with C + at low energies, a sole peak was obtained at 1545 cm -1 , which seems to indicate that SP2 bonds are predominant in the film formed and that, as the energy of the beam increases, a second peak appears. The same relation with energy is observed when bombarding with CH 3 + . The difference between the films obtained is that, in those formed with hydrogenated beams, there is always a second peak at lower frequencies, which seems to indicate that hydrogenated beams favor the formation of SP3 bonds. The Raman spectra of the films obtained with plasma are similar to those obtained with hydrogenated beams. But, generally, the former present peaks concentrated at higher frequencies. It is noteworthy that the relative amplitude of the two peaks does not quantify the ratio between the number of SP2 and SP3 bonds, since spectroscopy does not give a lineal result. This quantifying task has not yet been performed. The second peak was obtained by decomposing the Raman spectroscopy into the sum of the two Lorentz curves, by computer methods. When the diamond-type films are heated to 700° C in an inert atmosphere, they clearly present a peak at 1580 cm -1 , corresponding to graphite, and a second peak around 1360 cm -1 . This result is interpreted as the passing from a less stable stage (diamond) to another more stable (graphite) under the action of temperature. It is noteworthy that when a natural (crystalline) diamond is subjected to high temperatures, the same reaction takes place, with the difference that the temperatures at which this occurs are higher. We studied the influence of an argon beam on the structure obtained by applying the present procedure; the Raman spectra before and after argon bombarding do not show changes in the structure of the deposit. From the above explanation and the results obtained, it arises that it is possible to characterize the film formed by a net peak (not unique) at approximately 1295 cm -1 , presented in Raman spectroscopy, which does not appear in films obtained by other procedures. It is presumed that the procedure described will enable films to be obtained with similar characteristics and also with a significant proportion of SP3 bonds, i.e. which can be characterized by a peak similar to that described in the previous paragraph, forming the second beam with another carbo-hydrogenate, such as CH 4 + instead of CH 3 + . We thus described some examples of realization of the procedure for forming, on a solid substrate, an amorphous carbon film with properties similar to those of diamond, main object of the present invention.

Claims: PROCEDURE FOR FORMING, ON A SOLID SUBSTRATE, A FILM WITH PROPERTIES SIMILAR TO THOSE OF DIAMOND, obtainable at ambient temperature, characterized in that it includes the following stages: a) cleaning and degreasing the outer surfaces of the solid substrate; b) introducing the substrate in a first chamber, which is substantially at ground potential, with a layout which also includes an ion source at high positive voltage as compared to the ground, and a path between the ion source and the first chamber in which are found, at least, one set of electrostatic lenses and one magnetic mass separator; creating a vacuum in the layout; c) generating a first ion beam of C + , CH n + (n<5) in the ion source, at a high positive voltage as compared to the ground; d) forming and concentrating the first ion beam with the set of electrostatic lenses; e) homogenizing the first beam with the magnetic mass separator, capable of deviating the undesired ions, obtaining a second beam with carbon hydrogenated ions of a single type, having an energy of approximately 30 KeV, arising from the acceleration caused by the high positive voltage as compared to ground; f) applying the second homogenized ion beam in the mass separator on the surface of the substrate at approximately 2µA for about 10 hours, such that it is covered with an amorphous carbon diamondlike film, including SP2 and SP3 carbon, with properties similar to those of diamond. PROCEDURE FOR FORMING, ON A SOLID SUBSTRATE, A FILM WITH PROPERTIES SIMILAR TO THOSE OF DIAMOND, such as claimed in 1, characterized in that the ion source used in stage d) is made up of a second chamber at high positive voltage as compared to the ground, in which there is a thermo-emitting hot filament, negative as compared to the walls of the second chamber, capable of providing electrons; the second chamber, equipped with a needle valve through which methane enters in a controlled manner; thus establishing an arc between the filament and the walls, which ionizes and fragments the methane molecules, producing C + , CH 3 + and CH 4 + plasma. PROCEDURE FOR FORMING, ON A SOLID SUBSTRATE, A FILM WITH PROPERTIES SIMILAR TO THOSE OF DIAMOND, such as claimed in 1 or 2, characterized in that the second beam of carbon-hydrogenated ions of a single type is a beam of CH 3 + ions. PROCEDURE FOR FORMING, ON A SOLID SUBSTRATE, A FILM WITH PROPERTIES SIMILAR TO THOSE OF DIAMOND, such as claimed in 1, 2 or 3, characterized in that the substrate is permanently rotated in order to obtain total coating of the surface of the substrate. PROCEDURE FOR FORMING, ON A SOLID SUBSTRATE, A FILM WITH PROPERTIES SIMILAR TO THOSE OF DIAMOND, such as claimed in 1, 2, 3 or 4, characterized in that, after stage g), the solid substrate is dissolved in a solvent, obtaining a self-sustaining film with properties similar to those of diamond. PROCEDURE FOR FORMING, ON A SOLID SUBSTRATE, A FILM WITH PROPERTIES SIMILAR TO THOSE OF DIAMOND, such as claimed in 1, 2, 3, 4 or 5, characterized in that, after stage g), the solid substrate is melted, obtaining a self-sustaining film with properties similar to those of diamond. PROCEDURE FOR FORMING, ON A SOLID SUBSTRATE, A FILM WITH PROPERTIES SIMILAR TO THOSE OF DIAMOND, such as claimed in 1, 2, 3, 4, 5 or 6, characterized in that the second beam of carbon-hydrogenated ions of a single type is a beam of CH 4 + ions SOLID BODIES SO COATED, obtained from a solid substrate by applying the procedure claimed in clauses 1 through 7, characterized in that Raman spectroscopy applied to the film formed and analyzed by computer methods presents two peaks, one of them at approximately 1295 cm -1 . SELF-SUSTAINING AMORPHOUS CARBON FILM, obtained by the procedures under clauses 1 through 8, characterized in that Raman spectroscopy applied to the film and analyzed by computer methods presents two peaks, one of them at approximately 1295 cm -1 .

Inventors: HALAC EMILIA BEATRIZ, HUCK HUGO ALBERTO, JECH ALBERTO ESTANISLAO, NICOLAI JULIO ANTONIO, RIGHINI RAUL, RODRIGUEZ DE BENYACAR MARIA AN, HALAC, EMILIA BEATRIZ, HUCK, HUGO ALBERTO, JECH, ALBERTO ESTANISLAO, NICOLAI, JULIO ANTONIO, RIGHINI, RAUL, RODRIGUEZ DE BENYACAR, MARIA ANGELICA
Applicants: COMISION NAC ENERG ATOM, COMISION NACIONAL DE ENERGIA ATOMICA
Application year: 1992
Main classification: C23C14
IPC codes: A61F2, C23C14