Highly tetrahedral amorphous carbon coating on glass

Description: TECHNICAL FIELD [Detailed description of the invention]

The present invention relates to a diamond-characteristic carbon (DLC) coating provided (directly or indirectly) to glass or other substrates. In particular, as a preferred embodiment, the present invention is directed to a soda (soda compound) -containing glass substrate (eg, soda limestone glass) for the purpose of water resistance and / or corrosion reduction of the coated material. It relates to a high tetrahedral amorphous carbon coating that has the characteristics of diamond. Ion beam and filtered carbon cathode arc deposition are preferred methods of deposition for coatings. [0001]

(Background of invention) Soda-containing glasses are known in the art. For example, for reference, there is US Pat. No. 5,214,008. [0002]

Soda limestone quartz glass is used, for example, in architectural glass, automobile windshields, and the like. The above-mentioned Japanese Patent No. '008 discloses a form of soda limestone glass known in the technical field. [0003]

However, ordinary soda-containing glass is sensitive to environmental corrosion that occurs when sodium (Na) remains or diffuses inside the glass. The sodium may react with water on the surface of the glass so as to cause stains or stains (eg, sodium hydroxide stains) visible on the glass surface. Such glass also includes cases where it is used as a window of an automobile (eg, a backlight, a side window, and / or a windshield), and in many different environments, in retaining water on the glass surface. It is also sensitive to it. These glasses are also sensitive to fogging on the inner surface of windowpanes in automobiles and other environments. [0004]

From the above viewpoint, it is clear that it is technically necessary to prevent and / or minimize visible stains / corrosion of the coated glass surface, including soda. It is also technically necessary to apply a strong protective coating to the window substrate. In addition, a glass coating that reduces the sensitivity of the coated material to fogging in automobiles, and a coated glass material that can repel water and / or dirt are required. [0005]

Glass is known to have a carbon (DLC) coating that has the characteristics of diamond. For example, US Pat. No. 5,637,353 states that DLC may be applied to glass. The patent '353 states that there is a bonding problem between the glass and something like the DLC type, and that there is an intermediate layer between the bonds. However, Japanese Patent No. 353 does not reveal the hypertetrahedral amorphous form of DLC used in many examples, which is clarified below. DLC in Patent '353 has its low density (probably 2.0 g / cm)³Due to (below), in many cases it will not be an effective corrosion reducing material for glass. Furthermore, the DLC in Patent '353 is deposited without using the effective method of one embodiment of the present invention. [0006]

Many glass substrates are known to have small crevices defined on their surface. The stress required to break a glass typically decreases as the chances of exposure to water increase. When water invades the small crevice, the interatomic bond at the tip of the crevice breaks. This weakens the glass. Water can accelerate the growth rate of cracks by attacking the glass structure at the root or tip of the cracks thousands of times or more. The strength of the glass is somewhat controlled by the growth of crevices penetrating the glass. For reference, water in these fissures reacts with the glass, as described in The Fracturing of Glass by TAMichalske and Bruce C. Bunker. It makes it easier to crack. In the water molecule, the silicon-oxygen bond and the hydrogen-oxygen bond in the water molecule are broken at the tip of the crack in the glass, and two silanes (silanol) are broken. Causes chemical reactions as agreed upon, such as forming groups). The length of the crevice increases as one bond breaks, thereby weakening the glass. The reaction with water reduces the energy required to break the silicon-oxygen bond by about 20 factors, and such bond breakage accelerates the growth of glass crevices. [0007]

Therefore, in order to strengthen the glass, there is also a need for a technique for preventing water from reaching the silicon-oxygen bond at the tip of the crack in the glass substrate. [0008]

Different embodiments of the invention are intended to meet any or all of the technical needs set forth above, and once the following are disclosed, there are other needs for the parties as well. It will be clear. [0009]

(Outline of the invention) An object of the present invention is to provide a coated material so that it can repel water. (For example, car windshields, car backlights, car side windows, building windows). [0010]

Another object of the present invention is to provide a system or method for reducing or minimizing corrosion of coated objects, including soda, including coated glass objects. [0011]

Another object of the present invention is to provide a coated glass object, the DLC coating protecting the glass from acids such as HF, nitric acid, sodium hydroxide (the coating is chemically inert). May be). [0012]

Another object of the present invention is to provide a coated glass material that is not easily sensitive to fogging. [0013]

Another purpose is to create a pinhole-free protective layer on the glass substrate. [0014]

Another object of the present invention is to provide a coated glass material that provides abrasion resistance and / or can repel dust and the like. [0015]

Another object of the present invention is to provide a glass substrate containing a DLC coating of a high density tetrahedral amorphous carbon layer that abuts or indirectly contacts the substrate. [0016]

Another object of the present invention is to provide a DLC coating on a substrate, the coating having different densities and different sps.³It contains different moieties or layers with a carbon-carbon bond ratio. sp²Sp against³The ratio of carbon-carbon bonds in the coating may vary depending on the different layers or portions of the coating. Such compositionally changing coatings, adjacent to the basis of the substrate, alter the ion energy used in the deposition process so that the stress in the coating is immediately reduced at the boundary / layer of the DLC coating. As a result, it may be formed continuously. Therefore, the DLC coating has a constant density and sp in that respect.³Boundary layer with carbon-carbon bond ratio and higher density sp³It may include other layers with a carbon-carbon bond ratio. [0017]

In general, the present invention meets the above-mentioned technical needs / purposes by making coated glass. [0018]

Here, the coated glass is composed of the following. [0019]

Approximately 5% soda / Na by weight at least₂Glass substrate containing O; sp provided to the glass substrate to reduce corrosion or dirt on the coated glass²And sp³Amorphous carbon layer containing carbon-carbon bonds; where the amorphous carbon layer is sp²More sp than carbon-carbon bonds³It has a carbon-carbon bond. [0020]

As another embodiment, the present invention meets the above technical needs by making coated glass. [0021] [0021]

Here, the coated glass is composed of the following. [0022]

That is, on a weight basis, about 60-80% SiO₂, About 10-20% Na₂O, about 0-16% CaO, about 0-10% K₂O, about 0-10% MgO, about 0-5% Al₂O₃A soda-containing glass substrate composed of, and a carbon (DLC) coating that has the characteristics of amorphous diamond applied to the glass substrate, the DLC coating of which is at least about 35% sp.³It has a carbon-carbon bond and contains at least one hypertetrahedral amorphous layer. [0023]

One example is a soda lime silica float glass substrate. Also, as a preferred embodiment, either all DLC coatings, or the only layer inside the DLC coating, is approximately 2.4-3.4 g / cm.³Has a density of. The most preferred density is about 2.7-3.0 g / cm³Is. [0024]

In one example, the tetrahedral amorphous carbon layer has the density range and is at least about 70% sp.³Examples include those containing carbon-carbon bonds. Most preferred is at least about 80% sp³It has a carbon-carbon bond. [0025]

In one example, the DLC coating contains a top layer (eg, about 2-8 atomic layers, about 20 Å or less) and has a lower density than the rest of the DLC coating, thereby solid on the top surface of the DLC coating. Lubricating part is created. A layered graphene attached to a carbon atom is provided in this thin layer portion. The coefficient of friction of this thin layer portion is about 0.1 or less. [0026]

Another advantage of the present invention is that the temperature of the glass substrate during the deposition of the DLC material is about 200 ° C or less. The preferred temperature is about 150 ° C or less. The most preferred temperature is about 60-80 ° C. This makes it possible to minimize graphitization during the vapor deposition process. [0027]

The present invention then immediately provides a window with a substrate and a high tetrahedral amorphous carbon layer to further meet the above requirements in the art. In that respect, the substrate is made of and includes at least one borosilicate glass and soda limestone glass, plastic. [0028]

The present invention will be described with reference to examples thereof with reference to the accompanying drawings. [0029]

(Detailed Description of Examples of the Present Invention) Hereinafter, the attached drawings will be described in more detail, but the same members are assigned the same reference numbers throughout the drawings. [0030]

FIG. 1 shows a side sectional view of a coated glass object according to an embodiment of the present invention, in which a protective coating 3 made of carbon (DLC) coated to have the characteristics of at least one diamond contains soda. It is supplied directly to the sex glass substrate 1. The DLC coating 3 in the example of FIG. 1 has a high density (eg 2.4 g / cm).³It contains at least one hypertetrahedral amorphous carbon (ta-C) layer 7, which repels water (larger) and traps soda in a soda-containing glass substrate. The coating 3 further comprises a boundary layer 8 directly adjacent to at least one substrate 1. Where layer 8 is less dense than ta-C layer 7 and sp³The carbon-carbon bond ratio is also low. Thus, layer 8 is different from layer 7, but boundary layer 8 is at least about 2.4 g / cm, as described below.³It may or may not be suitable as ta-C having the density of. In certain embodiments, it is clear that the coating 3 comprises a plurality of ta-C layers 7 and / or a plurality of layers 8. Layers 7 and 8 of the coating may be formed during continuous or discontinuous deposition processes in different embodiments of the invention. [0031]

FIG. 2 shows a side sectional view of a coated glass object according to another embodiment of the present invention, and at least one DLC coating 3 is provided to the substrate 1. In the example of FIG. 2, virtually all DLC coatings 3 are composed of high tetrahedral amorphous carbon (ta-C) and resemble layer 7, at least about 2.4 g / cm.³A high proportion of sp (eg, at least about 35%, more preferably at least about 70%, most preferably about 80%)³It has a carbon-carbon bond. In other words, the ta-C layer 7 according to the embodiment of FIG. 1 forms the entire DLC coating 3 of the embodiment of FIG. The DLC coating 3 in the example of FIG. 2 sp.³The carbon-carbon bond ratio may or may not be the same, but these parameters are shown in FIGS. 1 and 2 by varying the ion energy used throughout the deposition process of coating 3. It may vary through layers 3, 7, and 8 in the examples. [0032]

In the embodiment of FIG. 3, low-E, or other coating 5, is provided between the substrate 1 and the DLC coating 3 (ie, the DLC in the embodiment of FIG. 1 or FIG. 2). coating). However, the DLC coating 3 is on the substrate 1 in the embodiment of FIG. 3 and is combined with the ta-C portion 7 of the coating 3. Therefore, the term ~ top (on) here means that substrate 1 supports DLC coating 3 or any layer thereof (eg, 7, 8) and the other layer. It doesn't matter if 5 is prepared in the meantime. Thus, the protective coating 3 may be provided directly to substrate 1 as shown in FIGS. 1 and 2, or as shown in FIG. 3, between its layers, low-e, or other. It may be provided to the substrate 1 with the coating 5 interposed therebetween. Instead of the position shown in FIG. 3, the coating 5 is placed so that the coating 3 (in the embodiment of FIG. 1 or 2) is located between the coating 5 and the substrate 1. It may be provided on the upper surface of the. In other embodiments, the DLC coating 3 may be applied to both sides of the low-e coating 5. [0033]

Typical coatings (in all or in some parts of these coatings) that can be used as low-e, or other coatings 5 on the top or bottom of the DLC coating are U.S. Pat. Nos. 5,837,108, 5,800,933, 5,770,321. , 5,557,462, 5,514,476, 5,425,861, 5,344,718, 5,376,455, 5,298,048, 5,242,560, 5,229,194, 5,188,887, and 4,960,645. These US patent numbers are listed for reference. A simple silicic acid and / or silicon nitride coating may be used as coating 5. [0034]

As described below, the high tetrahedral amorphous carbon (ta-C) layer 7 has a special shape of carbon (DLC) that has the characteristics of diamond, with at least about 35% sp.³It contains carbon-carbon bonds (ie, this is a hypertetrahedron). In one embodiment of the invention, ta-C layer 7 sps at least about 35% of total SP binding in the layer.³It has a carbon-carbon bond. More preferably, at least about 70%, most preferably at least about 80% SP, which increases the density of layer 7 and its binding strength.³It has a carbon-carbon bond. Total sp³Binding can be measured using Raman finger-printing and / or electron energy loss spectroscopy. High total sp³The bond increases the density of the layer and makes it possible to prevent the diffusion of the sodium compound on the surface of the coating. [0035]

The Ta-C layer 7 forms all of the DLC coating 3 in the example of FIG. 2, and the ta-C layer 7 forms only a part of the DLC coating 3 in the example of FIG. This is because the density of the amorphous carbon layer 8 at the boundary in the example of FIG. 1 is about 2.4 g / cm.³Smaller and / or sp³This is due to the occasional carbon-carbon bond being smaller than 35%. However, as mentioned above, it is clear that the DLC coating 3 has a boundary layer that is directly adjacent to the substrate 1 in each of the examples of FIG. 1 or FIG. Boundary layer at least about 2.4 g / cm³, And at least about 35% sp³There is a difference that it has a carbon-carbon bond (more preferably at least about 70%, most preferably at least about 80%). Therefore, layer 7 here refers to both layer 7 as shown in the example of FIG. 1, similar to DLC coating 3 in the example of FIG. [0036]

At least some carbon atoms in DLC coating 3 and / or some sp², And / or sp³Carbon-carbon bonds are supplied to crevices or crevices on the surface (eg, top surface) of the glass substrate, or the glass surface of the substrate 1 itself, or growth, to force the coating 3 to bond to the substrate 1. It may penetrate the surface of the DLC. Subimplantation of carbon atoms on the surface of substrate 1 allows coating 3 to bond strongly to substrate 1. [0037]

For simplicity, Figure 4 shows a typical sp³Carbon-carbon, or CC bond in coating 3 (ie, the bond between carbon and carbon that has the characteristics of diamond), typical sp in coating 3.²Figure 4 is a CC bond and Figure 5 is a typical sp. [0038]

High density of soda-containing glass substrate 1 (at least about 2.4 g / cm)³By providing the ta-C layer 7, the total amount of soda that is about to leave the substrate, or reaching the surface of the substrate or coating, is reduced (ie, ta-C is the sodium from the substrate). Limit diffusion). Therefore, it reduces the reaction of soda with water or other materials on the surface of the object. As a result, the provision of the ta-C layer 7 to the substrate reduces the fouling and / or corrosion of the glassy material formed over a long period of time. Many sp³Carbon-carbon bonds increase the density of layer 7, which also allows water to be repelled and soda diffusion from soda-containing glass to be minimized. [0039]

Coatings 3 and layers 7 and 8 also strengthen the glass and reduce the stress on the bonding surface between substrate 1 and coating 3. It also provides a solid lubrication surface for the object when the coating 3 is located on the surface of the object. Coating 3 and / or layer 7 may include a portion of the upper surface of the layer that is less dense than the central region of coating 3 (eg, upper layer 3 Å to 15 Å), thereby providing solid lubrication on the upper surface of coating 3 farthest from the substrate. The material can be provided. The Ta-C layer 7 also prevents water / moisture from entering the substrate 1. The coating 3 and the ta-C layer 7 are continuously formed / deposited on the opposite side of the glass substrate 1 in good condition without any small holes or gaps. [0040]

In one embodiment, layers 7 and / or 8 adjacent to the glass substrate allow a significant number of carbon atoms to penetrate the crevices on the glass surface, as shown in FIG. It is vapor-deposited where there is ion energy. The small size of the carbon atoms and the ion energy utilized prevent existing water from reaching the tip of the crevice. This strengthens the glass for extended periods of time by delaying and / or stopping the breakdown of the silicon-oxygen bond at the tip of the fissure caused by exposure to water. [0041]

Advantages of the present invention in certain embodiments include: (i) coated windows (eg, backlights, windshields, etc.) that can repel water in a variety of environments. Windows, or commercial and residential windows); (ii) Fog-resistant coatings to prevent fogging; (iii) Reinforced coated windows; (iv) Abrasion-resistant coatings Windows; (v) coated objects that can repel dirt; (vi) coated glass objects that reduce the susceptibility of the surface to visible corrosion. For example, in the embodiment of an automobile window, the outer surface of the substrate 1 exposed to the environment is coated with coating 3 according to any of the embodiments of FIGS. In the example, the surface of the substrate 1 of the automobile window may be coated with the coating 3 according to any of the examples of FIGS. [0042]

In one example, coating 3 is at least about 70% transparent or transparent to visible light. A transparency of at least about 80% of visible light is preferred, and even more preferably at least about 90%. [0043]

In one example, the DLC coating 3 (and layer 7 in the example of FIG. 2) may be about 30-3,000 Å thick, most preferably about 50-300 Å thick. .. With respect to the glass substrate 1, the thickness is about 1.5 to 5.0 mm, preferably about 2.3 to 4.8 mm, and most preferably about 3.7 to 4.8 mm. The Ta-C layer 7 in one example is at least about 2.4 g / cm.³Density, more preferably about 2.4-3.4 g / cm³The most preferable is about 2.7 ~ 3.0 g / cm.³Is. [0044]

In some embodiments of the present invention, the substrate 1 is soda or Na.₂Including O. Therefore, the ta-C layer 7 reaches the surface of the coated material and minimizes the total amount of soda that can cause fouling / corrosion. In one embodiment, substrate 1 is about 60-80% SiO by weight.₂, About 10-20% Na₂O, about 0-16% CaO, about 0-10% K₂O, about 0-10% MgO, and about 0-5% Al₂O₃including. In some other embodiment, substrate 1 is about 66-75% by weight SiO.₂, About 10-20% Na₂O, about 5 to 15% CaO, about 0 to 5% MgO, about 0 to 5% Al₂O₃, And about 0-5% K₂It may be soda limestone quartz glass containing O. Most preferably, substrate 1 is about 70-74% by weight SiO.₂, Approximately 12-16% Na₂O, about 7-12% CaO, about 3.5-4.5% MgO, about 0-2.0% Al₂O₃, Approximately 0-5% K₂It is a soda limestone quartz glass containing O and about 0.08 to 0.15% iron oxide. According to any of the above examples, the soda limestone quartz glass is about 150-160 lb / ft.³(Approximately 2402.8 ~ 2563.0kg / m³) (Preferably about 156 lb / ft³(Approximately 2498.9 kg / m³)), With an average short-time bending stress of about 6,500 to 7,500 psi (about 44.8 to 51.7 MPa) (preferably about 7,000 psi (about 48.3 MPa)), about 0.20 Btu / lb · ° F (about). It has a specific heat (0 to 100 ° C) of 1.82 J / kg · K), a softening point of about 1,330 to 1,345 ° F (about 721.1 to 729.4 ° C), and about 0.52 to 0.57 Btu. It has a thermal conductivity of / hr ft ° F (about 0.90 to 0.99 W / m K) and is about 4.7 × 10.^-6~5.0×10^-6It has a linear extension factor (room temperature relative to 350 ° C) of ° F (approximately -17.77777517 to -17.77777500 ° C). In some embodiments, any glass disclosed in U.S. Pat. No. 5,214,008 or U.S. Pat. No. 5,877,103 may be used as substrate 1, and each of these U.S. patents is cited for reference. did. Soda limestone quartz glass, which can be purchased from Guardian Industries, Inc. (Auburn Hills, Michigan), located in Auburn Hills, Michigan, may be used as substrate 1. [0045]

Any such glass substrate 1 may be green, blue, or gray, for example, provided a suitable colorant is provided for the glass. [0046]

In another embodiment of the invention, the substrate 1 may be borosilicate glass or a substantially transparent plastic, and in some borosilicate glass examples, the substrate 1 is about 75-85% SiO.₂, About 0-5% Na₂O, about 0-4% Al₂O₃, Approximately 0-5% K₂O, about 8 ~ 15% B₂O₃, And about 0-5% Li₂It may contain O. [0047]

In yet another embodiment, automobile windows (eg, windshields or side windows) containing any of the above glass substrates laminated to a plastic substrate are joined together to make the substrate 1. May be good. The substrate 1 comprises the coating 3 in any of the embodiments of FIGS. 1-3 provided on one or both sides of such a window. In another embodiment, the substrate 1 made of a sheet of soda limestone glass laminated in a layer may be provided with respect to the target plastic sheet used for the window of an automobile. It then has a coating 3 inside the substrate bonded to the plastic in any of the embodiments of FIGS. In other embodiments, in window use (eg, automotive windshields, residential windows, commercial windows, automotive side windows, automotive backlights, or rear windows) or in other similar environments, substrate 1 , As mentioned above, any of the glass materials layered with each other includes a first or second glass sheet. In one embodiment, the coating 3 and / or the ta-C layer 7 has an average hardness of about 30-80 GPa (most preferably about 40-75 GPa) and a bandgap of about 1.8-2.2 eV. You may. It is clear that the hardness and density of the coatings 3 and / or layers 7 and 8 there may be adjusted by modifying the ion energy of the vapor deposition apparatus or the process described below. [0048]

If all substrates 1 of the material are coated with at least DLC coating 3 according to any of the embodiments of FIGS. 1-3, the resulting coating will have the following characteristics in one embodiment: Visible light transmission (I11.A) of 60% (preferably 70% or more), UV (ultraviolet) transmission of about 38% or less, total solar transmission of about 45% or less, and about 35% IR (infrared) of the following (preferably 25% or less, most preferably 21% or less). Here, for reference, techniques for measuring the transmission rates of visible light, total sunlight, UV, and IR are disclosed in US Pat. No. 5,800,933, as in Patent No. '008. [0049]

Here, the carbon (DLC) having the characteristics of DLC diamond and the special tetrahedral amorphous carbon (ta-C) type 7 used in a certain embodiment will be described in detail below. .. All DLC3s shown in the figure here are amorphous. Ta-C7 is amorphous and still substantially CC tetrahedron (sp)³-Type) binding, hence at least about 35% sp³Carbon-carbon bond (preferably at least 70%, even more preferably at least about 80% SP³It is named tetrahedral amorphous carbon (ta-C) [or high ta-C] because it has a carbon-carbon bond). The diamond-characteristic bond gives the ta-C material a diamond-like luster, such as high hardness, high density, and chemical inertness. However, ta-C is also sp²The carbon-carbon triangular bond and its optical and electrical properties include being approximately determined by this bond construct. sp in ta-C layer²Part of the bond, and the density here, is due, for example, to the carbon ion energy used during the deposition period of coatings 3 and / or layers 7, 8. The characteristics of the given DLC coating are the coating, that is, sp at layers 7 and 8.³And sp²It is a function of a part of the bond. SP discussed here³SP such that the bond results in high density coatings 3 and / or 7.³Carbon-carbon bond, sp that cannot give high density³It is not a carbon-hydrogen bond. [0050]

According to vapor deposition technology, many ta-C layers 7 have a tetrahedral shape, or sp.²It has a carbon atom to have a two-dimensional shape of, or an amount of sp-mixed H (up to about 4%) in a linear polymerization-like shape. In other words, carbon-carbon, carbon-hydrogen, hydrogen-hydrogen, etc. are all correlated and contribute to the average structure of layer 7 in one embodiment. [0051]

When Ta-C is completely or at least about 90% hydrogen free, carbon-carbon bonds are considered local structures. Ta-C film is sp²Or it has a part of graphite bonding. Octahedron (sp) as well as layer density, strength, stress, etc.²) And the spatial distribution of tetrahedral carbon atoms make it possible to determine the bonding force of layer 3 to glass. The tetrahedral amorphous carbon (ta-C), and its hydrogenated form ta-C: H (which contains about 10% or so much H), is a high proportion of carbon-carbon (it contains about 10% or so much H). CC) sp³It has a bond and one of the layers 7 in the example of FIG. 1, the coating 3 of the example of FIG. 2 and any of these in FIG. 3 is used. The bonds characteristic of this tiremond are low density and / or graphite type sp.²And the sp carbon-carbon of the polymerization, or other form called DLC with a larger proportion of carbon-hydrogen bonds, gives unmatched ta-C7 properties. [0052]

Ta-C7 has a high density (at least about 2.4 g / cm), as well as a low coefficient of friction (see Table 1 below).³), High hardness, and high Young's modulus (700 to 800). [0053]

[table 1]

<img file="JP2002543035A_D0001.tif" /> 【0054】

The method of depositing the coating 3 on the substrate 1 according to the embodiment of the present invention will be described below. [0055]

Before the coating 3 is formed on the glass substrate, it is preferable that the uppermost surface of the substrate 1 is cleaned by the oxygen gas method using an ion beam in each of the examples of FIGS. 1 and 2. Since oxygen gas has an atomic weight of about 28-40 amu (most preferably about 32 amu), oxygen gas physically cleans the surface. Substrate 1 may be cleaned, for example, by sputter-cleaning the substrate prior to the actual deposition of ta-C or other DLC material. The cleaning may utilize oxygen and / or carbon atoms and can also use ion energy of about 800 to 1,200 eV (most preferably 1,000 eV). [0056]

In an embodiment where a plasma ion beam is used to deposit coatings 3, 7, and / or 8, the carbon ions are from the plasma towards substrate 1 such that carbon from the ions is deposited on substrate 1. Energy may be given to form a flow. Ion beams from the gas layer are C +, CH +, C₂H and / or C₂H₂+ Produces a beam of ions (ie, carbon or carbon-based activators). Preferably, the source gas for acetylene (C)₂H₂) Obtains the appropriate energy to prevent or minimize polymerization and to allow its ions to penetrate the surface of substrate 1 and be subimplanted therein. Is used for As a result, the atoms of the coating 3 are mixed with the surface of the substrate 1 consisting of several atomic layers. [0057]

The collision energy relative to the volume of coating 3 (eg, layer 7 in the examples of FIGS. 1 and 2) is a high density sp.³It may be about 100-200 eV per unit carbon atom to allow carbon-carbon bonds to form in the DLC layer. Preferred is about 100-150 eV. The ion is sp³It collides with the substrate with the energy, which facilitates the formation of carbon-carbon bonds. The collision energy of the active carbon ions may be in a range that facilitates the formation of the desired lattice structure, and such bonds (eg, layer 8 in the examples of FIG. 1) at the boundary of coating 3 are clearly apparent. At least a portion is formed by sub-implantation into the substrate as shown in FIG. The flow is arbitrarily composed of ions having a nearly uniform weight, and the collision energy is almost uniform. Substantially, the active ions that collide with the surface of the growth film and / or the substrate 1 densify the growth film and / or the substrate 1. The coating 3, especially the layer 7, preferably has no small holes, which can perfectly achieve the repulsive action of water and the suppression of soda diffusion. Therefore, its carbon-carbon sp³Bonds are preferably formed by having a predetermined range of ion energy before reaching substrate 1 or prior to the growth of ta-C on the substrate. The optimum ion energy window for the ta-C layer 7 configuration in the examples of FIGS. 1 and 2 is about 100 to 200 eV per unit carbon atom (preferably about 100 to 150 eV, and more preferably about 100 to 150 eV. Most preferred is about 100-140 eV). At these energies, the film 7 (ie, layer 3 in the examples of FIGS. 1 and 2) is comparable to diamond. However, compressive stress is generated in ta-C during vapor deposition at 100 to 150 eV. Such stresses can reach as high as 10 GPa and potentially cause desquamation from many substrates. It has been clarified that these stresses are controlled and reduced by increasing the ion energy in the energy range of about 200 to 1,000 eV during the deposition process. The plasma ion beam source has made it possible to control the ion energy within different ranges in the wide range of vapor deposition industrial processes utilized here. Its compressive stress in amorphous carbon is significantly reduced in the high ion energy range of 200-1,000 eV. [0058] [0058]

The high stress at the thin boundary 8 of the coating 3 in direct contact with the surface of the glass substrate 1 is not preferred. So, for example, at the first 1-40% thickness 8 of coating 3 (preferably the first 1-20% thickness, and most preferably the first 5-10% thickness). , A high stress-resistant energy level of about 200-1,000 eV (preferably about 400-500 eV) is deposited on substrate 1. Then, after the initial boundary portion 8 of the coating 3 has grown in order to grow the remaining portion ta-C layer 7 of the coating 3, the ion energy in the ion deposition process is (during vapor deposition, quickly or quickly, or Gradually) it decreases to about 100-200 eV (preferably about 100-150 eV). [0059]

For example, for Figure 1 only, assume that DLC coating 3 is 100 Å thick. The first 10 Å layer 8 of the coating 3 (ie, the boundary 8) reduces the compressive stress relative to the rest 7 of the coating 3 where the layer 8 of the coating 3 contacts the surface of the substrate 1. It may be deposited using an ion energy of about 400 to 500 eV. The boundary 8 of the coating 3 is sub-implanted into the substrate 1 at least in part so that it is mixed with the surface of the glass. In one embodiment, only C ions are used for deposition of boundary layer 8, which is a stepwise constitutive surface that is primarily SiC. This boundary layer 8 between the substrate 1 and the coating 3 improves the adhesion of the coating 3 to the substrate 1 and gradually changes its composition to disperse the strain at the boundary region instead of narrowly concentrating it. To do. Layer 8 of DLC coating 3 is at least about 2.4 g / cm in different examples.³Density may or may not be. Also, at least about 35%, 70%, or 80% sp in different examples.³It may or may not have a carbon-carbon bond. Coat first 10Å of coating 3 (i.e., the layer 8) after is deposited, the ion energy, the remaining coating 3: For (ta-C, or ta-C may be either H) 7, gradually, or It suddenly decreases to 100-150 eV. This makes layer 7 denser and sp higher than layer 8³It will have a carbon-carbon bond ratio. [0060]

Therefore, in one embodiment, due to the adjustment of ion energy during the deposition process, the ta-C coatings 3 of FIGS. 1-3 have different densities and sps in different regions here.³It has a carbon-carbon bond ratio. However, at least a portion of coating 3 is at least about 2.4 g / cm.³Density, and at least about 35% SP³It is a high tetrahedron ta-C layer 7 having. The high tetrahedron ta-C portion may be the portion farthest from substrate 1 in FIG. 1 or may be any other region of coating 3. Similarly, in coating 3, sp³The portion having a low carbon-carbon bond ratio is preferably a portion immediately adjacent to the substrate 1 (for example, the boundary layer 8). [0061]

In one embodiment, CH₄Is the C mentioned above₂H₂It may be used as a feedstock gas in combination with a gas or during an alternative vapor deposition process. [0062]

With reference to FIG. 8, it is clear that there are small or minimal cracks defined at that point on the surface of the glass substrate. In particular, when water seeps into the crevices and breaks further bonds in the crevices, these crevices can weaken the glass depending on the degree of its size. Therefore, another advantage of the present invention is that in some embodiments, the amorphous carbon atoms and / or the network of layers 7 or 8 are smaller carbon atoms (eg, atoms with a radius of about 100 pm or less, etc.). These are preferred because they are less than about 80 pm, even more preferably about 76.7 pm) and because they are 200-1,000 eV (preferably ion energy of about 400-500 eV) and because of their momentum. Fills small crevices or collects in crevices. This strengthens the mechanical strength of the glass. The nano-sized fissures on the glass surface, shown in Figure 8, sometimes range from about 0.4 nm to 1 nm. In these nano-sized fissures, their inert properties and the size of the carbon atoms will prevent water from attacking the bond at the tip 14 of the fissure and weakening the glass. The carbon atoms, due to their size and energy, create a path to a location near the tip 14 of these fissures. The tips 14 of these crevices are generally located approximately 0.5-50 nm below the surface of the glass substrate. The top surface of layer 7 and / or layer 8 remains smooth and / or nearly flat in the range below about 1.0 nm above the crevice. [0063]

At present, carbon is generally described in many forms, which helps to understand the present invention. [0064]

Carbon is capable of creating bonds-based structures that share a oriented electron pair in all three dimensions. Two of the six electrons of the carbon atom are present in the ls core and are therefore not involved in the bond. On the other hand, the remaining four electrons in 2s and 2p are chemically bonded to adjacent atoms. One 2s or three 2p electron orbitals of a carbon atom can form a mixture in three different ways. This allows carbon to exist as several allotropes. In effect, there are three allotropic crystal phases. That is, diamond, graphite, and fullerene, as well as amorphous plethora. [0065]

For diamond crystal allotropes, tetrahedron or sp³In the bond, all four bonding atoms form a sigma bond. The spatial lattice in diamond is shown in Fig. 4, and each carbon atom is bonded to four other carbon atoms so as to form a tetrahedron with a length of 0.154 nm and a bond angle of 109 ° 53 . The strength of such bonds is that diamond has the unique physical properties of diamond: high atomic density, transparency, extreme hardness, very high thermal conductivity, and very high electrical resistance (10).¹⁶It is paired with the fact that it is a macromolecule (a bond that completely shares an electron pair) that gives ohm-cm). [0066]

The characteristics of graphite are dominated by triangular bonds. As shown in Fig. 5, 2s, 2p of the outer circumference_xAnd 2p_yThe orbitals are sigma bond and sp²P-type II orbit 2p perpendicular to the orbital plane_zForm the three common planes sp²A mixture is formed by giving an orbit. Graphite consists of hexagonal layers separated from each other at a distance of 0.34 nm. One carbon atom is bonded to the remaining three carbon atoms by a sigma bond with a length of 0.142 nm in a hexagonal plane. These planes are why graphite, sp²It is connected by a weak van der Waals bond that can explain whether it is soft along the plane. [0067]

Regarding fullerenes, C₆₀And C₇₀Is the most accessible, sp²It is known as a member of a closed-cage molecule called fullerene, which is made entirely of carbon in the hybrid state. Each fullerene C_nConsists of 12 pentagonal rings and m hexagonal rings (m = (n-20) / 2 (satisfy Euler's theorem)). The sigma bond has a large strain and is wrapped in a rigid fullerene. [0068]

With respect to amorphous carbon, there are carbon types in a metastable state without a long range order. Material properties change when different deposition techniques are used or when the deposition parameters are varied in a single technique. In this prominent material category, we have up to 90% carbon-carbon sp in some suitable examples.³It has the most diamond-like ta-C (eg, layer 7) with bonds, and is produced by the thermal evaporation of carbon, while ac (amorphous carbon) is 95%. Graphite bonds are ubiquitous. In this regard, these two materials reflect the inherent diversity of the non-crystalline form of carbon. [0069]

Amorphous materials such as layers 3, 7, and 8 are metastable solids. In an amorphous solid, there is a set of equilibrium positions for the vibration of atoms. Atoms in amorphous materials are often extended to three-dimensional networks that do not have an order that exceeds the distance to the second closest neighbor. [0070]

If you refer to ta-C layer 7 again, sp³/ sp²A portion, or percentage (%) of the carbon-carbon bond is, for example, the vacuum arc deposition technique, the technique used in Patent '477, or the vapor deposition technique described above, but with C.⁺It can be controlled by changing the energy of the ions. The deposited film, which exists virtually metastable, is under high compressive stress. sp²Carbon atoms with hybrid orbitals sp³Embedded in the matrix. The degree of bonding of the latter gives ta-C the physical characteristics that are characteristic of diamond. sp²Some of the atoms with hybrid orbitals are sp²Determines the degree to which carbon atoms with hybrid orbitals are aggregated. II and II, as seen in the strain removal mechanism^*The degree to which the states are grouped to the extent that the electronic and optical properties of the film can be controlled shifts from the normal state. In the high density state, the II band blends the σ state so as to form conduction and valence mobility band-edges. In the low density end state, it is given to the pseudo-gap and is locally restricted. The term tetrahedral amorphous carbon (ta-C) refers to this high tetrahedral material and mostly sp.²It is used to distinguish carbons with other diamond characteristics that are carbon-carbon correlated in type. [0071]

Sp in coating 3³Bonding is believed to occur during the process of densification of active ions under impact. If more sp³Increases the density of sp²If the density of carbon atoms is low, the hybridization of carbon atoms is expected to be adjusted to the local density. The above can occur if the associated ions penetrate the first atomic layer and enter a position below the surface of the gap. Therefore, local bonds are reformed around and in the vicinity of this atom so that optimal hybrid orbitalization is adopted. High energy ions can, in principle, penetrate the surface layer of the substrate, or the growing DLC, sp.³Increases the density of deep layers that strengthen the bond. Ions with energies lower than the penetration threshold sp bind ac²Only add to the surface that forms. [0072]

According to any of the above examples, the coated material can be used. For example, it is used in situations such as automobile windows, automobile rear windows, automobile side windows, building glass, IG glass units, residential or commercial windows. [0073]

In any of the above examples, tungsten disulfide (WS) without small holes.₂) 12 may be provided on the top surface of layer 7 to prevent the DLC from being exposed to air and burning out. Layer 12 (see, eg, FIG. 8) may be applied by blowing plasma to a thickness of approximately 300-10,000 Å. WS₂Layer 12 cannot be removed in some embodiments. Other suitable materials may be used in place of layer 12. [0074]

Many other features, modifications, and improvements will be apparent to those skilled in the art once the statements made so far are disclosed. Such other features, modifications, and improvements are therefore considered to be part of the invention and the scope of the invention is determined in the following claims.

[Simple explanation of drawings]

[Figure 1]

FIG. 6 is a side sectional view of a substrate provided with a DLC coating containing at least two layers. [Figure 2]

FIG. 6 is a side sectional view of a substrate provided and in contact with a high tetrahedral amorphous carbon DLC coating. [Fig. 3]

FIG. 6 is a side sectional view of a substrate provided with a low-e or other coating. Here, the DLC coating of FIG. 1 or 2 above is also a coating on the substrate, but is present on an intermediate low-e or other coating layer. [Fig. 4]

sp³It is a figure which showed the typical example of the hybrid bond of a carbon atom. [Fig. 5]

sp²It is a figure which showed the typical example of the hybrid bond of a carbon atom. [Fig. 6]

It is a figure which showed a typical example of sp hybridization of a carbon atom. [Fig. 7]

It is a side sectional view of the carbon ion penetrating the substrate or the DLC surface which is strongly bonded. [Fig. 8]

It is a side sectional view of the coated glass substrate showing the DLC bond penetrating the crack on the surface of the glass substrate.