FI124358B - Coating on a glass substrate and coated glass product - Google Patents

Description

Field of the Invention

The invention relates generally to a method for coating large surface areas of glass products by ultra-short pulse laser cultivation. The invention also relates to products produced by the process. The invention has many beneficial effects such as high coating yield, excellent coating properties and low manufacturing costs.

Background 10 Glassware

Glass is a uniform material in the disputed phase and usually occurs when the molten material cools very rapidly below its glass transition temperature without the time required to form a regular crystal lattice structure. The most well-known form of glass 15 is a silica-based material used in household objects such as incandescent lamps and windows. Glass is a biologically inactive material that can be formed on flat and impermeable surfaces. In the stressed state, the glass is brittle and easily breaks into sharp fragments. When pressed, pure glass can withstand considerable forces. The properties of the glass are modified or modified mainly by the addition of other compounds or by heat treatment.

General glass comprises about 70 to 72 weight percent silica (SiCL). Synthetic amorphous silica contains virtually 100% silica, being the raw material for the most expensive special glasses.

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^ 25 Glass has been used in architectural and building products since the 11th century. The use of glass ° in buildings includes transparent window material, glass interior walls ° and architectural features. Existing glass in buildings may have a security type including Threaded, tempered and laminated glass.

“In addition to indoor and outdoor use, glass products can be found in all types of vehicles and

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£ 5 30 for ship windshields and also for the chemical industry, where both small and large cv scale installations are often built of glass. In addition, glass products are commonly used in various optical applications such as lenses and protective covers for various electronic devices 2, for consumer, scientific and military applications. In addition, glass is used as a sheet material in various mastering systems.

Certain radiation stabilized glass products can be found in sun lenses or cell covers.

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As with other products, maintenance costs, lifetime, and properties of mostly uncoated glass products with large surfaces and typically 3D structures could be dramatically improved, for example, by increasing wear resistance and scratch resistance, as well as chemical resistance, self-cleaning properties of the glass product - or by adding AR functions (Anti-Reflective).

At present, the highest quality optical lenses with relatively small surfaces can be coated with, for example, polysiloxane and certain DLC grades to improve wear resistance and increase scratch resistance. Coatings are carried out in batch type processes under high vacuum conditions with long processing times.

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Except for polymers, the only existing large-scale industrial technology for treating large surface glass products is to add a self-cleaning T1O2 coating to the glass by sputtering. The same function is achieved with recent nHALO (Hot-Aerosol-Layering Operation) 25 operations and ALD techniques. In ALD techniques, a typical coating growth rate is less than one molecular layer per deposit cycle, and the technology is thus unsuitable for non-high-end technical purposes 4 such as IC applications.

cp o 30 The same techniques can be utilized to add certain colorants to a glass product. In these techniques, the color is not a coating but a chemically and thermally stable modification of the surface zone.

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r-- o Laser education

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In recent years, significant advances in laser technology have provided the means for the development of ultra-high efficiency laser systems based on semiconductor fibers, thus supporting the so-called. development of cold ablation methods.

At the priority date of the present application, a purely fiber diode pumped semiconductor laser 5 competes with a lamp pump, both of which have the feature of first directing a laser beam into the fiber and then transmitting it to the target. Said fiber laser systems are the only ones used in industrial-scale laser education applications. Recent fibers of fiber lasers, as well as the resulting low radiation power, appear to limit the choice of materials to be used for vaporization / ablation. Evaporation / ablation of aluminum can be promoted through low-pulse power, while more challenging materials such as copper, tungsten, etc., need more pulse power in terms of vaporization / ablation. The same applies to the situation where new compounds were to be produced using the same conventional techniques. Notable examples include e.g. the direct fabrication of a diamond from carbon (graphite) or the production of alumina (alumina) directly from aluminum and oxygen through the vapor phase reaction of a suitable laser ablation space.

On the other hand, one of the major obstacles to transmitting advances in fiber laser technology appears to be the ability of the fiber to withstand high-power laser pulses without disrupting the fiber or degrading the quality of the laser beam.

When utilizing the new cold ablation, there were qualitative and production rate problems associated with the coating, an approach to thin film production as well as cutting / grooving / grooving, etc.

with a focus on increasing laser power and reducing the laser beam spot size in the subject. However, most of the power increase was spent on noise.

° Quality and production rate problems still persisted, even though some of the 0 laser manufacturers solved the problem of laser power.

i g 30 Coating / thin film type samples as well as 1 cutting / grooving / grooving etc. could only be produced at low reproduction speeds, narrow scan widths and long machining time, as such co outside industrial usability, with particular emphasis on large pieces, o

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If the energy content of the pulse is kept constant, the pulse power increases as the pulse duration becomes shorter, which greatly aggravates the problem. The problems are significant even with nanosecond pulse lasers, although they are not used as such in 4 cold ablation methods. A further reduction in pulse duration to the femto or even attosecond class renders the problem almost unsolvable. For example, in a picosecond laser system, with a pulse time of 10-15 ps, pulse energy should be 5 µs per 10-30 µm for a total laser power of 100 W and a repetition rate of 20 5 MHz. At the priority date of the present invention, the fiber that could withstand said pulse was not known to the author.

The output speed is directly proportional to the playback speed or frequency. On the other hand, in known mirror film scanners (galvanic scanners or reciprocating-type scanners) that perform their duty cycle characterized by 10 reciprocating movements, stopping the mirror at each end of the duty cycle is somewhat problematic, as well as turning point scan width. If production rates are to be increased by increasing the reproduction rate 15, acceleration and deceleration will cause either a narrow scan interval or an uneven distribution of radiation and thus plasma at the target when the radiation hits the target through an accelerating and / or slowing mirror.

If an attempt is made to increase the coating / film production rate simply by increasing the pulse repetition rate, the current above-mentioned scanners direct the pulses to the overlapping portion of the target region at low kHz region pulse repetition rates in an uncontrolled manner. At its worst, this approach results in the release of particles from the target material instead of plasma, or at least the formation of particles in plasma. When multiple consecutive laser pulses are directed to the same target material location, the cumulative effect appears to shatter the target material unevenly and may result in heating of the target material, thereby losing the benefits of cold ablation.

4o ^ The same problem occurs with nanosecond lasers, while the problem is naturally even more severe due to the long-lasting, high-energy pulses.

£ Then there is always heating of the target material, with the material temperature rising to about 5000 K. Thus, even a single nanosecond pulse

Ho radically destroys the target material with the above problems.

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In the prior art, not only can the target be irregularly drawn, but it can also easily fragment and impair plasma quality. Thus, the surface to be coated with the plasma in question also suffers from the adverse effects of the plasma. The surface 5 may contain lumps, the plasma may not be uniformly distributed to form the coating, etc., which is problematic in an operation requiring precision, but not necessarily in paint or pigment, for example, assuming that the defects remain below the detection limit of that application.

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Current methods consume an object per use, so the same target is not available for later use on the same surface. The problem has been solved by utilizing only the virgin surface of the object by moving the target material and / or the beam site respectively.

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In machining or machining applications, residual material or debris, including some pieces, may also render the cutting line uneven and thus unsuitable, for example, in the case of flow-control drilling. The surface may also have a curved appearance 15 due to the release of fragments, which may not be appropriate for example in the manufacture of certain semiconductors.

In addition, the reciprocating mirror-film scanners generate inertia forces which load the structure itself as well as the bearings to which the mirror is attached and / or which cause the mirror to move. This kind of inertia may gradually loosen the attachment of the mirror, especially if the mirror is operating within the extreme range of possible operating settings, and may lead to long wandering of the settings, which can be seen in the uneven reproducibility of the product quality. Due to stops, as well as the direction of movement and the associated speed changes, this mirror-film scanner has a very limited scanning width for use in ablation and plasma production. The effective duty cycle is relatively short compared to the full cycle, although the operation is in any case quite slow. From the viewpoint of increasing the productivity o of the mirror film scanner system, the plasma production rate is conditionally slow, g 30 Scanning width narrow, long term uncertainty, which also leads to x situation with very high likelihood of interfering with unwanted particle emission with plasma plasma contact via hardware and / or coating.

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No. 35 Summary of the Invention

The cost of maintaining glass products is huge and steadily increasing, so there is a great need for darkening technologies, especially for glass products with large areas. Product lifetime should be increased and maintenance costs reduced on sustainable terms. Coatings on large glass surfaces, especially homogeneous coatings, should have one or more of the following properties, which remain unresolved problems: excellent optical properties, chemical and / or abrasion resistance, scratch-resistant surface, thermal resistance, resistivity, coating adhesion, self-cleaning properties.

Recent high-tech coating techniques, as well as current coating techniques associated with laser cultivation in either the nanosecond or cold ablation region (pico, femtosecond lasers), are unable to provide any useful method for coating large surface glass products on an industrial scale. Current CVD and PVD coating technologies require high-vacuum conditions making the coating process 15 different and thus unsuitable for industrial scale coating of most current glass products. In addition, the distance between the material being coated and the ablation coating material is long, typically over 50 cm, making the coating chambers large and the vacuum pumping cycles time and energy consuming. Said large-volume vacuum chambers are also easily contaminated by the coating materials during the coating process itself, requiring continuous and time-consuming cleaning processes.

Attempts to increase the coating production rate in current laser assisted coating methods result in various defects such as micropores, increased surface roughness, reduced or lost optical properties, fine particles on the coating surface, fine particles in the surface structure, causing corrosion, diminished surface, .

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g 30 Current coating methods also radically limit usable x materials for coating applications in general and thus limit the range of different coated glass products available on the market. If appropriate, the surface of the target material is eroded in such a way that only the outer target material h? the layer can be used for coating purposes. The rest of the material is either discarded at £ 3 35 or subjected to reprocessing before reuse.

The object of the present invention is to solve or at least alleviate the problems of the prior art.

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It is a first object of the invention to provide a novel method for solving a problem in which a particular surface of a glass product is coated by pulsed laser cultivation so that the uniform surface to be coated comprises at least 0.2 dm 2.

Another object of the present invention is to provide novel glass products coated with pulsed laser education so that the uniform surface coated comprises at least 0.2 dm 2.

It is a third object of the present invention to provide at least a novel method and / or related means for solving the problem of producing fine quality plasma from virtually any object intended to be used for coating glass products such that the target material does not form any fine particles in plasma, i.e. plasma. is pure 15 plasma, or pieces, if present, are rare and at least smaller in size than the ablation depth at which plasma ablation is created from said subject.

It is a fourth object of the present invention to provide at least a novel method and / or related means for solving how a uniform surface of a glass product can be coated with fine quality plasma without fine particle size larger than the ablation depth to which plasma is ablated from said subject, i.e. pure plasma from virtually any material.

A fifth object of the present invention is to provide good adhesion of the coating to the uniform surface of the glass product by means of said clean plasma, such that the waste of kinetic energy on the fine particle particles is reduced by limiting their existence or size below the ablation depth. At the same time, the small particle fragments of g 30 do not form cool x surfaces, which could affect the homogeneity of the plasma cloud through nucleation and condensation-related phenomena, co

It is a sixth object of the invention to provide at least a new method and / or means for solving the problem of providing a wide scanning width simultaneously with finely divided plasma quality and of providing a wide coating width even for large glass bodies in an industrial manner.

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A seventh object of the invention is to provide at least a novel method and / or related means for solving the problem of providing high repetition rate in industrial scale applications for use in accordance with the aforementioned objects of the invention.

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An eighth object of the invention is to provide at least a novel process and / or related means for solving the problem of providing fine plasma for coating uniform glass surfaces and manufacturing products according to Objectives 1-7, while still retaining target material 10 for use in coating steps providing similar coatings / thin films.

Another object of the invention is to use such a method and means in accordance with the foregoing objectives to solve the problem of cold working and / or coating surfaces for coated products.

The present invention is based on the surprising finding that the surfaces of glass products with large surfaces can be coated at industrial production rates and excellent properties with one or more technical properties such as optical transparency, chemical and / or abrasion resistance, abrasion resistance, , coating adhesion, self-cleaning properties, and possibly tribological properties, fine particle-free coatings, microparticle-free coatings, and electrical conductivity by utilizing ultra-short pulse laser cultivation in a manner in which a laser pulse is scanned with a rotating optical scanner containing at least one

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In addition, the present method achieves an economical utilization rate of g 30 for target materials by ablating them in a manner that achieves the reuse of x material already in use while maintaining good coating results. The present invention further achieves coating of glass product surfaces under low vacuum conditions while providing good coating properties. In addition, the required coating chamber volumes for rC are dramatically less than £ 3 35 in competing methods. These features dramatically reduce the cost of overall hardware and increase coating production speed. In many advantageous cases, coating equipment can be installed on a production line in an online style.

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Coating growth rates on a 20W USPLD are 2 mm3 / min. As the laser power is increased to 80 W, the growth rate of the USPLD coating accordingly increases to 8 mm3 / min. According to the invention, the growth rate increase 5 can now be fully utilized for high quality coating production.

In this patent application, the term "coating" refers to the formation of a material of any thickness on a substrate. Thus, coating may also involve producing thin films, e.g., with a thickness of <1 µm.

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The various embodiments of the invention may be conveniently combined.

Those skilled in the art, having read and understood the invention, will know many different ways of modifying embodiments of the invention without departing from the scope of the invention, which is not limited to the embodiments shown, which are exemplified by the embodiments of the invention.

FIGS. 20 and other advantages of the invention will become apparent from the following detailed description with reference to the figures, in which:

Figure 1 illustrates an exemplary galvanic scanner assembly comprising two galvanic scanners utilized in the production of prior art 25 cold ablation coating / thin film as well as in machining and other machining applications. The number of galvanic scanners in guiding the laser beam varies, but is typically limited to one galvanic scanner; ° the abbreviations in Figure 1 correspond to the following references: LS - Laser beam, TS - § Folded beam; SS - Rectangular scanning area; GX - The galvanometer scans the X-g 30 axis; GY - The galvanometer scans the Y axis,

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Figure 2 illustrates an ITO coating on a polycarbonate sheet (~ 100 mm x 30 σ) mm) utilizing a prior art oscillating mirror (head scanner) produced at various ITO thin film thicknesses (30 nm, 60 nm and 90 nm), o 35 ° C.

Figure 3 illustrates a situation where a prior art galvanometric scanner is used to scan a laser beam at a laser dot scan rate of about 1 m / s, which results in highly overlapping pulses at a repetition rate of 2 MHz, 10

Figure 4 illustrates one embodiment of the invention in the form of an ITO-coated glass sheet,

Figure 5 shows one possible turbine scanner mirror used in the method of the invention,

Figure 6 shows the motion of the ablating beam achieved by each mirror of Figure 5; Figure 7 shows beam control through a single, possibly rotating, scanner used in accordance with the invention,

Figure 8 shows beam guidance through a single, possibly rotating, scanner used in accordance with the invention, 15

Figure 9 illustrates beam guidance through a single, possibly rotating, scanner used in accordance with the invention,

Figure 10 illustrates one embodiment of a product coated according to the invention (sample tube),

Figure 11 illustrates an embodiment of a product coated according to the invention (glass tube), Figure 12 illustrates an embodiment of a product coated according to the invention (drinking glass), ° Figure 13 illustrates an embodiment 0 (master plates) of the product coated according to the invention, p 30 Figures 14a-14c. illustrate certain embodiments (mirror surfaces) of a product coated according to the invention, comprising a plurality of different layers forming the mirror structure co, one layer always being glass,

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35 illustrates an embodiment (glass of an airplane, train or car) of a multilayer product according to the invention, 11

Figure 16 illustrates an embodiment (front surface OLED, LCD, plasma or other display) of a multi-coated product according to the invention,

Figure 17 illustrates two embodiments of a product coated according to the invention (left - spectacles, sunglasses; right - goggles and visors),

Figure 18 illustrates an embodiment (OLED, LCD, plasma, or other display structure) of a multi-coated product according to the invention; the arrow points to 10 active surfaces, contact surfaces,

Figure 19 illustrates two embodiments (armored glass) of a multi-coated product according to the invention; Figure 20 shows the transmission curve of an uncoated glass sheet; reference glasses, not ITO,

Figure 21 shows on one side the transmittance curve of an ITO coated glass sheet which is very transparent; high transparency ITO, resistivity ~ 6x x 10'3 20 Ωαη,

Figure 22 shows on one side the transmittance curve of an ITO-coated glass sheet which is moderately transparent; Figure 23 shows, on one side, the transmittance curve of an ITO-coated glass sheet having a low sheet transparency; low transparency ITO, resistivity ^ ~ 6 x 10'3 Ωαη, δ

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g Figure 24a. illustrates an example of scanning and ablation of the target material g 30 according to the invention using a rotary scanner (turbine scanner),

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Figure 24b. shows an exemplary portion of the target material of Fig. 24a, 't co [£? Figure 24c. illustrates an exemplary ablated region of the target material of Fig. 24b o o 35, where x = 1 μιη - 1000 μιη, e.g. 45 μηι; γ = 50-200 nm, e.g.

100 nm, 12

Figure 25 shows an example of targeting and ablation of a target material according to the invention using a turbine scanner (rotary scanner),

Figure 26a. illustrate the problems of prior art plasma technologies;

Figure 26b. illustrates problems with prior art plasma technologies.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION According to the invention, there is provided a method of coating a given surface of a glass product by laser culturing, wherein the uniform coating surface comprises at least 0.2 dm2 and wherein the coating is performed by targeting laser pulses at a pulse frequency MHz and wherein the pulsed laser beam is scanned by means of a rotating optical scanner which includes at least one mirror to reflect said laser beam.

"Glass products" shall be understood to mean, without limitation, glass products, for example, for use in construction as a whole, for interior and architectural and architectural purposes, for optics in consumer, scientific and military use, vehicles such as automobiles, trucks, motorcycles and tractors, aircraft, , rails, tools, medical products, lenses and shields for displays and portable devices, lighting, profiles, frames, component parts, process equipment, tubes 25 and tanks for various industries such as chemical, power and energy industries, spacecraft, water pipes, sheet material of various mastering systems, solar reflectors, solar cell covers etc. Some of the embodiments of the invention io are shown in Figures 4 and 10-19.

s 30 x Ultra Short Laser Pulse Deposition (USPD)

Laser Pulsed Deposition). Said growth is also referred to as cold ablation, where one of the features is that, unlike competing nanosecond lasers, for example, heat transfer from the exposed 35 target area to this environment is still not high enough for laser pulse energies to exceed the target material ablation limit. Pulse lengths are typically less than 50 ps, e.g., 5-30 ps, i.e., ultralight, with cold ablation at picosecond, femtosecond, and attosecond pulse lasers.

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The material evaporated from the subject by laser ablation is grown on a substrate maintained near room temperature. Still, the plasma temperature reaches 1,000,000 K in the exposed target area. Plasma velocity is superior, even reaching 100,000 m / s, thereby achieving a better prediction of sufficient adhesion of the produced coating / thin film 5.

In another embodiment of the invention, said uniform surface area comprises at least 0.5 dm 2. In yet another embodiment, said uniform surface area comprises at least 1.0 dm 2. The invention also readily accomplishes the coating of products having uniform coated surfaces greater than 0.5 m2, such as those of 1 m2 and larger. Because the process is particularly advantageous for coating large surfaces with high quality plasma, it faces an under-served or completely unserved market for a wide variety of glass products.

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In industrial applications, it is important to achieve high efficiency in laser processing.

In laser education based on cold ablation, the intensity of the laser pulses must exceed a predetermined threshold to promote the phenomenon of cold ablation. This limit depends on the target material. In order to achieve high processing efficiency and thus industrial productivity, the pulse repetition rate must be high, e.g., 1 MHz, preferably above 2 MHz and preferably above 5 MHz. As previously mentioned, it is preferable not to direct multiple pulses to the same location of the target material as this causes a cumulative effect in the target material, leading to poor quality plasma and thus poor quality coatings and thin films, to achieve a high degree of it is necessary to provide a high scanning speed for the laser beam. According to the invention, the beam velocity at the surface of the object should generally be greater than 10 m / s o for effective treatment, and preferably greater than 50 m / s and g 30 more preferably greater than 100 m / s, even at speeds such as 2000 m / s.

x However, in optical scanners based on a vibrating mirror, the moment of inertia prevents the mirror from reaching a sufficiently high angle. Thus, the received laser beam on the target surface has a velocity of only a few m / s, with Fig. 1c illustrating an example of such a vibrating mirror, also referred to as a galvanic scanner.

While current plating methods utilizing galvanic scanners can produce scanning widths of up to 10 cm, preferably less, the present invention also achieves much wider scanning widths such as 30 cm and even more than 1 meter simultaneously with excellent coating properties and production rates.

According to one embodiment of the invention, a rotating optical scanner here means 5 scanners comprising at least one mirror for reflecting a laser beam. Such a scanner and its applications are described in patent application FI20065867. According to another embodiment of the invention, the rotating optical scanner comprises at least three mirrors for reflecting the laser beam. In one embodiment of the invention, the polygonal prism shown in Figure 10 is utilized. Here, the polygonal prism has surfaces 21, 22, 23, 24, 25, 26, 27 and 28. The arrow 20 indicates that the prism can be rotated about its axis 19, which axis is prism axis of symmetry. When the prismatic surfaces of Figure 5 are mirror surfaces, preferably oblique, to provide a scanning line, arranged so that each surface alternately changes, with respect to reflection, the incident radiation direction of the mirror surface as the prism rotates about its axis, the prism is applicable to the method of transmitting such as a turbine scanner. Figure 5 shows 8 surfaces, but there may be considerably more surfaces, even dozens or hundreds. Figure 5 also shows that the mirrors are at the same angle with respect to the axis, but especially in the embodiment with 20 more mirrors, said angle may vary step by step so that within a certain range, a certain stepped transition at the working point is achieved in the object illustrated in Figure 6. Various embodiments of the invention are not limited to various turbine scanner mirror arrangements regarding, for example, the size, shape, and number of mirrors reflecting a laser beam.

The structure of the turbine scanner, Fig. 5, contains at least 2 mirrors, preferably more than 6 mirrors, e.g. 8 mirrors (21-28) disposed symmetrically about the central axis 10. As the prism 21 in the turbine scanner rotates 20 about the central axis 19, the mirrors g 30 direct the radiation reflected from the point 29, e.g., a laser beam, precisely to the area of line x, always starting from the same direction (Fig. 6).

The mirror structure of the turbine scanner may be non-inclined (Fig. 7) or inclined at a certain angle, e.g. Figs. 8 and 9. The size and dimensions of the turbine scanner can be freely selected. In one preferred embodiment of the coating method ° 35, it has a circumference of 30 cm, a diameter of 12 cm and a height of 5 cm.

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In one embodiment of the invention, it is preferable that the turbine mirrors 21-28 are preferably angled with respect to the central axis 19, since then the laser beam is easily guided to the scanner system.

In the turbine scanner used according to the embodiment of the invention (Fig. 5), the mirrors 21-29 may differ from each other in such a way that as many lines in the shape of a line (Fig. 6) are scanned during one revolution of rotation as there are 21-28 mirrors.

According to the invention, the surface to be coated may comprise all or only part of the surface of the glass product.

In a preferred embodiment, the laser cultivation is performed at a pressure of 10 to 8 kPa. High vacuum conditions require quite long pumping times and thus increased coating production times. This is not a big problem for certain high end products, but it is definitely the case, for example, for consumer products with larger surfaces. For example, if new abrasion and scratch resistant coatings, chemically inert coatings, resistive coatings, tribological coatings, heat-resistant and / or heat-conductive coatings, electrically conductive coatings, and possibly simultaneously excellent transparency are taken into account, there is simply no from an economic point of view.

Thus, in a particularly preferred embodiment of the invention, the laser cultivation is carried out at a pressure of 10 Pa to 10 kPa. According to the invention, excellent coating / thin film properties can be achieved already at low pressure resulting in dramatically reduced processing times and improved industrial usability.

According to the invention, it is possible to carry out the coating in a manner in which the distance m between the target material and said uniform surface to be coated is less than 25 cm, preferably less than 15 cm, and most preferably less than 10 cm. This results in the development of radially reduced volume coating chambers, making the total cost of coating production lines lower and further reducing the time required for vacuum pumping.

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In a preferred embodiment of the invention, the ablated surface of the target material can be repeatedly ablated to produce a defect-free coating. For most current coating technologies, the target material will wear unevenly in a manner where the exposed area cannot be reused for ablation and thus must be rejected or sent for regeneration after a given use. An attempt has been made to solve the problem by continuously developing various techniques for feeding new non-ablated target material for coating purposes, e.g., by moving the target material relative to the x / y axes or by rotating the cylindrical target material. The present invention provides simultaneously excellent coating properties and production rates as well as the use of a target material in a manner in which good quality plasma retains its properties through the use of substantially all of the target material. Preferably, more than 50% by weight of the single target material is consumed to produce good quality plasma according to the invention. By "good quality plasma" is meant plasma intended for producing defect-free coatings and thin films, while maintaining the good quality of the plasma cloud at high pulse rates and growth rates. Some of these features are described below.

In one embodiment of the invention, the coating produced has an average surface roughness of less than 100 nm scanned over a 1 pm2 area under an AFM microscope. More preferably, the average surface roughness is less than 30 nm. Most preferably, the average surface roughness is less than 10 nm. Mean surface roughness herein refers to the mean deviation from a fitted centerline mean curve by a suitable method, e.g., AFM or 25 profile gauge. The surface roughness affects e.g. abrasion and scratching properties, tribological properties as well as the translucency of coatings of glass products coated according to the invention.

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g In yet another preferred embodiment of the invention, the coating produced has an optical x transmittance at said uniform surface area of not less than 88%, preferably not less than 90%, and most preferably not less than 92%. It can even have a cS greater than 98%. In some cases it may be advantageous to achieve h? limited optical transparency. Examples of these are security screens, transparent windows, sunglasses, screen shields for either sunlight or UV or other radiation.

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In another embodiment of the invention, the coating produced in said uniform surface area contains less than one pinhole per 1 mm 2, preferably less than one micro hole per 1 cm 2, and preferably no micro holes at said uniform surface area. The micro-hole is a hole that passes through or substantially through the coating. The tiny holes provide a platform for the erosion of the originally coated material, for example through chemical and environmental factors. A single tiny hole in the coating of a chemical reactor or pipeline, for example, can easily lead to dramatically reduced product life.

Thus, in another preferred embodiment, said uniform surface area is coated in such a way that the first 50% of said coating area in said uniform surface area does not contain any particles having a diameter greater than 1000 nm, preferably 100 nm and most preferably 30 nm. If the steps during the coating manufacturing process produce micrometer size 15 particles, said particles may open up corrosion passages in subsequent layers of the produced coating. In addition, the irregular shape of the particles makes it very difficult to compact the surface below those particles. Further, said particles substantially increase the surface roughness. Even in this context, the present method allows for increased life expectancy and reduced maintenance costs for various glass products.

The glass product itself may comprise almost any glass (silicate glass, quartz, lead glass, etc.) According to one embodiment of the invention, said uniform surface of the glass product is coated with metal, metal oxide, metal nitride, metal carbide or a mixture thereof. Non-limiting examples of metals include aluminum, molybdenum, titanium, zirconium, copper, yttrium, magnesium, lead, zinc, ruthenium, chromium, rhodium, silver, gold, cobalt, tin, nickel, tantalum, gallium, cm manganese, vanadium, platinum and almost any metal.

When producing coatings of the invention having excellent optical, abrasion, and scratch resistance properties, particularly preferred EE metal oxides are, for example, alumina and various combinations thereof, such as aluminum fructan titanium oxide (ATO). Thanks to its resistivity, high-optical films

Already having high quality indium tin oxide (ITO) is particularly advantageous in applications where the coating can be used to heat the coated surface.

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35 It can also be used for solar control. Yttrium-stabilized zirconium oxide is another example of various oxides which have excellent optical, abrasion, and scratch resistance properties. Some metals 18 can be utilized in solar cell applications. As a result, actual cells are often grown on glass, and the demand for reproducible, inexpensive, high quality coatings is steadily increasing. In this case, the optical properties of the thin films of the metal derivatives differ slightly from those of the bulk metals. 5 In ultra-thin films (<100 Å thick), variations make the concept of optical constants difficult, with the coating (thin film) quality and surface roughness thus being critical technical features. These coatings can easily be produced by the process of the present invention.

Like most pure metals, all metals commonly used as mirrors 10 (Al, Ag, Au, Cu, Rh, and Pt), irrespective of their use, are subject to oxidation (AI), sulfide darkening (tarnishing, Ag), and mechanical scratching. For this reason, the mirrors should be coated with hard transparent protective layers. Thus, SiO, S1O2 and AECh films are often used to protect evaporated Al mirrors, but usually at the expense of increased absorbance. This problem 15 has been addressed by the present invention by producing hard coatings that include improved optical transparency and thermal conductivity. Today, various substrate film adhesives (e.g., Al2O3, SiO) are used to improve adhesion, but the use of Ag film in mirrors has remained limited. Adhesion of suitable films can be improved by producing both the presently used films 20 and other improved carbon-based films such as diamond and carbon nitride by the process of the present invention.

The dielectric materials used in current optical coating applications include fluorides (e.g., MgF2, CeK), oxides (e.g., Al2O3, T1O2, S1O2), sulfides (e.g., ZnS, CdS) and sorted compounds such as ZnSe and ZnTe. An essential feature common to dielectric optical materials is their very low ε absorption (α <103 / cm) on any relevant part of the spectrum; in this region they are substantially transparent (e.g., fluorides and oxides in visible and infrared, 9 chalcogenides in infrared).

Dielectric coatings can now advantageously be produced by the process of the present invention.

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Already somewhere between dielectric materials and metals, there is a class of materials called § transparent conductors. According to electromagnetic theory, large

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conductivity and optical transparency are mutually exclusive properties, since photons are efficiently absorbed by dense charge carriers. Although there are materials which, by themselves, are much more effective 19 or more transparent, the transparent guides discussed herein represent a workable compromise on both of these advantageous properties. Broadly speaking, transparent conductive films consist of either ultra-thin metals or semiconductor oxides, and more recently even nitrides such as indium gallium nitride 5 in solar cell applications. The first widespread use of such films occurred in transparent electric heaters for the de-icing of aircraft windshields during World War II. Today they are used to some extent in car and airplane window melters, liquid crystal and gas discharge displays, front solar cell electrodes, antistatic coatings, heating steps for 10 optical microscopes, IR reflectors, TV camera gadget photocells and Q-lasers for lasers.

Metals traditionally used as transparent conductors include e.g. Au, Pt, Rh, Ag, Cu, Fe and Ni. Simultaneous optimization of conductivity and transparency is a major challenge in film cultivation. At one end there are discontinuous islands of considerable transparency but high resistivity at one end, and at the other end membranes that merge early and are continuous and highly conductive but poorly transparent. For these reasons, semiconductor oxides such as SnCL, ImCL, CdO, and more frequently their compounds (e.g. ITO), doped ImCL (with Sn, Sb) and doped SnCl 2 (F, Cl, etc.) are used.

Prior art rearing systems include both chemical and physical methods. Hydrolysis of the chlorides and pyrolysis of organometallic compounds are examples of the former, while reactive evaporation and sputtering in an oxygen environment are examples of the latter - none of the systems being preferred to plastics. Optimal membrane properties require the maintenance of strict stoichiometry. Prior art techniques generally utilize glass substrates, and in these techniques, glass tissue is generally heated to near 9 softening temperatures. In such a system, the stresses and strains of the final product should be carefully avoided. The present method of the invention solves the problems of softening temperature (cold ablation) and produces said high quality films in an economically feasible manner.

C/O

rC Mostly fluoride and oxide films have a value of n less than 2 at a reference wavelength of 0.55 °. However, in many applications, it is important to use films with a higher refractive index in the visible area. Materials such as ZnS and XnSe are typically used to meet these needs 35. High transmittance is an essential requirement for an optical film, and as materials of arbitrary criterion only materials with an absorption constant of less than a = 103 / cm are added to the following list: NaF (c), LiF (c), CaF2 (c), Na3AlF6 (e). , AIF3 (a), MgF2 (c), TI1F4 (a), LaF3 (e), CeF3 (c), S1O2 (a), Ab03 (a), MgO (c), Y2O3 (a), La2O3 (a) , CeO2 (e), ZrCE (a), SiO (a), ZnO (c), TiCE, ZnS (e), CdS (c), ZnSe (e), PbTe, Si (a), 5 Ge (a) ; (e) = crystalline; (a) = amorphous.

In practice, however, only substantially less absorbent films may be allowed. For example, in AR laser coatings, the coating loss should be less than 0.01% corresponding to k ~ 4 x 10 -5 or a = 10 / cm when λ = 5500 Ä.

The process of the present invention solves the problems associated with producing films having a higher refractive index in the visible region and achieves the production of said films in a high quality and economically feasible manner. Furthermore, it is now possible to produce the above materials and compounds in crystalline form, thereby further improving the properties of the film.

15 If certain metal oxides, such as titanium oxide and zinc oxide, are used for surface thicknesses that provide the UV activity of the coating produced, the coating may have self-cleaning properties. These features are highly desirable in use and reduce maintenance costs for many metal products, both internally and externally.

Metal oxide coatings can be produced either by ablation of the metal or metals in an active oxygen atmosphere or by ablation of oxide materials. Even in the latter case, it is possible to improve the coating quality and / or production rate by performing ablation in reactive oxygen. When nitrides are produced, according to the invention, it is possible to use a nitrogen atmosphere or liquefied ammonia to improve the coating quality. A representative example of the invention 4 is the production of carbon nitride (C3N4 films).

O

According to another embodiment of the invention, the uniform surface 1 of the glass product is coated with a carbon material comprising more than 90 atomic percent carbon, of which more than 70% contains a sp3 bond. Preferred materials of this kind include amorphous t? 30 diamonds, nano-crystal diamonds or even pseudo-single crystal diamonds. Different diamond coatings give the glass product excellent tribological, abrasion and anti-scratch properties, but also increase thermal conductivity and resistance.

21

Diamond coatings for glasses are especially useful in protective eye products, electronic displays, goggles for hazardous conditions, and high quality eg crystal form, semiconductor applications, solar cells, eg diode pumps 5 for laser applications, etc.

Still, in another embodiment of the invention, said uniform surface of the glass product is coated with a material comprising carbon, nitrogen and / or boron in various ratios. Preferred materials of this type include boron carbon nitride, carbon nitride (both C2N2 and C3N4), boron nitride, boron carbide, or various hybridization steps of B-N, B-C and C-N10. These materials are diamond-like materials, which have a low density and are extremely durable and chemically inert. For example, carbon nitrides can be used to protect glass products against corrosive conditions, coatings on medical devices and implants, battery electrodes, humidity and gas sensors, semiconductor applications, solar cells, tools, etc.

According to one embodiment of the invention, a certain uniform surface of the glass product may be coated with an organic polymeric material. Such materials include but are not limited to chitosan and its derivatives, polysiloxanes, and various organic polymers.

20 Coating a glass product with chitosan provides promising prospects for the production of a new class of glass products for marine and other aquatic environments as well as new glass products for both internal and external use.

In this case, polysiloxanes are particularly advantageous in the manufacture of products with reasonably high abrasion resistance, scratch resistance, and at the same time 4 excellent optical transparency. In yet another embodiment of the invention, said uniform surface is coated with an inorganic material. Such materials include but are not limited to, for example, stone, glass and ceramic derivatives. In a particularly preferred embodiment of the invention, various glass sheets and 3D-glass structures were coated by ablation of a target material comprising red agate, resulting in a colored but opaque result.

22

According to one embodiment of the invention, said uniform surface of the glass product is coated with only one coating. According to another embodiment of the invention, said uniform surface of the glass product is coated with a multilayer coating. Several coatings can be produced for various reasons. One of the reasons may be to improve the adhesion of certain coatings to the coated glass product by making a first batch of coating which adheres better to the glass surface and has properties that facilitate the next coating layer to adhere to said layer better than the glass surface itself. In addition, the multilayer coating may contain a number of functions that are not possible without the structure in question. The present invention provides the production of multiple coatings in a single coating chamber or in adjacent chambers.

The present invention further provides for the production of composite coatings on a glass product surface by simultaneously ablating one composite material target or two or more target materials comprising one or more substances.

According to the invention, the thickness of said coating on the uniform surface of the glass product is between 20 nm and 20 µm, preferably between 100 nm and 5 µm. The coating thicknesses should not be limited to these, since the present invention provides for the production of molecular coatings on the one hand and very thick coatings on the other hand, such as 100 µm and more.

The present invention further provides the fabrication of 3D structures by utilizing a glass component as a scaffold to increase said 3D structure.

According to the invention there is also provided a glass product comprising a surface coated with a specific laser education o 25, wherein the uniform coated area comprises 4 at least 0.2 dm 2 and wherein the coating is performed using a cold ablation pulsed laser education, wherein said laser education has a pulse frequency wherein the pulsed laser beam is scanned by a rotating optical scanner containing at least one mirror to reflect said laser beam. The benefits of these products are described

Ho in more detail in the previous description of the method.

o o

CVJ

In a more preferred embodiment of the invention, said uniform surface area comprises at least 0.5 dm 2. In a more preferred embodiment, said uniform surface area comprises at least 1.0 dm 2. The invention is also readily applicable to the coating of products having uniform coated surfaces of more than 0.5 m2, such as those of 1 m2 and larger.

According to an embodiment of the invention, the coating produced has an average surface roughness of 5 at said uniform surface area scanned less than 100 nm from an area of 1 pm2 using an Atomic Force Microscope (AFM) microscope. Preferably, the average surface roughness is less than 50 nm and most preferably less than 25 nm.

In another embodiment of the invention, the coating produced has an optical transmittance of at least 88%, preferably not less than 90%, and most preferably not less than 92% of said uniform surface area. In some cases, the optical transmission may be greater than 98%.

Still further, the coating produced in accordance with another embodiment of the invention has less than one pinhole per 1 mm 2, preferably less than one micropore per 1 cm 2, and preferably no micro holes at said uniform surface area.

According to another embodiment of the invention, said uniform surface area is coated in such a way that the first 50% of said coating in said uniform surface area does not contain any particles having a diameter greater than 1000 nm, preferably 100 nm and most preferably 30 nm.

The glass product according to the invention may contain almost any glass or glass composite materials.

cm According to one embodiment of the invention, said uniform surface of the glass product i S is coated with metal, metal oxide, metal nitride, metal carbide or a mixture thereof. Possible metals were previously described in the context of the presently invented x coating process.

CL

According to another embodiment of the invention, said h? the uniform surface is coated with carbon material comprising more than 90 atomic percent of ^35 carbon, of which more than 70% comprises a sp3 bond. Possible carbon materials were previously described in connection with the description of the coating method now invented.

24

Still, in another embodiment of the invention, said uniform surface of the glass product is coated with a material comprising carbon, nitrogen and / or boron in various ratios. Such materials were previously described in connection with the description of the coating method now invented.

5

According to one embodiment of the invention, a certain uniform surface of the glass product is coated with an organic polymeric material. Such materials were previously described in connection with the description of the coating method now invented.

In yet another embodiment of the invention said uniform surface is coated with an inorganic material. Such materials were previously described in connection with the description of the coating method now invented.

According to another preferred embodiment of the invention, said uniform surface of the glass product is coated with a multilayer coating. According to another preferred embodiment, said uniform surface 15 of the glass product is coated with a single coating layer.

According to a preferred embodiment of the invention, the thickness of said coating on the uniform surface of the glass product is between 20 nm and 20 µm, preferably between 100 nm and 5 µm. The invention also provides coated glass products containing one or more atomic coatings and thick coatings 20 in excess of 100 µm, e.g. 1 mm. The present invention further provides the fabrication of 3D structures by utilizing a glass component as a scaffold to increase said 3D structure.

Examples of Demonstrating Prior Art Problems - ^ Laser Technology δ ^ 25 Example 1 og Figure 2 illustrates an ITO coating on a polycarbonate sheet (-100 mm x 30 x mm) using a state-of-the-art optical scanner, namely a vibrating mirror (head scanner). nm, 60 nm and 90 nm).

Although the ITO coating is not applied to the metal substrate, the figure clearly demonstrates some of the problems associated with the use of a vibrating mirror as an optical scanner, particularly in the case of ultra short pulse laser (USPLD) but also in laser assisted coatings in general. Because the oscillating mirror changes its direction of rotation in its end positions and due to the moment of inertia, the angular velocity of the mirror is not constant near the extreme positions. Because of the oscillatory motion, the mirror 25 continuously brakes and stops before being re-accelerated, thereby causing irregular treatment of the target material at the edges of the scanned area. As can be seen in Figure 2, this is converted to poor quality plasma containing particles, especially at the edges of the scanned area, and finally to poor quality and apparently uneven coating results. Although not an example for a glass substrate, it clearly demonstrates some of the disadvantages of using current scanners in the USPLD method.

The coating parameters are chosen to demonstrate an uneven distribution of the grown material due to the nature of the scanner used. If parameters are appropriately selected, the quality of the film can be improved, whereby problems become invisible but non-existent.

Example 2 Conventionally, galvanic scanners are typically used to scan a laser beam at a maximum speed of about 2-3 m / s, in practice about 1 m / s. This means that up to 40 to 60 pulses overlap at a repetition rate of 2 MHz (Figure 3).

Example 3 Plasma quality problems are illustrated in Figures 26a and 26b, which illustrate the creation of plasma according to prior art. The laser pulse 1114 hits the target surface 1111. Because it has a long pulse, the depth h and the beam diameter d are of the same order, the heat of the pulse 1114 also heats the surface at the point of impact but also below the surface 1111 deeper than the depth h.

25 The structure is subjected to thermal shock and tension is created which, when discharged, g produces fragments marked F. Because plasma in this example may be of relatively poor quality, the molecules and their clusters appear to be 9, which is indicated by small dots 1115, such as with reference to ° 1115, which has nuclei or similar structures | 26b, consisting of gases 1116 shown in Fig. 26b. The letters "o" - ^ demonstrate particles that can form and grow in condensation

C/O

and / or agglomeration. The liberated pieces may also o increase due to condensation and / or accumulation, indicated by curved ^ arrows from point to F and from o to F. The curved arrows also indicate 35 phase shifts from plasma 1113 to gas 1116 and further to particles 1115 and the grown particles 1117. Because the ablation cloud in Figure 26b can contain 26 fragments of F as well as vapor and gaseous particles due to poor plasma production, plasma is not continuous plasma. its quality variation can be encountered within a single pulse cloud. Under the depth h of the composition and structural defects h, and also due to the resulting depth variations (Fig. 26a), the target surface 1111 of Fig. 5b 26b is no longer available for multiple increments and the target is thus wasted even if some material remains.

EXAMPLES OF THE METHOD OF THE INVENTION Example 4 10

Fig. 24a demonstrates a target material ablated by a picosecond pulse laser utilizing a rotary scanner whose speed causes the target material to be ablated with slight overlapping of adjacent pulses, avoiding prior art galvanic scanner problems. Figure 24b shows an enlarged view of one portion of the ablated material, clearly showing the smooth and controlled ablation of the material on both the x and y axes, thereby generating high quality, particle-free plasma, plus high quality thin films and coatings. Figure 24c illustrates one example of the possible x- and y-dimensions of a single ablation point achieved with one or a few pulses. It can be clearly seen here that the invention results in the ablation of the material in such a way that the width of the ablated dot is always well above the depth of the ablated dot region. Theoretically, any particles (if any) could now be of maximum point size. The rotary scanner now provides good quality, particle-free plasma production at 25 excellent production speeds, at the same time, at a wide scanning speed, being particularly advantageous for substrates comprising large surface areas to be coated. In addition, Figures 24a, 24b and 24c clearly show that, unlike current 4 techniques, an already ablated target material region can be ablated for a new generation of high-grade plasma, thus radically reducing total coating / thin film production costs.

CC

CL

Example 5 co m r ».

Figure 25 shows an example in which the coating is carried out by utilization

CM

35 picosecond USPLD laser and scan laser pulses with a turbine scanner. Here, the scanning speed is 30 m / s with a laser spot width of 30 µm. In this example, there is 1/3 overlap between adjacent pulses.

Examples of coated products according to the invention

The following samples were grown on various glass substrates using ultra short pulse laser cultivation (USPLD) with a picosecond laser at 1064 nm (X-glass, 20-80 W). The substrate temperature was varied from room temperature to 10,400 ° C and the target temperature from room temperature to 700 ° C. Oxide, sintered graphite, sintered graphite C3N4HX (Carbodeon Ltd Oy) as well as various metal targets were used. When utilizing the oxygen atmosphere, the oxygen pressure ranged from 10'4 to 10'1 mbar (10'2 to 10 Pa). When utilizing a nitrogen atmosphere, the nitrogen pressure ranged from 10'4 to 10'1 mbar (10'2 to 10 Pa). As a scanner, a rotating mirror scanner was used, which was able to adjust the beam speed at the target surface from 1 to 350 m / s. Utilized playback speeds ranged from 1-30 MHz, clearly demonstrating the importance of both scanner and high playback speeds for producing high quality coatings in an industrial manner. The grown membranes were imaged with confocal microscopy, FTIR and Raman -20 spectroscopy, AFM, optical transmission measurements, ESEM and in some cases electronic measurements (University of Kuopio, Finland; ORC, Tampere, Finland and Corelase Oy, Tampere, Finland). . The electrical resistivity of the samples ranged from 2 to 40 x 10 3 Oem and was quite sensitive to growth parameters that were not fully optimized to obtain the lowest resistances. The resistances obtained are quite well comparable with those reported for sputtering ITO films (typically 2 to 6 x 10 3 x 3 3 cm).

δ c \ j 0 Spot sizes used ranged from 20 to 80 µm. The abrasion tests were carried out using the g-30 pin-on-disk method (University of Kuopio, Finland); tests 1 were carried out at room temperature at 22 ° C and 50% (AD coatings) or 25% (others) relative humidity (without lubrication) with loads between 10 and 125 g using hardened steel ball (AISI 420), 6 mm in diameter, rC as pin. For example, for AD coatings the rotation speed was 300-600 rpm and for ° 35 lenses 1 rpm. All coatings had excellent abrasion and adhesion properties.

Example 6 28

The single crystalline SiCh sheet was coated by ablating the sintered carbon at a pulse repetition rate of 4 MHz, a pulse energy of 2.5 µs, a pulse length of 20 ps, and a distance of 8 mm between the target material and the surface to be coated. The pressure during the coating process was 1 Pa. The process resulted in a uniform, light brown transparent coating. The coating had a thickness of 150 nm and an average surface roughness was determined to be 20 nm in the range of 1 pm2 as scanned by AFM microscope. No micropores or detectable particles were found in any of the measured areas.

10

Example 7

Several glass slabs with a surface area of 100mm x 150mm and a thickness of IT3mm were plated by ablation of ITO (IniCUSnOi; 9: 1; Sigma technology, China) at 15 repetition speeds of 4 MHz, pulse energy 2-10 µs, pulse length 20 µm of target material and coating. with a distance between the surface of 30 mm and 50 mm. The pressure during the coating process was 1 Pa. The process resulted in a uniform, transparent coating. The electrical resistivity of the samples ranged from 2 to 40 x 10 "3 Ωαη. The reference glass (uncoated), the high transparency ITO with the resistivity ~6 x 10'3 Ωαη, the average transparency ITO as well as the low transparency ITO, with a resistivity of 2 x 10 "3 Ωοη, examples of penetration curves are shown in Figures 20, 21, 22 and 23, respectively.

Example 8

One ITO-coated glass sheet of Example 7 was coated by ablating aluminum titanium oxide with a repetition rate of 1 MHz, a pulse energy of 12 µm, a pulse length of 20 ps, and a distance of 30 mm between the target material and the surface to be coated. The pressure during the coating process was 1 Pa. Process x resulted in a uniform, transparent coating. The thickness of the ATO coating was measured at 550 nm and the average surface roughness was determined to be 10 nm from 1 pm2 scanned using an AFM microscope. No micropores were observed in any of the ranges measured. The wear resistance of the oxide-coated final product and the anti-scratch properties of £ 3 35 were significantly better than that of uncoated glass. The adhesion of the multilayer structure was good.

29

Example 9

One ITO-coated glass sheet of Example 7 was coated by ablation of yttrium-stabilized zirconia with a repetition rate of 1 Mhz, a pulse energy of 5 to 10 µm, a pulse length of 20 ps, and a distance between the target material and the surface to be coated. The pressure during the coating process was 1 Pa. The process resulted in a uniform, transparent coating. The thickness of the YSZ coating was measured at 300 nm and the average surface roughness was determined to be 2 nm in the 1 pm2 area scanned using an AFM microscope. No micro-holes were detected in any of the 10 areas measured. The wear resistance and scratch resistance properties of the oxide-coated final product were significantly better than that of the uncoated glass material. The adhesion of the multilayer structure was good.

Example 10

A glass plate with a surface area of 100 mm x 150 mm and a thickness of 33 mm was coated by ablating the indium tin metal target (9: 1) in an activated oxygen atmosphere with oxygen pressure ranging from 10'4 to 10'1 mbar (10'2 to 10 Pa). The repetition rate 20 used was 4 MHz, pulse energy 5 µs, pulse length 20 ps, and the distance between the target material and the surface to be coated was 35 mm. The pressure was 1 Pa prior to the introduction of the reactive gas. The process resulted in a uniform, transparent ITO coating. The coating had a thickness of 150 nm and the average surface roughness was determined to be less than 1 nm when scanned using an AFM microscope. No micro-holes were detected in the measured area of the ITO-25 coating. The electrical resistivity of the sample was 2.2 x ΙΟ'3 Ωαη.

Example 11

A

cp g 30 The tumbler of Fig. 12 was coated by ablating red agate (pink agate) i (comminuted and sintered) at a pulse repetition rate of 30 MHz and a distance of 2 cm between the target material and the surface to be coated. The pressure during the coating process was 10 Pa. The process resulted in red-agate opaque coatings with a thickness of 150 nm. The mean surface roughness 35 was determined to be less than 2 nm when scanned using an AFM microscope. No micropores were observed in any of the measured areas of the agate coating.

Example 12 30

A glass plate with a surface area of 500 mm x 600 mm was coated by ablating cold-pressed chitosan at a pulse repetition rate of 10 Mhz, a pulse energy of 5 µm, a pulse length of 20 ps, and a distance of 20 mm between the target material and the surface to be coated. The glass material was preheated to approximately 120 ° C. The pressure during the coating process was 1 Pa. The process resulted in a partially opaque coating having a thickness of 260 nm. The average surface roughness of the coating was determined to be less than 4 nm when scanned using an AFM microscope. No micropores were observed in any of the measured areas of the polymer coating 10.

Example 13

A glass plate with a surface area of 300 mm x 300 mm was plated by ablating 15 vanadium metals in an active oxygen atmosphere with oxygen pressure ranging from 10'4 to 10'1 mbar (10'2 to 10 Pa). The pulse repetition rate was 25 MHz, pulse energy 5 µs, pulse length 20 ps, and the distance between the target material and the surface to be coated was 30 mm. The glass material was preheated to approximately 120 ° C. The pressure was maintained at 1 Pa prior to the actual coating process. The process resulted in a transparent coating having a thickness of 10 nm. The average surface roughness of the coating was determined to be 0.14 nm scanned over an area of 1 pm2 using an AFM microscope. No micropores were observed in any of the vanadium oxide coating regions measured.

Example 14 A 300 mm x 300 mm glass plate was coated by ablating the copper metal target. The pulse repetition rate was 17 MHz, pulse energy 4.5 µs, pulse i o length 20 ps, and the distance between the target material and the surface to be coated was 70 g 30 mm. The glass material was preheated to approximately 120 ° C. The pressure x during the coating process was 1 Pa. A short process resulted in a transparent coating having a thickness of 3 nm. The average surface roughness w of the coating was determined to be 0.14 nm scanned over an area of 1 pm2 using the AFC microscope rC. No micropores were observed in any of the copper plating ranges measured.

^ 35 The copper coating seemed to be easily oxidizable.

Example 15 31

The procedure of Example 14 was repeated on a copper plated glass sheet subjected to another plating process without opening the deposited plating chamber between subsequent plating steps. The following coating layer was produced by ablation of yttrium-stabilized zirconia at a pulse repetition rate of 5 MHz and a pulse length of 19 ps. The pressure was kept constant at 1 Pa during the coating process without any vacuum gap between subsequent coating procedures. The process resulted in a transparent YSZ coating with a thickness of 180 nm. The average surface roughness was determined to be 0.14 nm in the 1 pm2 area scanned using an AFM microscope. No micropores were observed in any of the 10 areas of the YSZ coating.

Example 16

The laboratory glass tube of Figure 10 was coated by ablating sintered graphite carbon nitride target material (C3N4HX, Carbodeon Ltd Oy). The pulse repetition rate was 2 MHz, pulse energy 5 µs, pulse length 20 ps, and the distance between the target material and the surface to be coated was adjusted to 15 mm. The glass material was preheated to about 120 ° C. The pressure during the coating process was 1 Pa. The process resulted in a C3N4 coating having a thickness of 19 nm. The average surface roughness was determined to be 0.14 nm in the 1 pm2 area scanned by the AFM microscope. No micropores were observed in any area of the coating.

Example 17 25

A glass plate with a surface area of 100 mm x 150 mm and a thickness of 33 mm was plated by ablating the gallium nitride target (GaN). The repetition rate used was 4 MHz, pulse energy 6 µs, pulse length 20 ps, and a distance of 60 mm between the target material and the surface to be coated. The pressure was maintained at 1 Pa. The process resulted in a uniform, transparent GaN coating having a thickness of 20 nm, g 30.

1 The average surface roughness of the coating was determined to be less than 1 nm when scanned using an AFM microscope. No micropores were observed in any of the measured areas.

LO

£ 3 35 Example 18

The gallium nitride-coated glass sheet of Example 17 was coated with ITO by ablating ITO (In203: SnO2; 9: 1; Sigma technology, China) at a repetition rate of 4 MHz with a pulse 32 energy of 6 µm, a pulse length of 20 ps and a distance between target material and surface to be coated. set to 50 mm. The pressure during the coating process was 1 Pa. The process resulted in a uniform, transparent ITO coating. The coating thickness was 150 nm with an average surface roughness determined to be 0.3 nm over a 1 pm2 area scanned using an AFM microscope. No micropores were observed in any of the measured areas.

Example 19 The gallium nitride and ITO coated glass sheet of Example 18 was coated with aluminum oxide (Al2O3) by ablating metal aluminum as a film fed in an activated oxygen atmosphere with oxygen pressure ranging from 10'4 to 10'1 mbar (10'2 -10 Pa). The repetition rate was 4 MHz, pulse energy 4.5 µs, pulse length 20 ps, and the distance between the target material and the surface to be coated was set at 50 mm. The pressure was maintained at 1 Pa prior to the actual coating process. The process resulted in a uniform, transparent alumina coating having a thickness of 300 nm and an average surface roughness determined to be less than 8 nm when scanned using an AFM microscope. No micropores were observed in any of the measured areas.

20

Example 20

A glass plate with a surface area of 300 mm x 300 mm was coated by ablating titanium in an active oxygen atmosphere with oxygen pressure ranging from ΙΟ-4 to 10'1 mbar (10'2 -25 10 Pa), pulse repetition rate 25 Mhz, pulse energy 20 µm ps and the distance between the target material and the surface to be coated is set at 30 mm. The glass material was preheated to approximately 120 ° C. The pressure was maintained at 1 Pa prior to the actual coating process.

The process resulted in a transparent coating having a thickness of 20 nm.

g 30 The average surface roughness of the coating was determined to be 0.14 nm over an area of 1 pm2 scanned using an AFM microscope. No micropores were observed in any of the titanium oxide coating regions measured. The coated product was exposed to organic dirt co after which it was exposed to light and a certain humidity, h? The coating had self-cleaning properties.

0 'JS

c \ j

Example 21 33

A glass plate with a surface area of 300 mm x 300 mm was coated with alumina (Al2O3) by ablating metallic aluminum as a film fed in an active oxygen atmosphere at an oxygen pressure ranging from ΙΟ "4 to 10" 1 mbar (10'2 to 10 Pa) at a repetition rate of 48 MHz, 5 psi with a pulse length of 20 ps and 5 psi with a distance of 25 mm between the target material and the surface to be coated. The pressure was maintained at 1 Pa prior to the actual coating process. The process resulted in a uniform aluminum oxide coating with a thickness of 2100 nm. The average surface roughness of the coating was determined to be less than 2 nm when scanned using an AFM microscope. No micro-holes were detected in any of the measured areas.

't δ

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cp M-

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Claims (32)

A method for coating a particular surface of a glass product by laser deposition, characterized in that the unitary area to be coated comprises at least 0.2 dm 2 the pulse laser beam being scanned with a rotatable optical scanner, which scanner comprises at least one mirror to reflect said laser beam. Method according to claim 1, characterized in that said uniform area comprises at least 0.5 dm2. Method according to claims 1-2, characterized in that said uniform area comprises at least 1.0 dm2. Method according to any of the preceding claims, characterized in that said laser deposition is carried out at a pressure of 10'8 Pa - 10 kPa. Method according to claim 4, characterized in that said laser deposition is carried out at a pressure of 10 Pa - 10 kPa. Process according to any of the preceding claims, characterized in that the distance between the grinding material and said uniform area to be coated is less than 25 cm, preferably below 15 cm and preferably below 10 cm. Process according to any one of the preceding claims, characterized in that the ablated surface of the abrasive material can be ablated to produce an error-free coating. Method according to claim 1, characterized in that the average surface roughness of the coating produced on said unitary area when scanning an area of 1, pm using an AFM (Atomic Force Microscope) microscope is less than 100 S5 nm r Method according to Claim 1, characterized in that the "optical permeability of the produced coating" on said uniform area is at least 88%, preferably at least 90. and preferably at least 92%. LO N- A method according to claim 1, characterized in that in said coating on said CM 2 uniform area there are fewer than one micro heel per 1 mm, preferably less than one micro heel per 1 cm2 and preferably no micro heel on said uniform area. Method according to claim 1, characterized in that said uniform area is coated in such a way that the first 50% of the coating on said uniform area does not contain particles whose diameter exceeds 1000 nm, preferably 100 nm and preferably 30 nm. Process according to claim 1, characterized in that said uniform area of the glass product is coated with metal, metal oxide, metal nitride, metal carbide or a mixture thereof. Process according to claim 1, characterized in that said uniform area of the glass product is coated with carbon material containing more than 90 atomic percent koi, of which more than 70% with sp3 bonds. Process according to claim 1, characterized in that said uniform area of the glass product is coated with materials containing koi, nitrogen and / or living in different conditions. Method according to claim 1, characterized in that said uniform area of the glass product is coated with organic polymer material. Process according to claim 1, characterized in that said uniform area of the glass product is coated with inorganic material. Method according to any of the preceding claims, characterized in that said uniform area of the glass product is coated with a multilayer coating. Method according to any of the preceding claims, characterized in that said coating thickness of the uniform area of the glass product is between 20 nm and 20 µm, preferably between 100 nm and 5 µm. δ 19. A glass product with a determined laser-coated surface Λ 9 characterized in that the coated uniform area comprises at least 0.2 dm and that the T coating has been made according to the method described in claim 1. X CC Glass product according to claim 19, characterized in that said uniform area co comprises at least 0.5 dm. δ Γ "- Glass product according to claims 19 - 20, characterized in that said uniform area C \ J 2 comprises at least 1.0 dm. Glass product according to claim 19, characterized in that the average surface roughness of the coating produced on said unitary area when scanning an area of 1 pm2 by means of an AFM (Atomic Force Microscope) microscope is less than 100 nm. Glass product according to claim 19, characterized in that the optical permeability of the produced coating on said uniform area is at least 88%, preferably at least 90% and preferably at least 92%. Glass product according to claim 19, characterized in that in said coating on said uniform area there is less than one micro heel per 1 mm 2, preferably less than one micro heel per 1 cm 2 and preferably no micro heel on said uniform area. Glass product according to claim 19, characterized in that said uniform area is coated in such a way that the first 50% of the coating on said uniform area does not contain particles whose diameter exceeds 1000 nm, preferably 100 nm and preferably 30 nm. Glass product according to claim 19, characterized in that said uniform area of the glass product is coated with metal, metal oxide, metal nitride, metal carbide or a mixture thereof. 27. Glass product according to claim 19, characterized in that said uniform area of the glass product is coated with carbon material containing more than 90 atomic percent koi, of which more than 70% with sp3 bonds. Glass product according to claim 19, characterized in that said uniform area of the glass product is coated with materials containing koi, nitrogen and / or living in different conditions. δ CM cm Glass product according to claim 19, characterized in that said uniform area of the glass product is coated with organic polymer material. ir Glass product according to claim 19, characterized in that said uniform area of the glass product is coated with inorganic material. CO Glass product according to any of the preceding claims 19 - 30, characterized in that the said uniform area of the glass product has been coated with a multilayer coating. Glass product according to any of the preceding claims 19-31, characterized in that said coating thickness of the uniform area of the glass product is between 20 nm and 20 µm, preferably between 100 nm and 5 µm. 't δ c \ j CM O X IX CL co δ o o CM