EP3044176A1 - Laser process for the modification of metallic nanoparticles on large size glass substrates - Google Patents

Laser process for the modification of metallic nanoparticles on large size glass substrates

Info

Publication number
EP3044176A1
EP3044176A1 EP14777281.8A EP14777281A EP3044176A1 EP 3044176 A1 EP3044176 A1 EP 3044176A1 EP 14777281 A EP14777281 A EP 14777281A EP 3044176 A1 EP3044176 A1 EP 3044176A1
Authority
EP
European Patent Office
Prior art keywords
containing layer
laser line
glass substrate
nanoparticle containing
laser
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14777281.8A
Other languages
German (de)
French (fr)
Inventor
Li-Ya Yeh
Michael BEHMKE
Lorenzo CANOVA
Nicolas Nadaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Priority to EP14777281.8A priority Critical patent/EP3044176A1/en
Publication of EP3044176A1 publication Critical patent/EP3044176A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/262—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used recording or marking of inorganic surfaces or materials, e.g. glass, metal, or ceramics
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/09—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the vapour phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment

Definitions

  • the invention relates to a laser process for the modification of metallic nanoparticles into the surface of large size glass substrates and its use.
  • Modern architecture often contains large glass surfaces, which are often colored to give an appealing impression.
  • Manufacturing of colored glass is usually done by addition of colorants, e.g. metals or metal oxides, to the molten glass or the raw materials for glass production. Changing the color or the composition of the glass is extremely time consuming and expensive as the float glass process is a continuous process and large scales of rejects are produced.
  • colorants e.g. metals or metal oxides
  • WO 2010/106370 describes a process for coloration of glass, in which a precursor containing metallic nanoparticles is sprayed onto a hot glass substrate.
  • the glass substrates are heated to a temperature of 350°C to 550 °C.
  • the tempering has to done for several minutes due to the time dependency of the diffusion process. Hence the process is rather time consuming.
  • Another method for coating glass substrates is flame spraying. Such a flame spraying process is for example disclosed in WO 2008/099048.
  • a precursor comprising coloring transition metal oxides is flame sprayed onto the substrate followed by a reduction step.
  • Another process leading to colored glass or glass with optically modified properties is alternating sputtering and co-sputtering of a dielectric matrix containing nanoparticles onto
  • the mechanical stability and resistivity of the obtained coating is quite low due to the low layer thickness between 10 nm and 500 nm.
  • US 2004/01 18157 A1 discloses a process for laser beam-assisted implementation of metallic nano particles into glass surfaces.
  • the object of the invention is to develop a method for marking glass or to produce multi colored decorations.
  • the laser processing is preferably realized by a C0 2 laser, whereat the deposition area is limited by the size of the laser spot.
  • the size of the processing area of such laser arrangements is typically limited between 10 ⁇ and several millimeters. Hence the laser process described in US 2004/01 18157 A1 is not suitable for processing of large sheets of glass.
  • the object of the present invention is to provide a profitable laser process for modification of metallic nanoparticles on coated glass substrates, wherein also large size substrates can be processed.
  • the solution of the object of the present invention is a laser process for modification of metallic nanoparticles on large size glass substrates and its use according to independent claims 1 and 9.
  • the method according to the invention for modification of optical properties of a glass substrate by modification of nanoparticles comprises the following steps:
  • a) at least one nanoparticle containing layer is applied onto the glass substrate, b) a laser line is focused onto this nanoparticle containing layer,
  • the glass substrate is moved in a direction x relative to the laser line and the glass substrate with nanoparticle containing layer is laser processed, wherein the glass substrate has got a width of 0.10 m to 5.00 m perpendicular to the direction x.
  • the laser processing during step c) leads to a modification of the optical properties of the nanoparticle containing layer.
  • the method according to the invention enables a homogeneous and time-saving laser processing of large size substrates.
  • the nanoparticle containing layer is heated by carefully targeted laser processing, whereas an increase of the core temperature of the glass substrate can be mostly avoided and only the temperature within the surface near region of the glass substrate is slightly raised.
  • a local heat treatment of the nanoparticle containing layer leads to the modification of their optical properties.
  • the process according to the invention is especially advantageous for the production of large-scale sheets of colored glass or diffractive glazing.
  • optical properties or color is governed by the size, number, depth and allocation of the nanoparticles. These values can be controlled by the heating process. Therefore the precise adjustment of the laser heating process allows a defined modification of the optical properties.
  • the change in optical properties or color of the modified glass is defined by the wavelength of the Surface Plasmon Resonance (SPR). This is manly governed on the material of the nanoparticles. For example cobalt leads to bluish, copper to ruby, nickel to grey and silver to yellow color change.
  • SPR Surface Plasmon Resonance
  • Oven processes according to the state of the art are rather time consuming, in general a few minutes are needed per substrate, whereas laser processes according to the state of the art use lasers providing a laser spot of very limited size, typically 10 pm to a few millimeters. Thus these processes are not suitable for processing of large size substrates.
  • the method according to the invention enables a fast processing of large substrates, in which a single substrate is typically processed within a few seconds, preferably a fraction of seconds.
  • the direction x is defined as the direction of relative movement between the laser line and the substrate during processing.
  • the glass substrates are placed onto a conveyor, which is spanned by a stationary laser arrangement generating the laser line.
  • the glass substrates are transported in direction x via the conveyor and processed by crossing the laser line. This embodiment is especially advantageous as the process could be performed in line with a float process and a deposition process.
  • the laser arrangement is mounted on a moveable track system while the glass substrates are held stationary.
  • the direction x is solely defined as positive value as the transportation of the glass sheet only takes place in one direction.
  • a backward transport of the glass substrate in direction -x is not necessary as the laser line covers the width of the substrate and the entire surface of the substrate is treated within one cycle. A time- consuming repeated passage of substrates is not required.
  • Nanoparticles which are already implemented in coatings of glass substrates or within the surface near-region of glass substrates can be modified by a second heating process according to the invention. It is possible to perform this post heating very precise by the method according to the invention. The modification of the nanoparticles leads to a change in optical properties of the glazing.
  • a first process for implementation of nanoparticles can be an oven process, laser process, physical or chemical vapor deposition process or other
  • the nanoparticle containing layer could for example be generated by a sputtering process, in which a metal compound containing layer is deposited.
  • the nanoparticles could be formed within the sputtering process by dewetting. Alternatively the sputtering could be followed by an oven process for generating nanoparticles.
  • An application of the method according to the invention is laser treatment of nanoparticles to gain colored glass.
  • the method according to the invention is especially advantageous within the production of mirrors, wherein the reflection properties of the mirrors are changed yielding a slightly pink reflection. The color of human skin appears more vivid in such mirrors.
  • the nanoparticle containing layer contains a transition metal or a transition metal compound, preferably silver, gold, iron, copper, chromium, cobalt, nickel, molybdenum, palladium, platinum, manganese, vanadium, rare earth metals or compounds or mixtures thereof, more preferably cobalt, nickel, palladium, silver, gold, copper or compounds or mixtures thereof.
  • a transition metal or a transition metal compound preferably silver, gold, iron, copper, chromium, cobalt, nickel, molybdenum, palladium, platinum, manganese, vanadium, rare earth metals or compounds or mixtures thereof, more preferably cobalt, nickel, palladium, silver, gold, copper or compounds or mixtures thereof.
  • the nanoparticle containing layer is one layer within a stack of multiple layers, at least two layers.
  • at least one nanoparticle containing layer is arranged alternating with at least two intermediate layers, wherein the intermediate layers are dielectric layers and/or TCO-layers.
  • the dielectric layers contain Si 3 N 4 , Si0 2 , Ti0 2 , Al 2 0 3 or compounds or mixtures thereof, more preferably Si 3 N 4 .
  • the TCO-layers (TCO: transparent conductive oxide) contain indium tin oxide (ITO).
  • nanoparticle containing layer consisting of a 2 nm silver layer applied in an alternate sputtering process with two dielectric layers of 10 nm Si 3 N 4 , wherein the nanoparticle containing layer is embedded between the dielectric layers.
  • the length of the laser line is defined as its maximum dimension, while the width of the laser line is its minimum dimension.
  • the laser line runs along direction y, perpendicular to direction x, so that the width of the laser line is measured along direction x, while the length of the laser line is measured along direction y.
  • a diagonal progression of the laser line is also possible.
  • the laser line according to the invention is preferably generated by a series of laser assemblies, mounted besides each other.
  • the areas illuminated by the single laser assemblies add up to the laser line.
  • the single laser assemblies can be operated independently, e.g. the power density could be modulated within the laser line.
  • the laser line is generated by a single laser.
  • the laser assemblies comprise diode lasers, fiber lasers and/or disk lasers, most preferably diode lasers.
  • the laser line has got a length of 0.10 m to 5.00m, preferably 0.25 m to 3.50 m, more preferably of 0.60 m to 3.30 m.
  • the general standard size of float glass sheets is 6 m x 3 m, the method according to the invention enables homogeneous and fast processing of such sheets.
  • the laser line has got a width of 10 ⁇ to 500 ⁇ , preferably 20 ⁇ to 250 ⁇ , most preferably 20 ⁇ to 100 ⁇ .
  • the power density of the laser line is between 50 W/mm 2 and 3000 W/mm 2 , preferably 300 W/mm 2 to 2000 W/mm 2 , most preferably 500 W/mm 2 to 1700 W/mm 2 .
  • the line width of the laser line is 40 ⁇ .
  • the line width should be chosen as small as possible to maximize the energy input per unit area.
  • a large energy input per surface area means that the processing time can be kept short. Hence only the surface area of the substrate is heated and the temperature rise of the glass is minimized.
  • the wave length of the laser line is between 250 nm to 2000 nm, preferably 500 nm to 1700 nm, most preferably 700 nm to 1300 nm.
  • the method according to the invention is suitable for heat treatment within the temperature range of 80 °C to 700 °C, preferably 100 °C to 600 °C.
  • the maximum core temperature of the glass substrate is 250 °C, preferably 100 °C, most preferably 80 °C.
  • the core temperature of the glass substrate is defined as the temperature outside the surface near region, wherein during processing the temperature of the surface near region is equal to or higher than the core temperature.
  • the surface near region has got a thickness of 1 ⁇ to 500 ⁇ , preferably 1 ⁇ to 100 ⁇ .
  • the laser line is turned off at least once during step c) and/or the power density of the laser line is modified during step c).
  • a modulation of the power density leads to a structuring of the substrate as nanoparticles are only modified in some regions, e.g. when the laser line is turned off during processing, or nanoparticles with different properties are formed. This could be desirable in terms of design aspects, for the production of diffractive glazing or other linear designs for gaining optical effects.
  • the power density along the laser line is not homogeneous and/or the power density along the laser line is modified during step c).
  • Such an embodiment of the process is for example advantageous in production of glazing with an inhomogeneous appearance or color.
  • Another solution of the present invention is the use of the method according to the invention for the production of colored glass substrates, preferably for processing of large-scale glass substrates with a size of at least 1 m 2 .
  • Figure 1 a and 1 b depict a glass substrate with a nanoparticle containing layer and a method for modification of the nanoparticle containing layer.
  • Figure 2 depicts a glass substrate with a stack of nanoparticle containing layers and intermediate layers and a method for modification of the nanoparticle containing layers.
  • Figure 3 depicts a flow chart of the method according to the invention.
  • Figure 1 a depicts a cross sectional view of a glass substrate (1 ) with a nanoparticle containing layer (2.2).
  • the nanoparticle containing layer (2.2) is deposited by sputtering of silver in step a).
  • a laser line (4) is focused onto the nanoparticle containing layer (2.2) in step b) and the glass substrate (1 ) is processed by moving the glass substrate in direction x relative to the laser line (4) in step c).
  • the laser line (4) runs along direction y, perpendicular
  • the laser line (4) has got a length of 3.1 m and runs along the width of the glass substrate (1 ), having a width of 3.0 m, along direction y, perpendicular to direction x.
  • the laser line (4) has got a line width of 40 ⁇ , a power density of 1000 W/mm 2 and a wave length of 980 nm.
  • Laser treatment of the nanoparticle containing layer (2.2) leads to a temperature increase, which leads to a change in optical properties and formation of a nanoparticle containing layer with modified optical properties (2.2').
  • Figure 1 b shows a top view of the glass substrate (1 ) with nanoparticle containing layer (2.2) according to Figure 1 a.
  • the laser line (4) runs along the direction x and covers the whole width of the glass substrate (1 ).
  • the glass substrate (1 ) is laser processed by transport of the substrate in direction x via a conveyor.
  • Figure 2 depicts a cross sectional view of a glass substrate (1 ) with a stack of nanoparticle containing layers (2.2) and intermediate layers (3) and a method for modification of the nanoparticle containing layers (2.2).
  • the nanoparticle containing layer (2.2) consists of a 3 nm gold layer applied in an alternate sputtering process with an intermediate layer (3) of 30 nm Ti0 2 .
  • the upper layer of the stack and the layer directly applied onto the glass substrate (1 ) are intermediate layers (3). Between this top and bottom intermediate layers (3) an alternating stack of three nanoparticle containing layers (2.2) and two intermediate layers (3) is applied.
  • the properties of the laser line (4) and the dimensions of the substrate are those already described in Figure 1 a.
  • Laser treatment of the nanoparticle containing layer (2.2) leads to a temperature increase, which leads to a change in optical properties and formation of a nanoparticle containing layer with modified optical properties (2.2').
  • Figure 3 shows a flow chart of the method according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
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  • Optics & Photonics (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

A method for modification of optical properties of a glass substrate (1) by modification of nanoparticles comprising a) application of at least one nanoparticle containing layer (2.2) onto the glass substrate (1), b) focusing a laser line (4) onto the nanoparticle containing layer (2.2), c) laser processing of the glass substrate (1) with nanoparticle containing layer (2.2) by movement of the glass substrate (1) in direction x relative to the laser line (4), wherein the glass substrate (1) has got a width of 0.10 m to 5.00 m perpendicular to the direction x and the optical properties of the nanoparticle containing layer (2.2) are modified in step c).

Description

Laser process for the modification of metallic nanoparticles on large size glass substrates
The invention relates to a laser process for the modification of metallic nanoparticles into the surface of large size glass substrates and its use.
Modern architecture often contains large glass surfaces, which are often colored to give an appealing impression. Manufacturing of colored glass is usually done by addition of colorants, e.g. metals or metal oxides, to the molten glass or the raw materials for glass production. Changing the color or the composition of the glass is extremely time consuming and expensive as the float glass process is a continuous process and large scales of rejects are produced.
Alternatively several post processes for coloration of glass are known. In these post processes metallic particles are applied into or onto the glass surface, whereby not only the color but also the optical properties of the glass can be modified. The modification of optical properties gives rise to a huge spectrum of possible applications for such glazing, e.g. selective solar absorbers, photo thermal conversion of solar energy or energy efficient windows.
Multiple thermal processes for generation of metallic nano particle in the surface near region of glass are disclosed. WO 2010/106370 describes a process for coloration of glass, in which a precursor containing metallic nanoparticles is sprayed onto a hot glass substrate. The glass substrates are heated to a temperature of 350°C to 550 °C. The tempering has to done for several minutes due to the time dependency of the diffusion process. Hence the process is rather time consuming. Another method for coating glass substrates is flame spraying. Such a flame spraying process is for example disclosed in WO 2008/099048. In a first step a precursor comprising coloring transition metal oxides is flame sprayed onto the substrate followed by a reduction step. Reduction of metal cations yields the corresponding metal, which arranges to nanometric collodials in the glass matrix. This process is less time consuming compared to the process disclosed in WO 2010/106370, nevertheless a substrate temperature between 500°C and 800°C is obtained.
Another process leading to colored glass or glass with optically modified properties is alternating sputtering and co-sputtering of a dielectric matrix containing nanoparticles onto
1 the glass surface. The mechanical stability and resistivity of the obtained coating is quite low due to the low layer thickness between 10 nm and 500 nm.
US 2004/01 18157 A1 discloses a process for laser beam-assisted implementation of metallic nano particles into glass surfaces. The object of the invention is to develop a method for marking glass or to produce multi colored decorations. The laser processing is preferably realized by a C02 laser, whereat the deposition area is limited by the size of the laser spot. The size of the processing area of such laser arrangements is typically limited between 10 μηη and several millimeters. Hence the laser process described in US 2004/01 18157 A1 is not suitable for processing of large sheets of glass.
The object of the present invention is to provide a profitable laser process for modification of metallic nanoparticles on coated glass substrates, wherein also large size substrates can be processed.
The solution of the object of the present invention is a laser process for modification of metallic nanoparticles on large size glass substrates and its use according to independent claims 1 and 9.
The method according to the invention for modification of optical properties of a glass substrate by modification of nanoparticles comprises the following steps:
a) at least one nanoparticle containing layer is applied onto the glass substrate, b) a laser line is focused onto this nanoparticle containing layer,
c) the glass substrate is moved in a direction x relative to the laser line and the glass substrate with nanoparticle containing layer is laser processed, wherein the glass substrate has got a width of 0.10 m to 5.00 m perpendicular to the direction x. The laser processing during step c) leads to a modification of the optical properties of the nanoparticle containing layer. The method according to the invention enables a homogeneous and time-saving laser processing of large size substrates. The nanoparticle containing layer is heated by carefully targeted laser processing, whereas an increase of the core temperature of the glass substrate can be mostly avoided and only the temperature within the surface near region of the glass substrate is slightly raised. A local heat treatment of the nanoparticle containing layer leads to the modification of their optical properties. Hence the process according to the invention is especially advantageous for the production of large-scale sheets of colored glass or diffractive glazing.
2 The change of optical properties or color is governed by the size, number, depth and allocation of the nanoparticles. These values can be controlled by the heating process. Therefore the precise adjustment of the laser heating process allows a defined modification of the optical properties.
The change in optical properties or color of the modified glass is defined by the wavelength of the Surface Plasmon Resonance (SPR). This is manly governed on the material of the nanoparticles. For example cobalt leads to bluish, copper to ruby, nickel to grey and silver to yellow color change.
Oven processes according to the state of the art are rather time consuming, in general a few minutes are needed per substrate, whereas laser processes according to the state of the art use lasers providing a laser spot of very limited size, typically 10 pm to a few millimeters. Thus these processes are not suitable for processing of large size substrates. The method according to the invention enables a fast processing of large substrates, in which a single substrate is typically processed within a few seconds, preferably a fraction of seconds.
The direction x is defined as the direction of relative movement between the laser line and the substrate during processing. In a preferred embodiment of the invention the glass substrates are placed onto a conveyor, which is spanned by a stationary laser arrangement generating the laser line. The glass substrates are transported in direction x via the conveyor and processed by crossing the laser line. This embodiment is especially advantageous as the process could be performed in line with a float process and a deposition process. In an alternative embodiment the laser arrangement is mounted on a moveable track system while the glass substrates are held stationary. The direction x is solely defined as positive value as the transportation of the glass sheet only takes place in one direction. A backward transport of the glass substrate in direction -x is not necessary as the laser line covers the width of the substrate and the entire surface of the substrate is treated within one cycle. A time- consuming repeated passage of substrates is not required.
Nanoparticles which are already implemented in coatings of glass substrates or within the surface near-region of glass substrates can be modified by a second heating process according to the invention. It is possible to perform this post heating very precise by the method according to the invention. The modification of the nanoparticles leads to a change in optical properties of the glazing. A first process for implementation of nanoparticles can be an oven process, laser process, physical or chemical vapor deposition process or other
3 methods according to the state of the art. The nanoparticle containing layer could for example be generated by a sputtering process, in which a metal compound containing layer is deposited. The nanoparticles could be formed within the sputtering process by dewetting. Alternatively the sputtering could be followed by an oven process for generating nanoparticles.
An application of the method according to the invention is laser treatment of nanoparticles to gain colored glass. The method according to the invention is especially advantageous within the production of mirrors, wherein the reflection properties of the mirrors are changed yielding a slightly pink reflection. The color of human skin appears more vivid in such mirrors.
The nanoparticle containing layer contains a transition metal or a transition metal compound, preferably silver, gold, iron, copper, chromium, cobalt, nickel, molybdenum, palladium, platinum, manganese, vanadium, rare earth metals or compounds or mixtures thereof, more preferably cobalt, nickel, palladium, silver, gold, copper or compounds or mixtures thereof.
In one possible embodiment the nanoparticle containing layer is one layer within a stack of multiple layers, at least two layers. In a preferred embodiment of such a stack at least one nanoparticle containing layer is arranged alternating with at least two intermediate layers, wherein the intermediate layers are dielectric layers and/or TCO-layers. Preferably the dielectric layers contain Si3N4, Si02, Ti02, Al203 or compounds or mixtures thereof, more preferably Si3N4. Preferably the TCO-layers (TCO: transparent conductive oxide) contain indium tin oxide (ITO).
One example for such a stack arrangement is a nanoparticle containing layer consisting of a 2 nm silver layer applied in an alternate sputtering process with two dielectric layers of 10 nm Si3N4, wherein the nanoparticle containing layer is embedded between the dielectric layers.
The general process parameters used for laser modification diffusion of nanoparticles within all embodiments mentioned are described in the following paragraphs:
The length of the laser line is defined as its maximum dimension, while the width of the laser line is its minimum dimension. Preferably the laser line runs along direction y, perpendicular to direction x, so that the width of the laser line is measured along direction x, while the length of the laser line is measured along direction y. Alternatively a diagonal progression of the laser line is also possible.
4 The laser line according to the invention is preferably generated by a series of laser assemblies, mounted besides each other. The areas illuminated by the single laser assemblies add up to the laser line. The single laser assemblies can be operated independently, e.g. the power density could be modulated within the laser line.
In an alternative embodiment of the invention the laser line is generated by a single laser.
Preferably the laser assemblies comprise diode lasers, fiber lasers and/or disk lasers, most preferably diode lasers.
In a preferred embodiment of the method according to the invention the laser line has got a length of 0.10 m to 5.00m, preferably 0.25 m to 3.50 m, more preferably of 0.60 m to 3.30 m. As the general standard size of float glass sheets is 6 m x 3 m, the method according to the invention enables homogeneous and fast processing of such sheets.
The laser line has got a width of 10 μηη to 500 μηη, preferably 20 μηη to 250 μηη, most preferably 20 μηη to 100 μηη. Within those line widths the power density of the laser line is between 50 W/mm2 and 3000 W/mm2, preferably 300 W/mm2 to 2000 W/mm2, most preferably 500 W/mm2 to 1700 W/mm2.
One example for the line width of the laser line is 40 μηη. The line width should be chosen as small as possible to maximize the energy input per unit area. A large energy input per surface area means that the processing time can be kept short. Hence only the surface area of the substrate is heated and the temperature rise of the glass is minimized.
The wave length of the laser line is between 250 nm to 2000 nm, preferably 500 nm to 1700 nm, most preferably 700 nm to 1300 nm.
The method according to the invention is suitable for heat treatment within the temperature range of 80 °C to 700 °C, preferably 100 °C to 600 °C. In a preferred embodiment the maximum core temperature of the glass substrate is 250 °C, preferably 100 °C, most preferably 80 °C. Thus also temperature sensitive substrates can be processed. The core temperature of the glass substrate is defined as the temperature outside the surface near region, wherein during processing the temperature of the surface near region is equal to or higher than the core temperature.
5 The surface near region has got a thickness of 1 μηι to 500 μηη, preferably 1 μηι to 100 μηι.
In one possible embodiment of the invention the laser line is turned off at least once during step c) and/or the power density of the laser line is modified during step c). Such a modulation of the power density leads to a structuring of the substrate as nanoparticles are only modified in some regions, e.g. when the laser line is turned off during processing, or nanoparticles with different properties are formed. This could be desirable in terms of design aspects, for the production of diffractive glazing or other linear designs for gaining optical effects.
In another embodiment according to the invention the power density along the laser line is not homogeneous and/or the power density along the laser line is modified during step c). Such an embodiment of the process is for example advantageous in production of glazing with an inhomogeneous appearance or color.
Another solution of the present invention is the use of the method according to the invention for the production of colored glass substrates, preferably for processing of large-scale glass substrates with a size of at least 1 m2.
Further advantages and details of the present invention can be taken from the description of several exemplary embodiments with reference to the drawings.
Figure 1 a and 1 b depict a glass substrate with a nanoparticle containing layer and a method for modification of the nanoparticle containing layer.
Figure 2 depicts a glass substrate with a stack of nanoparticle containing layers and intermediate layers and a method for modification of the nanoparticle containing layers.
Figure 3 depicts a flow chart of the method according to the invention.
Figure 1 a depicts a cross sectional view of a glass substrate (1 ) with a nanoparticle containing layer (2.2). The nanoparticle containing layer (2.2) is deposited by sputtering of silver in step a). A laser line (4) is focused onto the nanoparticle containing layer (2.2) in step b) and the glass substrate (1 ) is processed by moving the glass substrate in direction x relative to the laser line (4) in step c). The laser line (4) runs along direction y, perpendicular
6 to the direction x, to cover the whole width of the substrate by a laser line (4) being as short as possible. The laser line (4) has got a length of 3.1 m and runs along the width of the glass substrate (1 ), having a width of 3.0 m, along direction y, perpendicular to direction x. The laser line (4) has got a line width of 40 μηη, a power density of 1000 W/mm2 and a wave length of 980 nm. Laser treatment of the nanoparticle containing layer (2.2) leads to a temperature increase, which leads to a change in optical properties and formation of a nanoparticle containing layer with modified optical properties (2.2').
Figure 1 b shows a top view of the glass substrate (1 ) with nanoparticle containing layer (2.2) according to Figure 1 a. The laser line (4) runs along the direction x and covers the whole width of the glass substrate (1 ). The glass substrate (1 ) is laser processed by transport of the substrate in direction x via a conveyor.
Figure 2 depicts a cross sectional view of a glass substrate (1 ) with a stack of nanoparticle containing layers (2.2) and intermediate layers (3) and a method for modification of the nanoparticle containing layers (2.2). The nanoparticle containing layer (2.2) consists of a 3 nm gold layer applied in an alternate sputtering process with an intermediate layer (3) of 30 nm Ti02. The upper layer of the stack and the layer directly applied onto the glass substrate (1 ) are intermediate layers (3). Between this top and bottom intermediate layers (3) an alternating stack of three nanoparticle containing layers (2.2) and two intermediate layers (3) is applied. The properties of the laser line (4) and the dimensions of the substrate are those already described in Figure 1 a. Laser treatment of the nanoparticle containing layer (2.2) leads to a temperature increase, which leads to a change in optical properties and formation of a nanoparticle containing layer with modified optical properties (2.2').
Figure 3 shows a flow chart of the method according to the invention.
7 References
1 glass substrate
2.2 nanoparticle containing layer
2.2' nanoparticle containing layer with modified optical properties
3 intermediate layers
4 laser line
x direction of relative movement of laser line and glass substrate y direction perpendicular to direction x
8

Claims

Claims
1 . A method for modification of optical properties of a glass substrate (1 ) by modification of nanoparticles comprising
a) application of at least one nanoparticle containing layer (2.2) onto the glass substrate (1 ),
b) focusing a laser line (4) onto the nanoparticle containing layer (2.2), c) laser processing of the glass substrate (1 ) with nanoparticle containing layer (2.2) by movement of the glass substrate (1 ) in direction x relative to the laser line(4),
wherein the glass substrate (1 ) has got a width of 0.10 m to 5.00 m perpendicular to the direction x and
the optical properties of the nanoparticle containing layer (2.2) are modified in step c).
2. Method according to claim 1 , wherein the nanoparticle containing layer (2.2) contains a transition metal or transition metal compounds, preferably silver, gold, iron, copper, chromium, cobalt, nickel, palladium, platinum, manganese, vanadium, rare earth metals or compounds or mixtures thereof, more preferably cobalt, nickel, palladium, silver, gold, copper or compounds or mixtures thereof, most preferably silver or gold.
3. Method according to claims 1 or 2, wherein the nanoparticle containing layer (2.2) is embedded in a stack containing at least one nanoparticle containing layer (2.2) and at least two intermediate layers (3), the intermediate layers (3) being dielectric layers and/or TCO-layers.
4. Method according to one of the claims 1 to 3, wherein the laser line (4) has got a length of 0.10 m to 5.00 m, preferably 0.25 m to 3.50 m, most preferably of 0.60 m to 3.30 m.
5. Method according to one of the claims 1 to 4, wherein the wave length of the laser line (4) is between 250 nm to 2000 nm, preferably 500 nm to 1700 nm, most preferably 700 nm to 1300 nm.
6. Method according to one of the claims 1 to 5, wherein the maximum core temperature of the glass substrate (1 ) is 250 °C, preferably 100 °C, most preferably 80 °C.
9
7. Method according to one of the claims 1 to 6, wherein the laser line (4) is turned off at least once during step c) and/or the power density of the laser line (4) is modified during step c).
8. Method according to one of the claims 1 to 7, wherein the power density along the laser line (4) is not homogeneous and/or the power density along the laser line (4) is modified during step c).
9. Use of the method according to one of the claims 1 to 8 for the production of colored glass substrates, preferably for processing of large-scale glass substrates with a size of at least 1 m2.
10
EP14777281.8A 2013-09-10 2014-09-10 Laser process for the modification of metallic nanoparticles on large size glass substrates Withdrawn EP3044176A1 (en)

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EP13183701 2013-09-10
PCT/EP2014/069274 WO2015036427A1 (en) 2013-09-10 2014-09-10 Laser process for the modification of metallic nanoparticles on large size glass substrates
EP14777281.8A EP3044176A1 (en) 2013-09-10 2014-09-10 Laser process for the modification of metallic nanoparticles on large size glass substrates

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EP3491450B1 (en) 2016-07-27 2024-02-28 TRUMPF Laser GmbH Laser line illumination
WO2019149352A1 (en) 2018-01-31 2019-08-08 Trumpf Laser Gmbh Laser diode based line illumination source and laser line illumination

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US20050044895A1 (en) * 2002-04-16 2005-03-03 Central Glass Company, Limited Method for putting color to glass or erasing color from colored glass
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