WO2013160233A1 - Scratch resistant coating structure and use as optical filter or uv-blocking filter - Google Patents

Scratch resistant coating structure and use as optical filter or uv-blocking filter Download PDF

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Publication number
WO2013160233A1
WO2013160233A1 PCT/EP2013/058267 EP2013058267W WO2013160233A1 WO 2013160233 A1 WO2013160233 A1 WO 2013160233A1 EP 2013058267 W EP2013058267 W EP 2013058267W WO 2013160233 A1 WO2013160233 A1 WO 2013160233A1
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Prior art keywords
coating structure
optical filter
scratch resistant
ternary
structure according
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PCT/EP2013/058267
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French (fr)
Inventor
Erik Lewin
Jörg PATSCHEIDER
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Empa Eidgenössische Materialprüfungs- Und Forschungsanstalt
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Publication of WO2013160233A1 publication Critical patent/WO2013160233A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/281—Nitrides

Definitions

  • the present invention describes a scratch resistant optical filter coating structure, comprising at least a crystalline aluminium nitride based phase, an UV-blocking filter with tunable light absorption edge, use of a coating structure, comprising at least a crystalline aluminium nitride based phase and a synthesis method for forming a scratch resistant optical filter coating structure.
  • the present invention combines two fields: tunable UV-blocking filter coatings and hard transparent coatings.
  • the main benefit of the invention is the combination of these fields.
  • the present invention may be seen as a continuation of previous work as can be read in EP1705162 or for example A. Pelisson et al., Surf. Coat. Technol. 202 (2007) p884 and A. Pelisson, Al-Si-N transparent hard nanostructured coatings, University of Basel, Basel, 2009.
  • UV-absorbing filter material can be obtained in several ways, mainly: Organic molecules that absorb UV wavelengths. Such molecules may be embedded in an organic (polymer) or inorganic matrix to make a coating material. Such materials are generally soft, and thus not scratch resistant. See for example the paper of Zayat, M. et al., Chem. Soc. Rev. 36 (2007) pl270.
  • Inorganic substances are used, usually oxides such as Ti02, ZnO or Ce02.
  • oxides such as Ti02, ZnO or Ce02.
  • the effectiveness of materials based on these substances is tailored by controlling the mean particle size and thus leading to additional photon scattering. Absorption is given by the bandgap of the solid material, and may be influenced by doping with a further metal. Also these materials are soft as can be seen in Hwang, D.K. et al., Journal of Sol-Gel Sciences and Technology 26 (2003) p783, Kawakatsu, A. et al. or EP1746126.
  • UV-absorbing filter material consists of inorganic multilayer structures where the absorption is controlled by precise design of the multilayer and thus the destructive interference which gives the filter properties. See for example Abdel-Azis, M.M. et al., Appl Surf. Sci. 252 (2006) p8716.
  • the object of the present invention is to create a coating structure which is scratch resistant and shows optical filter characteristics with tunable absorption edge.
  • the present invention solves this problem by combining the hardness and thus scratch resistance of metal nitride based materials with the tunable absorption in the UV and visible wavelengths. This combination in the same coating will give a comparably simple production compared to a solution providing additional protection layer.
  • the present invention also allows for an easy way of continuously controlling the absorption edge position between circa 200nm and circa 500nm and therefore the coating structure can be used to produce optical filters, or create coloration effects on surfaces.
  • the material in the present invention can be deposited at low temperatures (through e.g., but not limited to, magnetron sputtering), thus enabling coating also of temperature-sensitive materials such as plastics, which is an important market for UV-blocking and scratch resistant coatings, as well as for optical filters.
  • Figure 2a Absorption spectra for coatings in the Al-Ge-N system, showing how the absorption edge moves to higher wavelengths as Ge concentration increases and Figure 2b) the absorption edge position (as defined by an absorbance, a > 10 4 cm "1 ) for coatings in the Al-Ge-N system, as a function of Ge content.
  • Figure 3a Absorption spectra for coatings in the Al-Sn-N system, showing how the absorption edge moves to higher wavelengths as Sn concentration increases and
  • Figure 4 Absorption spectra for coatings in the Al-Si-N system, showing how the absorption edge moves to higher wavelengths as amount of available N during synthesis is decreased.
  • Figure 5 a single layer coating providing optical filter properties and scratch resistance
  • Figure 6 shows a two layer system, with two deposited Al-A-O-N layers in a schematic drawing.
  • the invention pertains to the use of a specific group of materials systems for scratch-resistant coating structures with a tunable absorption edge giving a tunable long-pass optical filter properties. These properties can for example be used to produce a UV-blocking filter or to obtain colouring effects to produce decorative surfaces.
  • a coating structure comprising at least one coating layer formed with different materials is presented leading to a protective filter coating structure with a thickness between 100 and 10 000 nm.
  • the coating may be deposited on glass materials, metallic materials, ceramic materials, or polymeric materials.
  • the material is ternary (i.e. consisting of three different elements) or quaternary (i.e. consisting of four different elements).
  • the ternary coating material consists of Al (aluminium), N (nitrogen), and an element from group 14 of the periodic table, henceforth denoted "A"; i.e. coatings in the Al-A-N systems.
  • the quaternary coating material consist of Al, N, A and O (oxygen).
  • An embodiment of the present invention pertains to ternary coatings where the group 14 element A is Si (silicon) or more preferred Ge (germanium), or Sn (tin), i.e. coatings in the Al-Si-N, Al-Ge-N or Al- Sn-N systems.
  • a further preferred embodiment of the present invention pertains to quaternary coatings comprising oxygene where the group 14 element A is Si (silicon), Ge (germanium), or Sn (tin), i.e. coatings in the Al-Si- N-O, AI-Ge-N-0 or AI-Sn-N-0 systems.
  • a further embodiment of the present invention is that coatings consist of a solid solution phase based on AIN - (Ali -x A x )N y (where x and y are numbers between 0 and 1, allowing for different stoichiometries of the material).
  • a further embodiment of the present invention is that coatings consist of a nanocomposite consisting of a crystalline particle phase, AIN or (Ali -x A x )N y (as defined above), and a second phase, called tissue or matrix phase, consisting of group 14 nitride, AN Z .
  • group 14 nitrides of Si, Ge or Sn Si 3 N 4-z , Ge 3 N 4-z or Sn 3 N 4-z , where z is a number between 0 and 4, allowing for different stoichiometries of the material.
  • the particles have diameters from 1 to lOOnm.
  • the matrix phase may be crystalline or amorphous.
  • the matrix phase may have average thicknesses between one atomic layer to 20 nm.
  • a preferred embodiment of the invention is a nanocomposite consisting of (Ali -x Si x )N y / Si 3 N -z with a particle size of 2-50 nm, a total atomic ratio of Si/AI of 0.10 to 0.40, a nitrogen content of 40-55 at%, and a coating thickness of 500 to 2500 nm.
  • z is a number between 0 and 4 and x, y are numbers between 0 and 1
  • a preferred embodiment of the invention is a nanocomposite consisting of (Ali -x Ge x )Ny / Ge 3 N -z with a particle size of 5 to 35 nm, a atomic ratio of Ge/AI of 0.10 to 1.5, a nitrogen content of 45-55 at%, and a coating thickness of 500 to 2500 nm.
  • z is a number between 0 and 4 and x, y are numbers between 0 and 1.
  • a preferred embodiment of the invention is a solid solution phase of (Ali -x Sn x )Ny or a nanocomposite of (Ali -x Sn x )N y / Sn 3 N 4-z with a particle size of 2 to 20 nm, a atomic ratio of Sn/AI of 0.1 to 1.5, a nitrogen content of 45-60 at%, and a coating thickness of 500 to 2500 nm.
  • z is a number between 0 and 4 and x
  • y are numbers between 0 and 1.
  • ternary coatings may be modified in such a way that oxygen is added, thereby producing quaternary oxy-nitride materials Al-A-O-N systems, which may have other mechanical and/or optical properties.
  • Oxygen content may range from 0.1 atomic% to 50 atomic%.
  • Hardness and thereby scratch resistance is achieved by the proper choice of particle size and matrix phase average thickness, which is achieved by varying the coating composition and deposition conditions. This is previously published in scientific literature and in patent a applications regarding the Al-Si-N system, and the principle is also relevant for other Al-A-N systems. An example of this is shown in Fig. 1, where the hardness of coatings in the Al-Ge-N system is shown as a function of Ge concentration.
  • a tunable absorption edge can be achieved in three ways, both varying the composition of the coatings:
  • the absorption edge is controlled by two mechanisms: Firstly the amount of absorbing AN Z matrix phase, the more A-element, the more AN Z matrix phase, the higher is the wavelength position of the absorption edge. This has been demonstrated for coatings in the Al-Ge-N system, see Fig. 2, which shows absorption spectra, and the dependence of the absorption edge on Ge-content. In this way the absorption edge position can be tuned between 200 and 500 nm.
  • the amount of A-element in the crystalline AIN-based phase will also change the absorption edge position.
  • the absorption edge is controlled by the stochiometry of the AN Z matrix and / or (Ali -x A x )N y phases, in particular in regards to N content, i.e. the parameters z and/or y.
  • a low nitrogen content (higher value for z and/or y) will lead to a larger absorption, i.e. moving the absorption edge to longer wavelengths. This has been demonstrated for the Al-Si-N system, see Fig. 4 where the absorption spectra and edge positions are given as a function of nitrogen gas flow during deposition of the coatings (which will determine the N content of the coatings).
  • the two layers can, but must not, be made within the same Al-A-N materials system. If the two layers are made in the same Al-A-N materials system, they can easily be deposited sequentially, thus keeping the coating production simple. Also a two layer system, with two Al-A-O-N layers can be deposited, as depicted in Figure 6.
  • An additional use of the above described coatings may be to use them to protect a substrate (component on which the coating is deposited) not only from mechanical damage (scratch resistance), damage through electromagnetic radiation in UV or visual wavelengths (optical filter), but also from chemical damage. This is achieved by the high chemical inertness which is exhibited by AIN-based nitrides (i.e. ( ⁇ .
  • nitrides i.e. AN Z
  • Synthesis of the above described coatings may be carried out in numerous ways, such as: Sputter deposition, CVD deposition, sol-gel (through e.g. spin-coating or doctor-blading) or other PVD techniques (such as reactive arcing), or a nitridation of an Al-A coating.
  • Sputter deposition is preferably done in a reactive atmosphere containing one or several of the following gases: N 2 , Ar, NH 3 , Xe,
  • Targets may be run in DC, RF, pulsed or HIPIMS (High Power Impulse Magnetron Sputtering) modes
  • Sputter deposition may be conducted on heated (up to 600°C) or unheated substrates, which are electrically grounded, floating or given a bias potential (constant or time dependent).
  • a preferred method of synthesis is using DC-magnetron for co- sputtering from elemental targets of Al and the Al-element, in a gas- mixture of Ar and N 2 with the ratio N 2 /Ar between 0.4 and 1, a sputtering pressure of 1 to 100 pBar, a substrate temperature of 50 to 600°C, and a bias potential on the substrates between 0 and -75 V
  • Another preferred method of synthesis is using DC-magnetron for a compound target consisting of Al and the Al-element, in a gas-mixture of Ar and N 2 with the ratio N 2 /Ar between 0.4 and 1, a sputtering pressure of 1 to 10 ⁇ , a substrate temperature of 50 to 600°C, and a bias potential on the substrates between 0 and -75 V.
  • the object of the present invention is commercially applicable in different technical fields and interesting for industries like the optical industry and coating deposition industry.
  • the continuous change of the absorption edge position throughout the entire compositional range opens up potential application of the material as a UV-blocking and/or long pass optical filter with an absorption edge position which may be tuned (200-500 nm) to fit a specific usage.
  • the advantage of the present material compared to other tunable filter materials that are based on multilayers or nano- / mesoporous materials, is that the tuning is done through a single parameter - the A-element (e.g. Si, Ge or Sn) content, or the nitrogen content.

Abstract

The disclosed invention consists of optical filter and/or UV-blocking filter coating structures with tuned light absorption edge, where beside the tunability of the absorption edge for different use a scratch resistant coating for use in different technical fields is achieved. Therefore the coating structure comprises a layer in the form of a ternary Al-A-N system, where A is at least one element of the group 14 of the periodic table, namely Si, Ge or Sn. In another embodiment a quarternary Al-A-O-N is used.

Description

Scratch resistant coating structure and use as optical filter or
UV-blocking filter
TECHNICAL FIELD
The present invention describes a scratch resistant optical filter coating structure, comprising at least a crystalline aluminium nitride based phase, an UV-blocking filter with tunable light absorption edge, use of a coating structure, comprising at least a crystalline aluminium nitride based phase and a synthesis method for forming a scratch resistant optical filter coating structure.
STATE OF THE ART
The present invention combines two fields: tunable UV-blocking filter coatings and hard transparent coatings. The main benefit of the invention is the combination of these fields.
Regarding the hard, scratch resisting and transparent coating part, the present invention may be seen as a continuation of previous work as can be read in EP1705162 or for example A. Pelisson et al., Surf. Coat. Technol. 202 (2007) p884 and A. Pelisson, Al-Si-N transparent hard nanostructured coatings, University of Basel, Basel, 2009.
UV-absorbing filter material can be obtained in several ways, mainly: Organic molecules that absorb UV wavelengths. Such molecules may be embedded in an organic (polymer) or inorganic matrix to make a coating material. Such materials are generally soft, and thus not scratch resistant. See for example the paper of Zayat, M. et al., Chem. Soc. Rev. 36 (2007) pl270.
Inorganic substances are used, usually oxides such as Ti02, ZnO or Ce02. Sometimes the effectiveness of materials based on these substances is tailored by controlling the mean particle size and thus leading to additional photon scattering. Absorption is given by the bandgap of the solid material, and may be influenced by doping with a further metal. Also these materials are soft as can be seen in Hwang, D.K. et al., Journal of Sol-Gel Sciences and Technology 26 (2003) p783, Kawakatsu, A. et al. or EP1746126.
Another known UV-absorbing filter material consists of inorganic multilayer structures where the absorption is controlled by precise design of the multilayer and thus the destructive interference which gives the filter properties. See for example Abdel-Azis, M.M. et al., Appl Surf. Sci. 252 (2006) p8716.
Known but also not hard and not scratch resistant are inorganic oxide based nano- or mesoporous materials, where the photon scattering from the pores give the filter properties and tuning possibilities as written in Kochergin, V. et al., Phys. Stat. Sol. (c) 4 (2007), pl933. These materials are also comparably soft and cannot form scratch resistant surfaces.
DESCRIPTION OF THE INVENTION
The object of the present invention is to create a coating structure which is scratch resistant and shows optical filter characteristics with tunable absorption edge. The present invention solves this problem by combining the hardness and thus scratch resistance of metal nitride based materials with the tunable absorption in the UV and visible wavelengths. This combination in the same coating will give a comparably simple production compared to a solution providing additional protection layer.
The present invention also allows for an easy way of continuously controlling the absorption edge position between circa 200nm and circa 500nm and therefore the coating structure can be used to produce optical filters, or create coloration effects on surfaces.
The material in the present invention can be deposited at low temperatures (through e.g., but not limited to, magnetron sputtering), thus enabling coating also of temperature-sensitive materials such as plastics, which is an important market for UV-blocking and scratch resistant coatings, as well as for optical filters.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments of the scratch resistant UV-blocking filter coating with tunable absorption edge are described below in conjunction with the attached drawings.
Figure 1 Hardness of coatings in the Al-Ge-N system, as a function of Ge content, measured by nanoindentation.
Figure 2a) Absorption spectra for coatings in the Al-Ge-N system, showing how the absorption edge moves to higher wavelengths as Ge concentration increases and Figure 2b) the absorption edge position (as defined by an absorbance, a > 104 cm"1) for coatings in the Al-Ge-N system, as a function of Ge content. Figure 3a) Absorption spectra for coatings in the Al-Sn-N system, showing how the absorption edge moves to higher wavelengths as Sn concentration increases and
Figure 3b) the absorption edge position (as defined by an absorbance, a > 104 cm"1) for coatings in the Al-Sn-N system, as a function of Sn content.
Figure 4 Absorption spectra for coatings in the Al-Si-N system, showing how the absorption edge moves to higher wavelengths as amount of available N during synthesis is decreased.
Figure 5 a) a single layer coating providing optical filter properties and scratch resistance and
b) a dual layer coating where the two layers combined provides both scratch resistance and optical filter properties.
Figure 6 shows a two layer system, with two deposited Al-A-O-N layers in a schematic drawing.
DESCRIPTION
The invention pertains to the use of a specific group of materials systems for scratch-resistant coating structures with a tunable absorption edge giving a tunable long-pass optical filter properties. These properties can for example be used to produce a UV-blocking filter or to obtain colouring effects to produce decorative surfaces.
A coating structure comprising at least one coating layer formed with different materials is presented leading to a protective filter coating structure with a thickness between 100 and 10 000 nm.
The coating may be deposited on glass materials, metallic materials, ceramic materials, or polymeric materials.
The material is ternary (i.e. consisting of three different elements) or quaternary (i.e. consisting of four different elements). The ternary coating material consists of Al (aluminium), N (nitrogen), and an element from group 14 of the periodic table, henceforth denoted "A"; i.e. coatings in the Al-A-N systems.
The quaternary coating material consist of Al, N, A and O (oxygen).
An embodiment of the present invention pertains to ternary coatings where the group 14 element A is Si (silicon) or more preferred Ge (germanium), or Sn (tin), i.e. coatings in the Al-Si-N, Al-Ge-N or Al- Sn-N systems.
A further preferred embodiment of the present invention pertains to quaternary coatings comprising oxygene where the group 14 element A is Si (silicon), Ge (germanium), or Sn (tin), i.e. coatings in the Al-Si- N-O, AI-Ge-N-0 or AI-Sn-N-0 systems.
A further embodiment of the present invention is that coatings consist of a solid solution phase based on AIN - (Ali-xAx)Ny (where x and y are numbers between 0 and 1, allowing for different stoichiometries of the material).
A further embodiment of the present invention is that coatings consist of a nanocomposite consisting of a crystalline particle phase, AIN or (Ali-xAx)Ny (as defined above), and a second phase, called tissue or matrix phase, consisting of group 14 nitride, ANZ. Particularly the group 14 nitrides of Si, Ge or Sn: Si3N4-z, Ge3N4-z or Sn3N4-z , where z is a number between 0 and 4, allowing for different stoichiometries of the material.
In the nanocomposite the particles have diameters from 1 to lOOnm. The matrix phase may be crystalline or amorphous. The matrix phase may have average thicknesses between one atomic layer to 20 nm.
A preferred embodiment of the invention is a nanocomposite consisting of (Ali-xSix)Ny / Si3N -z with a particle size of 2-50 nm, a total atomic ratio of Si/AI of 0.10 to 0.40, a nitrogen content of 40-55 at%, and a coating thickness of 500 to 2500 nm. Where z is a number between 0 and 4 and x, y are numbers between 0 and 1
A preferred embodiment of the invention is a nanocomposite consisting of (Ali-xGex)Ny / Ge3N -z with a particle size of 5 to 35 nm, a atomic ratio of Ge/AI of 0.10 to 1.5, a nitrogen content of 45-55 at%, and a coating thickness of 500 to 2500 nm. Where z is a number between 0 and 4 and x, y are numbers between 0 and 1.
A preferred embodiment of the invention is a solid solution phase of (Ali-xSnx)Ny or a nanocomposite of (Ali-xSnx)Ny / Sn3N4-z with a particle size of 2 to 20 nm, a atomic ratio of Sn/AI of 0.1 to 1.5, a nitrogen content of 45-60 at%, and a coating thickness of 500 to 2500 nm. Where z is a number between 0 and 4 and x, y are numbers between 0 and 1. The above mentioned ternary coatings may be modified in such a way that oxygen is added, thereby producing quaternary oxy-nitride materials Al-A-O-N systems, which may have other mechanical and/or optical properties. Oxygen content may range from 0.1 atomic% to 50 atomic%.
Hardness and thereby scratch resistance is achieved by the proper choice of particle size and matrix phase average thickness, which is achieved by varying the coating composition and deposition conditions. This is previously published in scientific literature and in patent a applications regarding the Al-Si-N system, and the principle is also relevant for other Al-A-N systems. An example of this is shown in Fig. 1, where the hardness of coatings in the Al-Ge-N system is shown as a function of Ge concentration.
A tunable absorption edge can be achieved in three ways, both varying the composition of the coatings:
· At roughly constant nitrogen content, by varying the A/AI ratio (i.e. the concentration of element A)
• At a constant A/AI ratio, by varying the nitrogen content
• By a combination of varying A/AI and nitrogen content. In the first case the absorption edge is controlled by two mechanisms: Firstly the amount of absorbing ANZ matrix phase, the more A-element, the more ANZ matrix phase, the higher is the wavelength position of the absorption edge. This has been demonstrated for coatings in the Al-Ge-N system, see Fig. 2, which shows absorption spectra, and the dependence of the absorption edge on Ge-content. In this way the absorption edge position can be tuned between 200 and 500 nm.
Secondly the amount of A-element in the crystalline AIN-based phase will also change the absorption edge position. The more A-element, the higher is the wavelength position of the absorption edge. This is demonstrated in Fig. 2b (where the material is a single phase solid solution until a Ge-content of about 12 atomic%); and for the Al-Sn-N system (where all studied compositions are single phase solid soluitions) in Fig. 3a) and 3b) which shows absorption spectra, and the dependence of the absorption edge on Sn-content.
In the second case the absorption edge is controlled by the stochiometry of the ANZ matrix and / or (Ali-xAx)Ny phases, in particular in regards to N content, i.e. the parameters z and/or y.
A low nitrogen content (higher value for z and/or y) will lead to a larger absorption, i.e. moving the absorption edge to longer wavelengths. This has been demonstrated for the Al-Si-N system, see Fig. 4 where the absorption spectra and edge positions are given as a function of nitrogen gas flow during deposition of the coatings (which will determine the N content of the coatings).
As both coating hardness and thus scratch resistance and optical properties (absorption edge position) varies with coating composition, it may be difficult to attain optimised properties with respect to both these properties. A solution to this is to employ a two layer coating structure or at least double layer coating structure, where the top layer gives desired scratch resistance, and the bottom layer gives desired absorption properties, see Fig. 5.
The two layers can, but must not, be made within the same Al-A-N materials system. If the two layers are made in the same Al-A-N materials system, they can easily be deposited sequentially, thus keeping the coating production simple. Also a two layer system, with two Al-A-O-N layers can be deposited, as depicted in Figure 6. An additional use of the above described coatings may be to use them to protect a substrate (component on which the coating is deposited) not only from mechanical damage (scratch resistance), damage through electromagnetic radiation in UV or visual wavelengths (optical filter), but also from chemical damage. This is achieved by the high chemical inertness which is exhibited by AIN-based nitrides (i.e. (ΑΙχ. xAx)Ny) and some group 14 nitrides (i.e. ANZ), as well as the corresponding oxy-nitrides. Synthesis of the above described coatings may be carried out in numerous ways, such as: Sputter deposition, CVD deposition, sol-gel (through e.g. spin-coating or doctor-blading) or other PVD techniques (such as reactive arcing), or a nitridation of an Al-A coating.
The preferred way beeing sputter deposition, of which where several versions may be employed:
• Co-sputtering from elemental targets of Al and A or their nitirdes
• Sputtering from compound targets containing Al, A and/or their nitrides
• Sputter deposition is preferably done in a reactive atmosphere containing one or several of the following gases: N2, Ar, NH3, Xe,
Kr, Ne or N2H4.
• Targets may be run in DC, RF, pulsed or HIPIMS (High Power Impulse Magnetron Sputtering) modes
• Sputter deposition may be conducted on heated (up to 600°C) or unheated substrates, which are electrically grounded, floating or given a bias potential (constant or time dependent).
A preferred method of synthesis is using DC-magnetron for co- sputtering from elemental targets of Al and the Al-element, in a gas- mixture of Ar and N2 with the ratio N2/Ar between 0.4 and 1, a sputtering pressure of 1 to 100 pBar, a substrate temperature of 50 to 600°C, and a bias potential on the substrates between 0 and -75 V Another preferred method of synthesis is using DC-magnetron for a compound target consisting of Al and the Al-element, in a gas-mixture of Ar and N2 with the ratio N2/Ar between 0.4 and 1, a sputtering pressure of 1 to 10 μΒθΓ, a substrate temperature of 50 to 600°C, and a bias potential on the substrates between 0 and -75 V.
The object of the present invention is commercially applicable in different technical fields and interesting for industries like the optical industry and coating deposition industry.
The continuous change of the absorption edge position throughout the entire compositional range, opens up potential application of the material as a UV-blocking and/or long pass optical filter with an absorption edge position which may be tuned (200-500 nm) to fit a specific usage. The advantage of the present material compared to other tunable filter materials that are based on multilayers or nano- / mesoporous materials, is that the tuning is done through a single parameter - the A-element (e.g. Si, Ge or Sn) content, or the nitrogen content.

Claims

PATENT CLAIMS
Scratch resistant optical filter coating structure, comprising at least a crystalline aluminium nitride (AIN) based phase,
characterized in that
the crystalline aluminium nitride based phase is comprising (All xAx)Ny, where x and y are numbers between 0 and 1
and A is an element of group 14 of the periodic table,
forming at least a ternary Al-A-N system.
Scratch resistant optical filter coating structure according to claim 1, whereas the crystalline particle phase is formed by solid solution phase composed of (Ali-xSnx)Ny or (Ali-xGex)Ny where x and y are numbers between 0 and 1.
3. Scratch resistant optical filter coating structure according to claim 1 or 2, whereas the atomic ratio of the element (A) of the group 14 of the periodic table to aluminium A/AI is between 0.1 and 2.
4. Scratch resistant optical filter coating structure according to one of the claims 1 to 3, whereas the nitrogen content of the ternary Al-A-N system is between 40-60 atomic%.
5. Scratch resistant optical filter coating structure according to one of the preceding claims, whereas the coating structure comprises a ternary Al-A-N system and oxygen, thereby a quaternary oxy-nitride layer (Al-A-N-O) is formed.
6. Scratch resistant optical filter coating structure according to claim 5, whereas the oxygen content may range from 0.1 atomic% to 50 atomic%. Scratch resistant optical filter coating structure according to one of the preceding claims, whereas the coating structure comprises the crystalline aluminium nitride based phase composed of (Ali-xAx)Ny
and a matrix phase composed of at least one group 14 element nitride ANZ, where z is a number between 0 and 4.
8. Scratch resistant optical filter coating structure according to
claim 7, whereas the matrix phase comprises namely Si3N - Ge3N4-z or Sn3N4-z.
9. Scratch resistant optical filter coating structure according to claim 8, whereas the ternary Al-A-N system consists of (Ali- xSix)Ny / Si3N4-z with a particle size of 2-50 nm, a total atomic ratio of Si/AI of 0.10 to 0.40, a nitrogen content of 40-55 at%, and a coating thickness of 500 to 2500 nm.
10. Scratch resistant optical filter coating structure according to claim 8, whereas the ternary Al-A-N system consists of (ΑΙχ. xGex)Ny / Ge3N4-z with a particle size of 5 to 35 nm, a atomic ratio of Ge/AI of 0.10 to 1.5, a nitrogen content of 45-55 at%, and a coating thickness of 500 to 2500 nm. 11. Scratch resistant optical filter coating structure according to claim 8, whereas the ternary Al-A-N system consists of (Ali- xSnx)Ny or Ali-xSnx)Ny / Sn3N4-z with a particle size of 2 to 20 nm, a atomic ratio of Sn/AI of 0.10 to 1.5, a nitrogen content of 45-60 at%, and a coating thickness of 500 to 2500 nm.
12. UV-blocking filter with tunable light absorption edge,
whereas the UV-blocking filter comprises at least one bottom layer of a coating structure according to one of the preceding claims coated on a substrate and at least one top layer of a coating structure according to one of the preceding claims deposited on the bottom layer, where one or both layer comprising a ternary Al-A-N system or are formed of a quaternary oxy-nitride layer (Al-A-N-O).
13. Use of a coating structure according to claim 1, comprising at least a crystalline aluminium nitride (AIN) based phase,
whereas the crystalline aluminium nitride (AIN) based phase is composed of (Ali-xAx)Ny, where x and y are numbers between 0 and 1 and A is an element of group 14 of the periodic table, forming at least a ternary Al-A-N system, for formation of an UV-blocking filter with tunable light absorption edge or forming decoration of surfaces.
14. Use of a coating structure according to claim 7, whereas an additional matrix phase is composed of at least one group 14 element nitride ANZ, where z is a number between 0 and 4, for formation of an UV-blocking filter with tunable light absorption edge or forming decoration of surfaces.
15. Synthesis method for forming a scratch resistant optical filter coating structure, according to one of the claims 1 to 11, characterized in the steps
Sputter deposition, CVD deposition, sol-gel (through e.g. spin- coating or doctor-blading) or other PVD techniques (such as reactive arcing), and/or a nitridation of an Al-A coating for producing of the ternary Al-A-N system on a substrate. 16. Synthesis method according to claim 15, whereas
the substrate is fixed on substrate holder and introduction into high vacuum or ultra-high vacuum (1.5 10"8 mbar or below), followed by tempering the substrate holder with substrate between 50°C and up to 600 °C keeping the substrate holder at a floating potential or biased between 0 an -75V, creation of a reactive atmosphere of N2 while co-sputtering of targets, comprising Aluminium, the element (A) of the group 14 of the periodic table and/or their nitrides.
17. Synthesis method according to claim 15 or 16, whereas a
reactive nitrogen atmosphere and one or several of the following gases: Ar, Xe, Kr or Ne is used.
18. Synthesis method according to claim 17, whereas the nitrogen source is molecular N2 or NOx or NH3 or N2H4. 19. Synthesis method according to one of claims 15 to 18,
whereas the tempering is carried out at temperatures up to 200°C. 20. Synthesis method according to one of claims 15 to 19, whereas the ternary Al-A-N system is coated on the substrate with a thickness between 100 and 10 000 nm leading to an optical filter scratch resistance coating structure with thickness between 100 and 10000 nm.
21. Synthesis method according to claim 20, whereas at least two layers of the ternary Al-A-N system are coated on the substrate with a thickness between 50 and 10 000 nm leading to an optical filter scratch resistance coating structure with thickness between 100 and 20000 nm.
PCT/EP2013/058267 2012-04-24 2013-04-22 Scratch resistant coating structure and use as optical filter or uv-blocking filter WO2013160233A1 (en)

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