US20100279124A1 - Hafnium or zirconium oxide Coating - Google Patents
Hafnium or zirconium oxide Coating Download PDFInfo
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- US20100279124A1 US20100279124A1 US12/620,585 US62058509A US2010279124A1 US 20100279124 A1 US20100279124 A1 US 20100279124A1 US 62058509 A US62058509 A US 62058509A US 2010279124 A1 US2010279124 A1 US 2010279124A1
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- 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
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/481—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62222—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/354—Introduction of auxiliary energy into the plasma
Definitions
- the invention concerns a coating of hafnium- or zirconium-containing oxide according to the preamble of Claim 1 .
- the invention also concerns an optical component with a coating from a hafnium- or zirconium-containing oxide and a method for production of a coating or optical component.
- hafnium oxide or zirconium oxide as a coating material for optical elements.
- Hafnium oxide is therefore particularly suited for use as a coating material for optical components with low reflection and a high transparency and for mirrors, for example, for laser mirrors. The same applies to zirconium oxide.
- hafnium oxide or zirconium oxide coatings by means of ion beam sputtering.
- Qualitatively high-grade coatings with low absorption and scattering can be produced with this method, but deposition only occurs with comparatively low epitaxial growth rates of ⁇ 0.1 nm/s.
- the coatings deposited with ion beam sputtering also have high internal stresses (>1000 MPa).
- An amorphous oxide film containing silicon and at least one member of the group Zr, Ti, Hf, Sn, Ta and In, is known from DE 689 28 474 T2.
- Such an oxide film is supposed to have excellent scratch resistance, abrasion resistance and chemical durability. It is applied as such to objects, in which high lifetime is required, for example, as a protective layer, on glass that shields heat radiation. It can also be used as a diffusion barrier in a laminated glass.
- the applications described in DE 689 28 474 T2 therefore pertain to layers that are supposed to have high transparency in the visible range; properties in the UV range are not mentioned in this document.
- the underlying task of the invention is to furnish an optical coating that has the highest possible refractive index in a spectral range extending from the visible to the near UV range (i.e., to a wavelength of 230 nm) and good optical properties (especially low absorption and scatter) and the lowest possible internal stresses.
- Another underlying task of the invention is to provide such coatings and optical components with a coating and propose a method for their production.
- the coating consists of hafnium oxide with an admixture of silicon in an amount of 1 at. % to 10 at. %, at. % referring to a fraction of an amount of an element as an atomic percentage of the total amount.
- Hafnium oxide has a high refractive index of n>2 in the visible to the near infrared spectral range. Admixture of silicon reduces the refractive index, for which reason this limited amount should be reduced.
- the coating preferably has an O fraction (z) lying between 65 at. % and 68 at. %, so that this coating has only limited optical losses into the UV range.
- the optical properties of the hafnium oxide layer can be improved: at a silicon content between 1 at. % and 3 at. %, the Hf x Si y O z layer has lower absorption than pure hafnium oxide.
- the coating according to the invention preferably has an internal layer stress (compressive stress) between 100 MPa and 800 MPa, in which the refractive index is preferably greater than 1.9 at a wavelength of 550 nm and/or the extinction has a value ⁇ 3*10 ⁇ 3 at a wavelength of 242 nm, the Si content preferably lying between 1 at. % and 10 at. %.
- the internal layer stress is preferably less than 300 MPa.
- A is the degree of absorption
- T the degree of transmission
- R the degree of reflection
- the Hf x Si y O z coating according to the invention is produced by sputtering, especially DC or medium frequency magnetron sputtering.
- sputtering especially DC or medium frequency magnetron sputtering.
- high sputtering rates can be achieved and the internal stresses of the sputtered layer can be substantially reduced relative to those of pure hafnium oxide via the silicon content.
- Preparation of the Hf x Si y O z layer advantageously occurs by reactive co-magnetron sputtering of Hf and Si targets; as an alternative, co-sputtering targets of HfSi or Hf x Si y O z and Si can be used.
- the Hf x Si y O z layer can also be generated by reactive magnetron sputtering of a compound target containing Hf and Si in an appropriate composition.
- the method described in PCT/EP 2003/013649 permits, in particular, deposition of layers with an O fraction (z) between 65 at. % and 68 at. % and therefore having only slight optical losses into the UV range.
- the coating according to the invention can be present in amorphous, micro- or nanocrystalline form, or a mixed form between the mentioned forms.
- the coating according to the invention is particularly suited for use in multilayer systems, in which at least hafnium oxide is present, for example, for laser mirrors, edge filters and for UV transparent or reflecting filters, especially for a spectral range up to a limit of 220 nm.
- FIG. 1 a shows a schematic view of a substrate with an Hf x Si y O z coating
- FIG. 1 b shows a schematic view of a substrate with a multilayer system
- FIG. 2 a shows a view of transmission of uncoated quartz substrates and substrates coated with HfO 2 layers in the spectral range from 200 nm to 600 nm;
- FIG. 2 b shows a view of the transmission of an Hf 30.8 Si 2.5 O 66.7 layer and several HfO 2 layers on a quartz substrate in the spectral range from 220 nm to 260 nm.
- FIG. 3 shows measured values of the refractive index n at 550 nm and the internal stresses of an Hf x Si y O 66.7 layer as a function of silicon content y;
- FIG. 4 shows measured values of the refractive index n at 550 nm and the epitaxial growth rates during reactive magnetron sputtering of Hf x Si y O 66.7 layers as a function of power ratio PHf/(PHf+PSi);
- FIG. 5 shows measured values of the refractive index n at 550 nm, the extinction at 242 nm and the normalized internal stresses of Hf x Si y O 66.7 layers as a function of silicon content y;
- FIG. 6 shows measured values of extinction at 242 nm and the absorption edge of Hf x Si y O 66.7 layers as a function of sodium content y;
- FIG. 7 shows a graphic depiction of the relation between silicon content y of the Hf x Si y O z layer and the corresponding silicon content of an HfSi-mixed target
- FIG. 8 shows measured values of the refractive index n and the extinction k of a Zr x Si y O 66.66 layer and a ZrO 2 layer as a function of wavelength.
- FIG. 1 a shows a section of an optical component 1 with a substrate 2 , on which a coating 3 of Hf x Si y O z according to the invention is applied. The thickness of the coating 3 is then shown strongly exaggerated relative to thickness 6 of substrate 2 .
- the substrate 2 consists of a quartz, glass or plastic.
- Component 1 is a filter, which is supposed to have the lowest possible absorption in a stipulated spectral range. The spectral range considered here extends from visible light to UV radiation with a wavelength of about 230 nm.
- FIG. 2 a shows a graphic plot of transmission of uncoated quartz substrates and those coated with HfO 2 layers, which were applied by reactive magnetron sputtering with different process parameters (pressure, plasma energy, etc.) on substrate 2 .
- the uncoated quartz substrates over the entire considered spectral range show a transmission of greater than 90% (curve 21 ).
- the internal stress of an HfO 2 coating 3 with 1000 MPa-1500 MPa is very high: as shown in FIG. 3 , in a coating of pure HfO 2 , internal stresses of 1300-1400 MPa are measured. Such high internal stresses of coating 3 exert high forces on the underlying substrate 2 , which can lead to deformations of substrate 2 and/or layer detachment.
- the internal stresses of coating 3 can be reduced, if the hafnium of the HfO 2 coating is replaced partly by silicon: as is apparent from the measured values and the regression curve 23 in FIG. 3 , the internal stress of an Hf x Si y O 66.7 coating 3 at a silicon fraction of y ⁇ 1.5 at. % is only about 500 MPa, and a silicon fraction of y ⁇ 2.5 at. % of the internal stress has dropped even to below 200 MPa.
- ⁇ film ( x after - x before ) 12 ⁇ L ⁇ ⁇ a ⁇ E substrate 1 - v substrate ⁇ d substrate 2 d film E substrate Young ' ⁇ s ⁇ ⁇ modulus ⁇ ⁇ substrate v substrate Poisson ⁇ ⁇ ratio ⁇ ⁇ substrate d substrate Substrate ⁇ ⁇ thickness d film Layer ⁇ ⁇ thickness L Layer ⁇ ⁇ detector ⁇ ⁇ spacing a Laser ⁇ ⁇ beam ⁇ ⁇ spacing
- the individual coated wafers were then placed in the same alignment on the sample holder and the spacing of the two laser beams measured 5 times in succession on the detector (X after ), and also stored under the corresponding sample number.
- the stresses of the individual coatings were determined with the Stoney formula from the two measurements.
- the internal stresses of coating 3 can therefore be reduced at high sputtering rates.
- the silicon fraction y should therefore be as low as possible.
- the refractive index n is comparably large at about 2.05 in this Si concentration range.
- the internal stresses (regression curve 30 in FIG. 5 and regression curve 23 in FIG. 3 ) in this Si concentration range have already dropped to values below 500 MPa.
- the optical properties of the Hf x Si y O 66.7 coating 3 are also particularly favorable, since a local maximum of extinction is present there, measured at the UV wavelength of 242 nm (regression curve 31 in FIG. 5 and regression curve 32 in FIG. 6 ).
- a corresponding dependence of extinction of the Si concentration is found at wavelengths up to the corresponding absorption edge.
- the coating 3 according to the invention is produced by reactive co-magnetron sputtering of Hf and Si targets.
- targets of HfSi or Hf x Si y O z and Si can also be used.
- the Hf x Si y O 66.7 coating 3 can also be produced by other methods, for example, by using HfSi compound targets of appropriate composition.
- the layer can also be produced by partially reactive magnetron sputtering of a DC-conducting Hf x Si y O z target.
- layer production by one of the mentioned methods can be combined with reactive in situ plasma treatment.
- HfSi or Hf x Si y O, compound targets, whose Si content is set so that the sputtered layer has minimal extinction with simultaneously low internal stress and high refractive index, is particularly advantageous.
- different requirements can be optimized by co-magnetron sputtering with Si with the advantage of lower internal stresses of the layer growing on the HfSi or Hf x Si y O z cathode environment, which significantly reduces the probability of particle loading.
- FIG. 7 shows the relation between silicon content y of the Hf x Si y O z layer in at. % and the corresponding silicon content of an HfSi mixed target in weight % (line 39 ).
- the target should therefore have a silicon content between 0.5 wt % and 5 wt %.
- the target should have a silicon content between 0.5 wt % and 4 wt %.
- FIG. 8 shows measured values of the refractive index n and the extinction k of a Zr x Si y O 66.66 layer and a ZrO 2 layer as a function of wavelength.
- a layer with stoichiometric or almost stoichiometric composition (Zr 30.83 Si 2.5 O 66.66 ) is preferably produced or used, which offers optimal optical and mechanical properties, i.e., low optical losses into the UV spectral range, high refractive index >2.1 and low stress ⁇ 100 MPa.
- FIG. 1 b shows an optical component 1 ′, an edge filter, which is provided with an integrated reflection reduction layer or antireflection layer to increase its light transparency.
- Edge filters allow light to pass through almost unfiltered up to a limit frequency, but block most of the light from the limit frequency.
- a multilayer system 5 with several superimposed layers 3 ′, 4 from dielectric materials with different refractive indices are used as coating, in which layers 3 ′ from a high refractive material and layers 4 from a relatively low refractive material are arranged superimposed in alternation.
- the multilayer system typically consists of 10-100 individual layers 3 ′, 4 , in which the individual layers 3 ′, 4 typically have a thickness from 20 to 100 nm.
- the substrate 2 consists of a thin plate of quartz or plastic.
- the thickness 6 of the substrate is between 0.5 and 1.0 mm; the magnitude of the multilayer thickness 5 in FIG. 1 b is therefore shown strongly exaggerated relative to the thickness 6 of substrate 2 .
- the layers 3 ′, 4 of the multilayer system 5 are applied to the substrate 2 by a sputtering method and, depending on the size of the internal stresses in the individual layers, exert forces on substrate 2 .
- the forces of the individual layers are added, so that in a complex multilayer system 5 with internal stresses of >1 GPa, very high forces can act on the substrate 2 .
- the internal stresses of the individual layers 3 ′, 4 must therefore be as low as possible.
- the layers 3 ′ with high refractive index consist of Hf x Si y O 66.7 , the silicon content y preferably lying between 1.5 at. % and 3 at. %.
- the sputtering parameters such sputtering layers, as described above, have low internal stress with high refractive index and high transparency.
- the Hf x Si y O z and Zr x Si y O z coatings according to the invention are also suited for use in mirrors, especially laser mirrors and edge filters, and also for interference filters into the UV range.
- the coating in particular, can be used as an antireflection coating on semiconductor lasers.
Abstract
The invention concerns an optical coating (3, 3′), having a high refractive index and good optical properties (i.e., low absorption and scatter) and limited internal stresses in a spectral range extending from the visible to the near UV range (i.e., up to a wavelength of 220 nm). The coating (3, 3′) according to the invention consists of a hafnium- or zirconium-containing oxide HfxSiyOz or ZrxSiyOz, containing an silicon fraction (y) between 1 at. % and 10 at. %, especially between 1.5 at. % and 3 at. %.
Description
- The invention concerns a coating of hafnium- or zirconium-containing oxide according to the preamble of
Claim 1. The invention also concerns an optical component with a coating from a hafnium- or zirconium-containing oxide and a method for production of a coating or optical component. - The use of hafnium oxide or zirconium oxide as a coating material for optical elements is known. Hafnium oxide is characterized relative to other coating materials by a high refractive index in the visible spectral range (n=2.08 at λ=550 nm) and in the UV range (n=2.35 at λ=250 nm) and a high transparency, both in the visible and UV range (absorption edge at λ=220 nm). Hafnium oxide is therefore particularly suited for use as a coating material for optical components with low reflection and a high transparency and for mirrors, for example, for laser mirrors. The same applies to zirconium oxide.
- It is known to produce hafnium oxide or zirconium oxide coatings by means of ion beam sputtering. Qualitatively high-grade coatings with low absorption and scattering can be produced with this method, but deposition only occurs with comparatively low epitaxial growth rates of <0.1 nm/s. The coatings deposited with ion beam sputtering also have high internal stresses (>1000 MPa). It is also known to deposit hafnium oxide and zirconium oxide layers by magnetron sputtering. This method does permit high epitaxial growth rates of >0.4 nm/s, but the generated layers exhibit only moderate quality relative to absorption and scattering, and also have high internal stresses between 1000 and 2000 MPa.
- Both methods therefore yield layers with high internal stresses. The forces produced by such high internal stresses (depending on the substrate material) lead to deformations of the substrate surfaces and therefore an adverse effect on optical properties of the coated optical elements. High internal stresses can also result in layer detachments with or without damage to the substrate material.
- An amorphous oxide film, containing silicon and at least one member of the group Zr, Ti, Hf, Sn, Ta and In, is known from DE 689 28 474 T2. Such an oxide film is supposed to have excellent scratch resistance, abrasion resistance and chemical durability. It is applied as such to objects, in which high lifetime is required, for example, as a protective layer, on glass that shields heat radiation. It can also be used as a diffusion barrier in a laminated glass. The applications described in DE 689 28 474 T2 therefore pertain to layers that are supposed to have high transparency in the visible range; properties in the UV range are not mentioned in this document.
- The underlying task of the invention is to furnish an optical coating that has the highest possible refractive index in a spectral range extending from the visible to the near UV range (i.e., to a wavelength of 230 nm) and good optical properties (especially low absorption and scatter) and the lowest possible internal stresses. Another underlying task of the invention is to provide such coatings and optical components with a coating and propose a method for their production.
- The task is solved by the features of the independent claims. Advantageous embodiments are the object of dependent claims.
- Only the coating according to the invention with hafnium oxide and a mixture of silicon (HfxSiyOz) is taken up below. For coatings with zirconium oxide and a mixture of silicon (ZrxSiyOz), the same applies, unless otherwise stated.
- The coating consists of hafnium oxide with an admixture of silicon in an amount of 1 at. % to 10 at. %, at. % referring to a fraction of an amount of an element as an atomic percentage of the total amount. Hafnium oxide has a high refractive index of n>2 in the visible to the near infrared spectral range. Admixture of silicon reduces the refractive index, for which reason this limited amount should be reduced.
- However, it is surprisingly found that this limited admixture of silicon is already sufficient to substantially reduce the internal stresses of the coating.
- The coating preferably has an O fraction (z) lying between 65 at. % and 68 at. %, so that this coating has only limited optical losses into the UV range.
- It was also found that by limited admixture of silicon, the optical properties of the hafnium oxide layer can be improved: at a silicon content between 1 at. % and 3 at. %, the HfxSiyOz layer has lower absorption than pure hafnium oxide.
- The coating according to the invention preferably has an internal layer stress (compressive stress) between 100 MPa and 800 MPa, in which the refractive index is preferably greater than 1.9 at a wavelength of 550 nm and/or the extinction has a value <3*10−3 at a wavelength of 242 nm, the Si content preferably lying between 1 at. % and 10 at. %. The internal layer stress is preferably less than 300 MPa.
-
-
- in which A is the degree of absorption, T the degree of transmission and R the degree of reflection.
- The HfxSiyOz coating according to the invention is produced by sputtering, especially DC or medium frequency magnetron sputtering. By adjusting the process parameters, high sputtering rates can be achieved and the internal stresses of the sputtered layer can be substantially reduced relative to those of pure hafnium oxide via the silicon content. Preparation of the HfxSiyOz layer advantageously occurs by reactive co-magnetron sputtering of Hf and Si targets; as an alternative, co-sputtering targets of HfSi or HfxSiyOz and Si can be used. The HfxSiyOz layer can also be generated by reactive magnetron sputtering of a compound target containing Hf and Si in an appropriate composition. Layer production by partially reactive magnetron sputtering, using a conducting HfxSiyOz compound target, is also conceivable. It is particularly advantageous, if the reactive or partially reactive medium frequency magnetron sputtering is combined with reactive in situ plasma treatment, as described in PCT/EP 2003/013649, and which is included in this application by reference. The method described in PCT/EP 2003/013649 permits, in particular, deposition of layers with an O fraction (z) between 65 at. % and 68 at. % and therefore having only slight optical losses into the UV range.
- The coating according to the invention can be present in amorphous, micro- or nanocrystalline form, or a mixed form between the mentioned forms.
- The coating according to the invention is particularly suited for use in multilayer systems, in which at least hafnium oxide is present, for example, for laser mirrors, edge filters and for UV transparent or reflecting filters, especially for a spectral range up to a limit of 220 nm.
- The invention is further explained below with reference to a practical example depicted in the figures. In the figures:
-
FIG. 1 a shows a schematic view of a substrate with an HfxSiyOz coating; -
FIG. 1 b shows a schematic view of a substrate with a multilayer system; -
FIG. 2 a shows a view of transmission of uncoated quartz substrates and substrates coated with HfO2 layers in the spectral range from 200 nm to 600 nm; -
FIG. 2 b shows a view of the transmission of an Hf30.8Si2.5O66.7 layer and several HfO2 layers on a quartz substrate in the spectral range from 220 nm to 260 nm. -
FIG. 3 shows measured values of the refractive index n at 550 nm and the internal stresses of an HfxSiyO66.7 layer as a function of silicon content y; -
FIG. 4 shows measured values of the refractive index n at 550 nm and the epitaxial growth rates during reactive magnetron sputtering of HfxSiyO66.7 layers as a function of power ratio PHf/(PHf+PSi); -
FIG. 5 shows measured values of the refractive index n at 550 nm, the extinction at 242 nm and the normalized internal stresses of HfxSiyO66.7 layers as a function of silicon content y; -
FIG. 6 shows measured values of extinction at 242 nm and the absorption edge of HfxSiyO66.7 layers as a function of sodium content y; -
FIG. 7 shows a graphic depiction of the relation between silicon content y of the HfxSiyOz layer and the corresponding silicon content of an HfSi-mixed target, and -
FIG. 8 shows measured values of the refractive index n and the extinction k of a ZrxSiyO66.66 layer and a ZrO2 layer as a function of wavelength. -
FIG. 1 a shows a section of anoptical component 1 with asubstrate 2, on which acoating 3 of HfxSiyOz according to the invention is applied. The thickness of thecoating 3 is then shown strongly exaggerated relative tothickness 6 ofsubstrate 2. Thesubstrate 2 consists of a quartz, glass or plastic.Component 1 is a filter, which is supposed to have the lowest possible absorption in a stipulated spectral range. The spectral range considered here extends from visible light to UV radiation with a wavelength of about 230 nm. - It is known that individual layers or multilayer systems based on hafnium dioxide (HfO2) are particularly suited for such applications, since this material has low absorption in a spectral range from the visible to 220 nm.
FIG. 2 a shows a graphic plot of transmission of uncoated quartz substrates and those coated with HfO2 layers, which were applied by reactive magnetron sputtering with different process parameters (pressure, plasma energy, etc.) onsubstrate 2. The uncoated quartz substrates over the entire considered spectral range show a transmission of greater than 90% (curve 21). The quartz substrates coated with HfO2 layers show in the considered spectral range moderate absorption with an absorption edge (T=50%) of about 220 nm (curve 22). - However, the internal stress of an HfO2 coating 3 with 1000 MPa-1500 MPa is very high: as shown in
FIG. 3 , in a coating of pure HfO2, internal stresses of 1300-1400 MPa are measured. Such high internal stresses ofcoating 3 exert high forces on theunderlying substrate 2, which can lead to deformations ofsubstrate 2 and/or layer detachment. - The internal stresses of
coating 3 can be reduced, if the hafnium of the HfO2 coating is replaced partly by silicon: as is apparent from the measured values and theregression curve 23 inFIG. 3 , the internal stress of an HfxSiyO66.7 coating 3 at a silicon fraction of y≈1.5 at. % is only about 500 MPa, and a silicon fraction of y≈2.5 at. % of the internal stress has dropped even to below 200 MPa. - The measurements of internal stresses (stress σfilm) of
coating 3 occurred with a measurement system SIG-500SP from the company sigma-physik (D-37115 Duderstadt), using the Stoney formula (1909). -
-
Monocrystalline silicon wafers 3″ in diameter and 380 μm thick, polished on one side, were used as substrate material. These wafers are suitable because of their very limited roughness of 0.1 nm and very homogeneous surface for stress measurement. Uncoated wafers were first measured. For this purpose, the wafer was placed on the sample holder in precisely defined alignment and the spacing of the two laser beams was measured 5 times in succession on the detector (Xbefore) and stored under the sample number. The individual already measured silicon wafers were then coated with HfxSiyOz layers of different composition. The layer thickness was chosen at about 250 nm to increase the measurement accuracy. The precise layer thicknesses were determined with a spectral ellipsometer. The individual coated wafers were then placed in the same alignment on the sample holder and the spacing of the two laser beams measured 5 times in succession on the detector (Xafter), and also stored under the corresponding sample number. The stresses of the individual coatings were determined with the Stoney formula from the two measurements. - The generation of such HfxSiyO66.7 coatings 3 can occur, in particular, by reactive co-magnetron sputtering of Hf and Si targets, in which, with appropriate choice of process parameters, high sputtering rates can be achieved. It is apparent from
FIG. 4 that admixture of silicon even has a positive effect on the epitaxial growth rate; curves 25 and 26 show epitaxial growth rates during use of different sputtering parameters. - By partial replacement of Hf with Si in HfxSiyO66.7, the internal stresses of
coating 3 can therefore be reduced at high sputtering rates. However, with increasing silicon fraction y, the refractive index n of the HfxSiyO66.7 coating 3 diminishes (seeregression line 24 inFIG. 3 andregression lines FIG. 4 , which show the refractive index n as a function of Si content y at a wavelength λ=550 nm). To achieve a high refractive index, the silicon fraction y should therefore be as low as possible. These opposite requirements can be satisfied, if the silicon fraction y is set between 1 at. % and 10 at. %. - A particularly favorable Si concentration range lies between about y=1.5 at. % and y=3 at. % (see
FIG. 5 ). As is apparent from the trend of theregression line 29 of the measured values of refractive index n=550 nm, the refractive index n is comparably large at about 2.05 in this Si concentration range. At the same time, the internal stresses (regression curve 30 inFIG. 5 andregression curve 23 inFIG. 3 ) in this Si concentration range have already dropped to values below 500 MPa. In this Si concentration range, the optical properties of the HfxSiyO66.7 coating 3 are also particularly favorable, since a local maximum of extinction is present there, measured at the UV wavelength of 242 nm (regression curve 31 inFIG. 5 andregression curve 32 inFIG. 6 ). A corresponding dependence of extinction of the Si concentration is found at wavelengths up to the corresponding absorption edge. - In the Si concentration range 1.5 at. %<y<3 at. %, the absorption edge is also almost constant and only slightly shifted relative to the absorption edge of pure HfO2 (i.e., y=0) (see
regression curve 33 inFIG. 6 ); this indicates that the layer structure in the Si concentration range 1.5 at. %<y<3 at. % is HfO2-dominated. As shown in the detail view ofFIG. 2 b, co-sputtering of silicon also increases the transmission of the HfxSiyO66.7 layer: in the depicted spectral range, the measured transmission of a sample with a silicon content of y=2.5 at. % (curve 34) is higher than the layers of pure HfO2 prepared with difference process parameters (curves 35-37). - With an increase in Si concentration (y>5 at. %), an HfO2—SiO2 mixed oxide is increasingly formed, with a distinct shift in absorption edge into the shortwave spectral range (
regression curve 33 inFIG. 6 ), with diminishing extinction at 242 nm (regression curves 31 and 32 inFIG. 5 andFIG. 6 ), as well as a continuous reduction of refractive index n (regression line 29 inFIG. 5 ). - The
coating 3 according to the invention is produced by reactive co-magnetron sputtering of Hf and Si targets. During reactive co-magnetron sputtering, targets of HfSi or HfxSiyOz and Si can also be used. The HfxSiyO66.7 coating 3 can also be produced by other methods, for example, by using HfSi compound targets of appropriate composition. The layer can also be produced by partially reactive magnetron sputtering of a DC-conducting HfxSiyOz target. Finally, layer production by one of the mentioned methods can be combined with reactive in situ plasma treatment. - The use of HfSi or HfxSiyO, compound targets, whose Si content is set so that the sputtered layer has minimal extinction with simultaneously low internal stress and high refractive index, is particularly advantageous. With such targets, different requirements can be optimized by co-magnetron sputtering with Si with the advantage of lower internal stresses of the layer growing on the HfSi or HfxSiyOz cathode environment, which significantly reduces the probability of particle loading.
FIG. 7 shows the relation between silicon content y of the HfxSiyOz layer in at. % and the corresponding silicon content of an HfSi mixed target in weight % (line 39). For the preferred Si content y of the HfxSiyO66.7 layer (1 at. %<y<10 at. %) described above, during use of an HfSi compound target, the target should therefore have a silicon content between 0.5 wt % and 5 wt %. For a preferred Si content y of the HfxSiyO66.7 layer (1 at. %<y<7 at. %), during use of an HfSi compound target, the target should have a silicon content between 0.5 wt % and 4 wt %. -
FIG. 8 shows measured values of the refractive index n and the extinction k of a ZrxSiyO66.66 layer and a ZrO2 layer as a function of wavelength. As is apparent, a reduction of the optical losses in the UV range in ZrxSiyOz is even more pronounced than in HfxSiyOz, i.e., in pure ZrO2, the extinction reaches a value of 1E-3, already at a wavelength of 330 nm, whereas in Hf30.83Si2.5O66.66, this value is only reached at 280 nm. In this composition, coating at a high rate of about 0.5 nm/s can be accomplished, whereas in a coating with ZrO2, only half that rate was achieved. As in HfxSiyO66.7, the stress is also reduced in the corresponding zirconium compound by about the same factor relative to the pure metal oxide. - A layer with stoichiometric or almost stoichiometric composition (Zr30.83Si2.5O66.66) is preferably produced or used, which offers optimal optical and mechanical properties, i.e., low optical losses into the UV spectral range, high refractive index >2.1 and low stress <100 MPa.
-
FIG. 1 b shows anoptical component 1′, an edge filter, which is provided with an integrated reflection reduction layer or antireflection layer to increase its light transparency. Edge filters allow light to pass through almost unfiltered up to a limit frequency, but block most of the light from the limit frequency. Amultilayer system 5 with severalsuperimposed layers 3′, 4 from dielectric materials with different refractive indices are used as coating, in which layers 3′ from a high refractive material and layers 4 from a relatively low refractive material are arranged superimposed in alternation. The multilayer system typically consists of 10-100individual layers 3′, 4, in which theindividual layers 3′, 4 typically have a thickness from 20 to 100 nm. In the present practical example, thesubstrate 2 consists of a thin plate of quartz or plastic. Thethickness 6 of the substrate is between 0.5 and 1.0 mm; the magnitude of themultilayer thickness 5 inFIG. 1 b is therefore shown strongly exaggerated relative to thethickness 6 ofsubstrate 2. Thelayers 3′, 4 of themultilayer system 5 are applied to thesubstrate 2 by a sputtering method and, depending on the size of the internal stresses in the individual layers, exert forces onsubstrate 2. The forces of the individual layers are added, so that in acomplex multilayer system 5 with internal stresses of >1 GPa, very high forces can act on thesubstrate 2. In order to avoid deformation ofsubstrate 2 because of such layer stresses, the internal stresses of theindividual layers 3′, 4 must therefore be as low as possible. This is achieved in the present practical example in that thelayers 3′ with high refractive index consist of HfxSiyO66.7, the silicon content y preferably lying between 1.5 at. % and 3 at. %. With corresponding adjustment of the sputtering parameters, such sputtering layers, as described above, have low internal stress with high refractive index and high transparency. Theindividual layers 4 with low refractive index can consist of SiO2, which has a refractive index of about n=1.48 at 550 nm. - The HfxSiyOz and ZrxSiyOz coatings according to the invention are particularly suited for use of laser-resistant optical components with low residual reflection and high transparency for UV light from a wavelength range up to 230 nm, for example, for optical components that are used in laser optics in microlithography systems to produce microelectronic components (for example, for use in laser optics for KrF excimer lasers with a working wavelength of λ=248 nm). The HfxSiyOz and ZrxSiyOz coatings according to the invention are also suited for use in mirrors, especially laser mirrors and edge filters, and also for interference filters into the UV range. The coating, in particular, can be used as an antireflection coating on semiconductor lasers.
Claims (21)
1. Coating (3, 3′) from a hafnium- or zirconium-containing oxide, characterized by the fact that the hafnium- or zirconium-containing oxide contains a silicon fraction (y) between 1 at. % and 10 at. %, especially between 1.5 at. % and 3 at. %.
2. Coating (3, 3′) according to claim 1 , characterized by the fact that the coating (3, 3′) has a composition HfxSiyOz or ZrxSiyOz with an O fraction (z) between 65 at. % and 68 at. % and a silicon fraction (y) between 1 at. % and 10 at. %.
3. Coating (3, 3′) according to claim 2 , characterized by the fact that the coating (3, 3′) has a composition HfxSiyO66.7 or ZrxSiyO66.66.
4. Coating according to claim 3 , characterized by the fact that the coating (3, 3′) has a composition Zr30.83Si2.5O66.66.
5. Optical component (1) with substrate (2) and a coating (3) applies to the substrate (2) from a hafnium- or zirconium-containing oxide (HfxSiyOz or ZrxSiyOz), characterized by the fact that the hafnium- or zirconium-containing oxide (HfxSiyOz or ZrxSiyOz) contains a silicon fraction (y) between 1 at. % and 10 at. %, especially between 1.5 at. % and 3 at. %.
6. Optical component (1) according to claim 5 , characterized by the fact that the 0 fraction (z) lies between 65 at. % and 68 at. %.
7. Optical component (1′) with substrate (2) and a multilayer system (5) applied to substrate (2), in which the multilayer system (5) includes at least one layer (3′) from a hafnium- or zirconium-containing oxide (HfxSiyOz or ZrxSiyOz), characterized by the fact that the hafnium- or zirconium-containing oxide (HfxSiyOz or ZrxSiyOz) contains a silicon fraction (y) between 1 at. % and 10 at. %.
8. Optical component (1) according to claim 7 , characterized by the fact that the 0 fraction (z) lies between 65 at. % and 68 at. %.
9. Optical component (1, 1′) according to one of the claims 5 to 8 , characterized by the fact that substrate (2) consists of quartz.
10. Optical component (1, 1′) according to one of the preceding claims, characterized by the fact that the layer stress of layer (3) or the multilayer system is less than 800 MPa, preferably less than 300 MPa, and more preferably less than 100 MPa.
11. Method of production of coating according to one of the claims 1 to 4 , characterized by the fact that the coating (3) from the hafnium- or zirconium-containing oxide (HfxSiyOz or ZrxSiyOz) is produced by magnetron sputtering.
12. Method for production of an optical component (1, 1′) according to one of the claims 5 to 10, characterized by the fact that the coating (3) from the hafnium- or zirconium-containing oxide (HfxSiyOz or ZrxSiyOz) is applied on substrate (2) by means of magnetron sputtering.
13. Method according to claim 11 or 12 , characterized by the fact that production of the coating (3) occurs by reactive co-magnetron sputtering of Hr of Zr and Si.
14. Method according to claim 11 or 12 , characterized by the fact that production of the coating (3) occurs by reactive co-magnetron sputtering of HfSi or ZrSi and Si.
15. Method according to claim 11 or 12 , characterized by the fact that production of the coating (3) occurs by reactive co-magnetron sputtering of HfxSiyOz or ZrxSiyOz and Si.
16. Method according to claim 11 or 12 , characterized by the fact that production of the coating (3) occurs by reactive magnetron sputtering, using an Hf- or Zr- and Si-containing compound target.
17. Method according to claim 11 or 12 , characterized by the fact that production of the coating (3) occurs by partially reactive magnetron sputtering, using a conducting HfxSiyOz or ZrxSiyOz compound target.
18. Method according to one of the claims 11 to 17 , characterized by the fact that the reactive or partially reactive magnetron sputtering is accompanied by reactive in situ plasma treatment.
19. Method according to one of the claims 11 to 18 , characterized by the fact that the Si fraction is set so that the layer (3) has minimal extinction with simultaneously low layer stress and high refractive index.
20. Use of an optical component (1) according to one of the claims 5 to 10 , characterized by the fact that the optical component (1) is used as a laser mirror.
21. Use of an optical component (1) according to one of the claims 5 to 10 , characterized by the fact that the optical component (1) is used as an edge filter.
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US12/620,585 US20100279124A1 (en) | 2008-10-31 | 2009-11-17 | Hafnium or zirconium oxide Coating |
US14/744,138 US9983333B2 (en) | 2008-10-31 | 2015-06-19 | Hafnium or zirconium oxide coating |
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PCT/EP2008/009206 WO2010048975A1 (en) | 2008-10-31 | 2008-10-31 | Hafnium oxide coating |
US11518708P | 2008-11-17 | 2008-11-17 | |
US16284609P | 2009-03-24 | 2009-03-24 | |
PCT/EP2009/002138 WO2010049012A1 (en) | 2008-10-31 | 2009-03-24 | Hafnium oxide or zirconium oxide coating |
US12/620,585 US20100279124A1 (en) | 2008-10-31 | 2009-11-17 | Hafnium or zirconium oxide Coating |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4221649A (en) * | 1979-04-09 | 1980-09-09 | Gould Inc. | Thin film strain gage and process therefor |
US4848909A (en) * | 1986-01-31 | 1989-07-18 | Honeywell Inc. | Ion beam sputtered mirrors for ring laser gyros |
US5382342A (en) * | 1993-01-14 | 1995-01-17 | The United States Of America As Represented By The Department Of Energy | Fabrication process for a gradient index x-ray lens |
US5389606A (en) * | 1992-03-13 | 1995-02-14 | E. I. Du Pont De Nemours And Company | Process for producing thin films of inorganic oxides of controlled stoichiometry |
US5514485A (en) * | 1988-03-03 | 1996-05-07 | Asahi Glass Company Ltd. | Amorphous oxide film and article having such film thereon |
US20020093732A1 (en) * | 2001-01-18 | 2002-07-18 | Jamie Knapp | Selectively tuned ultraviolet optical filters and methods of use thereof |
US20030207549A1 (en) * | 2002-05-02 | 2003-11-06 | Jenq Jason Jyh-Shyang | Method of forming a silicate dielectric layer |
US20060087739A1 (en) * | 2004-10-21 | 2006-04-27 | Jds Uniphase Corporation | Low net stress multilayer thin film optical filter |
US20070095650A1 (en) * | 2005-10-28 | 2007-05-03 | Applied Materials, Inc. | Protective offset sputtering |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2950886B2 (en) | 1989-03-07 | 1999-09-20 | 旭硝子株式会社 | Method for manufacturing glass with permselective membrane |
JPH04291981A (en) | 1991-03-20 | 1992-10-16 | Fujitsu Ltd | Semiconductor laser device |
US6413386B1 (en) | 2000-07-19 | 2002-07-02 | International Business Machines Corporation | Reactive sputtering method for forming metal-silicon layer |
DE10141102A1 (en) | 2001-08-22 | 2003-04-03 | Schott Glas | Cadmium-free optical steep edge filters |
US7112485B2 (en) | 2002-08-28 | 2006-09-26 | Micron Technology, Inc. | Systems and methods for forming zirconium and/or hafnium-containing layers |
US20040198069A1 (en) | 2003-04-04 | 2004-10-07 | Applied Materials, Inc. | Method for hafnium nitride deposition |
JP4177857B2 (en) | 2006-04-28 | 2008-11-05 | 株式会社東芝 | Semiconductor device and manufacturing method thereof |
WO2010048975A1 (en) | 2008-10-31 | 2010-05-06 | Leybold Optics Gmbh | Hafnium oxide coating |
US20100279124A1 (en) * | 2008-10-31 | 2010-11-04 | Leybold Optics Gmbh | Hafnium or zirconium oxide Coating |
-
2009
- 2009-11-17 US US12/620,585 patent/US20100279124A1/en not_active Abandoned
-
2015
- 2015-06-19 US US14/744,138 patent/US9983333B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4221649A (en) * | 1979-04-09 | 1980-09-09 | Gould Inc. | Thin film strain gage and process therefor |
US4848909A (en) * | 1986-01-31 | 1989-07-18 | Honeywell Inc. | Ion beam sputtered mirrors for ring laser gyros |
US5514485A (en) * | 1988-03-03 | 1996-05-07 | Asahi Glass Company Ltd. | Amorphous oxide film and article having such film thereon |
US5389606A (en) * | 1992-03-13 | 1995-02-14 | E. I. Du Pont De Nemours And Company | Process for producing thin films of inorganic oxides of controlled stoichiometry |
US5382342A (en) * | 1993-01-14 | 1995-01-17 | The United States Of America As Represented By The Department Of Energy | Fabrication process for a gradient index x-ray lens |
US20020093732A1 (en) * | 2001-01-18 | 2002-07-18 | Jamie Knapp | Selectively tuned ultraviolet optical filters and methods of use thereof |
US20030207549A1 (en) * | 2002-05-02 | 2003-11-06 | Jenq Jason Jyh-Shyang | Method of forming a silicate dielectric layer |
US20060087739A1 (en) * | 2004-10-21 | 2006-04-27 | Jds Uniphase Corporation | Low net stress multilayer thin film optical filter |
US20070095650A1 (en) * | 2005-10-28 | 2007-05-03 | Applied Materials, Inc. | Protective offset sputtering |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150285957A1 (en) * | 2008-10-31 | 2015-10-08 | Leybold Optics Gmbh | Hafnium or Zirconium Oxide Coating |
US9983333B2 (en) * | 2008-10-31 | 2018-05-29 | Leybold Optics Gmbh | Hafnium or zirconium oxide coating |
US20110229660A1 (en) * | 2010-03-22 | 2011-09-22 | Timothy Ray Reynolds | Ion beam assisted deposition of ophthalmic lens coatings |
US20110229659A1 (en) * | 2010-03-22 | 2011-09-22 | Timothy Ray Reynolds | Ion beam assisted deposition of ophthalmic lens coatings |
US20110284773A1 (en) * | 2010-05-19 | 2011-11-24 | Pugh Randall B | Germicidal bulb disinfection base for ophthalmic lenses |
US9282796B2 (en) | 2010-05-19 | 2016-03-15 | Johnson & Johnson Vision Care, Inc. | UV radiation control for disinfecting of ophthalmic lenses |
US9789220B2 (en) | 2010-05-19 | 2017-10-17 | Johnson & Johnson Vision Care, Inc | Ophthalmic lens disinfecting base |
US9795704B2 (en) | 2010-05-19 | 2017-10-24 | Johnson & Johnson Vision Care, Inc | Ophthalmic lens disinfecting base |
US9872933B2 (en) | 2010-05-19 | 2018-01-23 | Johnson & Johnson Vision Care, Inc. | Light emitting diode disinfection base for ophthalmic lenses |
CN114369805A (en) * | 2022-01-13 | 2022-04-19 | 中国科学院上海硅酸盐研究所 | Magnetron sputtering preparation of high-surface-quality HfO2Method for base mixing thin film |
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