Deposition process of quantized nanolayers by magnetron sputtering

Abstract

A process for depositing nanolaminates on a surface of a flat substrate, comprising the steps of: mounting the substrate on a substrate support in a peripheral region (R) of a holder, the holder being rotatable about its central axis B, the receiver being attached to a sputtering source, the receiver comprising at least one magnetron sputtering station having a sputtering target spaced from the magnetron sputtering station, and at least one plasma treatment station having a plasma source, in each case both the sputtering target and the plasma source facing different points in the peripheral region (R); pumping down the receiver; rotating the holder about the central axis at a constant speed; introducing a sputtering gas into the receiver; introducing a reactive gas directly into at least one of the sputtering stations or the plasma station; igniting a magnetron discharge in the sputtering station and controlling a magnetron power level (P m igniting a plasma in the plasma processing station and setting a plasma power level (P p ) and continuously exposing the substrate by rotating the holder, wherein a layer L of high refractive index material is formed by magnetron discharge. h and a layer of low refractive index material L by plasma treatment. l and forming a magnetron power level (P m ) is the well layer L of high refractive index material h Layer thickness d h is 0.1≦d h 5nm≦5nm。

Description

[Technical Field]

[0001] The invention relates to a sputtering process for depositing quantized nanolaminates (QNL) on the surface of a substrate according to claim 1, an optical device according to claim 23 and a process system for depositing such nanolaminates according to claim 30. [Background technology]

[0002] Optical interference coatings, such as anti-reflection coatings, mirror coatings, and filter coatings, are based on stacks of materials with at least two different refractive indices n. The greater the difference between the refractive indices of the materials, the stronger the interference effect. As a result, stacks using materials with a large refractive index difference have fewer individual layers and a smaller overall thickness than stacks with a small refractive index difference. In addition to the refractive index, the materials must fulfill another requirement: they must be transparent with negligible losses in the wavelength range of interest.

[0003] However, it has long been known that there is a relationship between the refractive index and the absorption edge of dielectric materials: materials with high refractive index have an absorption edge at higher wavelengths, while materials with low refractive index have an absorption edge at lower wavelengths.

[0004] One way to break the relationship between the refractive index and the absorption edge is oblique deposition (oblique evaporation), which forms a columnar film structure that reduces the effective refractive index. This creates an interference effect between a continuous layer and a layer with a columnar structure of the same material. Since there is no interface between different materials, this can have interesting effects such as increased resistance to laser damage, but it also has the disadvantage of being more sensitive to environmental conditions.

[0005] A recent concept that reverses the relationship between these two properties is quantum nanolaminates (QNLs), first proposed by Jupe et al. in 2019. According to this concept, thin layers of high and low refractive index with thicknesses in the nanometer range or less are stacked. These layers are called well layers for the high-index material and barrier layers for the low-index material. The limited structure size leads to a change in the energy gap, which can be tuned by the physical thickness of the materials, and the ratio of the materials determines the effective refractive index of the QNL.

[0006] For optical interference coatings, the decoupling of bandgap and refractive index potentially offers the advantage of being able to design materials with specific refractive indices using material combinations, instead of searching through a limited number of known materials. For example, in the UV range, the bandgap of Ta2O5 can be pushed down to shorter wavelengths, thereby replacing the use of HfO2. This is desirable because hafnium targets are expensive and HfO2 has a tendency to polycrystallize and form grain boundaries, which can cause losses due to stray light.

[0007] Another example is detailed by Henning et al. in "Manufacturing of Si-based hybrid metamaterials for increasing the refractive index in interference coatings" (Md.1, OIC 2022 XX), which explains that the combination of amorphous silicon and SiO2 can be transparent in the visible wavelength range with an effective refractive index above 2.7. Such a material would be transparent in the visible wavelength range, offering a significant advantage over TiO2, the known material with the highest refractive index. However, to date, this effect has not been demonstrated by experimental evidence.

[0008] So far, the QNL effect has only been experimentally demonstrated for atomic layer deposition (ALD) and ion beam sputtering (IBS) coatings in the paper "Quantizing nanolaminates as versatile materials for optical interference coating" by Steinecke et al. (J. Optical Society of America, Vol. 59, No. 5 / 10, February 2020). While both alternative methods have shown promising results, they have drawbacks for mass production. ALD deposition results in a low growth rate because only one atomic layer is deposited per coating cycle. IBS, on the other hand, requires mechanical transfer of the zone target from one material in the nanolaminate to another, effectively limiting the deposition rate. The same paper explicitly notes that several attempts to deposit such layers by RF patterning (RF-puttering) have only resulted in reliable deposition at layer thicknesses greater than 5 nm, which are too thick to exhibit quantization effects. Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to overcome the problems of the prior art and to provide an industrially viable alternative process for depositing QNL films and corresponding vacuum process tools for producing such layers. A further object is to provide novel optical devices using QNL films produced by the respective processes. [Means for solving the problem]

[0010] These problems are solved by a process with the features of claim 1, a vacuum process system for depositing such nanolaminates according to claim 30, and an optical device according to claim 23. Further aspects of the process, process system, and device of the invention are indicated by the technical features of the respective dependent claims.

[0011] According to the present invention, the process for depositing so-called Quantized Nanolaminates (QNL) on the surface of a flat substrate comprises: - mounting the substrate on a substrate support in a peripheral area (R) of a holder, in a vacuum processing system, the holder being mounted rotatably about its central axis B and the receiver being attached to a sputtering source, the vacuum processing system comprising at least one magnetron sputtering station with a sputtering source spaced from the magnetron sputtering station, and at least one plasma treatment station with a further plasma source, in each case both the sputtering source and the plasma source facing different points in the peripheral area (R); - pumping down the receiver; - rotating the holder around a central axis at a constant speed; - introducing sputtering gas into the receiver, for example in the immediate vicinity of the sputtering station or directly into the sputtering station, which can be achieved either by a gas ring or other kind of circumferential gas source, such as a slotted gas source, which can be fitted around the opening of the sputtering station or within the sputtering station; - direct introduction of reactive gases into at least one of the sputtering station or the plasma station, characterized in that similar or identical gas ducts can be selected; - igniting a magnetron discharge in the sputtering station and controlling the magnetron power level (P m ) setting the - igniting a treatment discharge at the plasma treatment station and adjusting the plasma power level (P p ) setting the - successively, preferably repeatedly, exposing said substrate by rotating said holder, The magnetron discharge forms a layer L of high refractive index material. h and depositing The treatment discharge forms a layer L of low refractive index material l generating a compound represented by the formula: The rotation speed of the holder and the magnetron power level (P m ) is a well layer L of a high refractive index material whose refractive index can exceed 1.65. h Layer thickness d h (In some cases, well or t h )but 0.1≦d h ≦5 nm (see Steinecke), e.g., 0.1 ≦ d h ≦4.0 nm, particularly, for example, 0.1≦d h ≦3nm is set to be

[0012] In one aspect of the present invention, the plasma power level (P p ) is a barrier layer L of a low refractive index material whose refractive index may be 1.65 or less. l Layer thickness d l (d barrier or t l (also called) 0.1≦d l ≦30 nm, e.g., 0.1≦d l ≦20nm, especially 0.5≦d l ≦10nm is set to be

[0013] In one embodiment of the present invention, the target may be any one of Al, Si, Ti, Zr, Hf, Nb, Ta, Ge, their respective oxides, nitrides, or mixtures thereof, such as AlTi, TiZr, NbTa, or others, and their respective oxides or nitrides. High refractive index materials deposited with such targets include amorphous silicon (a-Si), transition metal oxides such as TiO, ZrO, HfO, NbO, and TaO, or mixtures thereof. However, as long as SiO is produced as a low refractive index material in the plasma station, AlO or SiN can also be deposited as a high refractive index material in the sputtering station.

[0014] In one aspect of the invention, the plasma station may comprise a plasma source, but here not a magnetron sputtering source, and reactive gases are introduced directly into the plasma station.

[0015] In one embodiment of the present invention, in which a plasma station other than a magnetron sputtering source is used to produce a second index layer, e.g., a low-index layer, the sputtering station target is operated, for example, with only a noble gas, and the sputtering station is set to a constant power level without further control. At the same time, the power of the plasma source can also be set to a constant level, and the plasma gas parameters in the plasma station, which can be, for example, total pressure, reactive gas pressure, or, preferably, reactive gas flow rate, can be controlled by a plasma emission monitor (PEM) based on the intensity of at least one defined line of gas plasma emission.

[0016] When such a plasma source is used, for example, to produce a low-refractive-index material layer, the target can be a sputtering gas including silicon and a noble gas, which can be introduced near or directly into the sputtering station to deposit a high-refractive-index a-Si layer on the surface of a substrate passing through an opening in the sputtering station. The reactive gas in the plasma source can be oxygen, which can be introduced directly into the plasma station to oxidize the surface region of the previously deposited a-Si layer as the substrate passes through the plasma exit opening of the plasma station. Introducing the reactive gas directly into the plasma source can prevent the plasma station from interfering with the sputtering process.

[0017] Specifically, when alternately depositing high and low refractive index layers (e.g., a-Si / SiO2), the following parameters can be selected for a combination of a sputtering station and a plasma station having a target of a Si-containing material (e.g., substantially pure silicon): Power sputtering source (P Sput): 0.5-10kW, e.g., 1-7kW Gas flow sputtering source (f Sput ): 10-300sccm, e.g., 30-250sccm Power Plasma Source (P PSC ): 0.1-5kW, e.g., 0.25-3kW Gas flow plasma source (f PSC ): 1-50sccm, e.g., 2-30sccm Total pressure resulting from both gas streams: 1e -3 -2e -2 mbar

[0018] In this case, the total pressure can be set relatively high by referring to known sputtering processes, and the ratio of sputtering gas to reactive gas (f Sput / f PSC ) should be around 5:30 and especially 6:15 respectively.

[0019] As a specific example, a 0.5 nm a-Si layer is deposited at a rotation speed of 3 seconds / pass, a target power of 2.5 kW, and an Ar flow rate of 200 sccm. Then, the following parameters are applied to the plasma source so that a 0.25 nm near-surface region of the a-Si layer can be oxidized to SiO2: P PSC =250W, f PSC = 2sccmO2, the total pressure is 6e -3 This allowed the production of a 0.25 nm a-Si layer, followed by a 0.25 nm SiO2 layer, in an Evatec Clusterline® BPM magnetron sputtering deposition system. Further aspects are described in the detailed description below.

[0020] In a further aspect of the invention, the plasma processing station is a further magnetron sputtering station with a further target. The further target for depositing the low refractive index material can be any of Si, SiO2, Si3N4, Al, Al2O3, or AlN. In this aspect, sputtering gas can be introduced into the sputtering station and the further sputtering station via separate gas ducts.

[0021] Power can be set at the target and / or the additional target. The reactive gas can be introduced simultaneously or later, e.g., through the same or a different gas inlet as the sputtering gas. The reactive gas parameters in the sputtering station and / or the additional sputtering station can be controlled by a plasma emission monitor (PEM) in the transition region of the reactive sputtering process, particularly the intensity of at least one predetermined line of the target plasma emission in the transition mode, where the target surface is neither pure metal nor completely contaminated (e.g., oxidized) by the reactive gas, making process control difficult without a PEM. This allows a fully reacted layer to be deposited on the substrate without completely contaminating the target surface, maintaining a high deposition rate and avoiding process instabilities.

[0022] This allows, for example, if high and low refractive index layers need to be deposited alternately, to select the following process parameters only for the combination of two sputtering stations (including the sputtering station and the additional sputtering station): High refractive index layer L h Sputtering source 1 for depositing: Power P Sput1 :0.5-10kW, e.g., 1-8kW Target material: Al, Si, Ti, Zr, Hf, Nb, Ta, Ge, their respective oxides, nitrides, or mixtures thereof. Deposition atmosphere: Usually a mixture of sputtering gas (any noble gas) and reactive gas such as oxygen or nitrogen. At least the reactive gas is supplied near or directly to the sputtering station. The applied gas flow rate is 10≦f noble ≦200sccm, 1≦f react ≦100sccm, but 10≦f noble A (pure) noble gas atmosphere should be used for the deposition of the a-Si layer so that the flow rate is ≦300 sccm. See also above.

[0023] Low refractive index layer L l Sputtering source 2 (further sputtering source) for depositing: Power P Sput2 :0.5-10kW, e.g., 1-8kW Target material: Al, Si, their respective oxides, nitrides, or mixtures thereof. Deposition atmosphere: usually a mixture of sputtering gas (any noble gas) and reactive gases such as nitrogen, preferably oxygen. At least the reactive gas is supplied near or directly to the sputtering station. The applied gas flow rates are 10≦f noble ≦200sccm, 1≦f react It can be ≦100 sccm.

[0024] In any aspect of the present invention, the sputtering gas may be any noble gas, such as at least one of argon, krypton, neon, xenon, or mixtures thereof.

[0025] In any embodiment of the invention in which a reactive gas and / or further reactive gas is used, the reactive gas and further reactive gas may or may not be the same and may be introduced directly into the sputtering station, directly into the plasma station instead of or in addition to the further sputtering station, for example by separate gas ducts to two, three, four or more stations, respectively. The reactive gas and / or further reactive gas may be oxygen or nitrogen.

[0026] In any aspect of the invention, the process shutter may be provided with a sputtering station and / or a further sputtering station, and the shutter may be opened during the deposition process of each layer, and the process shutter may be closed during the ignition process of each sputtering station until the sputtering process has stabilized and layer deposition can begin.

[0027] In one embodiment of the present invention, the n-layer L of high refractive index material h and n layers or n±1 layers L of low refractive index material l are deposited as an alternating stack on at least one surface of a flat substrate, and the number of layers in the stack, n, is determined by the number of layers L h and L l n is at least 1, 1≦n≦10,000, with 2≦n≦2,000 being the most realistic value.

[0028] An example of the thinnest layer combination that can be deposited is 0.1 nm Ta2O5 / 0.2 nm SiO2. A 500 nm thick nanolaminate contains 1,666 alternating high and low refractive index layers. Typical thicknesses of interference filters can be 1-300 nm. Further aspects are described below in the detailed description of the invention.

[0029] In a further aspect of the invention, which can be combined with any other aspect, at least one further layer or coating, which may consist of multiple layers, can be deposited between the stack and the glass substrate and / or between the stack and the atmosphere, respectively, such as an adhesion layer / coating for the substrate, a scratch protection layer / coating for the atmosphere, an AR or IR reflective coating, etc.

[0030] When layers of high and low refractive index materials are stacked alternately, the overall refractive index reflects the proportion of high and low refractive index material used in the well and barrier layers of the stack, and is expressed by the formula: n SUM 2 =x * n h 2 +y * n l 2 , where 0≦x≦1, 0≦y≦1, and x+y=1. In embodiments of the invention applicable to any aspect of the invention, unless inconsistent, the transmission edge T and respective absorption edge (TR) of the stack shifts towards lower wavelengths with decreasing well thickness. That is, for the same layer stack of high and low index materials and the same ratio of high index material to low index material, e.g., the total (optical) thickness (d h_tot =n * d h ) and a layer of low refractive index material (d l_tot =(n±1) * d l ) and when different well thicknesses are applied, the respective shifts of the transmission edge T are expressed as follows for the combination of high and low refractive index materials, oxide and / or nitride, as described above: ΔT 50 =T 50_THICK -T 50_THINN , where 2≦ΔT 50 ≦60 nm, e.g., 5≦ΔT 50 ≦40 nm.

[0031] Due to the high refractive index of a-Si, the shift of the transmission edge T becomes large in the a-Si / SiO2 material combination, and 20≦ΔT 50 ≦600 nm, e.g., 50≦ΔT 50 ≦400 nm.

[0032] Here, ΔT 50 is the difference in transmittance at 50% T 50_THICK -T 50_THINN This means that the well layer thickness is d h_THICK The transmittance of the layer stack is ≥ 5 nm (e.g., 5-50 nm) and the well layer thickness is d h_THIN ≦3 nm (e.g., 3-0.1 nm), and the transmittance T 50_THINN At least in the coatings deposited by the process of the present invention, the thickness of all well layers is preferably the same value d h and all barrier layers have the same thickness d l Although these values ​​are usually different and can be different, d h ≦d l or d h <d l is.

[0033] In a further aspect of the present invention, which can be combined with other aspects of the present invention, unless inconsistent, the free ground state and the well layer L h The gap energy E between the higher conducting states increases with decreasing gap teeth, ΔE gap =E gap_THINN -E gap_THICK And Here, for example, in the case of a combination of a high refractive index material and a low refractive index material such as oxides and / or nitrides, 0.01≦ΔE gap ≦0.8 eV, e.g., 0.02≦ΔE gap ≦0.4 eV.

[0034] For the material combination a-Si / SiO2, the range is 0.01≦ΔE gap≦2 eV, e.g., 0.02 ≦ ΔE gap ≦1.5 eV, Here, ΔE gap is the thin well layer d formed by the process of the present invention. h_THIN E of a layer having a thickness of ≦3 nm (e.g., 3-0.1 nm) gap_THINN and the well layer thickness is d h_THICK E of the layer stack is ≥ 5 nm (e.g., 5-50 nm) gap_THICK The lower energy gap is the well layer thickness d of about 2-1.5 nm. h and the high energy gap is due to the well layer thickness d of about 0.1-0.5 nm. h The absolute value within the range may vary depending on the combination of each low refractive index material and high refractive index material.

[0035] In a further aspect of the invention, which can be combined with other aspects of the invention, unless the combination is inconsistent, the holder is a turntable holder, and the peripheral region (R) is defined by an outer circular ring, but is defined on at least one major surface of the disk-shaped holder, i.e., the upper or lower surface of the turntable holder, with the substrate holder positioned along the ring, e.g., with the substrate holder's geometric center along the central diameter of the ring. A flat substrate is then mounted on or within a substrate support in a plane parallel to the turntable surface. While the latter can be vertical using a turntable holder with a horizontal rotation axis B, horizontal turntable holders, respective turntable holder planes P with vertical rotation axis B, and substrates are preferably positioned horizontally. For details of the respective turntable holders, see the examples and figures below.

[0036] In a further aspect of the present invention, which can be combined with other aspects of the invention, unless the combination is inconsistent, the holder is a cylindrical or cylindrical polyhedral holder, the peripheral region (R) is determined by the cylindrical or polyhedral surface of the holder, and the substrate support is positioned along at least one diameter with its center at a constant height above the cylindrical or polyhedral surface of the holder. A flat substrate can be mounted within or on the cylindrical or polyhedral surface in a plane substantially parallel to the cylindrical or polyhedral surface. Here, "substantially parallel" means a tangent to the cylindrical surface, typically determined based on the center of the substrate as a tangent point or the point closest to the cylindrical diameter of the holder, depending on the type of support. For polyhedral surfaces, this means parallel to the facets of the faceted surface. In either case, those skilled in the art will readily understand that the support geometry includes substrate positions several millimeters above or below the respective holder surface or holder diameter. While the axis B of the holder can be horizontal, in this case, it is preferred that the substrate be positioned vertically on a cylindrical holder having a vertical axis B.

[0037] In a further aspect of the invention which may be combined with other inventive aspects, unless the combination is inconsistent, the substrate may be a wafer, such as a silicon or glass wafer.

[0038] In a further embodiment of the invention, the substrate may be a wafer, the peripheral region (R) being at a radial distance of 535±60 mm from the central axis B, and the constant speed being set at 30-0.5 seconds per revolution, e.g., 2-20 seconds per pass, which is equal to seconds per revolution. In such a configuration, for example, 16 wafers (or 15 wafers plus a dummy wafer) up to 200 mm in diameter can be coated simultaneously.

[0039] For disk-shaped substrates such as wafers, a disk-shaped circular target with a substantially cylindrical magnetron source or a linear sputtering source with a linear target can be used, with the diameter or circumference of the active area, also called the racetrack, projecting laterally from the substrate to provide uniform coating quality and thickness across the entire substrate surface. To maximize the use of a circular target, the target or magnetic system may be rotated. However, as explained above and in the detailed description below, in the case of a turntable holder, a static asymmetric magnet system can be effective to compensate for different deposition rates due to different radial velocities in the outer and inner regions of the substrate surface, as explained in detail in Figures 4 and 2 of Applicant's WO 2017 / 042123 and the corresponding specification descriptions. To achieve optimal coating distribution and cost efficiency, the target diameter D T is 1.4 * D W ≦D T ≦1.7 * D W As shown in the example, the wafer D to be coated W The diameter of the target must be substantially larger than the diameter of the target, and ultimately the magnet system in combination with the rotation of the magnet or target will result in uniform material erosion over the entire target surface. For example, for a 200 mm wafer, the following range will give good results: 280≦D T ≦340, especially 300≦D T ≦320.

[0040] The present invention further provides an optical device comprising a substrate and an optical coating deposited on at least one side of the substrate, the optical coating comprising at least one film of a high refractive index material and at least one film of a low refractive index material, wherein at least one of the high refractive index material film and / or the low refractive index material film is configured as a Quantized Nanolaminate (QNL), the Quantized Nanolaminate (QNL) having an overall QNL (n QNL ), while a QNL film, i.e., a stack of quantum layers of high and low refractive index materials, has at least a barrier layer L of low refractive index material.l and well layers L of high refractive index material arranged alternately. h and a well layer L h Layer thickness d h is 0.1≦d h ≦6 nm, therefore preferably 0.1≦d h ≦4.0 nm, e.g., 0.1≦d h ≦3 nm.

[0041] In a further inventive aspect of the device which can be combined with other inventive aspects, unless the combination is inconsistent, a barrier layer L of low refractive index material is l Layer thickness d l is 0.1≦d l ≦30 nm, and therefore preferably 0.1≦d l ≦20 nm, for example, 0.5≦d l ≦10 nm.

[0042] In a further invention embodiment, the QNL film defines a high refractive index film for an optical coating.

[0043] In a further embodiment of the invention, the low refractive index material of the low refractive index film is the barrier layer L of the QNL film. l The low refractive index material may be the same as the low refractive index material of the first embodiment.

[0044] The number of layers of the stacked QNL film, n, is the number of layers L h and L l At least 1 for every n, and 1≦n≦10,000, for example, 2≦n≦2,000.

[0045] In either aspect of the invention, the device can be manufactured according to the process described above.

[0046] In embodiments of the present invention, the optical coating may be an interference coating, such as an anti-reflection (AR) coating (for visible or infrared light). The device may be a mirror, a semi-selective mirror, a filter, or a lens with a respective coating. When the device is a filter, it may be a notch, a short-pass or long-pass edge filter, a beam splitter, or a polarizer.

[0047] The present invention further comprises at least one well layer L of a high refractive index material. h and at least one barrier layer L of a low refractive index material. l a vacuum process system for depositing so-called Quantized Nanolaminates (QLN) on the surface of a flat substrate, the receiving part comprising: a holder rotatable about a central axis B, the holder having a substrate support in its peripheral region (R), at least one magnetron sputtering station having a sputtering target attached to a sputtering source, the sputtering target being located remotely from the magnetron sputtering station; at least one plasma treatment station having a plasma source, - a sputtering target and a plasma source, which in each case affect different sections of the peripheral region (R), for example via respective openings in the target station and the plasma station, a sputtering gas inlet for introducing sputtering gas into the receiver, which may preferably be located adjacent to or within the sputtering station, such as around the target, and may therefore comprise a gas ring or other kind of circumferential gas supply, for example a slot around an opening in the sputtering station or within the sputtering station; a reactive gas inlet and / or a further reactive gas inlet for introducing reactive gas into the receiving portion, where the reactive gas inlet may be at least adjacent to or within the sputtering station, and the further reactive gas inlet may be at least adjacent to or within the plasma station. In either case, the reactive gas inlet may be a gas ring or other kind of circumferential gas supply, for example around an opening in the plasma / sputtering station, such as around the target, or a slot in the plasma / sputtering station.

[0048] This allows the holder rotation speed to be set at 30-0.5 seconds per revolution, e.g., 2-20 seconds per revolution (seconds / pass), and the magnetron power level (P m ) can be set to 0.5-10kW, so for example, a well layer L of a high refractive index material with a refractive index of 1.65 or more can be used. h Layer thickness d h is 0.1≦d h ≦6 nm, therefore preferably 0.1≦d h ≦4.0 nm, e.g., 0.1≦d h These rotation speeds and magnetron power levels can be set for industrial coating equipment with holder diameters of 800-2000 mm and target diameters of 280-450 mm to coat wafers with diameters of 200 or 300 mm.

[0049] In a further aspect of the invention, which may be combined with other inventive aspects, the rotation speed of the holder and the magnetron power level (P m ) is a barrier layer L of low refractive index material l Layer thickness t l 0.1≦d l ≦30 nm, and therefore preferably 0.1≦d l ≦20 nm, for example, 0.5≦d l It can be set to ≦10 nm.

[0050] In a further aspect of the invention, which may be combined with other inventive aspects, unless the combination is inconsistent, the plasma station comprises an inductively or capacitively coupled plasma source and a reactive plasma gas inlet which is introduced directly into the plasma station, for example a further gas inlet arranged in the station, which may be connected to a nitrogen source, but preferably to an oxygen source.

[0051] In a further aspect of the present invention, which can be combined with other aspects of the present invention, unless the combination is inconsistent, the plasma station is a capacitively coupled HF plasma source. The plasma source may be an inductive plasma source such as the IS300, but a capacitively coupled RF plasma source such as the PSC303 is preferred. Both types of plasma source are available from Evatec, a Swiss manufacturer of vacuum and plasma equipment. Details regarding capacitively coupled RF plasma sources that can be advantageously used in the present invention are disclosed in Figures 2 and 6-8 of the applicant's International Publication No. 2020 / 161139 and their respective descriptions. Such a plasma source comprises a first capacitively coupled plasma generating electrode with a larger electrode surface and a second capacitively coupled plasma generating electrode with a smaller electrode surface within the vacuum receiver or plasma station and each process system of the process system, as well as a plasma exit opening and, here, a reactive gas inlet or reactive gas supply only from a reactive gas source. The plasma exit opening typically passes through the second electrode, which may comprise at least one grid with a transparency greater than 50%. The second electrode may also be set to a reference potential, which may be ground potential. At least one of the major and minor electrode surfaces may be variable.

[0052] Additionally, at least one coil arrangement may be provided in the space between the first and second electrodes to generate a magnetic field. In a further aspect of the plasma source, the first electrode may be cup-shaped, with its inner surface facing the second electrode, and a coil arrangement may be provided along the outer surface of the cup-shaped first electrode to generate a magnetic field having a predominant directional component directed toward or away from the second electrode. Such a coil arrangement may include at least two coils independently powered by respective current sources.

[0053] In a further aspect of the invention, the target may be a silicon target and the sputtering gas inlet is connected to a noble gas source only, for example, to deposit a silicon layer.

[0054] In a further aspect of the invention, which can be combined with other inventive aspects, a plasma emission monitor (PEM) can be connected via an optical path to the plasma region of the plasma source to control the plasma source power or reactive gas flow, provided the combination is consistent. Generally, all sputtering and plasma stations where reactive gas processes are performed are equipped with plasma emission monitor PEMs to exploit the hysteresis effect in the transition mode and ensure complete oxidation at high deposition rates. These monitors can be configured as broadband and / or monochromatic optical monitors.

[0055] In a further aspect of the invention, which may be combined with other inventive aspects, unless the combination is inconsistent, the plasma processing station is a further magnetron sputtering station with a further target. The further target may be any one of Si, SiO, SiN, Al, AlO, AlN, or mixtures thereof. In this case, a further reactive gas inlet to the further target station may be provided.

[0056] In a further aspect of the invention, which may be combined with other inventive aspects, unless the combination is inconsistent, the target of the target station is any one of an oxide, nitride, or mixture of Al, Si, Ti, Zr, Hf, Nb, Ta, or Ge.

[0057] In a further aspect of the invention, which can be combined with other inventive aspects, both sputtering stations, i.e., the sputtering station and the further sputtering station, can be provided with separate reactive gas inlets, provided that the combination is consistent. Each reactive gas inlet can be connected to the same or different gas sources by a respective separate reactive gas flow controller. Similarly, separate sputtering gas inlets can be provided in both sputtering stations by separately controllable sputtering gas flow controllers. The sputtering gas inlet and the reactive gas inlet can be matched in each chamber.

[0058] In a further embodiment of the invention that can be combined with any other inventive aspect, unless the combination is inconsistent, the holder is a turntable holder having a turntable holder plane (P), and the peripheral region (R) is defined by an outer circular ring, but on at least one major surface of the turntable holder, for example the upper or lower surface of the turntable holder, with the substrate holder arranged along the ring, e.g. the geometric center of the substrate holder is along the central diameter of the ring, and a flat substrate is mounted on or in the substrate support in a plane parallel to the turntable plane, which may be vertical, with the turntable holder having a horizontal rotation axis B, but preferably the horizontal turntable holder and the substrate are arranged horizontally with a vertical rotation axis B.

[0059] In either embodiment of the turntable holder, the magnetron sputtering station may comprise a circular target and a static magnet arrangement, said magnet arrangement being as follows: +It is located on a plane (M) parallel to the plane (P), and + It is not rotationally symmetric about the target axis (C) passing through the center of the magnet arrangement, but is perpendicular to a plane (M) that is also parallel to axis B.

[0060] In a further embodiment aspect of the present invention that can be combined with other inventive aspects, the distance between the target and the turntable holder can be varied in the Z direction, i.e., the direction perpendicular to the turntable and substrate surface, depending on the needs of the process, provided that the combination is consistent.

[0061] In a further embodiment, the magnet system can be separated along a line (K) in a plane (M) perpendicular to the target axis (C), with an outer region facing away from the center of the turntable and an inner region facing toward the center, the outer region being larger than the inner region, where outer and inner refer to distances closer or farther from the axis B.

[0062] The magnet arrangement (11) may be symmetric or asymmetric about an axis of symmetry (A) in a plane (M), where the axis (A) intersects the central axis (Z) of the turntable.

[0063] In either embodiment of the turntable holder, the target may be a rotating target, rotatably positioned about its central target axis (C), eg, parallel to the central axis B.

[0064] In a further aspect of the invention, which can be combined with other aspects of the invention, unless the combination is inconsistent, the holder is a cylindrical or cylindrical multi-sided holder, the peripheral region (R) is determined by the cylindrical or multi-sided surface of the holder, and the substrate support is positioned with its center along at least one high diameter of the cylindrical or multi-sided holder. This allows a flat substrate to be mounted within or on the cylindrical or multi-sided surface in a plane substantially parallel to the cylindrical or multi-sided surface. Here, substantially parallel typically means tangent to the cylindrical surface with the center of the substrate as the contact point with the cylinder, or parallel to the facets of the faceted surface. In either case, those skilled in the art will readily understand that the support geometry will position the substrate within a few millimeters above or below the respective surface or geometric diameter. While the axis B of the holder can be horizontal, in this case, it is preferred that the substrate be positioned vertically on a cylindrical holder having a vertical axis B.

[0065] For cylindrical or polygonal holders such as those described above, a vertically oriented planar or cylindrical rotating magnetron is typically used. However, when a disk-shaped target is used, the substrate support in the peripheral region (R) of the holder is preferably positioned so that the center of the substrate support and the center of the circular substrate can be aligned with the target axis (C) during holder rotation. In this case, the magnetron is provided with a rotating magnet or target to ensure uniform target erosion.

[0066] The features of the above aspects of the process, apparatus and / or receiver may be used in any combination as long as they are not inconsistent with each other.

[0067] Embodiments of the present invention will now be described in more detail with reference to the drawings, which are for illustrative purposes only and should not be construed as limiting the invention. [Brief explanation of the drawings]

[0068] [Figure 1] FIG. 1 shows the relationship between QNL energy and coating thickness. [Figure 2A] FIG. 1 is a top view of a process system with a cylindrical substrate holder. [Figure 2B] 1 is a cross-sectional view of a process system with a cylindrical substrate holder. [Figure 3A] FIG. 1 is a top view of a processing system with a turntable substrate holder. [Figure 3B] 1 is a cross-sectional view of a process system with a turntable substrate holder. [Figure 4A] FIG. 1 is a top view of a processing system with an additional turntable substrate holder. [Figure 4B] 1 is a cross-sectional view of a process system with an additional turntable substrate holder. [Figure 5] FIG. 10 is a diagram showing the relationship between transmittance and wavelength. [Figure 6] FIG. 1 is a diagram showing the relationship between the Tauc plot αhν1 / 2 [eV / m]1 / 2 and the photon energy. [Figure 7] FIG. 10 shows the energy gap and well thickness / throughput. [Figure 8] FIG. 10 is a diagram showing the relationship between the energy gap and the well thickness. [Figure 9] FIG. 10 is a diagram showing the relationship between the refractive index and the well thickness. [Figure 10] FIG. 1 is a diagram showing the relationship between the energy gap and the refractive index. [Figure 11] FIG. 10 is a diagram showing the relationship between transmittance and wavelength. [Figure 12] FIG. 10 is a diagram illustrating the relationship between reflectance and wavelength. [Figure 13A] 1 illustrates an optical device of the present invention; [Figure 13B] 1 illustrates an optical device of the present invention; [Figure 14] FIG. 10 is a diagram showing the transmittance spectrum of a mirror. [Figure 15] FIG. 2 is a diagram showing the reflectance spectrum of a mirror. [Figure 16] FIG. 10 is a diagram showing the relationship between transmittance and wavelength. [Figure 17] FIG. 10 is a diagram showing the relationship between the total thickness and the table rotation. [Figure 18] FIG. 1 shows the relationship between dSiO2 / passage and da-Si / passage. [Figure 19a] FIG. 10 is a diagram showing a transmittance spectrum. [Figure 19b] FIG. 10 is a diagram showing a transmittance spectrum. [Figure 20] FIG. 1 is a diagram showing the relationship between the Tauc plot αhν1 / 2 [eV / m]1 / 2 and the photon energy. [Figure 21] FIG. 10 is a diagram showing the relationship between Egap and da-Si / passage. [Figure 22] FIG. 10 is a diagram showing the relationship between Egap and oxygen flow. [Figure 23] FIG. 10 is a diagram showing the relationship between transmittance and wavelength of a long filter. DETAILED DESCRIPTION OF THE INVENTION

[0069] Figure 1 shows the relationship between energy and layer thickness for a technique based on the Steinecke general example, using a combination of SiO2 for the barrier layers and Ta2O5 for the well layers. Optical coatings are generally amorphous and lack a well-defined band structure, but there is an energy gap between the quasi-free ground state and the higher conduction states. This energy gap can be varied by restricting the structure size, e.g., layer thickness, in the optical coating system to very small values. The low-index material then acts as the barrier, and the high-index material acts as the quantum well. The periodic structure of high and low band gap regions limits electron mobility. A novel concept, so-called quantum nanolayers (QNLs), with the thickness of the well layers, allows for independent tuning of the optical band gap and refractive index. To achieve a large change in the energy gap, the quantum well layer thickness, here Ta2O5 layers, needs to be less than approximately 2 nm. The barrier thickness should also be in the same range as the well, preferably thin, to achieve a high effective refractive index.

[0070] FIG. 2A shows a simplified top view of a process system 30′, and FIG. 2B shows a simplified cross-sectional view thereof, with a cylindrical holder 1′ rotatable about axis B. The process system 30′ further includes a sputtering station 14, a further sputtering station 14′, and an optional plasma station 20 (dotted line) with a plasma source 21. Each sputtering station 14, 14′ includes a sputtering source 16, 16′, each having a planar, elongated sputtering target 15, 15′, also referred to as a linear target, connected to a separate gas supply 28, 28′ for introducing sputtering and / or reactive gases near the target. Wafers 10 are mounted on substrate supports 2, 3, 4, ... along the height diameter of the cylindrical holder 1′. The targets are directed toward the cylindrical surface on which the substrate holder is mounted, which in this type of process system is the peripheral region R.

[0071] A further vacuum processing system is described with reference to FIG. 3A, which shows a simplified top view of a turntable processing system with a turntable holder, and FIG. 3B, which shows a simplified cross-sectional view. The enclosure or vacuum processing receptacle 12 has at least two, and preferably three or more, sealable openings 13, 13′. These are provided to receive processing stations, here two sputtering stations 14, 14′ with sputtering sources 16, 16′ having targets 15, 15′, and an optional plasma station 20 with a plasma source 21. The target can be moved along axis C (see double-headed arrow in FIG. 3B), which is the Z axis relative to the substrate and turntable plane, to determine the substrate-target distance according to the needs of each process. Inside receptacle 12 is a substantially circular turntable holder 1 (only holders 2 and 8 are shown), which provides the location of substrate supports 2-9 for holding substrate 10. The entire surface of the turntable also defines a plane P. The substrate supports 2-9 may be recesses that conform to the contours of the substrate being processed, simple rims, pins, chucks, holders, clamps, or fixtures. If the substrate is held by a carrier, the fixture may be a support for such a carrier. Although the supports 2-9 are shown as circular, this is not intended to limit the shape of the substrate.

[0072] The turntable is provided with an axis of rotation B. In Figure 3, a drive that allows the turntable to rotate is omitted, but a person skilled in the art will choose a suitable solution.

[0073] The number and shape of the substrate supports are determined by the geometric constraints and specifications of the vacuum processing system.

[0074] The sputtering sources 14, 14' are located in the openings 13 and 13' and are connected to target power supplies 27, 27', respectively. The target power supplies can be RF, DC, or pulsed DC, and each source can be supplied with the same or different power sources depending on the process needs. The PVD source 14 includes a substantially circular material target 15 and a static magnet arrangement 11. The magnet arrangement defines a plane M that is parallel to plane P and thus perpendicular to axis B. A further axis C is the central axis of the circular target, perpendicular to plane M and therefore parallel to axis B. This axis C is also the center of the openings 13, 13'. The radial distance between axes B and C is selected to be equal to the distance between axis B and the center of each substrate support 2...9. In other words, with each rotation of the turntable, the areas of each substrate support and openings 13, 13' are perfectly aligned and perfectly opposed, at least for a fraction of a second, if certain conditions are met. The number of openings can match the number of substrate locations, but is often smaller. An optional shutter 31 (dotted line) may be provided to allow target deposition without sputtering towards the turntable and substrate. Without a shutter, or when the shutter is in the open position, the target is directed towards the top surface of the turntable holder where the substrate holder is mounted, which is the peripheral region R of this type of process system.

[0075] The PVD sources 16, 16' are equipped with static magnet systems 11, 11' configured to compensate for deposition non-uniformities caused by different track lengths of the rotational motion of substrates passing underneath, and are further designed to eliminate the need for screens, shapers, or shades.

[0076] The magnet system has a basic shape as shown in the top view of Figure 3A, with two rings of magnets, one surrounding the other of opposite polarity. During operation, the plasma tunnel is essentially confined between the magnetic arches created by these two magnet rings. The two magnet loops can essentially be trapezoidal or triangular in shape with rounded corners, but need not be symmetrical as shown.

[0077] The magnet systems 11, 11' are indicated by line K and axis A, which intersects axis B normally, but does not necessarily bisect it symmetrically as shown. Line K, which intersects axis C and lies in plane M, essentially separates the area defined by the outer boundary of the magnetic system, the area defined by the periphery of the outer coil in the plane determined by A / K, into two regions of different size: a small inner magnet region 17 radially closer to axis B, and a larger outer magnet region 18 (reference numerals are only shown for magnet system 11') further away from the center (indicated by the arrows on axis A). This configuration allows for uniform coating of the substrate and compensates for structural non-uniformities caused by the substrate as it passes through the curved arc path indicated by the three arrows below the sputtering sources 16, 16' as the turntable rotates.

[0078] A turntable process system equipped with such a magnetic system has been demonstrated to achieve coating uniformity of less than 1% over an equivalent substrate area of ​​a 6-inch wafer of SiO2 target. Details of such a magnetic system are described in applicant's WO 2017 / 042123.

[0079] A turntable processing system similar to that shown in FIGS. 3A and 3B is now described, again with reference to the top view in FIG. 4A and the cross-sectional view in FIG. 4B. This is a basic system 30 for depositing an a-Si layer using a single sputtering station 14 and subsequently oxidizing the layer using a plasma source 21 in a plasma station 20, shown here in a simplified form. Any target functions shown in FIG. 3 above may be the same, but have been omitted for clarity. An oxygen source is connected to the plasma station, and a cup-shaped first electrode 22 with a larger electrode surface is connected to a plasma power supply, which is an RF source 24, for igniting and maintaining the processing plasma. A grid 36 is attached to the plasma outlet as part of a second, grounded electrode with a smaller electrode surface (not shown in detail). The pumping arrangement 24 for exhausting the processing system 30 and the turntable drive are explicitly shown here. Separation of the pumping of the plasma station 20 and / or the target station 14 is optional (not shown). Additionally, FIG. 4B also shows a separate substrate drive 25 integrated into the turntable. These drives rotate the substrate about axis C to optimize layer distribution and processing during the various processing steps in stations 14, 20. The functionality described in Figures 4A and 4B can also be applied to other process systems, particularly the turntable system shown in Figures 3A and 3B. A containment shield 23 operating at ground potential, which is part of the smaller (grounded) electrode, extends nearly above the surface of the substrate and / or turntable and confines the plasma emerging from the grid 36 of the smaller electrode. This provides good and sufficient isolation of the plasma stations to prevent process disturbances in the sputtering station.

[0080] An optional additional dual magnetron sputtering source 14" with two rotating targets 15" is shown in dashed lines in FIG. 4A. Such a sputtering source, in which the targets alternately act as cathode and anode, thereby effectively avoiding target contamination, can be used in addition to or instead of target stations 14, 14' with disk-shaped targets 15, 15', as shown in FIG. 3B. Similarly, sputtering stations with two linear targets driven by a dual magnetron configuration, or simpler sputtering stations with a single linear planar or rotating sputtering cathode, can be used to suit the needs of each process.

[0081] Experimental condition setting

[0082] As described below, the QNL deposition and layer deposition of optical devices were performed using an Evatec Clusterline® BPM magnetron sputtering deposition system. This commercially available system includes a vacuum receiver with a turntable, a plasma station, and up to four magnetron sputtering sources in a sputtering-down configuration, as illustrated in Figures 3A and 3B and 4A and 4B. The plasma source can be used for standard deposition to influence layer properties such as stress and surface roughness. For Ta2O5-SiO2 QNL deposition, the plasma source allows the two sputtering sources to be activated over a very wide parameter range. However, for a-Si and SiO2 deposition, the plasma source has been used to oxidize the upper part of the a-Si layer deposited below the Si sputtering source. Together, the two sputtering stations and (additional) plasma station are highly versatile process systems, particularly featuring a receiver with a turntable holder, but also capable of being a receiver with a cylindrical or cylindrical multifaceted holder. All stations can be equipped with POM systems.

[0083] The deposition system can accommodate 15 200mm diameter substrates. Substrate loading is performed automatically through a load lock. The oxide is reactively deposited in pulsed DC mode, using a plasma emission monitoring PEM operating in transition mode near or within the hysteresis loop, thus ensuring complete oxidation at high deposition rates. Broadband and monochromatic monitoring is also provided.

[0084] The turntable configuration is ideal for the deposition of QNL. When a shutter is used while the table is continuously rotating, the substrate passes repeatedly under the active sputtering sources with the shutter open. This exposes the substrate to both sputtering sources with each rotation. By setting the sputtering power of the two sputtering sources to different values, it is possible to set and change the thickness ratio of the two materials, thereby forming a laminated QNL film, i.e., a stack of nanolayers (L). h The sum of and L l While the refractive index of the nanolayer stack can be varied (sum of the two materials), the stack of nanolayers combines the properties of the two materials in a novel way, a so-called metamaterial, as discussed below. The thickness of the individual layer pairs in the QNL film can be further determined by the table rotation speed, but not by the material ratio. Further deposition parameters that affect the growth rate and material properties include the argon and oxygen gas flow rates and the PEM set points, e.g., the intensity and spectral lines selected from the gas plasma, especially the target plasma emission.

[0085] For materials that combine amorphous silicon and SiO2, the QNL structure is obtained in a slightly different way: in this case, a Si source is used to deposit amorphous silicon in a pure Ar plasma, and oxidation is carried out as it passes under a plasma source, which in this case is always operated with oxygen. Again, the table speed and process settings of the sputtering and plasma source determine the thickness of the two nanolaminate materials.

[0086] The samples were deposited on double-side polished Herasil glass samples, which were characterized spectrophotometrically at the same location on the sample in both transmission and reflection at an angle of 8° using an EssentOptics PhotonRT spectrometer.

[0087] The effective refractive index n and extinction coefficient k in the transparent range of the coating were determined using OptiChar from Optilayer. The model used was normal dispersion for n and UV-Vis mode for k. This evaluation allowed us to determine the physical thickness d or d of the metamaterial. tot You can also ask for:

[0088] The effective refractive index of the resulting metamaterial is defined by the ratio of high-index material to low-index material and can be calculated by applying effective medium theory: where f is the volume ratio of high-index material to low-index material as described by A. Feldman, "Modeling of Optical Thin Films," (1988), Vol. 0821.

[0089]

number

[0090] Effective refractive index n eff is derived from spectral measurements of T and R as detailed above. The refractive index n high and n low is obtained from a single layer of Ta2O5 and SiO2. The values ​​are as follows: Ta2O5n high =2.168, SiO2n low = 1.474, both exponents are related to a wavelength of 500 nm. Equation (1) allows us to calculate the volume ratio f of the two materials.

[0091] The thickness per table pass can be calculated by dividing the physical thickness of the metamaterial, d, by the table speed in seconds per pass. The individual layer thicknesses of Ta2O5 and SiO2 can be calculated by multiplying the total thickness per pass by a factor f(1-f), respectively.

[0092] The optical band gap was determined using the Tauc plot method described in B.D. Viezbicke, S. Patel, B.D. Vis, and D.P. Birnie, "Evaluation of the tauc method for optical absorption edge determination: ZnO thin films as a model system," Phys. Status Solidi B 252, 1700-1710 (2015).

[0093] Ta 2 O 5 / SiO 2 -QNL results

[0094] In the first experiment, the Si and Ta sources were operated at 6 kW and 5 kW, respectively. The table speed was varied from 3 to 15 seconds per pass. This means that the ratio of high to low layers remained constant, but the thickness of each individual layer increased as the table rotation slowed, i.e., the time per rotational pass increased. Theoretically, the absorption edge was expected to shift to shorter wavelengths as the individual well layers became thinner, while the effective refractive index remained constant for all four samples. In Figure 5, the transmittance curves for the following experiments are shown below the Herasil silica reference curve:

[0095] #1: 3 seconds / pass #4: 12 seconds / pass #2: 6 seconds / pass #5: 15 seconds / pass #3: 9 seconds / pass

[0096] As can be seen in Figure 5, the predicted trend can indeed be observed, with sample #1's absorption edge at the shortest wavelength and sample #5's at the longest absorption edge, with a difference of approximately 19 nm in T50%. At longer wavelengths away from the absorption edge, all curves overlap, since they have the same effective refractive index. From these measurements, we can conclude that magnetron-sputtered nanolaminates exhibit quantization effects.

[0097] Figure 6 shows the Tauc curves for the same experiment, and αhν 1 / 2 [eV / m] 1 / 2 The relationship between the value of and the photon energy is shown. The gap energy is obtained by linearly extrapolating the transition region to αhν=0, and the intersection point with the photon energy axis at αhν=0 is equal to the gap energy, and the equation in Figure 1, ΔE gap =E gap_THINN -E gap_THICK =E gap_high -E gap_low As can be seen, the thinnest well layer L h Experiment #1 performed at 1000 nm shifts towards the highest photon energy, while experiment #5 with the thickest well layer shifts the least.

[0098] For the same sample set, the effective refractive index and energy gap were calculated, determined as described in the experimental setup. The curves shown in Figure 7 (refractive index: right-hand scale, sloping squares; energy gap: left-hand scale, triangles) show that the gap energy increases as the well thickness, d, of the Ta2O5 decreases. However, the refractive index remains constant at approximately 1.56, corresponding to a Ta2O5 to SiO2 thickness ratio of 1:9. Both results are in full agreement with the conclusions already drawn from the transmittance measurements. The shift in the absorption edge proves that these stacks consist of nanolaminates and not simply a mixture of both materials.

[0099] The total physical thickness of each layer stack in Figures 5-7 is in the range of 700-704 nm, which corresponds to 600 nanolaminate layer pairs at a table speed of 3 seconds per pass.

[0100] Subsequently, a series of experiments was carried out with different thickness ratios of Ta2O5 to SiO2. The main parameter was the target power for each target. As both sputtering processes were PEM controlled, the PEM settings also had to be adjusted to values ​​appropriate for the sputtering power. For each H:L ratio, a series of runs were carried out at different table speeds to vary the thickness of the individual nanolaminate layers. Typically, table speeds of 1.5, 3, 4.5, 6, 9, 12, and 15 seconds per pass were selected. The right side of Figure 8 shows the results of the deposition of high refractive index materials (d), as well as Figures 9 and 10, which relate to the same series of experiments. h_tot =n * d h ) and low refractive index material (here d l_tot =n * d l ) ratio (d h_tot / d l_tot ) is displayed for each series of experiments. Figure 8 also shows that the gap energy increases with decreasing well thickness. However, for Ta2O5, the gap energy remains nearly constant once the well thickness exceeds 2-3 nm, as the quantization effect disappears with increasing layer thickness.

[0101] On the other hand, the refractive index versus well thickness in Figure 9 and the refractive index versus energy gap in Figure 10 increase slightly but steadily with increasing well thickness, with the effect becoming more pronounced as the refractive index increases. As can be seen from Figures 9 and 10, the refractive index can be adjusted over a very wide range, essentially covering the entire refractive index range from SiO2 to Ta2O5.

[0102] Ta 2 O 5 / SiO 2 - Use of QNL in optical devices associated with QNL

[0103] The above results demonstrate that magnetron sputtering deposition can fabricate nanolaminates that exhibit quantum effects. Below, we show that by replacing high-refractive-index materials with QNL stacks of appropriate total thickness, optical interference coatings such as anti-reflection (AR) coatings, mirrors, and filters can be designed and fabricated.

[0104] For example, to demonstrate the validity of the QNL concept for optical interference coatings, an anti-reflection coating for UV LEDs centered at 280 nm was selected. The construction is based on a two-layer design. For the experiment, an effective refractive index of n = 1.7 at a wavelength of 550 nm, E gap A QNL film with a λ = 4.48 eV was designed. Such a nanolaminate stack consists of Ta2O5 and SiO2 layers with thicknesses of 0.31 nm and 0.76 nm, respectively. This design employs a total QNL thickness of 120 nm, i.e., a physical thickness of approximately 120 individual nanolayers of each material (120 / 1.07 = 112.14 layers), and a physical thickness of 136 nm for the SiO2. The total thickness corresponds to an optical thickness of approximately three times λ / 4 at λ = 280 nm.

[0105] Figures 11 and 12 show the transmittance and reflectance curves, respectively, of a double-sided coated quartz substrate suitable for use as an antireflection device. The minimum and maximum reflectance occur at the design wavelength of 280 nm. The curves for the device coated by deposition (#D) and the device annealed in further processing steps (#A) closely match the design curve (#X). The transmittance of the double-sided coated sample reaches 98.3% as deposited and 99.2% after 1 hour of annealing at 300°C in air. The corresponding absorption losses are 1% and 0.3%, respectively. In comparison, a two-layer antireflection coating with Ta2O5 (d = 100 nm) and SiO2 optimized for transmittance at 266 nm has the lowest reflectance at the design wavelength, but its absorption at 266 nm and 280 nm is only 66% and 25%, respectively. This clearly demonstrates that "bulk" Ta2O5 layers cannot be used at these UV wavelengths, while the use of QNL consisting of Ta2O5 / SiO2-QNL provides very good performance, opening the way to a wide range of further applications. In conclusion, QNL films can be treated as regular "bulk" layers with corresponding effective refractive indices for design and optical monitoring. The two sputtering sources were operated at a typical deposition rate of 0.71 nm / s for AR, resulting in faster QNL than the corresponding single layers of SiO2 or Ta2O5.

[0106] 13A shows an example of a single-sided configuration of an optical device 35 of the present invention, where the AR-device shown can be coated as a simple example of a two-film system with films 33, 34, either on only one side of substrate 10 as shown, or on both sides as described above. Here, QNL film 33 represents the high refractive index material of the AR coating, which can be configured to a particular desired refractive index, as described above, while low refractive index film 34 is selected from known low refractive index "bulk" materials, such as SiO2. For ease of manufacturing, the low refractive index "bulk" material and the low refractive index material of the QNL film can be the same.

[0107] Figure 13B shows a close-up of the same device, with thickness d h Layer L of high refractive index material h and thickness d l a layer L of low refractive index material l The QNL film 33 has a high refractive index layer L h Materials that can be used include amorphous silicon (a-Si), silicon nitride (e.g., Si3N4), and Me x O y , where Me is Al, Ti, Zr, Hf, Nb, Ta, or Ge. Low refractive index layer L l Possible materials for the QNL film 33 are silicon oxide (e.g., SiO2), silicon nitride (e.g., Si3N4), and aluminum oxide (e.g., Al2O3). Those skilled in the art will recognize that if silicon nitride or aluminum oxide is used as the high index layer material, the low index layer material will be silicon oxide, which has a low index of refraction. The metamaterial QNL film 33 can be deposited directly onto the substrate or via an optional adhesion layer 36. Alternatively, the first layer of low index material in the QNL stack can be used as the adhesion layer 36, in which case layer L l The same layer thickness d l The curves in Figures 13A and 13B are both incomplete representations of the substrate 10 due to the large difference in dimensions between the substrate and the film, and in Figure 13B the nanolayer L h , L l Since the dimensions of the low refractive index film 34 are different from those of the low refractive index film 34, the low refractive index film 34 is not completely described.

[0108] In-situ broadband optical monitoring was performed on reflectance in the wavelength range 380-980 nm. Due to the increased layer thickness, signals could be observed for longer periods at reflectance maxima. It was found that the QNL reflectance signal evolves perfectly regularly as the effective refractive index of the corresponding layer expands, and is therefore ideal for controlling the thickness of film stacks with QNL.

[0109] As a second example of the QNL concept for optical interference coatings, a 355 nm mirror was deposited consisting of 30 layers of quarter-wave optically thick SiO2 and QNL Ta2O5-SiO2. For comparison, a standard mirror design was deposited with a total of 26 layers of quarter-wave optically thick SiO2 and Ta2O5.

[0110] Both configurations were deposited with broadband optical monitoring. The good agreement between measurements and design values ​​indicates that the QNL layer can be applied like a normal layer, as shown in Figures 14 and 15, which show the transmittance and reflectance spectra for each coating. The curves for the device with the calculated QLN coating are labeled #D and #X, respectively. The curves for the device with the comparison coating are labeled #D' and #X'. Both mirrors are well-centered at the design wavelength. As expected, the mirror with QNL has a narrower reflection band due to the lower effective refractive index of the QNL. Comparing the transmission range below 300 nm reveals that the standard design has low transmittance, while the QNL mirror only experiences losses in the 2-5% range above the absorption edge.

[0111] a-Si / SiO 2 QNL Results

[0112] The samples were redeposited on double-side polished Herasil glass samples. The glass samples were fused silica glass, also known as quartz glass or silica glass, from grown quartz crystals. These glasses are high-quality optical glasses that are free of voids and inclusions and exhibit optical homogeneity, at least in the functional direction. All a-Si / SiO2 samples were annealed in air at 280°C or 500°C for 1 hour.

[0113] In the first experiment, the Si sputtering source and plasma source were operated at 5 kW and 1 kW, respectively. As the sample passed through the sputtering source, a film of amorphous silicon was deposited. As the table rotated, the sample was set to pass under the plasma source, where part of the previously deposited a-Si layer was oxidized. This procedure was repeated for the specified coating time.

[0114] In the first experiment, varying the table speed from 1.5 to 12 seconds per pass increased the thickness of each nanolaminate layer. For this series of four samples, the coating time was fixed, resulting in a nanolaminate stack thickness of approximately 180 nm. As shown in [False, link missing], the transmittance spectrophotometric curves for the four deposition runs show three characteristics of the layer: the wavelength of the absorption edge, the loss in the transparent wavelength range, and the refractive index of the layer. The transmittance curves for the following experiments are shown below the Herasil silica reference line curve:

[0115] #6: 1.5 seconds / pass #8: 6 seconds / pass #7: 3 seconds / pass #9: 12 seconds / pass

[0116] First, the absorption edge during this deposition sequence shifts toward shorter wavelengths as the table speed is set faster. The absorption edge of the 1.5 s / pass sample is at the shortest wavelength, while that of the 12 s / pass sample is at the longest wavelength, resulting in a difference of approximately 280 nm between the samples when the transmittance is fixed at 80%. For comparison, the black dashed line shows the transmission profile of a normal amorphous silicon layer.

[0117] Second, the transmittance maximum at half-wave optical thickness (λ / 2) is close to the solid line of uncoated quartz, indicating the low absorption of QNL in the longer wavelength range.

[0118] Third, the transmittance at 1500 nm increases with table speed, indicating a decrease in the effective refractive index of the nanolaminate. Below, we first discuss the change in refractive index and then the shift in the absorption edge.

[0119] As explained in the experimental section, the effective refractive index n eff and total layer thickness d tot can be determined from the measured transmittance and reflectance. The thickness deposited per table revolution is d tot This is obtained by dividing by the table rotation speed. As expected, the thickness deposited per revolution is linear with the table speed, as can be seen in [Incorrect, link unknown]. The individual thicknesses from a-Si to SiO2, calculated as described in the experimental section, do not increase linearly, as can be seen in [Incorrect, link unknown]. When run at the fastest table speed, a 0.7 nm thick a-Si layer was deposited, which was then oxidized by the PSC's oxygen plasma to a 0.6 nm thick SiO2 layer. However, at the slowest table speed of 12 seconds per pass, the 4.2 nm a-Si was only oxidized to a thickness of 1.8 nm SiO2. However, the energetic oxygen species generated by the plasma source have limited penetration depth, even with extended exposure times, so the oxidation rate is expected to decrease. As a result, the SiO2 fraction decreases with increasing layer thickness, resulting in a higher refractive index. Indeed, this increase in refractive index can also be seen in [Incorrect, link unknown] and is displayed on the right axis of the figure.

[0120] In the next step, the absorption edge shift was examined in more detail. The large shift in the absorption edge can be seen in [False, link unknown] and is primarily due to a change in the average stoichiometry across the entire thickness of the nanolaminate stack. To determine whether quantum effects are present, it was necessary to compare nanolaminate films with increasing a-Si and SiO2 thicknesses while maintaining a constant thickness ratio. To achieve this, it was necessary to adjust process settings such as the Si source power and oxygen flow rate.

[0121] An example of such an experiment can be found in [False, link unknown]. During deposition runs 10–12, the SiO2:a-Si ratio is constant, so the average composition is the same, but the total thickness increases with each pass: #10 = 0.5 nm, #11 = 1.1 nm, and #12 = 2.3 nm. Transmittance measurements during the three deposition runs indicate a shift in the absorption edge. The deposited films have previously been shown to exhibit quantization effects. In the first step, the refractive index and extinction coefficient of deposition #12 (solid line) were determined. The dashed lines labeled #10', #11', and #12' in Figures 19a and 19b show simulated transmittance curves based on this dispersion data, taking into account the slightly different layer thicknesses for deposition runs 10–12. As expected for a mixture, the three simulated curves overlap in the absorptance region below 600 nm. This differs from the measured curves for deposited coatings #10, #11, and #12, which show that the edge shifts to shorter wavelengths as the a-Si well material becomes thinner. A final confirmation of quantization is the shift in bandgap energy determined by the Tauc curve, as shown in [False, link unknown]. [False, link unknown] shows that decreasing the a-Si well thickness increases the gap energy, while the refractive index remains constant within the measurement accuracy. A shift of 0.15 eV is observed, corresponding to a 60 nm shift in wavelength. This observation confirms that quantization effects can also be observed in the a-Si / SiO2 material system deposited by magnetron sputtering.

[0122] Subsequent experiments were performed with various deposition parameters. [False, link unknown] shows the dependence of gap energy and refractive index on oxygen flow in the plasma source for a series of deposition runs at a table speed of 1.5 seconds per pass. As more oxygen is available in the plasma, the thickness of the SiO2 nanolayer increases, the refractive index decreases, and the gap energy increases.

[0123] a-Si / SiO 2 -Use of QNL in QNL optical equipment Longpass Filter

[0124] As previously mentioned, QNLs in the a-Si / SiO2 system can be fabricated over a wide range of refractive indices and gap energies. The nanolaminate in deposition run #10 described above was chosen as the high-index material, and SiO2 was chosen as the low-index material to deposit the long-pass filter. As explained in the experimental description, the QNL was deposited using a Si sputtering source coupled with a plasma source, and the SiO2 layer was deposited from an additional sputtering source. A 16-layer design with a quarter optical thickness was chosen, with some of the outer layers tailored to create an edge-forming curve. The refractive indices of material #10 were 3.18 and 2.79 at 550 nm and 1000 nm, respectively, and E gap is 1.72 eV. In this case, the quarter-optical thick high-index layer has a physical thickness of 49 nm and consists of a total of 180 alternating layers of a-Si and SiO2. Due to the turntable configuration of the BPM magnetron sputtering deposition system, the deposition rate of the nanolaminate is comparable to that of standard a-Si layers.

[0125] In-situ broadband optical monitoring by reflection in the wavelength range 380-980 nm has been used to monitor coating thickness. It was found that the reflection signal of QNL amplifies perfectly regularly, exactly as layers with the corresponding effective refractive index are grown. Therefore, it can be concluded that optical monitoring is optimal for controlling the thickness of film stacks using QNL.

[0126] For comparison, a similar filter based on the standard material combination SiO2-TiO2 was deposited using 16 layers, following the same design principles as the nanolaminate filter. As shown in [incorrect, link unknown], the curves for the device deposited with the calculated QLN coating are #D SiO2 / QNL and #X SiO2 / QNL where QNL is the respective a-Si / SiO2 stack. The curves of the deposited comparative coating and the calculated values ​​are #D', respectively. SiO2 / TiO2 , #X' SiO2 / TiO2 is.

[0127] It becomes immediately apparent that the standard design blocks only half of the visible range, whereas the QNL design blocks the entire range. Of course, it is possible to achieve complete blocking with the SiO2-TiO2 design, but at the cost of doubling the number of layers.

[0128] The total thickness of the standard SiO2-TiO2 coating is 1.4 μm, compared to the designed value of 1 μm for QNL-SiO2. Furthermore, the deposition rate of QNL is approximately twice that of TiO2. The reduced thickness and increased deposition rate halve the deposition time. Therefore, this comparison demonstrates that the new nanolaminate material has great potential to significantly improve productivity and reduce manufacturing costs.

[0129] As shown above, magnetron sputtering using a deposition tool with a turntable configuration is ideal for depositing quantum nanolaminate layers and coatings. The individual layers of the nanolaminate stack are deposited sequentially, with amorphous silicon being deposited as the substrate passes under the silicon source and SiO2 being formed by oxidation of the top of the a-Si layer as it passes through the plasma source. This procedure is repeated with each rotation of the turntable. By appropriately setting the rotation speed of the table, the total thickness of a-Si and SiO2 can be selected per revolution, while the power settings of the sputtering and plasma sources allow the thickness ratio of a-Si to SiO2 to be set. We have demonstrated that the individual layers can be deposited within a few tenths of a nanometer and over a wide range of a-Si volume fractions, f = V, from 0.1 to 0.75. a-Si / V SiO2 was demonstrated.

[0130] A large shift in the absorption edge is observed for single layers. Analysis of the data reveals two mechanisms causing the shift. First, the change in composition causes the absorption edge to shift to shorter wavelengths as the SiO2 fraction in the film increases. This is a known effect. However, the second effect, caused by quantization, has, to the inventors' knowledge, been demonstrated for the first time in a-Si / SiO2 layers. For QNLs with the same average composition, the absorption edge shifts with decreasing thickness of the a-Si barrier layer. This is based on the theory explained in Theory Section 2.

[0131] In a subsequent step, the QNL layer was used as a high-refractive index material for optical interference filters. It was demonstrated that the turntable configuration of the sputtering system is relevant for the fabrication of a viable long-pass filter that blocks the visible part of the spectrum while transmitting the NIR. From a technical point of view, the deposition of these filters is carried out similarly to standard processes, with the difference that the QNL layer has two sources. Furthermore, optical monitoring can be performed without any modifications.

[0132] The longpass filter coating matched the design well and showed good transmittance in the wavelength range above 700 nm, confirming accurate and reproducible deposition in the sub-nm range. As a comparison, a standard SiO2 / TiO2 longpass filter was also deposited. This shows that for the same number of layers, the blocking range is much narrower than in the QNL design. A standard filter with the same properties as the QNL filter would require twice the number of layers. This makes it clear that the QNL concept indeed opens up a wide range of new application areas, leading to significant productivity improvements. [Explanation of symbols]

[0133] 1,1' Rotating holder (turntable type and cylindrical type) 2-9 Board support 10 Substrate 11, 11' (further) magnet system 12 Receptor 13, 13' opening 14,14',14'' (more) sputtering stations 15,15',15'' (more) targets 16,16' (further) sputtering source 17 Inner magnet area 18 Outer magnet area 19 Turntable drive unit 20 Plasma Station 21 Plasma Source 22 Plasma generating electrode 23 Containment Shield 24 Pump arrangement 25 Substrate drive device 26 Plasma power supply 27 Target Supply 28, 28' Gas supply from sputtering source 29 Gas supply from plasma source 30, 30' Process System 31 Target Shutter 32 AR coating 33 QNL Films 34 Low refractive index material film 35 Optical equipment 36 Grid (ground electrode) 37 Dual Magnetron 38 Rotating Cathode A-axis B rotation axis C axis (arbitrary rotation) K Line L h ,L l Nanolayers of high and low refractive index materials d h ,d l L h , L l Thickness

Claims

1. 1. A process for depositing nanolaminates on a surface of a flat substrate, comprising: - mounting the substrate on a substrate support in a peripheral region (R) of a holder in a vacuum processing system, the holder being rotatable about its central axis B, the receiver comprising at least one magnetron sputtering station having a sputtering target attached to a sputtering source and spaced apart from the magnetron sputtering station, and at least one plasma treatment station having a plasma source, the sputtering target and the plasma source each facing different regions of the peripheral region (R); - pumping down the receiver; - rotating said holder around a central axis at a constant speed; - introducing a sputtering gas into said receiving area; - introducing a reactive gas directly into at least one of the sputtering station or the plasma station; - Ignite a magnetron discharge at the sputtering station and set the magnetron power level (P ｍ ) setting the - Ignite a plasma in the plasma processing station and set the plasma power level (P ｐ ) setting the - exposing the substrate continuously by rotating the holder, and forming a layer L of high refractive index material by the magnetron discharge ｈ and a layer L of low refractive index material is deposited by the treatment plasma. ｌ and forming Equipped with The rotation speed of the holder and the magnetron power level (P ｍ ) is the well layer L of the high refractive index material ｈ Layer thickness d ｈ is 0.1≦d ｈ 5nm≦5nm。

2. The plasma power level (P ｐ ) is the barrier layer L of the low refractive index material ｌ Layer thickness d ｌ is 0.1≦d ｈ 2. The process of claim 1, wherein the thickness is set to be ≦30 nm.

3. 3. The process of claim 1 or 2, wherein the target is one of Al, Si, Ti, Zr, Hf, Nb, Ta, Ge, their respective oxides, nitrides, or mixtures thereof.

4. 4. The process of claim 1, wherein the plasma station comprises a plasma source and the reactive gas is introduced directly into the plasma station.

5. 5. The process of claim 4, wherein the target is silicon and the sputtering gas is a noble gas introduced near or directly into the sputtering station.

6. 6. The process of claim 4 or 5, wherein the target power is set, the plasma source power is set at a constant level, and plasma gas parameters in the plasma station are controlled with a plasma emission monitor (PEM) by the intensity of at least one predetermined line of gas plasma emission.

7. 4. The process according to claim 1, wherein the plasma treatment station is a further magnetron sputtering station equipped with a further target.

8. The further target is Si, SiO ２ , Si ３ N ４ , Al, Al ２ O ３ 8. The process of claim 7, wherein the silicon dioxide is one of: GaN; GaN; or AlN.

9. 9. The process according to claim 7 or 8, characterized in that the sputtering gas is introduced into the sputtering station and / or the further sputtering station via separate gas ducts.

10. 10. The process according to claim 1, wherein the power is set to the target and / or the further target and reactive gas parameters in the sputtering station and / or the further sputtering station are controlled with a plasma emission monitor (PEM) by the intensity of at least one defined line of target plasma emission in a transition region in a transition mode of the reactive sputtering process.

11. 11. The process according to claim 1, wherein the sputtering station and / or the further sputtering station is provided with a process shutter, the process shutter being closed during the ignition process of the respective sputtering station and being opened during the deposition process of the respective layer.

12. 12. The process of any one of claims 1 to 11, wherein the sputtering gas is at least one of argon, krypton, neon, xenon, or mixtures thereof.

13. 13. The process according to claim 1, wherein the reactive gas and / or the further reactive gas is introduced directly into the sputtering station and directly into the plasma station or the further sputtering station.

14. 14. The process according to any one of claims 1 to 13, characterized in that the reactive gas and / or the further reactive gas is oxygen and / or nitrogen.

15. The n-layer L of the high refractive index material ｈ and n layers or n±1 layers L of the low refractive index material ｌ are deposited as an alternating stack on at least one surface of the flat substrate, and the number n of layers in each stack is equal to the number of layers L ｈ and L ｌ 15. The process according to claim 1, wherein n is at least 1 and 1≦n≦10,000.

16. 16. The method of claim 15, wherein at least one further layer or coating is deposited between the stack and a glass substrate and / or between the stack and the atmosphere.

17. The plasma treatment station is a further magnetron sputtering station, the reactive gas and the further reactive gas are oxygen and / or nitrogen, and the transmission edge T of the stack moves towards lower wavelengths as the well thickness decreases, ΔT ５０ =T ５０＿ＴＨＩＣＫ -T ５０＿ＴＨＩＮＮ Then 2≦ΔT ５０ ≦60 nm, where T ５０＿ＴＨＩＣＫ is the well thickness d ｈ＿ＴＨＩＣＫ is the transmittance at 50% of a layer stack of ≥ 5 nm, and T ５０＿ＴＨＩＮＮ is the well thickness d ｈ＿ＴＨＩＮ 17. The process according to claim 15 or 16, characterized in that the transmittance at 50% of the layer stack is ≦3 nm.

18. Gap energy E between the free ground state and the higher conducting state ｇａｐ is the well layer L ｈ As the thickness becomes thinner, ΔE ｇａｐ = E ｇａｐ＿ＴＨＩＮＮ -E ｇａｐ＿ＴＨＩＣＫ and ΔE ｇａｐ is 0.01≦ΔE ｇａｐ ≦0.8 eV, where E ｇａｐ＿ＴＨＩＮＮ is a thin well layer d ｈ＿ＴＨＩＮ is the energy gap of the layer stack deposited at ≦3 nm, E ｇａｐ＿ＴＨＩＣＫ is the thick well layer d ｈ＿ＴＨＩＣＫ 18. The process of claim 17, wherein the energy gap of the deposited layer stack is ≧5 nm.

19. The plasma processing station includes a plasma source, the reactive gas is introduced directly into the plasma station, the target is silicon, the sputtering gas is a noble gas, and the transmission edge T of the stack moves toward lower wavelengths as the well thickness decreases, and ΔT ５０ =T ５０＿ＴＨＩＣＫ -T ５０＿ＴＨＩＮＮ Then, 50≦ΔT ５０ ≦400 nm, where T ５０＿ＴＨＩＣＫ is the well thickness d ｈ＿ＴＨＩＣＫ is the transmittance at 50% of a layer stack of ≥ 5 nm, and T ５０＿ＴＨＩＮＮ is the well thickness d ｈ＿ＴＨＩＮ 17. The process according to claim 15 or 16, characterized in that the transmittance at 50% of the layer stack is ≦3 nm.

20. Gap energy E between the free ground state and the higher conducting state ｇａｐ is the well layer L ｈ increases as the thickness becomes thinner, and the increase is ΔE ｇａｐ = E ｇａｐ＿ＴＨＩＮＮ -E ｇａｐ＿ＴＨＩＣＫ and 0.01≦ΔE ｇａｐ ≦2 eV, where E ｇａｐ＿ＴＨＩＮＮ is a thin well layer d ｈ＿ＴＨＩＮ is the energy gap of the layer stack deposited at ≦3 nm, E ｇａｐ＿ＴＨＩＣＫ is the thick well layer d ｈ＿ＴＨＩＣＫ 20. The process of claim 19, wherein the energy gap of the deposited layer stack is ≧5 nm.

21. 21. The process of any one of claims 1 to 20, wherein the holder is a turntable holder and the peripheral region (R) is defined by an outer circular ring along which the substrate holders are arranged such that the flat substrate is positioned on at least one major surface of a disk-shaped holder mounted on or in a substrate support in a plane parallel to the turntable surface.

22. 19. The process of any one of claims 1 to 18, wherein the holder is a cylindrical or cylindrical multi-sided holder, the peripheral region (R) is determined by the cylindrical or multi-sided surface of the holder, the substrate support is positioned with its center along at least one height diameter of the cylindrical or multi-sided holder, and a flat substrate is mounted in or on the cylindrical or multi-sided surface in a plane substantially parallel to the cylindrical or multi-sided surface.

23. 23. The process of any one of claims 1 to 22, wherein the substrate is a wafer.

24. 24. The process according to any one of claims 1 to 23, wherein the substrate is a wafer, the peripheral region (R) is at a radial distance of 535±60 mm from the central axis (B), and is set at a constant speed of 30-0.5 seconds per revolution.

25. An optical device comprising a substrate and an optical coating deposited on at least one side of the substrate, the optical coating comprising at least one film of a high refractive index material and at least one film of a low refractive index material, at least one of the high refractive index material film and the low refractive index material film having a predetermined high or low refractive index QNL refractive index (n ＱＮＬ ) while the quantum nanolaminate (QNL) film is configured as a quantum nanolaminate (QNL) film having at least one well layer L of a high refractive index material. ｈ and at least one barrier layer L of a low refractive index material. ｌ and the well layer L ｈ Layer thickness d ｈ is 0.1≦d ｈ ≦6 nm.

26. The barrier layer L of the low refractive index material ｌ Layer thickness d ｌ is 0.1≦d ｌ 26. The device of claim 25, wherein the thickness is ≦30 nm.

27. 27. The device of claim 25 or 26, wherein the QNL film is the high refractive index film of the optical coating.

28. The low refractive index material of the low refractive index film is the barrier layer L of the QNL film. ｌ 28. The device according to claim 25, wherein the low refractive index material is the same as the low refractive index material of the first embodiment.

29. The number n of each layer of the QNL film is ｈ and L ｌ 29. The apparatus of claim 25, wherein in at least one of the above, 1≦n≦10,000.

30. 30. Apparatus according to any one of claims 25 to 29, characterized in that the QNL is manufactured according to a process according to at least one of claims 1 to 22.

31. 30. Apparatus according to any one of claims 25 to 29, characterized in that the optical coating is an interference coating and the apparatus is a mirror, a semi-selective mirror, a filter or a respectively coated lens.

32. 32. The device of claim 31, wherein the device is an edge filter, a beam splitter, a notch filter, or a polarizer.

33. At least one well layer L of a high refractive index material ｈ and at least one barrier layer L of a low refractive index material. ｌ 1. A vacuum processing system for depositing a quantized nanolaminate (QNL) on a surface of a flat substrate, the receiving portion of the vacuum processing system comprising: a holder rotatable about a central axis B and characterized in that it has substrate supports in its peripheral region (R); at least one magnetron sputtering station with a sputtering target attached to the sputtering source and remote from the magnetron sputtering station; at least one plasma treatment station having a plasma source; - both the sputtering target and the plasma source are each directed towards different sections of the peripheral region (R), a sputtering gas inlet for introducing a sputtering gas into said receiver; a reactive gas inlet and / or a further reactive gas inlet for introducing a reactive gas into the receiving portion; Equipped with The rotation speed of the holder can be set to 30-0.5 seconds per revolution, and the magnetron power level (P ｍ ) can be set to 0.5-10 kW, so that the well layer L of the high refractive index material can be ｈ Layer thickness d ｈ is 0.1≦d ｈ A process system characterized in that it can be set to ≦6 nm.

34. The rotation speed of the holder and the magnetron power level (P ｍ ) is the barrier layer L of the low refractive index material ｌ Layer thickness d ｌ is 0.1≦d ｌ 34. The process system of claim 33, configurable to be ≦30 nm.

35. 35. The process system of claim 33 or 34, wherein the plasma station comprises an inductively or capacitively coupled plasma source and a reactive gas inlet directly connected to the plasma station.

36. 36. The processing system of any one of claims 33 to 35, wherein the plasma station is a capacitively coupled HF plasma source.

37. 37. The processing system of any one of claims 33 to 36, wherein the target is a silicon target and the sputtering gas inlet is connected to a noble gas source.

38. 38. The process system of any one of claims 33 to 37, wherein a plasma emission monitor (PEM) is coupled to the plasma region of the plasma source via an optical path.

39. 39. The processing system of claim 33 or 38, wherein the plasma processing station is a further magnetron sputtering station with a further target.

40. The further target is Si, SiO ２ , Si ３ N ４ , Al, Al ２ O ３ 40. The process system of claim 39, wherein the silicon dioxide is either GaN, AlN, or a mixture thereof.

41. 41. The process system according to claim 39 or 40, wherein the target is any one of Al, Si, Ti, Zr, Hf, Nb, Ta, Ge, their respective oxides, nitrides, or mixtures thereof.

42. 42. The process system of any one of claims 39 to 41, wherein both sputtering stations are provided with separate reactive gas inlets.

43. 43. The process system of any one of claims 33 to 42, wherein the holder is a turntable holder having a turntable holder plane (P), and the peripheral region (R) is defined by an outer circular ring along which substrate holders are arranged such that a flat substrate is positioned on at least one major surface of the turntable holder mounted on or in the substrate support in a plane parallel to the turntable surface.

44. 44. The process system of claim 43, wherein the magnetron sputtering station comprises a circular target and a static magnet arrangement, the magnet arrangement being arranged on a plane (M) parallel to the plane (P) and not rotationally symmetric about a target axis (C) passing through the center of the magnet arrangement and perpendicular to the plane (M).

45. 45. The process system of claim 44, wherein the area adjacent to the magnet system can be divided into an outer area (16) facing away from the center of the turntable along a line (K) in a plane (M) perpendicular to and intersecting the target axis (C) and an inner area (17) facing it, the outer area (16) being larger than the inner area (17).

46. 46. ​​The process system of claim 45, wherein the magnet arrangement (11) is symmetric or asymmetric about an axis of symmetry (A) in the plane (M), the axis (A) intersecting the central axis (Z) of the turntable.

47. 47. A process system according to any one of claims 44 to 46, characterized in that the target is a rotating target, arranged rotatably about its central target axis (C).

48. 43. The process system of any one of claims 33 to 42, wherein the holder is a cylindrical or cylindrical multi-sided holder, the peripheral region (R) is determined by the cylindrical or multi-sided surface of the holder, the substrate support has its center positioned along at least one height diameter of the cylindrical or multi-sided holder, and a flat substrate is mounted in or on the cylindrical or multi-sided surface in a plane substantially parallel to the cylindrical or multi-sided surface, aligned at a height to match the height diameter.

49. 49. The processing system of any one of claims 33 to 48, comprising at least two magnetron sputtering stations and at least one plasma station that is not a magnetron station, each station comprising a plasma emission monitor for controlling the reactive process at the respective station.

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