SOLAR CONTROL GLASS WITH OPTICAL ABSORBER

Abstract

The invention refers to a glass substrate and a solar control layer stack on at least one face of the glass substrate, the layer stack comprising:at least one IR-reflective coating (II) comprising a silver containing layer (2):at least one absorption coating (IV) comprising an optical absorption layer (4) sandwiched and in direct contact to both between two silicon nitride layers (4, 4), the absorption layer (4) consisting of a sub-stoichiometric metal nitride MeN.sub.x, a sub-stoichiometric metal oxide MeO.sub.y, or a mixture thereof MeN.sub.xO.sub.y, where Me is at least one of an element from the transition metal group V or/and VI of the periodic system of the elements:a base coating (I) comprising at least one base layer (1) deposited directly on the substrate, and consisting of a silicon nitride or a metal oxide and thereby forming an inner layer of the solar control stack.

Claims

1. A glass substrate and a solar control layer stack on at least one face of the glass substrate, the solar control layer stack comprising: at least one IR-reflective coating (II) comprising a silver containing layer (2); at least one absorption coating (IV) comprising an optical absorption layer (4) sandwiched and in direct contact to both between two silicon nitride layers (4, 4), the absorption layer (4) consisting of a sub-stoichiometric metal nitride MeN.sub.x, a sub-stoichiometric metal oxide MeO.sub.y, or a mixture thereof MeN.sub.xO.sub.y, where Me is at least one of an element from the transition metal group V or/and VI of the periodic system of the elements; a base coating (I) comprising at least one base layer (1) deposited directly on the substrate, and consisting of a silicon nitride or a metal oxide and thereby forming an inner layer of the solar control stack.

2. The glass substrate according to claim 1, wherein the silver containing layer of the IR-reflective coating is sandwiched and in direct contact to both between a ZnO or ZnO:Al layer on the substrate side forming an inner layer of the IR-reflective coating and a NiCr or a TiO.sub.2 layer on the side of the silver containing layer which is directed towards the surface, and a further ZnO, a SnZnO or a SnO.sub.2 layer, or a respective Al-doped layer each in direct contact with the NiCr or the TiO.sub.2 layer and forming an outer layer of the IR-reflecting coating in a direction towards the surface of the layer stack.

3. The glass substrate according to claim 1, wherein the base coating (I) comprises at least one of a nitride or oxide layer (1, 1) of Si, Ti, Sn, Zn, SnZn, Nb, Zr, or a stack of such nitride or oxide layers different with respect to the metallic and/or semiconductive element(s) in consecutive layers.

4. The glass substrate according to claim 3, wherein the base layer (1) is the inner silicon nitride layer (4) of the absorption coating (IV).

5. The glass substrate according to claim 1, wherein at least one of the silicon nitride layers (4, 4), the ZnO (2), the further ZnO (2), the SnZnO (2), the SnO.sub.2 (2), and/or the nitride or oxide layer of Si, Ti, Sn, Zn, SnZn, Nb, Zr (1, 1) is an Al-doped layer.

6. The glass substrate according to claim 1, wherein the solar control layer stack further comprises a terminal scratch resistant coating (V), the scratch resistant coating (V) comprising at least a compound layer (5) consisting of the transition metals (TM) titanium and/or zirconium compound with the non-metal(s) oxygen and/or carbon.

7. The glass substrate according to claim 6, wherein the scratch resistant coating (V) consists of a titanium zirconium carbide layer (5) followed in a direction towards the surface and in direct contact to the titanium zirconium carbide layer by a hydrogen containing diamond-like carbon (DLCH) layer (5).

8. The glass substrate according to claim 6, wherein the scratch resistant coating is a titanium zirconium oxide layer.

9. The glass substrate according to claim 1, wherein the IR-reflective coating follows directly onto the absorption coating.

10. The glass substrate according to claim 6, comprising a further silicon nitride layer sandwiched and in direct contact to both between the terminal layer of the IR-reflecting coating and the scratch resistant coating.

11. The glass substrate according to claim 1, wherein the absorption coating or a further absorption coating follows directly onto the IR-reflective coating or a further IR-reflective coating.

12. The glass substrate according to claim 1, wherein the absorption layer is a sub-stoichiometric metal nitride MeN.sub.x and the stoichiometric value x is: 0.1<x1, especially 0.1x0.7.

13. The glass substrate according to claim 1, wherein the absorption layer is a sub-stoichiometric metal nitride MeN.sub.x or a sub-stoichiometric metal oxide MeO.sub.y.

14. The glass substrate according to claim 1, wherein Me is one of Mo, Ta, or W or a mixture thereof.

15. The glass substrate according to claim 1, wherein the sub-stoichiometric nitride, oxide or oxynitride is MoN.sub.xO.sub.y.

16. The glass substrate according to claim 1, wherein at least one of the two silicon nitride layers and/or the further silicon nitride layer are doped with aluminium.

17. The glass substrate according to claim 1, wherein at least one separating coating (III) is provided between and in direct contact to an IR-reflective coating (II) and the scratch resistant coating (V), between and in direct contact with two consecutive IR-reflective coatings (II), and/or between and in direct contact to an adsorption coating (IV) and an IR-reflective coating (II).

18. The glass substrate according to claim 17, wherein the separating coating (III) comprises or consists of another silicon nitride layer, another zinc oxide layer, another tin oxide, or another zinc tin oxide layer (3, 3).

19. The glass substrate according to claim 17, wherein the separating coating (III) consists of a silicon nitride layer (3) followed and in direct contact with the zinc tin oxide layer (3), whereat the silicon nitride layer is in direct contact with the terminal zinc oxide layer of the inner IR-reflective coating and the zinc tin oxide layer is in direct contact with the inner zinc oxide layer of the outer IR-reflecting coating.

20. The glass substrate according to claim 1, wherein the silver containing layer is a silver layer.

21. The glass substrate according to claim 1, wherein the difference k=k.sub.780k.sub.380 between the extinction coefficients of the absorption coating measured at 780 nm and at 380 nm is: $\left|0.4<k<1.\right|$

22. The glass substrate according to claim 1, wherein the extinction coefficient k.sub.550 of the MeN.sub.xO.sub.y layer measured at a wavelength of 550 nm is: $1.5<k_{550}<4.2$

23. The glass substrate according to claim 1, wherein the specific electric resistivity R of the MeN.sub.xO.sub.y layer is: $R<600*\mathrm{cm}$

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Embodiments of the current invention are described in more detail in the following with reference to the FIGURES. These are for illustrative purposes only and are not to be construed as limiting. It shows

[0041] FIG. 1 scheme of a solar control layer stack

[0042] FIG. 2 extinction coefficients versus wavelength

[0043] FIG. 3 extinction coefficient versus nitrogen flow per KW target power

[0044] FIG. 4 sputter rate versus nitrogen flow per kW target power

[0045] FIG. 5 resistivity versus nitrogen flow per kw target power

[0046] FIG. 6 XPS sputter depth profile

[0047] FIG. 7 fit curves for quantification of XPS profile

DETAILED DESCRIPTION OF THE INVENTION

[0048] FIG. 1 shows an exemplary scheme of a solar control layer stack S deposited on a surface of a glass substrate. The layer stack comprises coming from the surface of the substrate a base coating I consisting of two base layers 1,1 of respective materials as given in the drawing. In this case the silicon nitride or tin oxide base layer 1, forms an adhesion layer towards the substrate. The base coating I is followed by a first IR-reflective coating II comprising a silver IR-reflective layer 2. A separating coating III consisting of two separating layers 3,3 is provided between the first IR-reflective coating II and the second IR-reflective coating II, both having the same four-layer IR-reflective design (2/2/2/2). An absorption coating IV follows on coating II, whereat the absorption coating IV consists of a metal nitride layer 4 sandwiched between two silicon nitride or silicon oxynitride layers 4, 4 of the same composition. The utmost outer scratch resistant coating V again is a two layers coating consisting of a transition metal (TM) carbo oxide layer 5 and an amorphous hydrogenated diamond-like carbon (DLCH) layer 5 which forms the terminal layer of the layer stack towards atmosphere.

[0049] Layer materials can be one of the materials as given with the respective layer. When :Al follows after a comma, any of the forgoing materials can be doped with aluminium. Me of the absorption layer 5 can be Mo, Ta or W. Transition metals TM in respective layer 5 can be Ti and Zr.

[0050] Further examples for different combinations of the respective coatings and layers are given in table 1, examples 1 to 14.

[0051] It should be emphasized that with reference to examples 1, 8, 9, and 11 to 14, base layer 1 giving the adhesion to the substrate is formed by the inner silicon nitride layer 4 of the adsorption coating, which means that in this case a one layer base coating I consisting of the inner silicon nitride layer 4 which at the same time is base line 1 is integrated in an adsorption coating and in direct contact to the substrate surface. Therewith no separate base coating is necessary with such layer types.

[0052] Examples 1-8 show stacks comprising one IR-reflective coating, while examples 9-14 show stacks comprising two IR-reflective coatings. Absorption coatings can be foreseen above, see examples 2-7 and 10, below, see example 1 and 9, or on both sides of the IR-stack(s), see examples 8 and 11-14. Separation between two successive IR-stacks is provided by a one or two layered separation coating which can be applied between any successive IR-stack. Further separation coatings can be provided between an IR-coating and the scratch resistant coating (example 1 and 9), between an absorption coating and an IR-reflective coating as shown with example 14.

[0053] FIGS. 2-7 refer to specific experiments which have been performed with three selected absorber materials (MON.sub.x, TaN.sub.x, WN.sub.x), which when deposited sub-stoichiometrically showed an outstanding performance in their optical and process relevant material properties (see Table 2B).

[0054] Details about the respective deposition parameters can be found in Table 2A. In Table 4 the process parameters for the whole stack of the solar control glass as applied in an industrial coater with a target size of approx. 380 cm is described. Process parameters for the production of the absorbing stack are in line Si.sub.3N.sub.4 or Si.sub.3N.sub.4:Al and line MeN.sub.xO.sub.y.

[0055] For the chemical and optical characterization each optical absorbing film of interest has been sandwiched in a stack between two SiN:Al layers, as the surrounding layers have a strong impact on the properties of a thin film with a thickness <20 nm. All the stacks (material and layer thicknesses, as well as process parameters) used for chemical and optical characterization, are listed in Table 2A. The #-column has four group of samples 1 to 4, referring to Mo (1), W (2), and Ta-absorbers (3), and the glass substrate (4), followed by a respective sample number.

[0056] Chemical composition was measured by X-Ray photoelectron spectroscopy (XPS), optical properties were measured by ellipsometry and optical spectroscopy, thickness of stack was measured by stylus profilometry.

[0057] XPS sputter depth profile was performed though repetitive cycles: ion sputtering and consequent XPS measurement.

[0058] XPS measurements have been performed with the following parameters: monochromatic x-ray beam (Al K edge), spot size 100 m, pass energy 26 eV (energy resolution FWHM=0.6 eV (Ag 3d.sub.5/2), in scanning mode). Sputtering was performed with Zalar rotation to ensure the best depth resolution, with Ar+ ions, 1 kV 22, sputter time e.g. 1 min per cycle. Atomic concentrations (at. %) of elements were measured across the whole stack (Si.sub.3N.sub.4:Al/MeN.sub.xO.sub.y/Si.sub.3N.sub.4:Al) and the chemical composition of the MeN.sub.xO.sub.y was defined in the middle of the film. The chemical composition of the film is defined as follows: x=N (at. %)/Me (at. %), y=0 (at. %)/Me (at %), therefore MeN.sub.xO.sub.y.

[0059] For modelling the optical constants n() and k(), ellipsometric measurement (() and () for the angles 55-75 with step 5 were combined with optical spectroscopy (UV-Vis-NIR Spectrophotometer), film thickness has been determined by stylus profilometer for each layer of the stack, which for the measurement had been deposited separately as a single layer on a test glass, and then hold fix during the following modelling (CompleteEase Software). B-Spline and Gen-Osc models were used to model the absorber.

[0060] FIG. 2A, 2B, 2C show the dependency of the extinction coefficient k depending on the wavelength compared for MON.sub.x, WN.sub.x, respectively TaN.sub.x. Each of the FIGURES shows curves of the respective MeN.sub.x as reactively sputtered with different nitrogen amounts, which refer to respectively different MeN.sub.x stoichiometries as mentioned below. Sample numbers (# x.y) refer to Table 2A. The extinction coefficient is a good measure for the possible optical absorption of a layer or layer system. A neutral optical appearance can be efficiently achieved when the coefficient of the optical absorption k does not show a strong k-variation in the visible wave-range . This was the case with low nitrogen flows from 5 to 75 sccm/kW, especially from 8 to 20 sccm/kW. These amounts refer to sub-stoichiometric MeN.sub.x species with x from 0.2 to 0.7. Therewith the shape of the k-curve is homogeneous, almost linear and the variation of K is small. Also the highest extinction coefficient could be achieved in the same flow range, whereat best results could be reached for MoN.sub.x, in a range of 105 sccm/kW. Important to mention that the optimal reactive gas flow per kW power (sccm/kW) is strongly dependent on the coater size and geometry, pumping efficiency, length of sputtering target and power on the sputtering target used. Therefore the decisive description of the absorbing layer is at the end the stoichiometry MeNx of the sputtered layer, as defined e.g. with XPS.

[0061] FIG. 3 shows the extinction coefficient at 550 nm of respectively sandwiched MON.sub.x, WN.sub.x, TaN.sub.x adsorbers versus nitrogen flow per kW power. With all 3 target materials (Mo, W, Ta) sputter rate started to diminish significantly with increasing nitrogen flow, at the latest from 50 sccm/kW and higher. FIG. 4-5 show sputter rate and the resistivity of MON.sub.x samples #1.7-1.12, WN.sub.x samples #2.6-2.10, and TaN.sub.x samples #3.3-3.7 depending on the N.sub.2 amount (for respective nitrogen flow values in sccm/kW, see Table 2A, column 4).

[0062] Specific electrical resistivity is also a good indicator of the absorptive properties and thereby gives a possibility to set-up and/or control the reactive sputter process as shown in FIG. 5. This means, the lower the electrical resistivity is, the higher is the extinction coefficient k (see FIG. 3). For process efficiency, lower resistivity values are preferred as well, as can be seen in the range between 10 and 75 sccm/kW for MON and 10-50 sccm/kW for WN.

[0063] It can be seen that absolute k-values of W and especiallyof Mo as shown exemplarily in FIG. 3, can be set significantly higher than respective values of well known and documented materials as for example of TiN.sub.x (k (550 nm) which is 2.1 according to J. Pflger, J. Fink. Determination of optical constants by high-energy, electron-energy-loss spectroscopy (EELS), in Handbook of optical constants of solids II, Edward D. Palik, ed. Academic Press, 1991. pp. 293-310; 2) J. Pflger, J. Fink, W. Weber, K. P. Bohnen, G. Crecelius. Dielectric properties of TiCx, TiNx, VCx, and VNx from 1.5 to 40 eV determined by electron-energy-loss spectroscopy, Phys. Rev. B 30, 1155-1163 (1984)). Ta substoichiometric nitrides perform similar as TiN.sub.x.

[0064] Moreover, surprisingly a favorable N-range to obtain highest possible optical absorption in visible range has been found. Surprisingly, layers with a very low N content (MeN.sub.x, x0.7, e.g. 0.040.1) in most cases show an even higher optical absorption than could be observed with pure metallic layers in the case of WN.sub.x and of MON.sub.x, see FIG. 2B, #2.12, 2D, #1.8, 2E, #2.8. Such nitride layers with a low N content always had a higher optical absorption than layers with a high N content (MeN.sub.x, x>0.7) or stoichiometric metal nitride layers, see FIG. 2A-2E. Improvement of optical absorbing properties (vs metal) due to low N content is exemplified in single layers (Mo, W), and in a stack in case of W. Note, in an extreme case, where a metallically deposited absorbing layer is <5 nm, the following reactive gas containing process to deposit silicon nitride introduces a low amount of N to the metallic layer giving rise to an even higher optical absorption coefficient k (see as an example stack number #2.11 in Table 2A with d.sub.WNx=4.0 nm and x=0.08, and the respective curve in FIG. 2B). This can be seen in comparison to a stack with a thicker metallic film (e.g. d>5 nm, see as an example stack number #2.3 in Table 2A with d.sub.WNx=8.0 nm and x=0.003, and the respective curve in FIG. 2B), or compared to a pure metallic layer without following Si.sub.3N.sub.4 process (see as an example stack number #2.6 in Table 2A, with d.sub.WNx=55.3 nm and x=0, as shown in FIG. 2E). The most stable absorption layer coating with reference to chemical and mechanical properties can be achieved when the dielectric layer is Si.sub.3N.sub.4 (optionally doped, e.g., with Al) and is in direct contact with the absorbing layer from both sides. The minimal thickness of the respective silicon nitride sandwich layers to protect the absorbing layer during tempering processes is d>8 nm, e.g. 8-30 nm, especially 10-20 nm.

[0065] As the thermal expansion coefficient of Si-containing sandwich layers is expected to be virtually identical to the one of Mo, W, Ta being <7.5 m/(m*K), with Si: 2.6 m/(m*K), Mo: 4.8 m/(m*K), W: 4.5 m/(m*K), Ta: 6.6 m/(m*K), and shear modulus is similar >60 GPa, with Mo: 120 GPa, W: 161 GPa, and Ta: 69 GPa, even though the exact values depend on the chemical composition (stoichiometry of the metal nitride) and electronic structure [Ozsdolay, B., WNx and MoNx Layers: Elastic Properties and Crystal Structure, PhDT, 2016; Kindlund, H., Sangiovanni, D., Petrov, I., Greene, J. E, Hultman, L., (2019), A review of the intrinsic ductility and toughness of hard transition-metal nitride alloy thin films, Thin Solid Films, 688, 137479; W. Chen, J. Z. Jiang, Elastic properties and electronic structures of 4d- and 5d-transition metal mononitrides, Journal of Alloys and Compounds, Volume 499, Issue 2,2010, Pages 243-254; C. Kral et al., Critical review on the elastic properties of transition metal carbides, nitrides and carbonitrides, Journal of Alloys and Compounds 265 (1998) 215-233], respectively stacked adsorbing coatings are perfectly mechanically matched for solar control layer stacks on glass substrates which are subject to heat-treatment or shear stress during washing of the coated glass pane. Such adsorption coatings can be applied preferably below and/or above the IR-reflecting stack(s), i.e., between the substrate and lowest or inner IR-reflecting stack, and/or between the highest or outer IR-reflecting stack and the terminal (outer) surface of the solar control layer stack towards atmosphere. When the terminal surface of the layer stack is formed by an optional scratch resistant coating a respective single layer or inner layer of the scratch resistant coating can be in direct contact with the outer silicon nitride layer of the adsorption coating.

[0066] In FIG. 6 an XPS sputter depth profile of the three layers stack of an adsorption coating according to sample #1.13 is shown. From there the respective distribution of the elements Mo, N, Si within the three layers stack and O, Si, Na within the glass substrate can be seen in dependency of the sputter time, which refers to the sputter-etch time of the etching device used for sputtering away (=etching) the sample surface before the XPS analysis. The analysis starts at the left (0 min) on the surface of the sample and ends after 25 minutes of sputter etching of the sample with Ar.sup.+ ions as described above, in some nm depth within the surface of the glass substrate. The Mo-peak of the MON.sub.x layer, i.e. the optical absorbing film with x=0.31, is sandwiched between the two Si.sub.3N.sub.4 layers showing a respective higher nitrogen concentration.

[0067] The two graphs in FIG. 7A, 7B show XPS spectra for MON.sub.x sample #1.13 at the maximum of the Mo-intensity signal (see FIG. 6) and a respective fit curve for the quantification of the atomic concentrations. Where the graph in FIG. 7A shows the Mo3d core-level spectrum and the fit curve in a binding energy region between about 223-232 eV and the graph in FIG. 7B shows the Mo3p.sub.3/2 core-level spectrum and the fit curve for the N1s in the region from about 385-399 eV. Both FIGURES show a very good correlation of the fit curve (solid line), representing the sum of the bond contributions (Mo, MoN, MoO different dashed lines), and the measured curve (filled circles).

REFERENCE SIGNS LIST

[0068] S layer stack [0069] I base coating [0070] 1,1 layers of the base coating [0071] 1 base layer (can be integrated in the absorption coating) [0072] II IR-reflective coating [0073] 2, 2, 2, 2 layers of the IR-reflective coating [0074] 2 silver containing layer [0075] III separation coating [0076] 3,3 layers of the separation coating [0077] IV absorption coating [0078] 4,4 layers of the absorption coating [0079] V scratch resistant coating [0080] 5,5 layers of the scratch resistant coating [0081] 5 TM containing layer [0082] 5 DLCH layer (optional)

TABLE-US-00001 TABLE 1 Exemplary solar layer stacks according to the invention 1 2 3 4 5 6 7 8 9 10 11 12 13 14 type DLC Scrat. TiZrC.sub.x resis. DLC Si.sub.3N.sub.4 Further DLC TiZrC.sub.x MoN.sub.x absorpt. TiZrO.sub.2 TiZrC.sub.x Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 MoN.sub.x ZnO IR-reflective TiZrO.sub.2 TiZrO.sub.2 MoN.sub.x MoN.sub.x Si.sub.3N.sub.4 NiCr Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 ZnO Ag ZnO MoN.sub.x ZnO ZnO NiCr ZnO Se- TiZrO.sub.2 TiZrO.sub.2 TiZrO.sub.2 NiCr Si.sub.3N.sub.4 NiCr NiCr Ag ZnSnO parat. TiZrO.sub.2 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Ag ZnO Ag Ag ZnO Si.sub.3N.sub.4 TiZrO.sub.2 TiZrO.sub.2 TiZrO.sub.2 TiZrO.sub.2 Si.sub.3N.sub.4 MoN.sub.x MoN.sub.x MoN.sub.x ZnO NiCr ZnO ZnO ZnSnO ZnO IR-reflective Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 MoN.sub.x Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 ZnSnO Ag ZnSnO ZnSnO Si.sub.3N.sub.4 NiCr ZnO MoN.sub.x MoN.sub.x MoN.sub.x Si.sub.3N.sub.4 ZnO ZnO ZnO ZnO ZnO ZnO ZnO ZnO Ag NiCr Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 ZnO NiCr NiCr NiCr NiCr ZnSnO NiCr NiCr NiCr ZnO Ag ZnO ZnO ZnO NiCr Ag Ag Ag Ag ZnO Ag Ag Ag TiO2 Furth.se- ZnO NiCr NiCr NiCr Ag ZnO ZnO ZnO ZnO NiCr ZnO ZnO ZnO ZnSnO parat. Si.sub.3N.sub.4 Ag Ag Ag ZnO TiO.sub.2 TiO.sub.2 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Ag Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Absorpt. MoN.sub.x ZnO ZnO ZnO TiO.sub.2 SnZnO SnZnO MoN.sub.x MoN.sub.x ZnO MoN.sub.x MoN.sub.x MoN.sub.x MoN.sub.x Si.sub.3N.sub.4 Si.sub.3N.sub.4 TiO.sub.2 SnO.sub.2 SnO.sub.2 SnO.sub.2 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Si.sub.3N.sub.4 Substrat Substrat Substrat Substrat Substrat Substrat Substrat Substrat Substrat Substrat Substrat Substrat Substrat Substrat

TABLE-US-00002 TABLE 2A Properties and production parameters of absorption layer stacks. The stacks were produced by RF reactive sputtering process, working with metal target, Ar process gas and N.sub.2 reactive gas, whereat the sputter target dimension: 748.5 mm 87.5 mm (approx. 660 cm.sup.2). Thickness N2 Glas, MeN.sub.x # Stack materials* [nm [sccm/kW] [kW] [mm] x = 1.1 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 9.8/0.9/13.8 71 0.7 5.8 n.m. 1.2 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 9.8/4.6/13.8 71 0.7 5.8 0.53 1.3 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 9.8/7/13.8 0 1 5.8 0 1.4 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 9.8/7/13.8 10 1 5.8 n.m. 1.5 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 9.8/7/13.8 50 1 5.8 0.5 1.6 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 9.8/7/13.8 200 1 5.8 n.m. 1.7 Mo 75.5 0 1 3.8 0 1.8 MON.sub.x 62.9 10 1 3.8 0.25 1.9 MON.sub.x 90.0 20 1 3.8 n.m. 1.10 MON.sub.x 84.9 50 1 3.8 0.47 1.11 MON.sub.x 65.5 100 1 3.8 0.69 1.12 MON.sub.x 44.8 200 1 3.8 0.75 1.13 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 12/5.5/13.8 29 0.7 5.8 0.31 2.1 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 14/1.2/11 50 1 5.8 n.m. 2.2 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 12/5.2/12 50 1 5.8 n.m. 2.3 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 12/8.0/12 0 1 5.8 0.003 2.4 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 12/8.0/12 50 1 5.8 0.2 2.5 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 12/8.0/12 200 1 5.8 0.33 2.6 Si.sub.3N.sub.4/W 55.3 0 1 3.8 0 2.7 WN.sub.x 65.9 10 1 3.8 n.m. 2.8 WN.sub.x 66.7 20 1 3.8 0.14 2.9 WN.sub.x 86.2 50 1 3.8 n.m. *All Si.sub.3N.sub.4 layers were sputtered with 33.3 sccm/kW. Si Target is Al doped (8-10 wt. %). n.m. not measured

TABLE-US-00003 TABLE 2A Continuation N2 Stack Thickness [sccm/ Glas, MeNx # materials* [nm] kW] [kW] [mm] x = 2.10 WN.sub.x 77.7 200 1 3.8 n.m. 2.11 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 12/4.0/12 0 1 5.8 0.08 2.12 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 12/8.0/12 10 1 5.8 0.09 3.1 Si.sub.3N.sub.4/TaN.sub.x/Si.sub.3N.sub.4 11/2.4/11 50 1 5.8 n.m. 3.2 Si.sub.3N.sub.4/TaN.sub.x/Si.sub.3N.sub.4 11/10.0/11 50 1 5.8 n.m. 3.3 Si.sub.3N.sub.4/TaN.sub.x/Si.sub.3N.sub.4 6.7/17.6/8.2 20 1 5.8 0.57 3.4 Si.sub.3N.sub.4/TaN.sub.x/Si.sub.3N.sub.4 6.7/16.1/8.2 50 1 5.8 0.76 3.5 Si.sub.3N.sub.4/TaN.sub.x/Si.sub.3N.sub.4 6.7/15.1/8.2 100 1 5.8 n.m. 3.6 Si.sub.3N.sub.4/TaN.sub.x/Si.sub.3N.sub.4 6.7/8.1/8.2 200 1 5.8 0.88 3.7 Ta 22 0 1 5.8 0 4 Float glass 5.8 n.m. *All Si.sub.3N.sub.4 layers were sputtered with 33.3 sccm/kW. Si Target is Al doped (8-10 wt. %). n.m. not measured

TABLE-US-00004 TABLE 2B Properties of absorption layer stacks as used with table 1 Thickness, BRA RA TA # Stack nm Y L* a* b* Y L* a* b* Y L* a* b* 1.1 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 9.8/0.9/13.8 12.3 41.7 1.3 5.4 15.1 45.8 0.9 4.6 73.9 88.9 0.7 2.2 2.1 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 14/1.2/11 11.3 40.1 1.3 5.0 15.5 46.3 0.9 4.7 71.0 87.5 0.7 2.2 3.1 Si.sub.3N.sub.4/TaN.sub.x/Si.sub.3N.sub.4 11/2.4/11 12.5 41.9 1.8 5.2 16.5 47.6 1.0 5.7 72.5 88.2 0.9 3.8 1.2 Si.sub.3N.sub.4/MON.sub.x/Si.sub.3N.sub.4 9.8/4.6/13.8 11.4 40.3 1.3 3.6 21.4 53.4 0.5 0.1 43.8 72.1 0.4 0.9 2.2 Si.sub.3N.sub.4/WN.sub.x/Si.sub.3N.sub.4 12/5.2/12 12.3 41.6 1.4 3.5 24.5 56.6 0.5 1.4 39.5 69.1 0.4 1.7 3.2 Si.sub.3N.sub.4/TaN.sub.x/Si.sub.3N.sub.4 11/10.0/11 13.7 43.7 1.3 5.9 27.2 59.1 0.3 2.8 41.7 70.7 0.9 2.5 4 Float glass RGS 55 # Y L* a* b* Abs, % T, % E.sub.T E.sub.BR 0.005 1.1 18.0 49.5 1.0 2.8 11.0 0.4 0.3 1.4 0.801 2.1 17.0 48.2 0.9 2.5 13.5 0.8 0.5 1.7 0.826 3.1 17.8 49.2 1.3 2.3 11.0 1.2 0.6 1.0 0.825 1.2 16.5 47.7 0.9 1.8 34.8 1.1 0.8 0.8 0.768 2.2 17.5 48.8 1.1 1.8 36.0 0.5 0.4 0.8 0.739 3.2 17.9 49.4 1.0 3.4 31.1 0.2 1.6 1.8 0.801 4 0.836

TABLE-US-00005 TABLE 3 Glass with scratch resistant solar control layer stack (exemplary stack according to example 7 and respective variations): coating Layer-Material d [nm] Composition scratch DLCH 1-100, e.g. 5-20, 8-12 DLCH (without metal), e.g. ta-C:H resistant TiZrC.sub.x, TiZrO.sub.xC.sub.y 1-20, e.g. 2-6 TM:C 1:1-1:6, e.g. 1:3 (or 25-85 at. % C) TM, e.g. TiZr.sub.x, x = 0-1, e.g. 0.1-0.5 absorption Silicon nitride or aluminum 1-100, e.g. 3-60, 5-30 Si.sub.3N.sub.4 or Si.sub.3N.sub.4:Al, N can be stoichiometric or sub-st. up to 15%, doped silicon nitride e.g. SiN.sub.xAl.sub.y, x = 1-1.4, y = 0-0.35, e.g. SiN.sub.1.33Al.sub.0.18 Absorption layer: Me.sup.VN.sub.xO.sub.y 0.1-50, e.g. 0.4-10 O, N sub- stoichiom. (5-60 at. %), e.g. MoN.sub.0.1-1, MoN.sub.0.1-0.6, (Me: Mo, Ta, W) WN.sub.0.1-1, WN.sub.0.1-0.6, TaN.sub.0.1-1, TaN.sub.0.1-0.6. Whereat O might be present till 20 at. %, preferentially < 10 at. %. Silicon nitride or aluminum 1-100, e.g. 3-60, 5-30 Si.sub.3N.sub.4 or Si.sub.3N.sub.4:Al, N can be stoichiom. or sub-st. up to 15 at. %, doped silicon nitride Al content variable, e.g. SiN.sub.xAl.sub.y, x = 1-1.4, y = 0-0.35, SiN.sub.1.33Al.sub.0.18 separating ZnO, SnO.sub.2, SnZnO or coat: <150, e.g. <100 O can be stoichiom. or sub-st. (up to 15 at. %), Al 0-20 at. % e.g. ZnO:Al, SnO.sub.2:Al, single layer: 0.5-100, ZnAl.sub.xO.sub.y, x = 0-0.3, e.g. 0-0.1, y = 0.8-1.2, e.g. ZnO.sub.0.8-1Al.sub.0.04-0.06 SnZnO:Al, SiN.sub.xAl.sub.y e.g. 4-30, 4-20 SnZn.sub.xO.sub.y, x = 1-4, e.g. x = 1-2.5, y = 2-4, e.g. y = 2.5-3.5, SnZn.sub.2O.sub.3 IR-reflective ZnO, SnO.sub.2, SnZnO or 0.5-100, e.g. 4-30, 4-20 O can be stoichiometric or sub-st. (up to 15 at. %), Al 0-20 at. % ZnO:Al, SnO.sub.2:Al, e.g. ZnAl.sub.xO.sub.y, x = 0-0.3, e.g.0-0.1, y = 0.8-1.2, e.g. ZnO.sub.0.8-1Al.sub.0.04-0.06 SnZnO:Al, SiN.sub.xAl.sub.y SnZn.sub.xO.sub.y, x = 1-4, e.g. x = 1-2.5, y = 2-4, e.g. y = 2.5-3.5, SnZn.sub.2O.sub.3. NiCr.sub.x (mandatory for 0.3-20, e.g. 0.5-10 metallic, or oxidized. O can be stoichiometric or sub-st. NiCr.sub.x tempering), or TiO.sub.sub (no temp.) containing layer, metallic ratio e.g. 0.1 x.sub.cr 0.5 (see descr.) Ag 1-30, e.g. 5-20 metallic ZnO, SnZnO or ZnO:Al, 0.5-30, e.g. 3-15 O can be stoichiom. or sub-st. (up to 15 at. %), Al 0-20 at. %, e.g. SnZnO:Al ZnAl.sub.xO.sub.y, x = 0-0.3, pref. 0-0.1, y = 0.8-1.2; e.g. ZnO.sub.0.8-1Al.sub.0.04-0.06 SnZn.sub.xO.sub.y, x = 1-4, pref. 1-2.5, y = 2-4, pref. 2.5-3.5, e.g. SnZn.sub.2O.sub.3. base Dielectric, e.g .: TiO.sub.2, 1-60, e.g. 1-15, 3-7 TiO.sub.2, or TiZr.sub.xO.sub.2, x = 0-1, e.g. 0.2-0.5 TiZrO.sub.2, ZrO.sub.2, NbO.sub.x SnO.sub.2, SnZnO, ZnO or 1-100, e.g. 5-30, 5-15 O can be stoichiometric or sub-st. (up to 15 at. %) SnZnO:Al, ZnO:Al Silicon nitride, titanium oxide, 1-60, e.g. 1-40, 5-30 Si.sub.3N.sub.4 or Si.sub.3N.sub.4:Al, SiN.sub.xAl.sub.y, x = 1-1.4, y = 0-0.35, e.g. SiN.sub.1.33Al.sub.0.18, silicon metal nitrides, -oxides, SiN.sub.xO.sub.yMe.sub.2 (Me: Nb, Ti, Zr), x = 0-1.4, y = 0-2, z = 0-2. -oxinitides (Me: Al, Nb, Ti, Zr) Substr. Glass 1-20 [mm] Any type of window (architectural, automotive) glass, or composite glass pane

TABLE-US-00006 TABLE 4 Process parameters for different layer materials at the industrial coater: Layer-Material Process Process parameters per 1 cathode DLCH PECVD (ICP-plasma In. gas (Ar) and C.sub.2H.sub.2, r.sub.C2H2 = 10-50%, e.g. 15-45%, p: 1 10.sup.4-2 10.sup.2 mbar; ICP-generator 13.56 source.sup.+) MHz, ion current 0.01 to 3.5 mA/cm.sup.2, plasma density 10.sup.9-10.sup.12 cm.sup.3, ion energy 10 to 70 eV (further details DLC see WO 2020/164735, p. 9-10 and table 4) TiZrCx, React. RF- or DC-puls. or Inert gas (Ar) and CH.sub.4, r.sub.CH4 = 5-50%, p: 1 10.sup.4-9 10.sup.3 mbar, 1-200 kW/cathode.sup.++, 30-120 TiZrOxCy DC or AC-MF (co-)sputter..sup.+++ kW (further details TM see WO 2020/164735, p.7-9) Si.sub.3N.sub.4 or React. RF- or DC-pulsed or N.sub.2 and inert gas (Ar) facultatively, p: 1 10.sup.4-9 10.sup.3 mbar, Si.sub.3N.sub.4 target + Al-target, or Si.sub.3N.sub.4:Al Si.sub.3N.sub.4:Al DC or AC-MF (co-)sputter..sup.+++ target, 1-200 kW/cathode.sup.++, 30-120 kW; MeN.sub.xO.sub.y Reactive RF- or DC-pulsed or Inert gas (Ar) + O.sub.2, metallic (or oxidic) Me-target, DC or AC-MF sputter. p: 1 10.sup.4-9 10.sup.3 mbar, 1-200 kW/cathode.sup.++, e.g. 3-100 kW, e.g., 3-60 kW; NiCr, TiO.sub.sub React. or not-reactive RF- or Inert gas (Ar) + O.sub.2 facult., metallic NiCr- or Ti-target, DC-pulsed or DC or AC-MF p: 1 10.sup.4-9 10.sup.3 mbar, 1-200 kW/cathode.sup.++; NiCr 3-45 kW, e.g. 3-24 kW; (co-) sputter..sup.+++ Ag RF- or DC-pulsed or DC or Inert gas (Ar) only, p: 1 10.sup.4-9 10.sup.3 mbar, Ag-target AC-MF sputter. 1-150 kW/cathode.sup.++ DC, e.g. 3-30 kW. ZnO, SnO.sub.2, React. RF- or DC-pulsed or O.sub.2 and inert gas (Ar) facultatively, p: 1 10.sup.4-9 10.sup.3 mbar, ZnO-, SnO.sub.2-, SnZn-target SnZnO DC or AC-MF (co-)sputter..sup.+++ 1-200 kW/cathode.sup.++, 20-120 kW, 15-120 kW; optionally Al:doped Me or Si React. RF- or DC-pulsed or O.sub.2 or/and N.sub.2 and inert gas (Ar) facultatively, p: 1 10.sup.4-9 10.sup.3 mbar, resp. metal or Si.sub.3N.sub.4 oxides, DC or AC-MF (co-)sputter..sup.+++ target, 1-200 kW/cathode.sup.++; oxynitrides, nitrides Glas Cleaning in aqueous solution, Rinsing with deionized water .sup.+Single-turn excitation electrode ICP-plasma sources having coupling windows of 3360 cm.sup.2 were used for all experiences in an industrial inline coating system, whereat PVD and PECVD processing stations were combined in respective process sequence to process a glass substrate of width of up to 3.21 m and variable length up to 9 m. Three ICP-plasma sources arranged linearly across the substrate width in a distance of 100 to 300 mm window to substrate surface were used at an ICP-power of 1-17 kW per source, which translates to 0.3-5 W/cm.sup.2 power per area of coupling window. .sup.++Planar cathodes with target dimensions l b = 375 cm 24 cm, or/and rotatable cathode targets with the length 380 cm were used for all experiences. Cathodes were arranged across the substrate width with a distance of 100-116 mm target to substrate surface, depending on the respective substrate thickness, were used for every PVD-coating station. .sup.+++(co-)sputter.: means sputtering or co-sputtering.