SUBSTRATE PROVIDED WITH A STACK HAVING THERMAL PROPERTIES COMPRISING AT LEAST ONE NICKEL OXIDE LAYER
20180362397 ยท 2018-12-20
Assignee
Inventors
Cpc classification
C03C17/3681
CHEMISTRY; METALLURGY
C03C2217/73
CHEMISTRY; METALLURGY
International classification
Abstract
A transparent substrate is provided, on a main face, with a stack of thin layers including at least one, metallic functional layer having properties of reflection in the infrared region and/or in the solar radiation region, based on silver or on silver-containing metal alloy, and two antireflective coatings. The antireflective coatings each include at least one dielectric layer. The functional layer is positioned between the two antireflective coatings. At least one nickel oxide Ni.sub.xO layer is located under the functional layer in the direction of the substrate and/or above the functional layer, with interposition of at least one layer or of just one layer made of a different material between the or each nickel oxide Ni.sub.xO layer and the functional layer.
Claims
1. A transparent substrate provided, on a main face, with a stack of thin layers comprising at least one metallic functional layer having properties of reflection in the infrared region and/or in the solar radiation region, and two antireflective coatings, said antireflective coatings each comprising at least one dielectric layer, said functional layer being positioned between the two antireflective coatings, wherein at least one nickel oxide Ni.sub.xO layer is located under said functional layer in the direction of the substrate and/or above said functional layer, with interposition of at least one layer or of just one layer made of a different material between said nickel oxide Ni.sub.xO layer and said functional layer.
2. The substrate as claimed in claim 1, wherein a single oxide-based layer is interposed under said functional layer in the direction of the substrate, between said nickel oxide Ni.sub.x O layer and said functional layer.
3. The substrate as claimed in claim 1, wherein a single metallic layer is interposed between said nickel oxide Ni.sub.xO layer and said functional layer under said functional layer in the direction of the substrate and/or above said functional layer on the opposite side from the substrate.
4. The substrate as claimed in claim 1, wherein a metallic layer is located under and in contact with the functional layer, with a physical thickness of said metallic layer of at least 0.3 nm and an oxide-based layer interposed between said metallic layer and said nickel oxide Ni.sub.xO layer which is located under said functional layer in the direction of the substrate.
5. The substrate as claimed in claim 1, wherein a layer based on zinc oxide is located below and in contact with said nickel oxide Ni.sub.xO layer.
6. The substrate as claimed in claim 1, wherein said nickel oxide Ni.sub.xO layer exhibits an x between 1.2 and 0.5.
7. The substrate as claimed in claim 1, wherein the physical thickness of said nickel oxide Ni.sub.xO layer is between 0.3 and 10.0 nm.
8. The substrate as claimed in claim 1, wherein the physical thickness of the only or of all the layers interposed between said nickel oxide Ni.sub.xO layer and said functional layer is between 0.5 and 15.0 nm.
9. The substrate as claimed in claim 1, wherein two nickel oxide layers in contact with one another are located under said functional layer in the direction of the substrate and/or above said functional layer the nickel oxide Ni.sub.yO layer closest to said functional layer being less oxidized than the other, more distant, nickel oxide Ni.sub.xO layer.
10. The substrate as claimed in claim 1, wherein said underlying antireflective and overlying antireflective coatings each comprise at least one dielectric layer based on silicon nitride.
11. A glazing comprising at least one substrate as claimed in claim 1.
12. The glazing as claimed in claim 11, mounted as a monolithic unit or as a multiple glazing unit of the double glazing or triple glazing or laminated glazing type, wherein at least the substrate carrying the stack is bent and/or tempered.
13. A method of using the substrate as claimed in claim 1, for comprising producing a transparent electrode of a heated glazing or of an electrochromic glazing or of a lighting device or of a display device or of a photovoltaic panel from the substrate.
14. The substrate as claimed in claim 1, wherein the functional layer is based on silver or on silver-containing metal alloy.
15. The substrate as claimed in claim 2, wherein the single oxide-based layer is a layer based on zinc oxide.
16. The substrate as claimed in claim 3, wherein the single oxide-based layer is a layer comprising Ni and/or Cr or a layer comprising Ge.
17. The substrate as claimed in claim 4, wherein the metallic layer comprises nickel and chromium and the thickness of the metallic layer is between 1.0 and 5.0 nm, and the oxide-based layer is a layer based on zinc oxide.
18. The substrate as claimed in claim 6, wherein said nickel oxide Ni.sub.xO layer exhibits an x between 0.9 and 0.6.
19. The substrate as claimed in claim 7, wherein the physical thickness of said nickel oxide Ni.sub.xO layer between 1.0 and 5.0 nm.
20. The substrate as claimed in claim 8, wherein the physical thickness of the only or of all the layers interposed between said nickel oxide Ni.sub.xO layer and said functional layer is between 1.0 and 6.0 nm.
Description
[0045] The details and advantageous characteristics of the invention emerge from the following nonlimiting examples, illustrated by means of the appended figures which illustrate:
[0046] in
[0047] in
[0048] in
[0049] in
[0050] in
[0051] in
[0052] in
[0053] In
[0054]
[0055] These two antireflective coatings 120, 160 each comprise at least one dielectric layer 122, 126; 162, 168 and preferably each comprise at least two dielectric layers: in each dielectric coating, a dielectric layer 126, 162, preferably based on zinc oxide, which is closer to the functional layer 140, and a dielectric layer 122, 168, preferably based on silicon nitride, further from the functional layer 140.
[0056] Optionally, on the one hand, the functional layer 140 can be deposited directly on an underblocker coating 130 positioned between the underlying antireflective coating 120 and the functional layer 140 and, on the other hand, the functional layer 140 can be deposited directly under an overblocker coating 150 positioned between the functional layer 140 and the overlying antireflective coating 160.
[0057] The underblocker and/or overblocker layers, although deposited in metallic form and presented as being metallic layers, are sometimes in practice oxidized layers since one of their functions (in particular for the overblocker layer) is to become oxidized during the deposition of the stack in order to protect the functional layer.
[0058] According to the invention, at least one nickel oxide Ni.sub.xO layer (the layer 127 in tables 1 to 3, 6 below) is located under said functional layer 140 in the direction of the substrate 30 and/or at least one nickel oxide Ni.sub.xO layer (the layer 167 in tables 1 to 3, 6 below) is located above said functional layer 140, with interposition of at least one layer or of just one layer made of a different material between: [0059] said nickel oxide Ni.sub.xO layer 127, 167 and said functional layer 140, or each nickel oxide Ni.sub.xO layer 127, 167 and said functional layer 140.
[0060] When a stack is used in a multiple glazing 100 of double glazing structure, as illustrated in
[0061] The glazing thus provides a separation between an external space ES and an internal space IS.
[0062] The stack can be positioned on face 3 (on the sheet furthest inside the building when considering the incident direction of the sunlight entering the building and on its face facing the gas-filled cavity).
[0063]
[0064] However, it can also be envisaged that, in this double glazing structure, one of the substrates exhibits a laminated structure.
[0065] For all the examples below, the conditions for deposition of the layers are:
TABLE-US-00001 Deposition Layer Target employed pressure Gas Si.sub.3N.sub.4 Si:Al at 92:8 wt % 1.5 10.sup.3 mbar.sup. Ar/(Ar + N.sub.2) at 22% ZnO Zn:O at 50:50 atom % 2 10.sup.3 mbar Ar/(Ar + O.sub.2) at 90% SnZnO Zn:Sn at 55:45 atom % 2 10.sup.3 mbar Ar/(Ar + O.sub.2) at 30% NiCr Ni:Cr at 80:20 atom % 8 10.sup.3 mbar Ar at 100% Ni.sub.xO Ni 5 10.sup.3 mbar Ar/(Ar + O.sub.2) at 87% Ni.sub.yO Ni 5 10.sup.3 mbar Ar/(Ar + O.sub.2) at 81% Ag Ag 8 10.sup.3 mbar Ar at 100%
[0066] The layers deposited can thus be classified into four categories:
[0067] ilayers of antireflective/dielectric material exhibiting an n/k ratio over the entire wavelength range of the visible region of greater than 5: Si.sub.3N.sub.4, ZnO;
[0068] iimetallic functional layers made of material having properties of reflection in the infrared region and/or in the solar radiation region: Ag; it has been observed that silver exhibits a ratio 0<n/k<5 over the entire wavelength range of the visible region and its bulk electrical resistivity is less than 10.sup.6 .cm;
[0069] iiiunderblocker and overblocker layers intended to protect the functional layer from a modification to its nature during the deposition of the stack;
[0070] ivnickel oxide Ni.sub.xO and Ni.sub.yO layers;
[0071] It should be noted that a Ni.sub.1O.sub.1 ceramic target has also been tested and led to similar results to those found with the examples below.
[0072] In all the examples below, the stack of thin layers is deposited on a substrate made of clear soda-lime glass with a thickness of 4 mm of the Planiclear brand, distributed by Saint-Gobain.
[0073] The physical thicknesses in nanometers of each of the layers or of the coatings of the examples, with reference to the configuration of
[0074] In tables 1 to 3, the No. column shows the number of the layer and the second column shows the coating, in connection with the configuration of
[0075] In these tables 1 to 3, the substrate 30 is located under the layer 122 and the layers of the examples are located in the order shown by the left-hand column, from the bottom upward starting from this substrate 30; the layers numbered in these tables which are not shown in
TABLE-US-00002 TABLE 1 Ex. No. 1 2 10 11 12 13 168 160 Si.sub.3N.sub.4 20 20 20 20 20 20 162 ZnO 5 5 5 5 5 5 150 NiCr 1 1 1 1 1 1 140 Ag 10 10 10 10 10 10 129 120 Ge 1 1 128 ZnO 5 5 127 Ni.sub.yO 2 127 Ni.sub.xO 5 5 5 3 5 126 ZnO 5 5 5 5 5 122 Si.sub.3N.sub.4 20 20 20 20 20 20
[0076] In the first series of examples, that of table 1, for examples 10 to 13, the nickel oxide Ni.sub.xO layer 127 is in the underlying antireflective coating 120 and is separated from the metallic functional layer 140 by a dielectric layer 128 (ex. 10 and 13) based on zinc oxide, by a metallic layer 129 (ex. 11) made of germanium or by two layers, one of which, the layer 129, is metallic and made of germanium and the other of which, the layer 127, is an oxide and more specifically is made of nickel oxide Ni.sub.yO (ex. 12).
[0077] This nickel oxide Ni.sub.yO of the layer 127 is different from the nickel oxide Ni.sub.xO of the layer 127: with reference to
TABLE-US-00003 TABLE 2 Ex. No. 1 20 21 22 23 168 160 Si.sub.3N.sub.4 20 20 20 20 20 167 Ni.sub.xO 5 5 5 4 167 Ni.sub.yO 1 162 SnZnO 5 162 ZnO 5 5 5 150 NiCr 1 1 1 1 1 140 Ag 10 10 10 10 10 126 120 ZnO 5 5 5 5 5 122 Si.sub.3N.sub.4 20 20 20 20 20
[0078] In the second series of examples, that of table 2, for examples 20 to 23, the nickel oxide Ni.sub.xO layer 167 is in the overlying antireflective coating 160 and is separated from the metallic functional layer 140 by a metallic layer 150 made of nickel-chromium alloy (ex. 21) or by two layers, one of which, the layer 150, is metallic and made of nickel-chromium alloy and the other of which, the layer 162, is an oxide based on zinc oxide (ex. 20) or is a nickel oxide Ni.sub.yO layer 167 (ex. 23), which are deposited in this order on the metallic functional layer, or by three layers (ex. 22) which are, in this order starting from the metallic functional layer: a metallic layer 150 made of nickel-chromium alloy, then a layer 162 based on zinc oxide and then a dielectric layer 162, which can be a mixed zinc tin oxide, a tin oxide or also a titanium oxide.
TABLE-US-00004 TABLE 3 Ex. No. 1 14 15 24 26 27 16 168 160 Si.sub.3N.sub.4 20 20 20 20 20 20 20 167 Ni.sub.xO 5 5 4 167 Ni.sub.yO 1 162 SnZnO 5 162 ZnO 5 5 5 5 5 150 NiCr 1 1 1 1 1 1 1 140 Ag 10 10 10 10 10 10 10 130 NiCr 1 1 1 1 1 1 1 128 120 ZnO 5 127 Ni.sub.xO 5 5 5 126 ZnO 5 5 5 5 5 5 122 Si.sub.3N.sub.4 20 20 20 20 20 20 20
[0079] In the third series of examples, that of table 3, for examples 14 to 16, the nickel oxide Ni.sub.xO layer 127 is in the underlying antireflective coating 120 and is separated from the metallic functional layer 140 by a metallic layer 130 made of nickel-chromium alloy (ex. 14 and 16) or by two layers, one of which is a metallic layer 150 made of nickel-chromium alloy and the other of which is a dielectric layer 128 made of oxide and more particularly based on zinc oxide (ex. 15).
[0080] For examples 24 to 27, the nickel oxide Ni.sub.xO layer 167 is in the overlying antireflective coating 160 and is separated from the metallic functional layer 140 by a metallic layer 150 made of nickel-chromium alloy (ex. 26) or by two layers, one of which is a layer 150 made of nickel-chromium alloy is metallic and the other of which is either a layer 162, which is an oxide and is based on zinc oxide (ex. 24), or is a nickel oxide Ni.sub.yO layer 167 (ex. 27), or by three layers (ex. 25) which are, in this order starting from the metallic functional layer: a metallic layer 150 made of nickel-chromium alloy, then a layer 162 based on zinc oxide and then a dielectric layer 162, which can be a mixed zinc tin oxide, a silicon oxide or also a titanium oxide.
TABLE-US-00005 TABLE 4 Ex. 1 2 10 20 21 R (/square) 4.7 4.5 3.5 3.8 4.1 (5%) (25%) (19%) (13%) Abs (%) 9.4 9.4 7.0 10.0 10.0
TABLE-US-00006 TABLE 5 Ex. 1 14 R (/square) 6.6 4.5 (32%) Abs (%) 17.0 14.0
[0081] The characteristics of the substrate coated with the stack which are presented in tables 4 and 5 consist of the measurement, after a tempering heat treatment at 650 C. for 10 minutes and then a cooling operation:
[0082] for R, of the sheet resistance measured as usual with a four-point probe, in ohms per square, and
[0083] for Abs, of the light absorption in the visible region in %, measured according to illuminant D65 2, on the side opposite the main face of the substrate on which the stack of thin layers is deposited.
[0084] The value in brackets indicates, for table 4, the improvement (the decrease) in the sheet resistance with respect to the reference consisting of example 1 and, for table 5, the improvement (the decrease) in the sheet resistance with respect to the reference consisting of example 1.
[0085] The difference between example 16 and example 14 is that, in the context of example 14 (as for the other examples), the nickel oxide Ni.sub.xO layer 127 is deposited directly on a layer based on zinc oxide 126 whereas, in the context of example 16, the nickel oxide Ni.sub.xO layer 127 is deposited directly on a layer 122 based on silicon nitride. It has been noticed that the sheet resistance of example 16 is higher than that of example 14 as this example 16 does not benefit from the favorable conditions obtained when the nickel oxide layer is deposited directly on a layer based on zinc oxide.
[0086] The heat treatment would have been able to consist of a forward progression of the substrate 30 at a rate of 10 m/min under a laser line 8. By way of example, such a laser line can have a width of 60 m and a power of 25 W/mm with the laser line oriented perpendicularly to the face 29 and in the direction of the terminal layer of the stack, that furthest from the face 29, that is to say by positioning the laser line (illustrated by the straight black arrow) above the stack and by orienting the laser in the direction of the stack, as seen in
[0087] Other tests have been carried out with a nickel oxide Ni.sub.xO layer 127 and/or a nickel oxide Ni.sub.xO layer 167 with a thickness of 1 nm and have given similar results.
[0088] Other tests have been carried out. Tests have been carried out on the basis of examples 1, 2 and 10, with a metallic functional layer 140 made of silver, the thickness of this metallic functional layer 140 being modified.
[0089] for reference stacks based on example 1: noncontinuous curve,
[0090] for reference stacks based on example 2, curve with squares,
[0091] for stacks according to the invention based on example 10: curve with circles, and
[0092] for stacks according to the invention based on example 10 but with, as additional difference, a layer 128 no longer of 5 nm but of 2 nm: curve with triangles.
[0093] This
[0094]
[0095] for stacks based on example 10 and with a metallic functional layer 140 exhibiting a thickness of 10 nm: square points,
[0096] for stacks based on example 10 but with a metallic functional layer 140 exhibiting a thickness of 15 nm: round points.
[0097] This
[0098] Tests have been carried out on the basis of example 20 of table 2: the thickness of the layer 167, initially 5 nm, was
[0099] decreased in order to achieve the value of 1 nm and the sheet resistance of the stack after heat treatment then decreased by 18%, with respect to that of example 1 after heat treatment;
[0100] increased in order to achieve the value of 15 nm and the sheet resistance of the stack after heat treatment then decreased by 20%, with respect to that of example 1 after heat treatment;
[0101] Entirely surprisingly, the effect on the sheet resistance after heat treatment is comparable, whatever the thickness of the layer 167.
[0102] Tests have been carried out on the basis of examples 1 and 14 of table 3, with a metallic functional layer 140 made of silver, the thickness of this metallic functional layer 140 being modified.
[0103] for reference stacks based on example 1: noncontinuous curve, and
[0104] for reference stacks based on example 14: curve with squares.
[0105] This
[0106] Furthermore, tests have been carried out in an attempt to understand if the method of deposition of the Ni.sub.xO layer 127 and/or 167 could influence the improvements obtained. This is because a Ni.sub.xO layer can be obtained: [0107] i. either by sputtering a metal target containing only Ni, in an atmosphere containing oxygen, indeed even, in addition, a neutral gas, such as argon; [0108] ii. or by sputtering a ceramic target containing both Ni and oxygen, in an atmosphere containing a neutral gas, such as argon, indeed even, in addition, oxygen.
[0109] It has been found that the diffraction peak by XRD of the silver of the metallic functional layer 140 according to <200> was more pronounced in the case i; however, at an identical thickness (5 nm) of Ni.sub.xO layer 127 and/or 137, the improvement (decrease) in the sheet resistance with respect to the reference examples is the same.
[0110] On the basis of example 10, it has been found that a thick Ni.sub.xO layer 127, of 19 nm, deposited in the case i, improved even more (decreased even more) the sheet resistance, with a decrease of 22%, with respect to that of example 1 after heat treatment; however, the light absorption in the visible region, Abs, then rose to 22% after heat treatment.
[0111] It has furthermore been found that the resistivity of the Ni.sub.xO deposited according to the case i above, before heat treatment, was of the order of 190 .cm, i.e. a value close to that of ITO (approximately 200 .cm) and much higher than the resistivity of the silver used for the functional layer 140, which is of the order of 3 .cm; after the heat treatment at 650 C. for 10 minutes, the resistivity of this same Ni.sub.xO deposited according to the case i above fell to approximately 30 .cm.
[0112] The mechanical strength of example 10 has been tested and compared with that of example 1: it is as good for low loads and better for high loads.
[0113]
[0114] These three antireflective coatings 120, 160 and 200 each comprise at least one dielectric layer 122, 126; 162, 166, 168; 202, 204 and preferably each comprise at least two dielectric layers: in each dielectric coating, a dielectric layer 126, 162, 168, 202, preferably based on zinc oxide, which is closer to the functional layer, and a dielectric layer 122, 168, 204, preferably based on silicon nitride.
[0115] Optionally,
[0116] on the one hand, at least one, and preferably each, functional layer 140, 180 can be deposited directly on a underblocker coating 130, 170 positioned between the antireflective coating located immediately below, respectively 120, 160, and the functional layer 140, 180, and
[0117] on the other hand, at least one, and preferably each, functional layer 140, 180 can be deposited directly under an overblocker coating 150, 190 positioned between the functional layer 140, 180 and the antireflective coating located immediately above, respectively 160, 200.
[0118] Tests have been carried out in order to measure the effects of the invention for a stack comprising several functional layers. The structure of the stacks comprising two metallic functional layers 140, 180 are set out in table 6 below, which stacks were tested using a table structure similar to those of tables 1 to 3: the No. column shows the number of the layer and the second column shows the coating, in connection with the configuration of
[0119] In this table 6, the substrate 30 is located under the layer 122 and the layers of the examples are located in the order shown by the left-hand column, from the bottom upward starting from this substrate 30; the layers numbered in this table which are not shown in
TABLE-US-00007 TABLE 6 Ex. No. 4 40 41 42 208 200 Si.sub.3N.sub.4 25 25 25 25 202 ZnO 5 5 5 5 190 NiCr 1 1 1 1 180 Ag 20 20 20 20 170 NiCr 1 1 1 1 168 160 ZnO 5 5 167 Ni.sub.xO 5 5 166 ZnO 5 5 5 5 164 Si.sub.3N.sub.4 80 80 80 80 162 ZnO 5 5 5 5 150 NiCr 1 1 1 1 140 Ag 8 8 8 8 130 NiCr 1 1 1 1 128 120 ZnO 5 5 127 Ni.sub.xO 5 5 126 ZnO 5 5 5 5 122 Si.sub.3N.sub.4 40 40 40 20
[0120] This series of examples has made it possible to measure the effects on the sheet resistance of the use of a nickel oxide layer: [0121] with example 40: under the first metallic functional layer 140 only of a functional bilayer stack, [0122] with example 41: under the second metallic functional layer 180 only of a functional bilayer stack, and [0123] with example 42: both under the first metallic functional layer 140 and under the second metallic functional layer 180 of a functional bilayer stack.
[0124] The sheet resistances R of the four examples, measured as above with a four-point probe, in ohms per square, after a tempering heat treatment at 650 C. for 10 minutes and then a cooling operation, are presented in table 7.
TABLE-US-00008 TABLE 7 Ex. 4 40 41 42 R (/square) 2.12 1.98 1.84 1.70 (7%) (13%) (20%)
[0125] Thus, the use of a Ni.sub.xO layer 127 and/or 167 improves (decreases) the sheet resistance and there is a cumulative effect on applying the invention under each metallic functional layer of a stack comprising several metallic functional layers.
[0126] Furthermore, this improvement in the sheet resistance has also been observed on the basis of example 42, with the thickness of four blocker layers 130, 150, 170 and 190 each at 0.7 nm for one example and then decreased to 0.5 nm for another example, each compared with an example of the type of example 40 with, for one, the four blocker layers 130, 150, 170 and 190 at 0.7 nm and, for the other, these four layers at 0.5 nm.
[0127] In addition, this improvement in the sheet resistance has also been observed on the basis of example 42, with the thickness of two Ni.sub.xO layers 127 and 167 each at 2 nm, and also by decreasing the thickness of four blocker layers 130, 150, 170 and 190, each at 0.7 nm for one example and then at 0.5 nm for another example, and by comparing each with an example of the type of example 40 with, for one, the four blocker layers 130, 150, 170 and 190 at 0.7 nm and, for the other, these four layers at 0.5 nm.
[0128] As a result of the low sheet resistance obtained and also of the good optical properties (in particular the light transmission in the visible region), it is furthermore possible to use the substrate coated with the stack according to the invention to produce a transparent electrode substrate.
[0129] Generally, the transparent electrode substrate may be suitable for any heated glazing, for any electrochromic glazing, any display screen, or also for a photovoltaic cell (or panel) and in particular for a transparent photovoltaic cell backsheet.
[0130] The present invention is described in the preceding text by way of example. It is understood that a person skilled in the art is able to produce different alternative forms of the invention without, however, departing from the scope of the patent as defined by the claims.