CN103879088A - High-performance double-silver-layer low-radiation glass and preparation method thereof - Google Patents
High-performance double-silver-layer low-radiation glass and preparation method thereof Download PDFInfo
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- CN103879088A CN103879088A CN201210562713.8A CN201210562713A CN103879088A CN 103879088 A CN103879088 A CN 103879088A CN 201210562713 A CN201210562713 A CN 201210562713A CN 103879088 A CN103879088 A CN 103879088A
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- 239000011521 glass Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010410 layer Substances 0.000 claims abstract description 167
- 239000011241 protective layer Substances 0.000 claims abstract description 54
- 229910052709 silver Inorganic materials 0.000 claims abstract description 46
- 239000004332 silver Substances 0.000 claims abstract description 46
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 35
- 238000005229 chemical vapour deposition Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 229910001120 nichrome Inorganic materials 0.000 claims description 14
- 150000004767 nitrides Chemical class 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 6
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000005344 low-emissivity glass Substances 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 abstract description 6
- 238000009413 insulation Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
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Abstract
本发明涉及一种高性能双银低辐射玻璃及其制备方法。高性能双银低辐射玻璃包括玻璃基片及依次形成于该玻璃基片上的第一低面电阻透明导电层、第一银层、第一保护层、第二低面电阻透明导电层、第二银层、第二保护层、第三低面电阻透明导电层与顶部保护层。上述高性能双银低辐射玻璃在具有较佳透光率的前提下，还可提高隔热性能。
The invention relates to a high-performance double-silver low-radiation glass and a preparation method thereof. The high-performance double-silver low-emissivity glass includes a glass substrate and a first low-surface-resistance transparent conductive layer, a first silver layer, a first protective layer, a second low-surface-resistance transparent conductive layer, and a second A silver layer, a second protective layer, a third transparent conductive layer with low surface resistance and a top protective layer. The above-mentioned high-performance double-silver low-emissivity glass can also improve heat insulation performance under the premise of better light transmittance.
Description
Technical field
The present invention relates to a kind of energy-saving glass, two silver-layer low-radiation glass of especially a kind of high-performance and preparation method thereof.
Background technology
The implementation dynamics that reduces discharging policy along with national energy-saving strengthens and the reinforcement of people to low-carbon environment-friendly consciousness, and the application of the energy-saving glass take low emissivity glass as representative in door and window, glass curtain wall is more and more extensive.In low emissivity glass family, two silver-layer low-radiation glass of energy-efficient performance excellence are widely applied.
Low emissivity glass is to form at surface of ordinary glass deposition low-radiation film layer, due to the silver layer that contains electric conductivity excellence in low-radiation film layer, so the surface resistance of low-radiation film layer is lower, and radiance ε and surface resistance R
□meet formula: ε=0.0106R
□, the surface resistance of rete is lower, and radiance is also just lower, just higher to the reflection of infra-red heat, and heat-proof quality is just better.
The film layer structure of existing pair of silver-layer low-radiation glass is by glass surface outwards successively: the first compound medium layer, the first silver layer, the first protective layer, the second compound medium layer, the second silver layer, the second protective layer and the 3rd compound medium layer.Wherein, the first compound medium layer, the second compound medium layer and the 3rd compound medium layer are the combinations by one or more layers dielectric layer, and material used is all electric non-conductor, i.e. insulating materials conventionally.It is mainly due to two silver layers that electric conductivity is good that existing pair of silver-layer low-radiation glass has lower surface resistance.Thereby increase silver thickness can reduce the surface resistance of rete promotes heat-proof quality; But the thickness increase of two silver layers is limited, the too thick visible light transmissivity that can reduce low emissivity glass of silver layer, slackens the effect of glass printing opacity.
Summary of the invention
In view of above-mentioned condition, be necessary to provide two silver-layer low-radiation glass of a kind of high-performance and preparation method thereof, it also can improve heat-proof quality under the prerequisite with better light transmittance.
The invention provides the two silver-layer low-radiation glass of a kind of high-performance; it comprises glass substrate, and the two silver-layer low-radiation glass of this high-performance also comprise the first low surface resistance transparency conducting layer, the first silver layer, the first protective layer, the second low surface resistance transparency conducting layer, the second silver layer, the second protective layer, the 3rd low surface resistance transparency conducting layer and the top protective layer that are formed at successively on this glass substrate.
The material of this first low surface resistance transparency conducting layer, this second low surface resistance transparency conducting layer or the 3rd low surface resistance transparency conducting layer comprises tin indium oxide, Al-Doped ZnO or fluorine doped tin oxide.
The thickness of this first low surface resistance transparency conducting layer, this second low surface resistance transparency conducting layer or the 3rd low surface resistance transparency conducting layer is 10 ~ 100nm.
The thickness of this first silver layer or this second silver layer is 5 ~ 35nm.
The thickness of this first silver layer or this second silver layer is 8 ~ 20nm.
The material of this first protective layer or this second protective layer is metal, metal oxide, metal nitride, alloy, alloyed oxide or alloy nitride.
The material of this first protective layer or this second protective layer is titanium, nichrome, nickel chromium triangle oxide or nickel chromium triangle nitride.
The thickness of this first protective layer or this second protective layer is 0 ~ 10nm.
The material of this top protective layer is zirconia, and thickness is 5 ~ 50nm.
The present invention also provides the preparation method of the two silver-layer low-radiation glass of a kind of high-performance, and it comprises the steps: to provide glass substrate; On this glass substrate, deposit the first low surface resistance transparency conducting layer by the mode of magnetron sputtering or chemical vapour deposition (CVD); The mode that adds pulsed magnetron sputtering by direct current or direct current deposits the first silver layer on this first low surface resistance transparency conducting layer; The mode that adds pulsed magnetron sputtering by direct current or direct current deposits the first protective layer on this first silver layer; Mode by magnetron sputtering or chemical vapour deposition (CVD) deposits the second low surface resistance transparency conducting layer on this first protective layer; The mode that adds pulsed magnetron sputtering by direct current or direct current deposits the second silver layer on this second low surface resistance transparency conducting layer; The mode that adds pulsed magnetron sputtering by direct current or direct current deposits the second protective layer on this second silver layer; Mode by magnetron sputtering or chemical vapour deposition (CVD) deposits the 3rd low surface resistance transparency conducting layer on this second protective layer; And the mode that adds pulsed magnetron sputtering by direct current or direct current deposits top protective layer on the 3rd low surface resistance transparency conducting layer.
The first low surface resistance transparency conducting layer, the second low surface resistance transparency conducting layer and the 3rd low surface resistance transparency conducting layer of the two silver-layer low-radiation glass of above-mentioned high-performance are owing to having good electric conductivity and lower surface resistance, therefore can reduce radiance, improve the heat-proof quality of two silver-layer low-radiation glass, and can not have influence on two silver-layer low-radiation glass light transmittances; Thereby can guarantee that two silver-layer low-radiation glass, under the prerequisite with better light transmittance, also can improve heat-proof quality.
Accompanying drawing explanation
Fig. 1 is the two silver-layer low-radiation glass schematic diagrames of the high-performance of the embodiment of the present invention.
The specific embodiment
Below in conjunction with drawings and Examples, two silver-layer low-radiation glass of high-performance of the present invention and preparation method thereof are described in further detail.
Refer to Fig. 1, the two silver-layer low-radiation glass 100 of high-performance of the embodiment of the present invention comprise glass substrate 11 and the first low surface resistance transparency conducting layer 11, the first silver layer 12, the first protective layer 13, the second low surface resistance transparency conducting layer 14, the second silver layer 15, the second protective layer 16, the 3rd low surface resistance transparency conducting layer 17 and top protective layer 18 that are formed at successively on glass substrate 10.
Specifically in the present embodiment, the first low surface resistance transparency conducting layer 11, the second low surface resistance transparency conducting layer 14 or the 3rd low surface resistance transparency conducting layer 17 are to have good electric conductivity and lower surface resistance, its material can comprise tin indium oxide (ITO), Al-Doped ZnO (AZO) or fluorine doped tin oxide (FTO), is preferably tin indium oxide.And the thickness of the first low surface resistance transparency conducting layer 11, the second low surface resistance transparency conducting layer 14 or the 3rd low surface resistance transparency conducting layer 17 can be 10 ~ 100 nanometers (nm).
The thickness of the first silver layer 12 or the second silver layer 15 can be 5 ~ 35nm, is preferably 8 ~ 20nm.
The effect of the first protective layer 13 and the second protective layer 16 is the first silver layer 12 and second silver layers 15 of protecting respectively its below, thereby prevents the oxidized or sulfuration in process of production of the first silver layer 12 and the second silver layer 15.The material of the first protective layer 13 and the second protective layer 16 can be metal, metal oxide, metal nitride, and alloy, alloyed oxide or alloy nitride are for example titanium (Ti), nichrome (NiCr), nickel chromium triangle oxide (NiCrO
x) or nickel chromium triangle nitride (NiCrN
x).The thickness of the first protective layer 13 or the second protective layer 16 can be 0 ~ 10nm.
Top protective layer 18 should have good scratch resistance, decay resistance, thereby whole rete is shielded.The material of top protective layer 18 can be zirconia (ZrO
2), its thickness can be 5 ~ 50nm.
The first low surface resistance transparency conducting layer 11, the second low surface resistance transparency conducting layer 14 and the 3rd low surface resistance transparency conducting layer 17 of the two silver-layer low-radiation glass 100 of above-mentioned high-performance are owing to having good electric conductivity and lower surface resistance, therefore can reduce radiance, improve the heat-proof quality of two silver-layer low-radiation glass 100, and can not have influence on two silver-layer low-radiation glass 100 light transmittances; Thereby guarantee that two silver-layer low-radiation glass 100, under the prerequisite with better light transmittance, also can improve heat-proof quality.
The embodiment of the present invention also provides the preparation method of the two silver-layer low-radiation glass of a kind of high-performance, and first it be to provide glass substrate 10.
Then, on glass substrate 10, deposit the first low surface resistance transparency conducting layer 11 by the mode of magnetron sputtering or chemical vapour deposition (CVD).Wherein, when the material adopting when the first low surface resistance transparency conducting layer 11 is ITO or AZO, can adopt the mode of direct current or medium frequency magnetron sputtering to deposit; When the material adopting when the first low surface resistance transparency conducting layer 11 is FTO, can adopt the mode of aumospheric pressure cvd (APCVD) to deposit.
Then the mode that, adds pulsed magnetron sputtering by direct current or direct current deposits the first silver layer 12 on this first low surface resistance transparency conducting layer 11;
Then the mode that, adds pulsed magnetron sputtering by direct current or direct current deposits the first protective layer 13 on this first silver layer 12;
Then, on this first protective layer 13, deposit the second low surface resistance transparency conducting layer 14 by the mode of magnetron sputtering or chemical vapour deposition (CVD).Wherein, when the material adopting when the second low surface resistance transparency conducting layer 14 is ITO or AZO, can adopt the mode of direct current or medium frequency magnetron sputtering to deposit; When the material adopting when the second low surface resistance transparency conducting layer 14 is FTO, can adopt the mode of aumospheric pressure cvd (APCVD) to deposit.
Then the mode that, adds pulsed magnetron sputtering by direct current or direct current deposits the second silver layer 15 on this second low surface resistance transparency conducting layer 14;
Then the mode that, adds pulsed magnetron sputtering by direct current or direct current deposits the second protective layer 16 on this second silver layer 15;
Then, on this second protective layer 16, deposit the 3rd low surface resistance transparency conducting layer 17 by the mode of magnetron sputtering or chemical vapour deposition (CVD).Wherein, when the material adopting when the 3rd low surface resistance transparency conducting layer 17 is ITO or AZO, can adopt the mode of direct current or medium frequency magnetron sputtering to deposit; When the material adopting when the 3rd low surface resistance transparency conducting layer 17 is FTO, can adopt the mode of aumospheric pressure cvd (APCVD) to deposit.
Finally, the mode that adds pulsed magnetron sputtering by direct current or direct current deposits top protective layer 18 on the 3rd low surface resistance transparency conducting layer 17.
Specific embodiment
Embodiment 1
The two silver-layer low-radiation glass of a kind of high-performance, film layer structure from glass substrate outwards successively: glass substrate/ITO/Ag/NiCr/ITO/Ag/NiCr/ITO/ZrO
2.Wherein, the thickness of the first low surface resistance transparency conducting layer (ITO) is 30nm; The thickness of the first silver layer (Ag) is 12nm; The thickness of the first protective layer (NiCr) is 1.5nm; The thickness of the second low surface resistance transparency conducting layer (ITO) is 60nm; The thickness of the second silver layer (Ag) is 14nm; The thickness of the second protective layer (NiCr) is 2nm; The thickness of the 3rd low surface resistance transparency conducting layer (ITO) is 40nm; Top protective layer (ZrO
2) thickness is 20nm.
Prepare the step of the two silver-layer low-radiation glass of above-mentioned high-performance successively:
(1) provide glass substrate, and cleaned up, dry up, be placed in vacuum sputtering district;
(2) on glass substrate, adopt the mode of magnetron sputtering to deposit ITO layer, target used is ITO flat target or rotary target, and power supply is dc source, and power is 10 ~ 100 kilowatts (KW), and process gas is the mist of argon gas and oxygen;
(3) on ITO layer, adopt the mode of magnetron sputtering to deposit Ag layer, target used is metal A g flat target, and power supply is dc source, and power is 1 ~ 10KW, and process gas is pure argon;
(4) on Ag layer, adopt the mode of magnetron sputtering to deposit NiCr layer, target used is NiCr alloy (mass ratio of Ni and Cr is Ni:Cr=80%:20%) flat target, and power supply is dc source, and power is 1 ~ 10KW, and process gas is pure argon;
(5) on NiCr layer, adopt the mode of magnetron sputtering to deposit ITO layer, target used is ITO flat target or rotary target, and power supply is dc source, and power is 10 ~ 100KW, and process gas is the mist of argon gas and oxygen;
(6) on ITO layer, adopt the mode of magnetron sputtering to deposit Ag layer, target used is metal A g flat target, and power supply is dc source, and power is 1 ~ 10KW, and process gas is pure argon;
(7) on Ag layer, adopt the mode of magnetron sputtering to deposit NiCr layer, target used is NiCr alloy (mass ratio of Ni and Cr is Ni:Cr=80%:20%) flat target, and power supply is dc source, and power is 1 ~ 10KW, and process gas is argon gas;
(8) on NiCr layer, adopt the mode of magnetron sputtering to deposit ITO layer, target used is ITO flat target or rotary target, and power supply is dc source, and power is 10 ~ 100KW, and process gas is the mist of argon gas and oxygen;
(9) on ITO layer, adopt the mode of magnetron sputtering to deposit ZrO
2layer, target used is metallic Z r flat target, and power supply is dc source, and power is 10 ~ 100KW, and process gas is the mist of argon gas and oxygen.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, although the present invention discloses as above with preferred embodiment, but not in order to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, when can utilizing the technology contents of above-mentioned announcement to make a little change or being modified to the equivalent embodiment of equivalent variations, in every case be not depart from technical solution of the present invention content, any simple modification of above embodiment being done according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. the two silver-layer low-radiation glass of high-performance; it comprises glass substrate; it is characterized in that, the two silver-layer low-radiation glass of this high-performance also comprise the first low surface resistance transparency conducting layer, the first silver layer, the first protective layer, the second low surface resistance transparency conducting layer, the second silver layer, the second protective layer, the 3rd low surface resistance transparency conducting layer and the top protective layer that are formed at successively on this glass substrate.
2. the two silver-layer low-radiation glass of high-performance as claimed in claim 1, is characterized in that: the material of this first low surface resistance transparency conducting layer, this second low surface resistance transparency conducting layer or the 3rd low surface resistance transparency conducting layer comprises tin indium oxide, Al-Doped ZnO or fluorine doped tin oxide.
3. the two silver-layer low-radiation glass of high-performance as claimed in claim 1, is characterized in that: the thickness of this first low surface resistance transparency conducting layer, this second low surface resistance transparency conducting layer or the 3rd low surface resistance transparency conducting layer is 10 ~ 100nm.
4. the two silver-layer low-radiation glass of high-performance as claimed in claim 1, is characterized in that: the thickness of this first silver layer or this second silver layer is 5 ~ 35nm.
5. the two silver-layer low-radiation glass of high-performance as claimed in claim 4, is characterized in that: the thickness of this first silver layer or this second silver layer is 8 ~ 20nm.
6. the two silver-layer low-radiation glass of high-performance as claimed in claim 1, is characterized in that: the material of this first protective layer or this second protective layer is metal, metal oxide, metal nitride, alloy, alloyed oxide or alloy nitride.
7. the two silver-layer low-radiation glass of high-performance as claimed in claim 6, is characterized in that: the material of this first protective layer or this second protective layer is titanium, nichrome, nickel chromium triangle oxide or nickel chromium triangle nitride.
8. the two silver-layer low-radiation glass of high-performance as claimed in claim 1, is characterized in that: the thickness of this first protective layer or this second protective layer is 0 ~ 10nm.
9. the two silver-layer low-radiation glass of high-performance as claimed in claim 1, it is characterized in that: the material of this top protective layer is zirconia, and thickness are 5 ~ 50nm.
10. a preparation method for the two silver-layer low-radiation glass of high-performance, it comprises the steps:
Glass substrate is provided;
On this glass substrate, deposit the first low surface resistance transparency conducting layer by the mode of magnetron sputtering or chemical vapour deposition (CVD);
The mode that adds pulsed magnetron sputtering by direct current or direct current deposits the first silver layer on this first low surface resistance transparency conducting layer;
The mode that adds pulsed magnetron sputtering by direct current or direct current deposits the first protective layer on this first silver layer;
Mode by magnetron sputtering or chemical vapour deposition (CVD) deposits the second low surface resistance transparency conducting layer on this first protective layer;
The mode that adds pulsed magnetron sputtering by direct current or direct current deposits the second silver layer on this second low surface resistance transparency conducting layer;
The mode that adds pulsed magnetron sputtering by direct current or direct current deposits the second protective layer on this second silver layer;
Mode by magnetron sputtering or chemical vapour deposition (CVD) deposits the 3rd low surface resistance transparency conducting layer on this second protective layer; And
The mode that adds pulsed magnetron sputtering by direct current or direct current deposits top protective layer on the 3rd low surface resistance transparency conducting layer.
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| CN106746734A (en) * | 2017-02-20 | 2017-05-31 | 揭阳市宏光镀膜玻璃有限公司 | A kind of high infrared reflection coated glass and preparation method thereof |
| CN111217539A (en) * | 2018-11-27 | 2020-06-02 | 宜城市泳瑞玻璃科技有限公司 | Coating process of optical glass |
| CN109987857A (en) * | 2019-04-29 | 2019-07-09 | 布勒莱宝光学设备（北京）有限公司 | Novel Low emissivity energy conservation membrane system and its preparation method and application |
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Application publication date: 20140625 |