NL2012010C2 - A method for texturing a glass surface. - Google Patents
A method for texturing a glass surface. Download PDFInfo
- Publication number
- NL2012010C2 NL2012010C2 NL2012010A NL2012010A NL2012010C2 NL 2012010 C2 NL2012010 C2 NL 2012010C2 NL 2012010 A NL2012010 A NL 2012010A NL 2012010 A NL2012010 A NL 2012010A NL 2012010 C2 NL2012010 C2 NL 2012010C2
- Authority
- NL
- Netherlands
- Prior art keywords
- zinc oxide
- glass surface
- glass
- etching
- oxide layer
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 113
- 239000011787 zinc oxide Substances 0.000 claims description 56
- 238000005530 etching Methods 0.000 claims description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 13
- 238000004544 sputter deposition Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000002019 doping agent Substances 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 3
- 238000000089 atomic force micrograph Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/216—ZnO
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/328—Partly or completely removing a coating
- C03C2218/33—Partly or completely removing a coating by etching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Surface Treatment Of Glass (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a new method of texturing a glass surface. In further aspects, the present invention relates to the resulting textured glass surface; to a photovoltaic device comprising the textured glass surface; and, to use of the textured glass surface for scattering light.
Description
A method for texturing a glass surface
The present invention relates to a new method of texturing a glass surface.
In further aspects, the present invention relates to a textured glass surface; to a photovoltaic device; and, to use of a textured glass surface for scattering light.
Methods of texturing glass surfaces are known in the prior art from e.g. EP 1 613 562 B1. EP 1 613 562 B1 recites a method of texturing a glass surface, the method comprising the steps of coating the glass surface with a material film, stimulating a reaction at the interface between the glass and the material film resulting in the formation of reaction products, and removing the material film and the reaction products from the glass surface.
Examples of EP 1 613 562 B1 relate to use of aluminium as the material film. The step of stimulating a reaction comprises annealing the coated glass at a relatively high temperature of 630°C for a long period of time. This temperature is very close to the softening temperature of glass and the melting temperature of aluminium and can lead to problems with handling of the coated glass during and after annealing. The process of EP 1 613 562 B1 is also problematic in practice since during annealing it is essential that there is temperature uniformity across the surface of the coated glass.
It is an object of the present invention to overcome one or more disadvantages of methods of texturing glass surfaces of the prior art.
In a first aspect, the present invention relates to a method of texturing a glass surface, the method comprising the steps of: (a) providing glass having a glass surface; (b) de positing a sacrificial zinc oxide layer on at least a portion of the glass surface; (c) contacting the sacrificial zinc ox ide layer with an etching solution for etching zinc oxide and glass; and, (d) removing the sacrificial zinc oxide layer and at least a portion of the glass thereunder.
Zinc oxide is a heterogeneous polycrystalline material. When the sacrificial zinc oxide layer is exposed to the etching solution, the sacrificial zinc oxide layer is etched inhomogeneously. Some parts of the sacrificial zinc oxide layer etch faster than other areas (e.g. at crystal boundaries). Where the sacrificial zinc oxide layer etches faster, the glass surface is exposed sooner to the etching solution. Once the etching solution contacts the glass it will begin to etch the glass. Once the entire sacrificial zinc oxide layer has been consumed by the etching solution a textured glass surface remains .
Experimentation by the inventors has revealed that the morphology of a glass surface textured according to the present invention is dependent on characteristics of the sacrificial zinc oxide layer and on the composition of the etching solution.
Whilst for certain applications a uniformly textured glass surface may be preferred, for other applications less uniformly textured glass may be more desirable.
In a first preferred embodiment, the sacrificial zinc oxide layer further comprises a dopant selected from a group consisting F, B, Al, Ga, In, and Sn and combinations thereof, such as wherein the dopant is at an amount in the range of 0.1 to 10 % w/w dopant/zinc oxide, preferably 0.2 to 5 % w/w, most preferably 0.5 to 3 % w/w.
Doping influences the crystal structure and crystallinity of zinc oxide (see e.g. Journal of Applied Physics 108, 103721 (2010); doi: 10.1063/1.3511346, and/or Journal of Physics and Chemistry of Solids 71 (2010) 784-787). As a result, doping may be used as a means of control over texturing of a glass surface. An example of texturing a glass surface using aluminium doped zinc oxide as the sacrificial zinc oxide layer is provided below. A number of techniques may be used for applying the sacrificial zinc oxide layer such as MOCVD, LPCVD, PLD, ALD, evaporation, etc.
In a second preferred embodiment, the sacrificial zinc oxide layer is deposited by sputtering, preferably at a sputtering temperature in the range of 50 to 250°C. By sputtering the zinc oxide or doped zinc oxide, the thickness and physical characteristics of the resulting film can be tuned.
In particular, the degree of crystallinity and size of crystals can be chosen e.g. by choosing a suitable sputtering temperature falling within the above range, taking into account the drawing of Figures 2-5.
In a third preferred embodiment the sacrificial zinc oxide layer of claim 1 step (b) has a thickness in the range of 50 nm to 1000 nm, preferably 100 nm to 900 nm, most preferably 150 nm to 600 nm. I.e. the sacrificial zinc oxide layer is deposited at- or to- a thickness falling within these ranges. When the layer is too thin, the glass surface barely becomes textured; when the layer is too thick, the surface becomes textured beyond that which is desirable e.g. for light scattering applications.
In a fourth preferred embodiment, the etchant is an etching solution comprising a first etching component for etching zinc oxide and a second etching component for etching glass. Thus a high degree of control over the etching process may be achieved.
In a fifth preferred embodiment, the first etching component is nitric acid and/or the second etching component is hydrofluoric acid. Nitric acid etches only zinc oxide, whereas hydrofluoric acid is also able to etch glass. Both are cheap and readily available etchants.
In a sixth preferred embodiment, the first etching component is nitric acid and the second etching component is hydrofluoric acid and the ratio of concentrations of nitric acid to hydrofluoric acid is in the range of 1:1 to 20:1, preferably 2:1 to 15:1, most preferably 4:1 to 11:1, such as 4:1 to 8:1.
In a second aspect, the present invention relates to a textured glass surface prepared according to one or more embodiments of the above method.
Scattering of light is used for light incoupling into a photovoltaic device. We claim that it can also be used the other way around, so for light outcoupling. This may be of use in the fabrication of (O)LEDs, scattering the light generated by the device and thereby making it more diffuse.
Also for flexible opto-electronic devices scattering of light can be of interest. According to the invention it is possible to quickly make master stamps that can be used to texture the surface of a flexible substrate.
In a third aspect, the present invention relates to photovoltaic device comprising a textured glass surface prepared according to one or more embodiments of the above method .
In a fourth aspect the present invention relates to use of a textured glass surface prepared according to one or more embodiments of the above method for scattering light, e.g. for incoupling of light into a photovoltaic device (increasing an optical light path of light within the photovoltaic device), or for outcoupling of light, such as from (O)LEDs (scattering the light generated by the device and thereby making it more diffuse).
The invention is further elucidated with reference to the Drawings of Figures 1-5. It is noted that the Drawings are provided to facilitate understanding of the invention and are not intended to limit its scope.
Fig. 1 is a schematic representation of the method of the invention;
Fig. 2 relates to an exemplary embodiment of the present invention using aluminium doped zinc oxide (ZnO:Al) as the sacrificial zinc oxide layer and shows the influence of varying sputtering temperature, sacrificial zinc oxide layer thickness and etching solution composition on the RMS roughness of the resulting textured glass surface;
Fig. 3 shows atomic force microscope images of glass surfaces textured according to the present invention with aluminium doped zinc oxide as the sacrificial zinc oxide layer.
Fig. 4 relates to a further exemplary embodiment of the present invention using intrinsic zinc oxide (ZnO) as the sacrificial zinc oxide layer and shows the influence of varying sputtering temperature, sacrificial zinc oxide layer thickness and etching solution composition on the RMS roughness of the resulting textured glass surface;
Fig. 5 shows atomic force microscope images of glass surfaces textured according to the present invention with intrinsic zinc oxide as the sacrificial zinc oxide layer.
With reference to Figure 1, a schematic representa- tion of the method for texturing a glass surface of the invention is shown.
Textured glass surfaces used for the measurements whose results are shown in the drawings of Figures 2-5 were prepared according to this method. Specifically, sacrificial zinc oxide layers were deposited on Corning Eagle XG glass using a magnetron sputtering system with a ZnO:Al or ZnO ceramic target at a range of sputtering temperatures. Glass surfaces were prepared having ZnO:Al or intrinsic ZnO layers of various thicknesses. The resulting ZnO:Al- or intrinsic ZnO- covered glass surfaces were etched with etching solutions comprising hydrofluoric acid and nitric acid for 15 s to 60 s depending on the thickness of the zinc oxide layer to be etched.
The surface morphologies of the resulting textured glass surfaces were studied by atomic force microscopy (AFM). The roughness of the surfaces are defined in terms of their root mean square roughness (RMS).
Fig. 2 and 4 relate to sacrificial zinc oxide layers of ZnO:Al and to intrinsic ZnO respectively, and show the influence of sputtering conditions and the composition of the etching solution on the RMS of the resulting textured glass. Corresponding AFM images are shown in Fig. 3 and 5 respectively.
The RMS of textured glass decreases as the ratio [HNO3]/[HF] increases i.e. increasing the amount of HF relative to HNO3 results in a less uniformly textured surface.
Increasing the zinc oxide film thickness increases the RMS of the glass surface after etching.
Decreasing the heater temperature during zinc oxide sputtering causes the RMS after etching to increase.
Glass with a higher roughness and lateral feature size is obtained when using intrinsic ZnO deposited and etched at the same conditions as ZnO:Al.
By choosing an appropriate combination of dopant, extent of doping, sputtering temperature, deposition thickness and etching solution composition, a predictable morphology of texturing can be arrived at that is suitable for a particular application .
Although the invention has been discussed in the foregoing with reference to an exemplary embodiment of the method of texturing a glass surface of the invention, the invention is not restricted to this particular embodiment which can be varied in many ways without departing from the gist of the invention. The discussed exemplary embodiment shall therefore not be used to construe the appended claims strictly in accordance therewith. On the contrary the embodiment is merely intended to explain the wording of the appended claims without intent to limit the claims to this exemplary embodiment. The scope of protection of the invention shall therefore be construed in accordance with the appended claims only, wherein a possible ambiguity in the wording of the claims shall be resolved using this exemplary embodiment.
Claims (10)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2012010A NL2012010C2 (en) | 2013-12-20 | 2013-12-20 | A method for texturing a glass surface. |
| PCT/NL2014/050895 WO2015093966A1 (en) | 2013-12-20 | 2014-12-19 | A method for texturing a glass surface |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2012010A NL2012010C2 (en) | 2013-12-20 | 2013-12-20 | A method for texturing a glass surface. |
| NL2012010 | 2013-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL2012010C2 true NL2012010C2 (en) | 2015-06-26 |
Family
ID=50114507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL2012010A NL2012010C2 (en) | 2013-12-20 | 2013-12-20 | A method for texturing a glass surface. |
Country Status (2)
| Country | Link |
|---|---|
| NL (1) | NL2012010C2 (en) |
| WO (1) | WO2015093966A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362590A (en) * | 2020-03-25 | 2020-07-03 | 四川猛犸半导体科技有限公司 | Thin film device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2359072A (en) * | 1943-03-13 | 1944-09-26 | Pittsburgh Plate Glass Co | Method of providing a matte finish upon polished glass surfaces |
| WO2009019376A2 (en) * | 2007-07-20 | 2009-02-12 | Saint-Gobain Glass France | Method for texturing the surface of a substrate having a glass function, and glass product comprising a textured surface |
| US20120097239A1 (en) * | 2009-07-14 | 2012-04-26 | Mitsubishi Electric Corporation | Method for roughening substrate surface, method for manufacturing photovoltaic device, and photovoltaic device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003901559A0 (en) | 2003-04-07 | 2003-05-01 | Unisearch Limited | Glass texturing method |
-
2013
- 2013-12-20 NL NL2012010A patent/NL2012010C2/en not_active IP Right Cessation
-
2014
- 2014-12-19 WO PCT/NL2014/050895 patent/WO2015093966A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2359072A (en) * | 1943-03-13 | 1944-09-26 | Pittsburgh Plate Glass Co | Method of providing a matte finish upon polished glass surfaces |
| WO2009019376A2 (en) * | 2007-07-20 | 2009-02-12 | Saint-Gobain Glass France | Method for texturing the surface of a substrate having a glass function, and glass product comprising a textured surface |
| US20120097239A1 (en) * | 2009-07-14 | 2012-04-26 | Mitsubishi Electric Corporation | Method for roughening substrate surface, method for manufacturing photovoltaic device, and photovoltaic device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015093966A1 (en) | 2015-06-25 |
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| Date | Code | Title | Description |
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| MM | Lapsed because of non-payment of the annual fee |
Effective date: 20170101 |