WO2021167787A1 - Gravure de surfaces de verre pour réduire la charge électrostatique pendant le traitement - Google Patents

Gravure de surfaces de verre pour réduire la charge électrostatique pendant le traitement Download PDF

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Publication number
WO2021167787A1
WO2021167787A1 PCT/US2021/016339 US2021016339W WO2021167787A1 WO 2021167787 A1 WO2021167787 A1 WO 2021167787A1 US 2021016339 W US2021016339 W US 2021016339W WO 2021167787 A1 WO2021167787 A1 WO 2021167787A1
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WIPO (PCT)
Prior art keywords
wall portion
glass substrate
flow
nozzle
treatment fluid
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Application number
PCT/US2021/016339
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English (en)
Inventor
Hsueh-Hung Fu
Shinya HONKAWA
Mitsuo Kimura
Siva Venkatachalam
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Corning Incorporated
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Publication date
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Publication of WO2021167787A1 publication Critical patent/WO2021167787A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • 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

Definitions

  • the disclosure relates to the use of treatment processes on glass surfaces to reduce electrostatic charging that otherwise may occur during processing of the glass.
  • Flat or curved substrates made of an optically transparent material such as glass are often used for flat panel displays, photovoltaic devices, and other suitable applications. These displays and devices are made through a series of manufacturing steps in which the glass material is handled in various processing steps. Interaction between a glass substrate and processing equipment can cause a charge to be imparted to or otherwise accumulate on one or more of the glass substrate surfaces. Such charge can, for example, cause difficulty separating glass substrates during processing or degrade sensitive electronic components that might be deposited on these surfaces thereafter.
  • the present disclosure provides a treated glass substrate with a surface topography (e.g, roughness) and surface composition that reduces the electrostatic charging of the glass surface.
  • a method of treating a glass substrate comprising heating the glass substrate, directing a first flow of air through a first plurality of apertures disposed in an aperture plate toward a first side of the heated glass substrate, exposing a second side of the heated glass substrate to a treatment fluid comprising HF while directing the first flow of air, the treatment fluid etching the second side of the glass substrate to form a treated glass substrate.
  • a diameter of each aperture of the first plurality of apertures can be in a range from about 0.5 millimeters to about 10 millimeters.
  • a distance between adjacent apertures of the first plurality of apertures can be in a range from about 3 millimeters to about 25 millimeters.
  • the treatment fluid can comprise a gas, for example an inert gas.
  • the aperture plate can comprise a second plurality of apertures and a flow of air directed through the second plurality of apertures is controlled independently of the flow of air directed through the first plurality of apertures.
  • a flow rate of the second flow of air can be different than a flow rate of the first flow of air.
  • a flow rate of the first air flow can be in a range from about 10 liters/minute to about 300 liters/minute.
  • a velocity of the first flow of air can be in a range from about 0.01 millimeters/second to about 100 millimeters/second.
  • the method may further comprise filtering the first flow of air with a filter before directing the first flow of air through the first plurality of apertures, the filter and the aperture plate comprising a cover positioned over the glass substrate.
  • the filter can be configured to remove particles equal to or greater than about 0.3 pm from the first flow of air. In some embodiments, the filter can be configured to remove particles equal to or greater than about 1 pm from the first flow of air.
  • the first flow of air can be flowed into a first portion of an etching zone located proximate the first side of the glass substrate and the treatment fluid is flowed into a second portion of the etching zone located proximate the second side of the glass substrate.
  • the method may further comprise reducing a flow of the treatment fluid from the second portion of the etching zone into the first portion of the etching zone with a flow modifier, the flow modifier comprising a first wall portion extending from an inlet channel through which the treatment fluid enters the second portion of the etching zone and an exhaust channel through which the treatment fluid is removed from the second portion of the etching zone.
  • the first wall portion can extend parallel with an edge of the glass substrate.
  • the first wall portion can extend from a nozzle comprising the inlet channel to the aperture plate. In some embodiments, a distance of the first wall portion from an edge of the glass substrate proximate the inlet channel can be less than a distance of the first wall portion from the edge of the glass substrate proximate the exhaust channel.
  • the flow modifier can comprise a second wall portion spaced apart from the first wall portion and connected to the first wall portion by a third wall portion extending between the first and second wall portions.
  • the flow modifier may further comprise a fourth wall portion extending between and connected to the first wall portion, the second wall portion, and the third wall portion, the fourth wall portion forming a flow channel for the treatment fluid between the nozzle and the fourth wall portion and further bounded by the first wall portion and the second wall portion.
  • the treatment fluid can be flowed into the second portion of the etching zone through a nozzle and a height of the flow modifier above an upper-most surface of the nozzle is less than a height of the second side of the glass substrate above the upper-most surface of the nozzle.
  • the exposing can comprise flowing the treatment fluid through an inlet channel of a nozzle, the method further comprising blocking at least a portion of the inlet channel with a flow modifier inserted into the inlet channel.
  • the flow modifier can comprise a passage therethrough configured to allow a seepage of the treatment fluid through the flow modifier.
  • the exposing can comprise reacting CF 4 and H 2 0 to form the HF.
  • a method of treating a glass substrate comprising heating the glass substrate to a predetermined treatment temperature, directing a first flow of air from a cover positioned over the glass substrate into a first portion of an etching zone located proximate the first side of the glass substrate, directing a flow of a treatment fluid comprising HF into a second portion of the etching zone located proximate the second side of the glass substrate while directing the first flow of air, and reducing the flow of the treatment fluid from the second portion of the etching zone into the first portion of the etching zone with a flow modifier positioned adjacent an edge of the glass substrate, the flow modifier comprising a first wall portion extending from an inlet channel through which the treatment fluid enters the second portion of the etching zone and an exhaust channel through which the treatment fluid is removed fromthe second portion of the etching zone.
  • the first wall portion can extend parallel with an edge of the glass substrate.
  • the first wall portion can extend from a nozzle comprising the inlet channel to the aperture plate.
  • a distance of the first wall portion from an edge of the glass substrate proximate the inlet channel can be less than a distance of the first wall portion from the edge of the glass substrate proximate the exhaust channel.
  • the flow modifier can comprise a second wall portion spaced apart from the first wall portion and connected to the first wall portion by a third wall portion extending between the first and second wall portions.
  • the flow modifier may further comprise a fourth wall portion extending between and connected to the first wall portion, the second wall portion, and the third wall portion, the fourth wall portion forming a flow channel for the treatment fluid between the nozzle and the fourth wall portion and further bounded by the first wall portion and the second wall portion.
  • the treatment fluid can be flowed into the second portion of the etching zone through a nozzle and a height of the flow modifier above an upper-most surface of the nozzle is less than a height of the second side of the glass substrate above the upper-most surface of the nozzle.
  • a method of treating a glass substrate comprising heating the glass substrate to a predetermined treatment temperature, directing a first flow of air from a cover positioned over the glass substrate into a first portion of an etching zone located proximate the first side of the glass substrate, directing a flow of a treatment fluid comprising HF from an inlet channel of a nozzle into a second portion of the etching zone located proximate the second side of the glass substrate while directing the first flow of air, and reducing the flow of the treatment fluid from the second portion of the etching zone into the first portion of the etching zone with a flow modifier inserted into the inlet channel of the nozzle.
  • the flow modifier can define a passage extending through the flow modifier, the passage configured to allow a seepage of the treatment fluid through the flow modifier.
  • an apparatus for treating a glass substrate comprising an etching chamber, a nozzle positioned in the etching chamber, the nozzle in fluid communication with a source of a treatment fluid comprising HF, a cover positioned over ihe nozzle, the cover comprising an aperture plate comprising a first plurality of apertures in fluid communication with a source of pressurized air through a first control valve.
  • the cover may further comprise a filter positioned in a flow path of the pressurized air.
  • the filter can be configured to remove particles with a particle size equal to or greater than about 0.3 micrometers.
  • the aperture plate can comprise a second plurality of apertures in fluid communication with the sourceof pressurizedair through a second control valve.
  • the second control valve can be separately controllable from the first control valve.
  • the cover and the nozzle can form an etching zone therebetween, the apparatus further comprising a flow modifier positioned adjacent a travel path of the glass substrate, the flow modifier comprising a first wall portion extending from an inlet channel through which the treatment fluid enters the etching zone and an exhaust channel through which the treatment fluid is removed from the etching zone.
  • the first wall portion can extend parallel with the travel path.
  • the first wall portion can extend between the nozzle and the aperture plate.
  • the flow modifier may further comprise a second wall portion spaced from the first wall portion and extending from the inlet to the exhaust channel and connected to the first wall portion by a third wall portion.
  • the flow modifier may further comprise a fourth wall portion connected to the first wall portion, the second wall portion, and the third wall portion, the fourth wall portion forming a flow channel between the nozzle and the aperture plate.
  • the nozzle can comprise an inlet channel configured to receive the treatment fluid, the apparatus further comprising a flow modifier inserted into at least a portion of the inlet channel.
  • the flow modifier can comprise at least one passage extending therethrough and configured to allow a seepage of the treatment fluid through the flow modifier.
  • an apparatus for treating a glass substrate comprising an etching chamber, a nozzle positioned in the etching chamber, the nozzle in fluid communication with a source of a treatment fluid comprising HF, a cover positioned over ihe nozzle, the cover comprising an aperture plate comprising a first plurality of apertures in fluid communication with a source of pressurized air through a first control valve, the cover and the nozzle forming an etching zone therebetween, and a flow modifier positioned adjacent a travel path of the glass substrate, the flow modifier comprising a first wall portion extending from an inlet channel through which the treatment fluid enters the etching zone and an exhaust channel through which the treatment fluid is removed from the etching zone.
  • the first wall portion can extend parallel with the travel path.
  • the first wall portion can extend between the nozzle and the aperture plate.
  • the flow modifier may further comprise a second wall portion spaced from the first wall portion and extending from the inlet to the exhaust channel and connected to the first wall portion by a third wall portion.
  • the flow modifier may further comprise a fourth wall portion connected to the first wall portion, the second wall portion, and the third wall portion, the fourth wall portion forming a flow channel between the nozzle and the aperture plate.
  • an apparatus for treating a glass substrate comprising an etching chamber, a nozzle positioned in the etching chamber, the nozzle in fluid communication with a source of a treatment fluid comprising HF, a cover positioned over the nozzle, the cover comprising an aperture plate comprising a first plurality of apertures in fluid communication with a source of pressurizedair through a first control valve, the cover and the nozzle forming an etching zone therebetween, and a flow modifier inserted into the inlet channel of the nozzle.
  • the flow modifier can define a passage extending through the flow modifier, the passage configuredto allow a seepage of the treatment fluid through the flow modifier.
  • FIG. 1 is a perspective view illustrating an exemplary treated glass substrate in accordance with some embodiments of the present disclosure
  • FIG. 2 is a cross-sectional view illustrating various exemplary layers of the treated glass substrate of FIG. 1;
  • FIG. 3 is a flow chart illustrating an exemplary method of producing the treated glass substrate of FIGS. 1 & 2;
  • FIG. 4 is a flow chart illustrating an exemplary method of etching the glass substrate of FIGS. 1 & 2;
  • FIG. 5 is a schematic illustrating an exemplary treatment apparatus that can be used to produce the treated glass substrate of FIGS. 1 & 2;
  • FIG. 6 is a schematic view of a portion of the treatment apparatus of FIG. 5 showing portions of a nozzle and a cover positioned over the nozzle;
  • FIG. 7 is a top view of an aperture plate comprising the cover of FIG. 6;
  • FIGS. 8 A and 8B are top and side views, respectively, of a flow modifier that can be used with the treatment apparatus of FIG. 5 ;
  • FIG. 9 is a top view of another exemplary flow modifier that can be used with the treatment apparatus of FIG. 5 comprising an angled wall portion
  • FIG. 10A is a top view of still another embodiment of an exemplary flow modifier that can be used with the treatment apparatus of FIG. 5
  • FIG. 10B is a side cross-sectional view of the flow modifier of FIG. 10A;
  • FIG. IOC is an alternative embodiment of the flow modifier of FIGS. 10A and 10B, wherein a height of the flow modifier is less than a distance from the nozzle to the glass substrate;
  • FIG. 11 A is a side view of another exemplary flow modifier that can be used with the apparatus of FIG. 5;
  • FIG. 1 IB is a side view of the flow modifier of FIG. 11A;
  • FIG. 12A is a top view of another exemplary embodiment of a flow modifier that can be used with the treatment apparatus of FIG. 5 comprising a plug portion inserted into an inlet channel of the nozzle;
  • FIG. 12B is a side cross-sectional view of the flow modifier of FIG. 12A;
  • FIG. 13 is an alternative embodiment of the flow modifier of FIGS. 12A and 12B; and [0047] FIGS. 14A-14D are cross-sectional views of glass substrate 20 as the glass substrate progresses through an etching zone of the treatment apparatus of FIG. 5.
  • substrates of the present disclosure may be configured for manufacturing a flat panel display device such as a liquid crystal display (LCD), light emitting diode (LED) display or an organic light emitting diode (OLED) display.
  • a flat panel display device such as a liquid crystal display (LCD), light emitting diode (LED) display or an organic light emitting diode (OLED) display.
  • LCD liquid crystal display
  • LED light emitting diode
  • OLED organic light emitting diode
  • glass substrate or “glass” used herein is understood to encompass any object made wholly or partly of glass. Glass substrates include monolithic substrates, or laminates of glass and glass, glass and non-glass materials, glass and crystalline materials, and glass and glass-ceramic materials (a glass-ceramic material includes an amorphous phase and a crystalline phase).
  • a substrate such as a glass substrate
  • Substrates may be flat or curved and can be transparent or substantially transparent.
  • the term “transparent” denotes the substrate, at a thickness of approximately 1 millimeter (mm), has an optical transmission greater than about85% inthevisible region of the spectrum (400-700 nanometers).
  • an exemplary transparent glass substrate may have greater than about 85% transmittance in the visible light range, such as greater than about 90%, greater than about 95%, or greater than about 99% transmittance, including all ranges and subranges therebetween.
  • an exemplary substrate may have a transmittance of greater than about 50% in the ultraviolet (UV) region (100-400 nm), such as greater than about 55%, greater than about 60%, greater than about 65%, greater than about 70%, greater than about75%, greater than about 80%, greater than about 85%, greater than about 90%, greater than about 95%, or greater than about 99% transmittance, including all ranges and subranges therebetween.
  • UV ultraviolet
  • Exemplary glass substrates disclosed herein can comprise, but are not limited to, aluminosilicate glass, alkali-aluminosilicate glass, borosilicate glass, alkali-borosilicate glass, aluminoborosilicate glass, alkali-aluminoborosilicate glass, and other suitable glasses.
  • Non- limiting examples of available glasses suitable for use as a glass substrate in accordance with the present disclosure can include, for instance, LOTUSTM NXT, IRISTM, GORILLA ® , ASTRATM and Eagle XG ® glasses from Corning Incorporated. While various principles and teachings of the present disclosure may be used in connection with other types of glass substrates, the glass substrate can be an alkaline earth boroaluminosilicate fusion drawn glass such as, LOTUSTM NXT glass from Corning Incorporated.
  • Thin glass substrates used inflatpaneldisplays canhaveafunctionalA-sidesurface.
  • Thin- film transistors can be fabricated on the functional A-side surface.
  • the glass substrate can further include a non-functional B-side surface opposite the A-side surface.
  • the B-side surface of the glass substrate may come into contact with conveyance and/or handling equipment.
  • conveyance and/or handling equipment can be made of various materials including, for example, metals, ceramics, polymeric materials, and the like. Interaction between these various types of dissimilar materials and the glass substrate can result in electrostatic charging of the glass substrate through the triboelectric effect or contact electrification.
  • the triboelectric effect can occur when certain materials become electrically charged after they are separated from another material in which 1hey were in contact. For example, rubbing two materials together (e.g., glass with fur) can increase contact between their surfaces, thereby increasing electrical charging.
  • Contact charging can occur by conduction of charge from a first object to another object in which the first object is in contact with. In either instance, electrical charge can accumulate on the surfaces of the glass substrate. As the charge accumulates on the glass surfaces, the surface voltage of the glass substrate can also change.
  • the accumulation of charge on one or more surfaces of the glass substrate by whatever means, can be termed electrostatic charging (ESC).
  • Electrostatic charging of the B-side surface of the glass substrate can be undesirable because electrostatic charging can degrade certain performance characteristics of the glass substrate and/or damage the glass substrate or electronic devices deposited on the glass substrate.
  • electrostatic charging of the B-side of the glass substrate can cause gate damage to thin film transistor (TFT) devices that may be deposited on the A-side (or functional) surface of the glass substrate.
  • TFT thin film transistor
  • Such gate damage can be caused through dielectric breakdown and/or electric field-induced charging.
  • Electrostatic charging of the glass substrate can also be undesirable because such charging can attract particles, such as dust or other contaminants to the glass surface. This attraction and/or accumulation of particulate debris can damage the glass substrate or degrade the surface quality of the glass substrate.
  • the B-side surface of the glass substrate canbe etched using one or more of the methods described below to change the surface topography of the B-side surface and change the surface chemistry in one or more regions on the B-side surface.
  • a changed surface topography and a change in chemistry in one or more surface layers of the B-side surface can reduce electrostatic charge accumulation on the B-side surface.
  • a change in surface topography and/or a change in chemistry can also reduce friction between the glass substrate and handling and/or conveyance equipment used during processing of the glass substrate.
  • a reduction in friction can reduce wear on such equipment. This reduction in wear can increase the service life of the handling and/or conveyance equipment and can decrease the required maintenance to such equipment. This, in turn, can increase process up-time, increase manufacturing yields, and reduce costs for the overall flat panel display manufacturing process.
  • glass substrate 20 can be formed using a fusion drawing process.
  • molten material is supplied to a forming body comprising an open channel in an upper surface of the forming body and converging exterior forming surfaces that join along a bottom edge of the forming body.
  • the molten material (e.g., “molten glass”) is supplied to the channel and overflows the channel along opposing sides.
  • the separate streams of molten material meet at the bottom edge of the forming body to form a ribbon of molten material that cools and solidifies into a glass ribbon.
  • the glass ribbon can be cut-to-length to provide glass substrates of desired length.
  • glass substrate 20 can be formed using any suitable glass fabrication process, for example a floatprocess, a slot draw process, or a redraw process.
  • a float process the molten material is supplied to a container comprising, for example, a molten tin bath.
  • the molten material spreads on the molten tin bath and is drawn forward along the length of the bath into a ribbon, cooling as it moves forward.
  • the resultant ribbon is further moved into and through a cooling lehr where the ribbon continues to cool into a glass ribbon.
  • the glass ribbon can be cut into desired lengths.
  • a glass preform for example a glass sheet
  • a glass ribbon with a thickness less than a thickness of the preform.
  • the resultant glass ribbon can be cut into a glass substrate of desired length.
  • the glass substrate 20 can include a first side 22 (A-side).
  • First side 22 can be the side of glass substrate 20 on which thin-film transistors (TFT) can be fabricated.
  • Glass substrate 20 can also include a second side 24 (B-side) opposite first side 22.
  • Second side 24 is the side of glass substrate 20 that may come into contact with one or more pieces of conveyance or handling equipment during the processing and/or fabrication of a flat panel display.
  • Glass substrate 20 can be treated with a treatment fluid to cause second side 24 to have one or more characteristics that result in reduced electrostatic charging when compared to an untreated glass substrate or when compared to a glass substrate treated with traditional surface treatments.
  • the treatment fluid can be an etchant that etches the second side of the glass substrate.
  • One such characteristic changed using one or more etching processes of the present disclosure is a surface composition of second side 24 of glass substrate 20.
  • the chemical composition of secondside24 canbemeasuredusing any suitable technique to one or more depths from an external surface 26 of second side 24.
  • Such techniques can measure the surface composition of second side 24 of one or more compositional elements (or a ratio thereof) that can be expressedas an average value of the compositional element (or ratio of elements) from the external surface 26 to a particular depth.
  • Example techniques can include time-of-flight secondary ion mass spectrometry (TOF-SIMS) and x-ray photoelectron spectroscopy (XPS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • XPS x-ray photoelectron spectroscopy
  • measurements may be described in the present disclosure as “to” a particular depth.
  • the surface composition of second side 24 can be measured to a first depth D1 from external surface 26.
  • the surface composition of second side 24 can also be measured to a second depth D2 from external surface 26.
  • the surface composition of second side 24 can be measured to a first depth D1 of about 1 nanometer (nm)andto a second depth D2 of about 10 nm.
  • first depth D1 and second depth D2 can be other depths measured from external surface 26.
  • Etching processes of the present disclosure may cause the chemical composition for some elements present in the glass substrate 20 to be different at first depth D1 than at second depth D2.
  • the chemical composition may be the same or substantially the same to first depth D 1 and to second depth D2.
  • the surface composition of second side 24 can be measured to determine its aluminum/silicon (Al/Si) ratio.
  • This ratio can be determined using any suitable technique such as time-of-flight secondary ion mass spectrometry (TOF-SIMS), x-ray photoelectron spectroscopy (XPS), or x-ray fluorescence (XRF).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • XPS x-ray photoelectron spectroscopy
  • XRF x-ray fluorescence
  • TOF- SIMS time-of-flight secondary ion mass spectrometry
  • XPS x-ray photoelectron spectroscopy
  • Such techniques can be used to measure the surface chemical composition of second side 24 at first depth D1 and at second depth D2.
  • the surface chemical composition of second side 24 after treatment with etching processes of the present disclosure can be compared to a chemical composition of second side 24 in which no treatment has been made. In such a manner, the difference between the chemical compositions of the treated versus untreated second sides 24 can be measured.
  • second side 24 after treatment can have a chemical composition with an Al/Si ratio in a range from about 38% to about 42% of a chemical composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and a Al/Si ratio in a range from about 71% to about 73% of a chemical composition of an untreated glass substrate 20 to a second depth D2 of 10 nm.
  • treated second side 24 can have a chemical composition with an Al/Si ratio in a range from about 35% to about 45% of a chemical composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and an Al/Si ratio in a range from about 70% to about 74% of a chemical composition of an untreated glass substrate 20 to a second depth D2 of 10 nm.
  • treated second side 24 can have a chemical composition with an Al/Si ratio in a range from about 30% to about 50% of a surface composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and an Al/Si ratio in a range from about 65% to about 75% of a chemical composition of an untreated glass substrate 20 to a second depth D2 of 10 nm.
  • a chemical composition of second side 24 can be measured to determine its magnesium/silicon (Mg/Si) ratio.
  • the Mg/Si ratio can be measured using one or more of the techniques described above with respect to the Al/Si ratio.
  • Treated second side 24 can have a chemical composition with a Mg/Si ratio in a range from about 72% to about 81% of a surface composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and a Mg/Si ratio in a range from about 72% to about 81 % of a chemical composition of an untreated glass substrate 20 to a second depth D2 of 10 nm.
  • the Mg/Si ratio can be substantially the same at first depth D 1 of 1 nm and at second depth D2 of 10 nm.
  • treated second side 24 can have a chemical composition with a Mg/Si ratio in a range from about 70% to about 83% of a chemical composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and to a second depth D2 of 10 nm.
  • treated second side 24 can have a chemical composition with a Mg/Si ratio in a range from about 65% to about 88% of a chemical composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and to a second depth D2 of 10 nm.
  • the chemical composition of treated second side 24 can be measured to determine its calcium/silicon (Ca/Si) ratio.
  • the Ca/Si ratio can be measured using one or more of the techniques described above with respect to the Al/Si ratio.
  • Treated second side 24 can have a chemical composition with a Ca/Si ratio in a range from about 33% to about 34% of a chemical composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and a Ca/Si ratio in a range from about 77% to about 99% of a chemical composition of an untreated glass substrate 20 to a second depth D2 of 10 nm.
  • treated second side 24 can have a chemical composition with a Ca/Si ratio in a range from about 31 % to about 35% of a chemical composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and a Ca/Si ratio in a range from about 75% to about 99% of a chemical composition of an untreated glass substrate 20 to a second depthD2 of 10 nm.
  • treated second side 24 can have a surface composition with a Ca/Si ratio in a range from about 30% to about 36% of a surface composition of an untreated glass substrate 20 to a first depth D1 of 1 nm and a Ca/Si ratio in a range from about 72% to about 99% of a surface composition of an untreated glass substrate 20 to a second depth D2 of 10 nm.
  • the surface composition of second side 24 can also be measured to determine a concentration of fluorine (F) at one or more depths. The measurement techniques described above can be used to determine the concentration of F in the chemical composition of treated second side 24.
  • the concentration of fluorine (F) at treated second side 24 at first deplh D1 of 1 nm can be in a range from about 290% to about 330% of a concentration of F in an untreated glass substrate 20.
  • the concentration of F at second side 24 at the first depth D1 of 1 nm can be in a range from about 270% to about 350% of a concentration of F in an untreated glass substrate 20.
  • the surface compositions are described separately but it should be appreciated that the surface composition of second side 24 can have more than one or all of the characteristics described above.
  • the chemical composition of second side 24 can have one or all of the Al/Si ratio, the Mg/Si ratio, the Ca/Si ratio and F concentration described above.
  • the chemical composition of second side 24 can have a AFSi ratio in a range from about 38% to about 42%, a Mg/Si ratio in a range from about 72% to about 8%, and a Ca/Si ratio in a range from about 33% to about 34% of a chemical composition of an untreated glass substrate to a first depth of 1 nm and a Al/Si ratio in a range from about 71% to about 73%, a Mg/Si ratio in a range from about 72% to about 81%, and a Ca/Si ratio in a range from about 77% to about 99% of an untreated glass substrate to a second depth of 10 nm.
  • This same example can also have a F concentration in a range from about 290% to about 330% of a surface concentration of the untreated glass substrate.
  • Etching processes of the present disclosure may also cause second side 24 to have a predetermined topography.
  • a topography of second side 24 after treatment (etching) can be greater than a topography of first side 22.
  • treated second side 24 can have an average surface roughness value Ra in range from about 0.6 nanometers to about 1.0 nm.
  • Surface topography may be represented by other characteristic values as well, such as an average area roughness Sa, correlation length, skewness, kurtosis, etc.
  • treated second side 24 can have an average roughness value Ra in a range from about 0.5 nanometers to about 1.2 nanometers.
  • other suitable topography values can also be produced.
  • the topography can be measured to determine the above ranges using any suitable technique including a profilometer or the like.
  • Etching processes of the present disclosure and the accompanying changes to surface chemical compositions and/or topography of second side 24 can result in reduced electrostatic charging.
  • the treated glass substrates can have at least a 50% reduction in accumulated voltage over that of untreated glass substrates.
  • the treated glass substrates can have at least a 60% reduction in voltage over that of untreated glass substrates.
  • the treated glass substrates can have at least a 65% reduction in voltage over that of untreated glass substrates.
  • etching processes of the present disclosure do not result in adverse effects on glass substrate 20. Some etching processes can result in the treated glass substrate having an unacceptable amount of haze to the treated glass substrate. Etching processes of the present disclosure do not result in an excessive amount of haze to the treated glass substrate. That is, the etching processes do not impart haze that would negatively result in the use of the glass substrate in a flat panel display.
  • FIG. 3 illustrates one example method 100 of processing a glass substrate using the principles and teachings of the present disclosure.
  • the glass substrate can be produced using any suitable method.
  • the glass substrate can be formed using a fusion drawing process.
  • the glass substrate can be any suitable glass substrate for use in a flat panel display previously described.
  • the glass substrate for example, can be an alkaline earth boro -aluminosilicate glass such as Coming’s LotusTM NXT glass.
  • the glass substrate can be pre-heatedto a predetermined etching temperature. Any suitable oven or heating source can be used at step 102 to heat the glass substrate to the predetermined etching temperature.
  • the predetermined etching temperature can be, for example, in a range from about 20C to about lOOC, such as in a range from about 45°C to about 50°C.
  • the glass substrate can be etched using one of the etching processes of the present disclosure as will be further described below. In one example, the etching process at step 104 can utilize an HF gas mixture to etch second side 24 of glass substrate 20.
  • precursor materials CF andH 2 0 e.g., water vapor
  • precursor materials CF andH 2 0 can be exposed to ionizing energy, e.g., via a plasma generator, wherein the resultant HF gas mixture can be used to produce glass substrate 20 with the characteristics of second side 24 previously described.
  • first side 22 of the heated glass substrate can be exposed to air while exposing second side 24 of the heated glass substrate to the HF gas mixture to etch second side 24 of glass substrate 20 and change a chemical composition of the second side to form a treated glass substrate.
  • the HF gas produced during the ionizing energy exposure can be combined wilh a carrier gas, for example an inert gas like argon, and the resultant gaseous mixture directed against second side 24 to etch the second side.
  • a carrier gas for example an inert gas like argon
  • a gas mixture comprising HF gas is referred to as an HF gas mixture. Air provided to or directed toward or against second side 24 can help reduce or prevent the HF gas mixture from etching first side 22.
  • the glass substrate can be rinsed and dried. Any suitable rinsing and drying process can be used.
  • FIG. 4 illustrates an example method 200 for etching a glass substrate 20.
  • the method 200 details one or more steps that may occur during step 104 of method 100.
  • the treatment apparatus 300 depicted in FIG. 5 can be used during one or more steps of the method 200 as will be described. However, FIGS. 4 and 5 are discussed together for illustration purposes only. The method 200 and the treatment apparatus 300 illustrated in FIGS. 4 and 5, respectively, can be used in embodiments other than the specific example described herein.
  • an HF gas can be generated by one or more generators, for example a plasma generator, e.g., an atmospheric pressure plasma generator.
  • two or more generators can be fluidly coupled downstream of the generators to mix the separate HF gas streams produced by the multiple generators and inject a carrier gas.
  • Suitable carrier gasses can comprise inert gases, including, for example, nitrogen, helium, neon, argon, krypton, xenon, and/or radon.
  • the HF gas e.g. , HF gas mixture
  • the HF gas can contactthe glass substrate in the etching zone.
  • the etching zone can be configured, for example, to cause second side 24 of glass substrate 20 to be contacted by the HF gas (e.g., HF gas mixture) to cause changes to the chemical composition and/or the topography of the surface while preventing or limiting a substantial amount of the HF gas mixture from contacting first side 22 of glass substrate 20, as will be described more fully below.
  • the HF gas e.g., HF gas mixture
  • second side 24 undergoes the changes previously described while first side 22 is largely unimpacted by the HF gas mixture such that first side 22 remains suitable for the fabrication of thin-film transistors used to fabricate a flat panel display.
  • the HF gas mixture can be removed from the etching zone.
  • etching zone can be in fluid communication with an exhaust channel through which the HF gas mixture can be drawn from the etching zone and away from the glass substrate.
  • the HF gas mixture can be circulated through the etching zone (and in contact with the glass substrate) to cause the etching of the glass substrate to occur.
  • HF gas mixture exit data can be collected from the HF gas mixture removed from the etching zone.
  • Any suitable sensor or data processing equipment can be used.
  • FT-IR Fourier-transform infrared
  • spectrometer can be used to collect and process data about characteristics of the HF gas mixture exiting the etching zone. This data and/or other information can be used to monitor the process and adjust gaseous flow rates, the HF gas mixture (e.g. , concentration), the conveyance speed of the glass substrate or other process attributes.
  • method 200 can include other steps as well. Such additional steps may include collecting data at other points in the process or scrubbing or otherwise processing the HF gas mixture that may exit the etching zone.
  • the steps of method 100 and/or method 200 may be performed by a computer-implemented program or other processing device. Data collection and analysis can also be output to a screen (display) or other output device.
  • the methods and systems described herein may be at least partially embodied in the form of computer-implemented processes and apparatus for practicing those processes.
  • the disclosed methods may also be at least partially embodied in the form of tangible, non-transient machine-readable storage media encoded with computer program code.
  • the media may include, for example, RAMs, ROMs, CD-ROMs, DVD-ROMs, BD-ROMs, hard disk drives, flash memories, or any other non-transient machine-readable storage medium, or any combination of these mediums, wherein, when the computer program code is loaded into and executed by a computer, the computer becomes an apparatus for practicing the method.
  • the methods may also be at least partially embodied in the form of a computer into which computer program code is loaded and/or executed, such that the computer becomes an apparatus for practicing the methods.
  • the computer program code segments configure the processor to create specific logic circuits.
  • the methods may alternatively be at least partially embodied in a digital signal processor formed of application specific integrated circuits for performing the methods.
  • FIG. 5 illustrates an example treatment apparatus 300 for treating glass substrate 20, for example etching glass substrate 20.
  • treatment apparatus 300 can comprise heating chamber 302, etching chamber 304, and rinsing chamber 306.
  • Treatment apparatus 300 can be used, in various embodiments, in performing the methods 100 and 200 previously described.
  • Treatment apparatus 300 may further comprise a conveyor 307 configured to convey glass substrate 20 through treatment apparatus 300 along conveyance path 310 in conveyance direction 312.
  • conveyor 307 may comprise one or more conveyance rollers configured to convey substrate 20 along conveyance path 310.
  • other suitable conveyance devices may be used.
  • heating chamber 302 can comprise one or more heating elements 314, f or example electrical resistance heating elements, in electrical communication with a suitable electrical power source (not shown).
  • heating elements 314 can heat glass substrate 20 to a predetermined temperature.
  • glass substrate 20 can be heated to a temperature in a range from about 30°C to about 100°C, for example from about 35C to about 65C or from about 40C to about 55C.
  • etching chamber 304 can one or more comprise nozzles 316 configured to direct a treatment fluid, e.g., a treatment gas, toward glass substrate 20 as glass substrate 20 is conveyed through etching chamber 304.
  • nozzle 316 can be in fluid communication with generator 318.
  • Generator 318 can be any suitable generator, such as a plasma generator, for reacting HF precursor materials, such as CF 4 and H 2 0, to produce HF gas 320.
  • Other suitable precursor materials can include C2H6, C 3 F 8 , CHF 3 , SF 6 , CeF ⁇ , and/or CgF ⁇ .
  • generator 318 can be an atmospheric-pressure plasma generator.
  • Nozzle 316 can comprise an inlet channel 322 configured to direct the treatment fluid into an etching zone 324 of etching chamber 304 and an exhaust channel 326 configured to evacuate the treatment fluid from etching zone 324 and etching chamber 304.
  • Generator 318 can be in fluid communication with inlet channel 322 through suitable piping formed with a material selected to not react with the HF gas.
  • the piping can comprise, for example, a fluoropolymer or PVC/C-PVC (polyvinyl chloride) material.
  • Inlet channel 322 provides a passage through which HF gas 320, mixed with a carrier gas from carrier gas source 327, at mixing chamber 328 for example, to move from generator 318 into nozzle 316.
  • the resultant HF gas mixture 330 after leaving nozzle 316 (e.g., inlet channel 322) can contact glass substrate 20 (e.g., second side 24) as the glass substrate is conveyed through etching chamber 304 in conveyance direction 312.
  • two or more generators 318 may be used, wherein the HF gas produced by the two or more generators is mixed in mixing chamber 328 before passingto nozzle 316.
  • treatment apparatus 300 may comprise two or more generators 318 and two or more nozzles 316.
  • the two or more nozzles 316 may be identical nozzles. Accordingly, only one nozzle description is provided below.
  • glass substrate 20 can be positioned within (e.g., move through) etching chamber 304 such that second side 24 of glass substrate 20 is located opposite (facing) inlet channel 322.
  • the HF gas mixture can contact second side 24 of glass substrate 20 when HF gas mixture 330 flows into etching zone 324.
  • HF gas mixture 330 can be removed from etching zone 324 through exhaust channel 326.
  • a vacuum can be applied at exhaust channel 326 to cause HF gas mixture 330 to flow from inlet channel 322 through etching zone 324 and out exhaust channel 326.
  • the HF gas mixture exhausted through exhaust channel 326 can be directedto a containment and/or processing apparatus, for example a pollution abatement apparatus 332 configured to remove environmentally-undesirable materials (e.g., HF gas) from the exhausted HF gas mixture.
  • a pollution abatement apparatus 332 configured to remove environmentally-undesirable materials (e.g., HF gas) from the exhausted HF gas mixture.
  • glass substrate 20 can be supported in etching zone 324 by rollers 334.
  • Rollers 334 can be positioned at opposite ends of etching zone 324 and can seal the ends of etching zone 324 to limit or preventHF gas mixture 330 from escapingthe etchingzone.
  • the portion of second side 24 between rollers 334 is exposed to HF gas mixture 330 without being supported or without having other intermediate members contacting second side 24. Such a configuration can result in consistent etching and consistent surface characteristics of second side 24.
  • Treatment apparatus 300 can be configured to limit or prevent first side 22 of glass substrate 20 from being exposed to a significant amount of HF gas mixture 330. While second side 24 is exposed to HF gas (via HF gas mixture 330) in a first portion of etching zone 324 below glass substrate 20 (e.g., B-side etching zone 324b), first side 22 of glass substrate 20 can be exposed to air in a second portion of etchingzone 324 above glass substrate 20 (e.g., A-side etching zone324a).
  • HF gas mixture 330 can be limited from moving from B-side etchingzone 324bto A-side etching zone 324a, as will be described in more detail below.
  • exhaust channel 326 can be placed in fluid communication with detector 336.
  • Detector 336 can be any suitable sensor and/or data collection or analyzer unit.
  • detector 336 can be aFourier-transform infrared (FT-IR) spectrometer which can be usedto collect and process data about the characteristics of the HF gas mixture that exits etching zone 324.
  • FT-IR Fourier-transform infrared
  • other sensors or data collection units can be used.
  • HF gas 320 produced by the reaction of CF and H 2 0, e.g. , water vapor, in an etching chamber to etch second side 24 (B-side) of glass substrate 20.
  • HF gas mixture 330 comprisingHF gas 320 is mixed wilh a carrier gas, for example an inert carrier gas, enters etching zone 324 and can, in some instances initially contact both first side 22 and second side 24 of glass substrate 20 as the glass substrate enters etching zone 324. This temporarily exposes first side 22 to HF gas mixture 330, but may potentially etch second side 24, which is not desired.
  • treatment apparatus 300 may further comprise a cover 340 positioned to be over, e.g., proximate to, first side 22, opposite nozzle 316.
  • etching zone 324 is defined between nozzle 316 and cover 340.
  • Cover 340 can comprise an aperture plate 342 defining a plurality of apertures 344 extending through a thickness 345 of the aperture plate and through which air 346, e.g., clean dry air, can be flowed into etching zone 324 (see FIG. 6).
  • the thickness of the aperture plate is defined in a direction orthogonal with at least one major surface of the aperture plate.
  • Aperture plate 342 may be formed, for example, from a fluoropolymer or PVC/C-PVC (polyvinyl chloride) material to provide resistance to HF exposure.
  • Cover 340 may further comprise a filter to provide for reduced contamination of supplied air 346.
  • Filter 348 may be a layer of cover 340 positioned above aperture plate 342.
  • filtered air may be supplied through a common plenum.
  • the presence of a filter just above the aperture plate helps provide uniform distribution of the air, which may not be possible if the air is supplied through a common plenum.
  • cover 340 can be arranged into aperture zones 350, wherein apertures 344 in each aperture zone can be supplied through an individual control valve 352 controlled by a controller (not shown) such lhat the flow of air through cover 340 in each aperture zone can be independently controlled.
  • the aperture zones can be separated by walls (along the thickness direction), with individual filters in each zone controlled by a separate valve to provide better control.
  • Filter 348 can comprise a high efficiency particulate air (HEP A) filter configured such that equal or greater than about 99.95% of particles larger than about 0.3 micrometers (e.g., in accordance with European Standard EN 1822-1 :2009), for example equal to or greater than about 99.97% (e.g., in accordance with A8ME AG-1 a-2004), are removed from air 346 supplied to cover 340 and prevented from flowing through aperture plate 342, although in further embodiments, depending on need, filter 348 can be configured to remove particles equal to or greater than about 1 micrometer may be used.
  • HEP A high efficiency particulate air
  • Apertures 344 can be arranged, for example, in two-dimensional arrays, e.g., rows and columns, with periodic (e.g., uniform) spacing between adjacent apertures (i.e., nearest neighboring apertures).
  • the apertures can be conical in a direction of the thickness of the aperture plate (between a first major surface of the aperture plate and a second major surface of the aperture plate).
  • apertures 344 can be uniformly distributed such that spacing between adjacent apertures in the rows of an aperture zone can be equal to the spacing between adjacent apertures in columns of apertures in the aperture zone. In other embodiments, however, apertures of an aperture zone can be randomly distributed.
  • Spacing between adjacent apertures in an aperture zone can be in a range from about 3 millimeters to about 25 millimeters depending on the desired flow of air through the apertures, for example in a range from about 4 millimeters to about 22 millimeters, in a range from about 5 millimeters to about 18 millimeters, in a range from about 6 millimeters to about 12 millimeters, or in a range from about 6 millimeters to about 10 millimeters.
  • the apertures 344 of one aperture zone 350 can be arranged differently than the apertures 344 in another aperture zone 350. That is, aperture plate 342 may comprise a firstplurabty of apertures anda second plurality of apertures, wherein sizes and spacing of apertures 344 of the firstplurabty of apertures are different than the size and spacing of apertures 344 of the second plurality of apertures. In various embodiments, there can be more than two aperture zones, for example three aperture zones, four aperture zones, five aperture zones, six aperture zones, seven aperture zones, eight aperture zones, nine aperture zones, or ten aperture zones. In some embodiments, there can be greater than ten aperture zones. In some embodiments, each aperture zone 350 can have apertures of a uniform diameter.
  • all apertures 344 in a specific aperture zone 350 can be of equal diameter.
  • all apertures 344 of all aperture zones 350 can be of equal diameter.
  • apertures 344 may be of unequal diameter.
  • the diameter of apertures 344 comprising a certain aperture zone 350 may be of differing diameter.
  • apertures 344 of a given aperturezone 350 may be of uniform diameter but may differ from the diameter of apertures 344 of a different aperture zone 350.
  • Aperture diameter in any of the preceding embodiments can be in a range from about 0.5 millimeters to about 10 mm, such as in a range from about 1 millimeter to about 8 millimeters, or in a range from about 2 millimeters to about 8 millimeters.
  • the flow rate (volume of air per unit time) and flow velocity of air 346 supplied to individual aperture zones 350 through control valves 352 can be controlled depending on the process conditions.
  • the providing of air to A-side etching zone 324a can be performed in multiple modes during glass etching.
  • air flow can be turned ON (by activating one or more control valves 352) as glass substrate 20 enters etching zone 324. This causes a flow of air from cover 340 that mixes with HF gas mixture 330 present in etching zone 324.
  • cover 340 that mixes with HF gas mixture 330 present in etching zone 324.
  • etching zone 324 When glass substrate 20 is at nozzle 316, bifurcating etching zone 324 into A-side and B-side etching zones 324a, 324b, some of HF gas mixture 330 can migrate to the A-side etching zone, which HF gas mixture is diluted by the flow of air 346 from aperture plate 342.
  • Air 346 supplied to aperture plate 342 can also be turned ON after glass substrate 20 has just covered nozzle 316 as well, thereby diluting HF gas mixture that may have migrated to A-side etching zone 324a. In other words, as the glass leading edge moves into the etching zone/chamber, the leading edge first covers the exhaust on the B-side and then proceeds to cover the nozzle inlet (where HF flows in to meet the glass B-side surface).
  • the gas turn ON sequence can be based on when the glass reaches the inlet and fully covers the nozzle (inlet and exhaust). In other embodiments, the gas can be turned ON just before the glass moves in to the nozzlearea. Since the control of airflowto aperture plate 342 can be divided into multiple aperture zones 350, flow of air 346 can be controlled more effectively, thereby facilitating processing multiple sizes of glass substrates.
  • HF gas mixture flow from inlet channel 322 to exhaust channel 326 can depend on the position of glass substrate 20 in etching zone 324. As glass substrate 20 enters etching zone 324, the glass substrate encounters HF gas mixture 330 on both sides (first and second sides 22, 24) as the etching zone is typically filled with HF gas mixture. This is because nozzle 316 is typically always ON and HF gas mixture 330 is flowing therethrough. HF gas mixture 330 from inlet channel 322 will flow toward exhaust channel 326 while also filling etching zone 324. Ambient air within etching zone 324 is also drawn toward exhaust channel 326.
  • HF gas mixture 330 is in contact wilh both sides of the glass substrate.
  • Cover 340 can be turned ON (control valves 352 activated so that air flows through the control valves) right before glass substrate 20 enters etching zone 324. Once the glass substrate enters etching zone 324, air 346 provided through cover 340 further dilutes HF gas in A-side etching zone 324a above and proximate to first side 22 causing little or no reaction on first side 22 of glass substrate 20.
  • the timing of air introduction to etching zone 324 (e.g., A-side etching zone 324a) through cover 340 can be controlled to occur either just before glass substrate 20 enters etching zone 324 or when the glass substrate just covers exhaust channel 326.
  • a flow velocity of the supplied air 346 can range, for example, from about 0.01 millimeters/second to about 100 millimeters/second, depending on desired air volume.
  • the total air flow rate into cover 340 can also vary, for example, in a range from about 10 liters/minute to about 300 liters/minute.
  • treatment apparatus 300 may further comprises a flow modifier configured to redirect HF gas mixture 330 from inlet channel 322 to exhaust channel 326.
  • a flow modifier configured to redirect HF gas mixture 330 from inlet channel 322 to exhaust channel 326.
  • FIGS. 8 A and 8B illustrate an exemplary flow modifier 400 configured to reduce or eliminate migration of HF gas mixture 330 from B-side etching zone 324b to A-side etching zone 324a.
  • flow modifier 400 can comprise a first wall portion 402 extending from inlet channel 322 to exhaust channel 326. Indeed, first wall portion 402 can extend over both the inlet channel and the exhaust channel.
  • Flow modifier 400 may further comprise end wall portions 404 extending from ends of first wall portion 402 in a direction away from glass substrate 20.
  • end wall portions 404 may extend orthogonal to first wall portion 402.
  • flow modifier 400 is of a straight configuration. That is, first wall portion 402 can be linear between inlet channel 322 and exhaust channel 326 and extend parallel with conveyance direction 312.
  • Flow modifier 400 can be placed in close proximity to side edge 406 of glass substrate 20 such thatHF gas mixture flow to the space 408 outside flow modifier 400 (e.g., on the side of flow modifier 400 opposite glass substrate 20) does not enter the space containing glass substrate 20, e.g., etching zone 324.
  • Side edge 406 extends parallel with conveyance direction 312.
  • Flow modifier 400 can extend the entire distance from the top (upper-most) surface 410 of nozzle 316 to the bottom surface 412 of cover 340 (e.g., bottom surface of aperture plate 342). Accordingly, the space 408 on the side of the flow modifier opposite glass substrate 20 can be physically blocked off from the space on the side of first wall portion 402 adjacent glass substrate 20 (e.g.
  • Flow modifier 400 can be formed, for example, from any fluoro-polymer that can withstand the effects of HF gas.
  • a thickness 413 of first wall portion 402 defined orthogonally between opposing faces of first wall portion 402 can vary based on need and design. For example, in some embodiments, thickness 413 of first wall portion 402 can be in a range from about 3 millimeters to about 10 millimeters, although in further embodiments, the thickness of first wall portion 402 may be greater than 10 millimeters. In FIG.
  • the space 408 to the left of flow modifier 400 is physically separated from the space 414 to the right of the flow modifier, ensuring gas from the left side space 408 of flow modifier 400 does not enter the space 414 on the right side of the flow modifier.
  • the gap 416 between side edge 406 and flow modifier 400 should be as small as possible to prevent contact between the flow modifier and the glass substrate (see FIG. 8B). In some embodiments, gap 416 can be in a range from about 0.5 to about 2 millimeters. Contact between flow modifier 400 and glass substrate 20 while glass substrate 20 is conveyed through etching zone 324 can damage the glass substrate, for example chip or crack side edge 406.
  • gap 416 can vary along conveyance direction 312, e.g., increases in a direction from inlet channel 322 toward exhaust channel 326. Expansion of gap 416 in a direction toward exhaust channel 326 from inlet channel 322 can provide a better flow of HF gas mixture 330 from inlet channel 322 to exhaust channel 326 and can reduce seepage of HF gas mixture 330 from inlet channel 322 to A-side etching zone 324a and subsequent contact with first side 22 of glass substrate 20.
  • first wall portion 402 comprising a plurality of wall segments, e.g., wall segments 402a and 402b, and a single end wall portion 404.
  • a second flowmodifier 400 can be positioned proximate an opposing side edge of glass substrate 20.
  • treatment apparatus 300 may comprise a flow modifier 500, as shown in FIGS. 10 A and 10B, to aid in redirecting the flow of HF gas mixture 330 from inlet channel 322 to exhaust channel 326 and reduce or prevent migration of HF gas mixture 330 from B-side etching zone 324b to A-side etching zone 324a.
  • Flow modifier 500 can comprise a first wall portion 502 extending proximate side edge 406, for example parallel with conveyance direction 312.
  • Flow modifier 500 may further comprise a second wall portion 504 spaced apart from first wall portion 502 in a direction away from glass substrate 20.
  • second wall portion 504 may be parallel with first wall portion 502.
  • Flow modifier 500 may still further comprise a third wall portion 506 extending between first wall portion 502 and second wall portion 504.
  • third wall portion 506 may extend between and connect ends of first wall portion 502 and second wall portion 504.
  • first wall portion 502, second wall portion 504, and third wall portion 506 can form a U-shape, wherein first wall portion 502 and second wall portion 504 are spaced apart and parallel with conveyance direction 312, and third wall portion 506 is orthogonal to first and second wall portions 502, 504. Accordingly, flowmodifier500canformaflowchannel508thatdirectsHF gas mixture 330 flowing from inlet channel 322 adjacent side edge 406 to exhaust channel 326.
  • the height 512 (see FIG.
  • flow modifier 500 can be such that it can extend from upper-most surface 410 of nozzle 316 to the bottom surface 412 of aperture plate 342. In this configuration flow modifier 500 will be on the outside of side edge 406, with a gap 516 between the flow modifier and the edge of the glass substrate 20 to prevent interference between flow modifier 500 and the glass substrate.
  • Nozzle 316 may further compriserollers 518 configured to support glass substrate 20 as the glass substrate passes through etching zone 324. For example, rollers 518 can be arranged to contact only edge portions of the glass substrate as the glass substrate traverses along conveyance path 310.
  • flow modifier 500 may be configured with a covering wall portion extending over at least a portion of inlet channel 322 and a portion of exhaust channel 326, for example portions of the inlet channel and the exhaust channel that extend outside side edge 406.
  • flowmodifier 500 in alternative embodiments may include first wall portion 502, second wall portion 504 (not shown in FIG. IOC) spaced apart from first wall portion 502, third wall portion 506 (see FIG.
  • first wall portion 502 and second wall portion 504, and fourth wall portion 510 (cover) that extends orthogonally between first wall portion 502 and second wall portion 504, and over third wall portion 506, thereby forming enclosed flow channel 508 beneath fourth wall portion 510 and extending between inlet channel 322 and exhaust channel 326 that conveys the HF gas mixture entering flow channel 508 from inlet channel 322 to exhaust channel 326.
  • Flow channel 508 may further bebounded by first, second, and third wall portions 502, 504, and 506.
  • flow modifier 500 may be sized such that the height 512 of flowmodifier 500 above the upper-most surface 410 of nozzle 316 is less than the distance 514 between upper-most surface 410 of nozzle 316 and second surface 24 of glass substrate 20 as glass substrate 20 is guided through etching zone 324 so that glass substrate 20 can past flow modifier 500 without interfering with glass substrate 20. Accordingly, an edge of flow modifier 500 can be placed directly beneath side edge 406, or even beneath glass substrate 20, without contacting glass substrate 20. For example, in some embodiments, height 512 of flow modifier 500 can be less than about 3 millimeters. In some embodiments, an interior surface of flow channel 508 can be radiused where first wall portion 502 and/or second wall portion 504 meet fourth wall portion 510.
  • flow modifier 500 may omit third wall portion 506 such that first wall portion 502, second wall portion 504 and fourth wall portion 510 form a covered structure with two side walls and a covering wall, wherein flow channel 508 is bounded on sides of the flow channel by first and second wall portions 502, 503, and bounded at the top and bottom of the flow channel by fourth wall portion 510 and nozzle 316, respectively.
  • flow modifier 500 in addition to first, second, third, and fourth wall portions 502, 504, 506, and 510, respectively, flow modifier 500 may further comprises a fifth wall portion 513 spaced apart from opposing third wall portion 506.
  • Fifth wall portion 513 connects first wall portion 502, second wall portion 504, and fourth wall portion 510.
  • Third wall portion 506 and fifth wall portion 513 are located outside inlet channel 322 and exhaust channel 326, respectively, such that inlet channel 322 can inject the treatment gas into flow channel 508 of flow modifier 500.
  • the first through fifth wall portions form a five-sided, open-sided box attached on nozzle 316 and extending over at least a portion of inlet channel 322 and exhaust channel 326 such that HF gas mixture 330 can flow from the at least a portion of inlet channel 322 through the open side of the flow modifier, through flow channel 508 and into the at least a portion of exhaust channel 326. While only a single flow modifier 500 is shown, multiple flow modifiers may be employed, for example a flow modifier 500 along each longitudinal edge of glass substrate 20
  • treatment apparatus 300 may comprise a flow modifier 600 configured to at least partially block or restrict the flow of HF gas mixture 330 from inlet channel 322, for example that portion of inlet channel 322 that extends outside of and away from side edge 406 of glass substrate 20, thereby reducing the overall usable cross-sectional area of inlet channel 322 in a plane parallel with a plane of glass substrate 20.
  • the resultant reduction in the cross-sectional area of inlet channel 322 can cause the HF gas mixture velocity to increase, assuming a constant flow rate of the HF gas mixture.
  • the HF gas mixture flow can be adjusted.
  • the flow rate (Q) is related to the velocity of flow(V) by
  • V b V L /(L -L b ).
  • Vb resultant velocity of HF gas mixture with flowmodifier 600 positioned in inlet channel 322 is higher than the velocity without flow modifier 600 due to a decrease in cross- sectional area of the inlet channel.
  • a height 604 of flow modifier 600 can be less than the distance 514 between upper-most surface 410 of nozzle 316 and second side 24 of glass substrate 20.
  • flow modifier 600 can comprise a plug portion 606 sized to fit snugly within inlet channel 322.
  • flow modifier 600 may further comprise cap portion 608 attached to an end of plug portion 606 and sizedto prevent the cap portionfromfitting within inlet channel 322.
  • a width 610 of cap portion 608 taken orthogonal to longitudinal axis 602 can be greater than a width 612 of plug portion 606, and the width 612 of plug portion 606 can be equal to (if, for example, plug portion 606 is formed of a resilient, e.g.
  • flow modifier 600 can be perforated with one or more narrow passages 616 (not shown to scale) extending through flow modifier 600 from inlet channel 322 to etching zone 324 to facilitate “breathing” and reduce or eliminate opportunities for condensationto form within inlet channel 322. While only a single flow modifier 600 is shown, multiple flow modifiers may be employed, for example a flowmodifier 600 along each longitudinal edge of glass substrate 20. [00105] In still other embodiments, as shown in FIG.
  • treatment apparatus 300 may comprise a flow modifier 700 configured, like flow modifier 600, to at least partially block or restrict the flow of HF gas mixture 330 from inlet channel 322, for example that portion of inlet channel 322 that extends outside of and away from side edge 406 of glass substrate 20, thereby reducing the overall usable cross-sectional area of inlet channel 322 in a plane parallel with a plane of glass substrate 20.
  • Flow modifier 700 can include a plug portion 702 configured with a gradual change in cross-sectional area inside inlet channel 322 as shown in FIG. 13. For example, in some embodiments, width 614 of inlet channel 322 can vary.
  • width 614 of inlet channel 322 can be greater at upper-most surface 410 than at a distance within nozzle 316 farther from upper-most surface 410. That is, the width 614 of inlet channel 322 can increase in a flow direction of HF gas mixture 330 within the inlet channel. Accordingly, width 704 of plug portion 702 may also vary, for example by the same amount as inlet channel 322, such that width 704 of plug portion 606 is equal to or less than width 614 of inlet channel 322 where plug portion 702 is in contact with inside surfaces of inlet channel 322.
  • a gradual change in width e.g., 614, 704 can aid in preventing condensation that may occur within inlet channel 322 if there is a sudden change in channel width.
  • flow modifier 700 can be perforated with one or more narrow passages 706 (not shown to scale) extending through flow modifier 700 from inlet channel 322 to etching zone 324 to facilitate “breathing” and reduce or eliminate opportunities for condensation to form within inlet channel 322.
  • Flow modifier 700 may further comprise cap portion 708 attached to an end of plug portion 702 and sized to preventthe cap portionfromfitting within inlet channel 322.
  • a width 710 of cap portion 708 taken orthogonal to longitudinal axis 602 can be greater than width 704 of plug portion 702, and the width 704 of plug portion 702 can be equal to (if, for example, plug portion 702 is formed of a resilient, e.g., compressible, material) or less than a width 614 of inlet channel 322 (if plug portion 702 is formed of a non-resilient material).
  • a height 718 of flow modifier 700 can be less than the distance 514 between upper-most surface 410 of nozzle 316 and second side 24 of glass substrate 20. While only a single flow modifier 700 is shown, multiple flow modifiers may be employed, for example a flow modifier 700 along each longitudinal edge of glass substrate 20.
  • the HF gas mixture flow from inlet channel 322 to exhaust channel 326 can be varied depending on the position of glass substrate 20 in etching zone 324.
  • the glass substrate encounters the HF gas mixture on both sides of the glass substrate as etching chamber 304 is typically filled with the HF gas mixture. This is because nozzle 316 is always ON and HF gas mixture 330 flowing.
  • HF gas mixture 330 from inlet channel 322 will flow toward exhaust channel 326 while also filling etching chamber 304.
  • Ambient air within etching chamber 304 is also drawn into exhaust channel 326.
  • the timing of providing air 346 to first side 22 of glass substrate 20 can be controlled to occur either right before glass substrate 20 enters etching chamber 304 or when glass substrate 20 just covers exhaust channel 326. Once glass substrate 20 covers exhaust channel 326 (FIG. 14B), HF gas mixture 330 will be in contact with both first side 22 and second side 24 of glass substrate20. Air 346 supplied to cover 340 and directed through apertures 344 further dilutes the HF gas mixture over and in contact with the first side 22 in B-side etching zone 324b, but with little or no reaction on first side 22 of the glass substrate (FIG. 14C).
  • HF gas mixture flow to second side 24 of glass substrate 20 may become more uniform while air 346 directed to first side 22 of the glass substrate continues to dilute and displace HF gas mixture that may be present in A-side etching zone 324a.
  • exhaust channel 326 continues to draw HF r s mixture 330 and air 346 (FIG. 14D).
  • Air 346 supplied to cover 340 can then be turned OFF: etching chamber 304 fills with HF gas mixture 330 and the cycle repeats.
  • the flow velocity of supplied air 346 can range from about 0.01 millimeters/secondto about 100 millimeters/second, depending on desired air volume.
  • the air flow volume into cover 340 can also vary in a range from about 10 to about 300 liters/minute.
  • the glass substrate can pass through rinsing chamber 306, wherein a rinsing fluid, e.g., deionized water, can be directed from a washing nozzle 800 toward glass substrate 20, e.g., second side 24.
  • a rinsing fluid e.g., deionized water
  • the glass substrate can thereafter be dried.
  • substantially is intended to represent that a described feature is equal or approximately equal to a value or description.
  • a “substantially planar” surface is intended to denote a surface that is planar or approximately planar.
  • substantially is intended to denote that two values are equal or approximately equal. In some embodiments, “substantially” may denote values within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.
  • the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not, and need not be, exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. Accordingly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood the particular value forms another embodiment.
  • “about X” refers to ⁇ 10% of the recited value, inclusive. For example, the phrase “about 8” refers to a value of 7.2 to 8.8, inclusive.
  • ranges can be expressed herein as from “about” one value, and/or to “about” another value. When such a range is expressed, another embodiment includes from the one value to the other value.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne un procédé de traitement d'un substrat de verre consistant à chauffer le substrat de verre, diriger un premier flux d'air à travers une première pluralité d'ouvertures disposées dans une plaque d'ouvertures vers un premier côté du substrat de verre chauffé, et exposer un second côté du substrat de verre chauffé à un fluide de traitement comprenant du HF tout en dirigeant le premier flux d'air, le fluide de traitement gravant le second côté du substrat de verre pour former un substrat de verre traité.
PCT/US2021/016339 2020-02-18 2021-02-03 Gravure de surfaces de verre pour réduire la charge électrostatique pendant le traitement WO2021167787A1 (fr)

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Cited By (1)

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CN115057623A (zh) * 2021-10-27 2022-09-16 西实显示高新材料(沈阳)有限公司 防眩光玻璃的加工设备及加工其的方法

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US20060196527A1 (en) * 2005-02-23 2006-09-07 Tokyo Electron Limited Method of surface processing substrate, method of cleaning substrate, and programs for implementing the methods
US20140231387A1 (en) * 2013-02-21 2014-08-21 Matthew R. Holloway Process to attach thermal stencils to a glass substrate and permanently etch a mark therein
US20150318187A1 (en) * 2014-04-30 2015-11-05 Corning Incorporated Etch back processes of bonding material for the manufacture of through-glass vias
US20160340231A1 (en) * 2014-01-31 2016-11-24 Nippon Sheet Glass Company, Limited Method for producing glass sheet, and glass sheet
US9598310B2 (en) * 2010-10-28 2017-03-21 Samsung Display Co., Ltd. Apparatus of etching glass substrate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060196527A1 (en) * 2005-02-23 2006-09-07 Tokyo Electron Limited Method of surface processing substrate, method of cleaning substrate, and programs for implementing the methods
US9598310B2 (en) * 2010-10-28 2017-03-21 Samsung Display Co., Ltd. Apparatus of etching glass substrate
US20140231387A1 (en) * 2013-02-21 2014-08-21 Matthew R. Holloway Process to attach thermal stencils to a glass substrate and permanently etch a mark therein
US20160340231A1 (en) * 2014-01-31 2016-11-24 Nippon Sheet Glass Company, Limited Method for producing glass sheet, and glass sheet
US20150318187A1 (en) * 2014-04-30 2015-11-05 Corning Incorporated Etch back processes of bonding material for the manufacture of through-glass vias

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115057623A (zh) * 2021-10-27 2022-09-16 西实显示高新材料(沈阳)有限公司 防眩光玻璃的加工设备及加工其的方法
CN115057623B (zh) * 2021-10-27 2023-11-28 西实显示高新材料(沈阳)有限公司 防眩光玻璃的加工设备及加工其的方法

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