CN105269891A - Glass member with chemically prestressed substrate and compensation layer and manufacturing method thereof - Google Patents
Glass member with chemically prestressed substrate and compensation layer and manufacturing method thereof Download PDFInfo
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- CN105269891A CN105269891A CN201510307319.3A CN201510307319A CN105269891A CN 105269891 A CN105269891 A CN 105269891A CN 201510307319 A CN201510307319 A CN 201510307319A CN 105269891 A CN105269891 A CN 105269891A
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- compensation
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- glass workpiece
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Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
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- 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
- C03C2217/213—SiO2
-
- 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
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
-
- 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
- C03C2218/365—Coating different sides of a glass substrate
Abstract
The invention relates generally to a glass-made glass member with a thin-plate or sheet shaped substrate. The substrate has at least one chemically prestressed layer which has high requirements on the platness and evenness. A coating includes a hard antireflection layer system which is applied to the first surface of the substrate. A compensation layer for reducing a deformation of the substrate is applied on the relatively opposite surface. The invention further relates to a method for manufacturing such a glass member.
Description
Technical field
Present invention relates in general to the glass workpiece comprising thin tabular or the sheet-like substrates be made up of glass, it has, and at least one is chemical pre-stressed and flatness and flatness are had to the layer of very high request.In addition, the present invention relates to a kind of method for the manufacture of this glass workpiece.
Background technology
Comprise the thin tabular or sheet-like substrates that are made up of glass, namely comprise so-called thin glass substrate, and nowadays the glass workpiece with at least one functional layer has multiple application as cover glass or cover glass.Such as this glass workpiece has multiple application as the cloche of smart phone or panel computer.The requirement such as in flatness or flatness proposed this glass workpiece or thin glass substrate is very high and constantly increase.
Except the requirement that there is small deformation as far as possible except requiring glass workpiece, also there are other requirements, such as, require hardness large as far as possible, thus the scratch that opposing may produce on surface, or also require the interference reflection that reduces as far as possible on substrate.Therefore carry out prestressing force to thin glass substrate, thus improve the mechanical stability on surface, and usually arrange extra layer, these layers have specific function, such as antireflective property.
This thin glass substrate is made up of thin glass tape usually, isolates substrate by suitable separation method by glass tape.This thin glass tape then can with float glass process manufacture, and wherein import in tin bath by the glass melt of liquid state, in this tin bath, glass melt carries out stretching, extension and can be drawn out completely continuously subsequently.
If pull out very thin glass tape, it is roughly suitable for the manufacture of thin glass substrate, so this manufacturing process can cause having the different glass surface of different internal stress due to different media, wherein the upper side and lower side of glass tape and these medium contacts.This may cause the less desirable distortion of thin glass substrate.
For the use as cover glass and cover glass, usually so-called prestressing force is carried out to glass, thus improve impact strength and flexural strength.Except general more deflection is used for compared with except the calorifics prestressing force of heavy sheet glass substrate, usually carry out chemical pre-stressed for thinner glass substrate, this further improves scratch resistance except making surface have except higher-strength.Such as in document DE102012213071A1, describe the chemical pre-stressed of thin glass substrate.Usually in the region on the close surface of substrate, compression is generated in chemical pre-stressed.
The stress in glass substrate may be caused asymmetric to the chemical pre-stressed of surface with different internal stress, because effect has the power of varying strength on a glass substrate.Usually there will be glass substrate thus; the particularly distortion of thin glass substrate; this distortion can affect thin glass as the use of the cover glass of smart phone or panel computer or obviously reduce productivity ratio, because only have the obtained thin glass substrate of small part to use.
Therefore, usually also two kinds of glass are used for glass workpiece: the prestressed cover glass of harsh chemical and be used for applying another glass substrate of electronic component.But this thinks disadvantageous due to the material consumption increased.The extra reprocessing of known substrate in addition, such as polishing, to reduce distortion.This is also included into as troublesome and cost up.
If thin glass substrate chemical pre-stressed so is additionally also provided with the layer of a such as ARC, so more increase the risk of distortion, because effect has extra power on a glass substrate.Thus, the particularly layer of mechanically stable, namely so-called hard material layer or wear-resistant protective layer can cause distortion strong especially, because these layers have high internal stress usually in order to have large effect in layer.Similarly, when thin glass substrate is provided with ARC, also there is such problem.Therefore may generate thin glass substrate that is chemical pre-stressed, that have functional layer hardly, it has sufficiently high flatness and flatness simultaneously.
Summary of the invention
Therefore, the object of the invention is to, there is provided a kind of glass workpiece and the manufacture method thereof with chemical pre-stressed substrate, this substrate has at least one hard anti-reflection coating or transparent hard material layer, and this glass workpiece can meet the very high requirement to flatness and flatness.
Surprisingly, this object is achieved simply by the glass workpiece any one of independent claims or its manufacture method.Of the present inventionly preferred embodiment to draw from each dependent claims with expansion scheme.
Therefore, the present invention relates to a kind of glass workpiece with chemical pre-stressed substrate, it has hard anti-reflection layer system and layer on the other side, wherein substrate has 2mm or following thickness and at least one direction, has the length of at least 100mm, and wherein hard anti-reflection layer system on the first surface has to least two layers, this refractive index to least two layers is different.Extraly or replace hard anti-reflection layer system transparent hard material layer can be set.
Next according to the hard anti-reflection layer system as coating, the present invention is described.But extraly or replace this hard anti-reflection layer system a transparent hard material layer also can be set respectively.This transparent hard material layer can be respectively single or multiple lift.
In addition the feature of this glass workpiece is, the layer relative with hard anti-reflection layer for be applied on relative substrate surface, for reducing at least one layer of compensation of substrate distortion, thus the maximum deviation of the flatness (flexibility) measured along the diagonal of substrate surface on catercorner length is less than 300 μm, preferably be less than 200 μm, and be very particularly preferably less than 100 μm.
The invention still further relates to a kind of glass workpiece, it meets effects on surface geometry, particularly to the very high requirement of flatness and flatness.This substrate also comprise at least one apply at least one surface, the layer that is formed as layer of compensation, thus to reduce or full remuneration distortion ideally, such as, produce the substrate distortion caused.At least can be reduced the distortion of substrate by this layer of compensation like this, namely make the distortion of substrate be in the tolerance of regulation.
In other words, this glass workpiece or substrate meet the strict demand of applying for the cover glass as smart phone or touch pad due to layer of compensation according to the present invention, this layer of compensation decreases the distortion of substrate, makes in the margin of tolerance that the distortion of the back substrate applying layer of compensation is in regulation or fully compensate for distortion ideally.
Be two surfaces and thickness thereof in the feature of this substrate, these two surfaces opposed and by two of substrate comparatively long side surface determine, its thickness extends perpendicular to surface.At this, the shape on surface is generally rectangle.At this, be at least 100mm according to the surface length at least one direction of substrate of the present invention, preferred 120mm, and particularly preferably 140mm, thus can be used in the stock size of smart phone display screen, this size, usually in the scope of 4 inches (1 inches=2.54cm), is preferably at least 5 inches, and is particularly preferably at least 6 inches.Therefore this glass workpiece also particularly advantageously can be used as cover glass or the cover glass of smart phone stock size.
Very thin substrate is easily out of shape due to the internal stress in the material that can cause by manufacture method.May occur the surface of substrate and the deviation of ideal surfaced geometry thus, thus the surface geometry of substrate is in beyond the tolerance of intended application.Therefore substrate and/or the glass workpiece be made up of it are not suitable for further application due to its distortion, such as, as the cover glass of smart phone or touch pad.At this, thin substrate may have corresponding little thickness, and this thickness can be less than 2mm, is advantageously less than 1mm, is preferably equal to or less than 700 μm.
Correspondingly, glass workpiece according to the present invention has very high flatness
usually also referred to as flatness
this is interpreted as in meaning of the present invention, glass workpiece to be placed on base plate that is smooth, that be desirably plane and to be only subject to earth attraction under uncharge state, in the geometry that such glass workpiece has, the open surface of glass workpiece and the face of ideal plane almost do not have or do not have deviation completely ideally, the face of this ideal plane and the surface of glass workpiece abreast or plane extend abreast.
In other words, substrate according to the present invention is placed on the base plate of ideal plane, and wherein substrate is complete plane, that is, specific region not lifting or the only lifting within the scope of predetermined tolerance partly of substrate.
Correspondingly, be in glass workpiece deviate from the surface of base plate a little all regulation the margin of tolerance in.Therefore, high flatness is interpreted as that the space of each point on the surface of substrate or glass workpiece is arranged, the spacing that can not exceed regulation between faces of ideal plane is arranged in spaces of these points, and the face of this ideal plane is parallel to the surface of substrate or glass workpiece.
The deviation in each point on surface and the face of ideal plane is also referred to as the deviation with flatness (flexibility).The diagonal that flatness can go up surfacewise is measured.This measurement is preferably carried out according to the narrow and small measurement point in multiple diagonally interval, and the measurement point wherein on surface and the yardstick interval between the face of ideal plane are parallel to surface respectively and determine.At this, on diagonal line length, namely measure in cornerwise length.
Illustrate surprisingly, the quality of the surface geometry of thin substrate can significantly improve by applying layer of compensation, and this thin substrate has caused the distortion of surface geometry due to production, namely have the deviation of flatness.
According to the present invention, by the internal stress of substrate cause and cause the power of substrate distortion by cause due to the internal stress of layer of compensation, the power of opposing substrate above-mentioned power and reduce and offset completely ideally, thus reduce distortion and eliminate distortion completely in the ideal case.
Due to produce the internal stress that causes and thus different stress in the substrate such as may cause, if be placed on by substrate on smooth base plate, then the zone line of substrate can from base plate lifting.Therefore the protrusion of substrate can be caused to be out of shape, thus substrate have the deviation of flatness.According to the present invention, can at the concave surface of substrate, apply layer of compensation namely at substrate away from the surface of base plate, this layer of compensation causes compression.Reduce distortion thus or compensate completely ideally.Similarly, can apply layer of compensation on the opposed convex surface of substrate, this layer of compensation causes tension and reduces distortion or full remuneration ideally by this way.
According to of the present invention, comprise at least one and have in the glass workpiece of the substrate of layer of compensation, along the diagonal on substrate surface, particularly measure in the length of 150mm be less than 300 μm with the maximum deviation of flatness (flexibility), preferably be less than 200 μm, and be particularly preferably less than 100 μm.Thus, this glass workpiece meets the high request of flatness and the flatness applied for the cover glass as smart phone or touch pad.
In addition, the present invention also relates to a kind of method of glass workpiece for the manufacture of having chemical pre-stressed substrate, this substrate has hard anti-reflection layer system and layer of compensation, and this glass workpiece meets the very high requirement of effects on surface geometry.At this, this substrate has 2mm or following thickness and has the length of at least 100mm at least one direction, and wherein hard anti-reflection layer system has on the first surface to least two layers, and the refractive index of these two layers is different.In addition, the feature of this glass workpiece is, the layer relative with hard anti-reflection layer be apply on opposite surfaces of the substrate, for reducing at least one layer of compensation of substrate distortion, thus measure on catercorner length along the diagonal on substrate surface be less than 300 μm with the maximum deviation of flatness (flexibility), preferably be less than 200 μm, and be very particularly preferably less than 100 μm.
In addition, the feature of particularly advantageous substrate is, its thickness is 700 μm or following, and is less than 80 μm with the maximum deviation of flatness (flexibility), is preferably less than 50 μm, is particularly preferably less than 30 μm.
Glass workpiece is made to be applicable to the cover glass of smart phone or touch pad very well by the very high flatness of substrate.Therefore such as also can simply conveniently industrial standard process this glass workpiece.In addition, also less desirable optical effect can be reduced by hard anti-reflection layer, such as optical appearance defect or aberration.Very high impact strength and flexural strength and very high scratch resistance is also according to the feature of glass workpiece of the present invention.Knoop hardness HK0.1/2 can at least 600, and preferably at least 615, and particularly preferably at least 630.
Preferably on the face of the depressed deformation of substrate, apply layer of compensation, under this layer of compensation is in compression, reduce distortion thus, full remuneration distortion ideally.
Similarly, preferably on the face that the protrusion of substrate is out of shape, apply layer of compensation, under this layer of compensation is in tension, reduce distortion thus, preferred full remuneration distortion.
Also both can apply the layer of compensation causing compression of the substrate on one side, on the relative facade of substrate, apply again the layer of compensation causing tension.When the distortion needing compensate for slower large, can be favourable like this.
Particularly advantageously, make the refractive index of layer of compensation adapt to the refractive index of substrate, thus do not affect optical characteristics and avoid open defect.But the refractive index of layer of compensation also can correspond to according to the purposes after glass workpiece of the present invention, the purposes of the such as corresponding cover glass as smart phone or touch pad and selecting, thus do not affect optical characteristics or realize specific optical effect.
Illustrate, be less than 0.3 when the refractive index of layer of compensation is chosen as with the refractive index of substrate, when being preferably less than 0.2, only can produce optical appearance defect that is very little or that can ignore.Optically very outstanding perception can be caused thus.
In addition, advantageously can select the layer of compensation with high internal stress, thus form layer thin as far as possible.Particularly advantageously, the internal stress of layer of compensation is higher than the internal stress of hard anti-reflection layer system.This causes well being out of shape recovery.
Although can make to be applied with layer of compensation by thin layer of compensation but still keep substrate flexibility and substrate such as also can spooling.In addition, when layer of compensation is chosen as thin as far as possible, coating time period can be reduced thus.In addition, in coating procedure, make every effort to high coating speed, thus realize deposition economic as far as possible.In addition, very thin can manufacture thin and elongated terminal device according to glass workpiece of the present invention, such as smart phone.
Consider inorganic material, particularly glass as substrate, transparent or dense glass is ceramic or the diamond dust of sapphire and synthesis.Composite is also fine, such as, have the compound glass (Mehrfachverglasung) of multiple glass, wherein usually has two glass to be combined with each other by film.Preferred glass is borosilicate glass, such as boron float glass, alumina silicate glass, lithium alumina silicate glass, soda lime glass and glass ceramics.
Substrate can be formed as smooth sheet or tabular.The thin substrate be made up of glass, so-called thin glass substrate nowadays can by various known method manufacture, and the thickness of this thin substrate can being less than 2mm until be less than 500 μm or be even less than in the scope of 100 μm.This is comprised to float glass process, glass tube down-drawing or spilling-melting method.Usually generate thin glass tape in this approach, be separated subsequently thus and cut out single substrate.
At this, the thin glass substrate such as manufactured by float glass process has the surface containing different qualities producing and cause.Therefore the surface being usually arranged in top in the fabrication process wherein contacts atmosphere at float process, and another surface that is relative, that be correspondingly positioned at below contacts tin bath in float process.This different internal stress that just can cause from the contact of different medium in the fabrication process in substrate, the different internal stress particularly in the region on each surface, this can cause the less desirable distortion of substrate surface geometry.
For different application, such as, when substrate is that when should be used as the thin glass substrate of the cover glass of smart phone, substrate carries out extra sclerosis, thus obtains higher impact strength and flexural strength.For this carries out prestressing force to substrate.Except more application more than about 1mm thickness compared with except the calorifics prestressing force of heavy sheet glass substrate, usually also carry out chemical pre-stressed in thin glass substrate.
In chemical pre-stressed process, in the close surf zone of substrate, carry out ion-exchange, carry out alternative sodium ion by larger potassium ion wherein especially.The compression of side direction can be caused thus, thus improve hardness.
The distortion that the substrate before chemical pre-stressed with high-quality surface geometry also may have outside the tolerance being in requirement due to the compression generated after prestressing force.If substrate just had distortion before prestressing force, so this distortion will be stronger.
The layer of compensation be applied on the side of substrate or surface produces a kind of internal stress ideally, and this internal stress is in size corresponding to the substrate internal stress causing substrate distortion.At this, substrate also can have hard anti-reflection layer on the first side.In the ideal case, layer of compensation due to its internal stress on substrate active force, this power equals the power caused due to substrate internal stress just, thus these power is offset or approximate to be offset and distortion reduces or full remuneration.
This can carry out with method substantially in a different manner.If substrate is such as out of shape like this, that is, the zone line of substrate is from flat base plate lifting, so layer of compensation can be applied to towards on the surface of base plate side, be namely applied on the concave surface of substrate, this layer of compensation causes compression on substrate, reduce distortion thus, preferred full remuneration.
Similarly, alternatively or extraly can apply layer of compensation on the surface away from base plate side of substrate, this layer of compensation causes tension on substrate.In other words, when layer of compensation produces the internal stress of opposing substrate internal stress, be suitable.
Therefore, can by applying the layer of compensation of the internal stress with generation compression or apply the layer of compensation with the internal stress producing tension or the compensation undertaken substrate distortion by the combination of above-mentioned layer of compensation on the side of substrate depressed deformation on the side of substrate protrusion distortion.
Illustrate, vapour deposition process, particularly spraying process and particularly advantageously magnetron sputtering method be suitable for being formed on substrate according to layer of compensation of the present invention, this layer of compensation causes compression.In cathodic sputtering, obtain material by Ions Bombardment from target, this material can condense on the surface of a substrate and form a layer there.Hard anti-reflection layer system also by these class methods, particularly can apply by magnetron sputtering.Therefore possible that, generate layer of compensation and hard anti-reflection layer by a kind of identical method, glass workpiece can be generated especially economically thus.
In addition illustrate, the method for processing with the raw material of liquid state is very suitable for forming layer of compensation on substrate, and this layer of compensation causes tension.Japanning, immersion plating, spraying or blade coating are such as comprised to this.
Substrate according to the present invention, except having hard anti-reflection layer system, can also have at least one layer with another predetermined function at least one surface.This is comprised to scratch resistance function, anti-fingerprint function or function easy to clean.These functions also can be combined in layer of compensation and/or be combined in anti-reflecting layer.
Can manufacture the glass workpiece with high flatness according to the present invention, this glass workpiece comprises substrate that is chemical pre-stressed, that have hard anti-reflection layer system, and this glass workpiece is provided with other layer or functional layer.This can be the layer of mechanically stable, i.e. so-called hard material layer or anti abrasion layer, and these layers can be applied on the one or both sides of substrate, thus improves scratch resistance performance.
Such as, under this kind of layer of resistance to scratch layers and/or anti-reflecting layer and/or anti-finger print layer and/or easy cleaning layer can be in high internal stress and therefore substrate is out of shape further.The selection of coating material, coating layer thickness and the setting for functional layer being applied to the procedure parameter on substrate particularly advantageously can be implemented based on the present invention, and also without the need to considering the impact on distortion.
Therefore, the restriction that may propose for distortion little is as far as possible avoided by being applied for the layer of compensation of minimizing distortion.Therefore, it is possible to particularly advantageously select coating material, coating layer thickness and the setting for the procedure parameter that applies functional layer from the angle forming best-of-breed functionality layer.In other words, the invention provides very large advantage arranges other functional layer to substrate, and limit procedure can not control and the version of equivalent layer due to possible substrate distortion.
Correspondingly, process control for applying resistance to scratch layers and/or hard anti-reflection layer and/or anti-finger print layer and/or easy cleaning layer and functional can be optimized.
At this, two or more functions can be combined in one layer.Therefore, in meaning of the present invention, wearing layer can be applied on substrate with the alternating layer system with multiple individual layer together with anti-reflecting layer and to form hard anti-reflection layer system.
Extraordinary case hardness can be realized thus and surface is not easily reflected for the irradiation in limit of visible spectrum.At this, substrate also can be chemical pre-stressed.Also the opposed side on substrate can apply the layer with difference in functionality.
In order to generate hard anti-reflection layer, substrate can particularly advantageously form the anti-reflecting layer with multiple layering.Can apply the layer with different refractivity at this, the layer wherein with high index replaces with the layer had compared with low-refraction car.Hard anti-reflection layer system according to the present invention comprises to least two layers, and the refractive index of these two layers is different.
In a particularly advantageous design, have and be made up of the silica with aluminium share compared with the layer of low-refraction, wherein the thing mass ratio of aluminium and silicon is greater than 0.05, be preferably greater than 0.08, but the material amount of silicon exceedes the material amount of aluminium, and the layer wherein with high index contains silicide, oxide or nitride.Can not only degree of reflection be reduced thus, but also can case hardness be improved.
Layer of compensation particularly advantageously comprises the hard anti-reflection layer system had to least two layers, this anti-reflecting layer system preferably has identical coating material with the hard anti-reflection layer system on first surface, is particularly preferably included in anti-reflecting layer system that is textural and the identical type of anti-reflecting layer system on first surface.
Can be applied in Anywhere following according to glass workpiece of the present invention, the thin or very thin substrate of these local requirements, i.e. so-called thin glass substrate, and wherein to flatness and flatness, there is very high requirement simultaneously.
This glass workpiece can be used as cover glass on smart phone, touch pad or touch-screen or display screen and display or cloche or so-called cover glass.For the flatness of glass workpiece and flatness, there is very high requirement in this type of application.
Correspondingly, the present invention also relates to a kind of cover glass, this cover glass is suitable as the multifunction protection glass on smart phone, touch pad or touch-screen or display screen, and this cover glass can by obtaining according to method of the present invention foregoing.
Following basis preferred embodiment and invention will be described in detail with reference to the attached drawing.
Accompanying drawing explanation
Fig. 1 show in cross section an embodiment of the substrate with distortion;
Fig. 2 show in cross section an embodiment of the substrate additionally had according to layer of compensation of the present invention;
Fig. 3 show in cross section another embodiment of the substrate additionally had according to layer of compensation of the present invention;
Fig. 4 show in cross section the substrate that comprises and have hard anti-reflection layer system and has an embodiment of the glass workpiece of distortion;
Fig. 5 show in cross section an embodiment of the glass workpiece comprising the substrate with hard anti-reflection layer system and layer of compensation;
Fig. 6 shows substrate with top view, and
Fig. 7 show in cross section a section of the glass workpiece comprising different layers.
Detailed description of the invention
Following to detailed description of the preferred embodiment in for the sake of clarity represent parts substantially identical in each embodiment with identical Reference numeral.
Those skilled in the art are obviously known, that illustrate with reference to the accompanying drawings described in the present invention is not limited to, only exemplary embodiment, but can change in the scope of claim main body in many ways.Particularly also the feature of single embodiment can be combined with each other.
The embodiment of the glass workpiece 1 shown in Fig. 1 relates to substrate 10, and this substrate illustrates in the sectional views.At this, this substrate can be sheet glass or glass ceramics sheet or also can be sapphire sheet.Be preferably thin glass substrate.The present invention is suitable for the substrate of different-thickness substantially, in thin or very thin substrate, wherein easily occur the substrate distortion because internal stress causes.
Embodiment illustrated in the accompanying drawings is for Dimensions metrology, and the thickness of such as substrate, the distortion of substrate and layer thickness for the sake of clarity only illustrate specific dimensions, and this size must not provide in the middle of reality.Therefore the substrate 10 in Fig. 1 such as shows the thickness of increase and the distortion of increase, and this is only used to better understanding.
Because the impact of producing makes substrate 10 have distortion.This distortion may occur due to internal stress, and this internal stress is caused by manufacture process.Can adjust the internal stress with tension or compression form according to material or manufacture method in thin substrate, this internal stress appears in the specific region of substrate.
This is such as known by thin glass substrate, namely comprises the substrate of thin flat glass, and this substrate is usually by float glass process manufacture.At this, the relation due to method makes the surface of substrate be exposed in floating process process in different media; The upper contact atmosphere of substrate and the contacts-side-down tin bath of substrate.Internal stress thus described in adjustable, this internal stress can apply one or more power on substrate.After isolating substrate by glass tape, the less desirable distortion of substrate may be caused.
In order to the mechanical stability improving substrate surface can carry out Chemical Pretreatment to substrate, thus improve mechanical stability.Such as can improve the scratch resistance of substrate surface thus.Such as thin glass substrate, particularly these have been had to the thin glass substrate of internal stress due to production, chemical pre-stressedly cause extra stress, because carried out ion-exchange in the region close to surface of substrate, this ion-exchange may produce extra compression.Extra distortion can be caused thus.
Substrate 10 in Fig. 1 illustrates the embodiment through chemical pre-stressed thin glass substrate, and this substrate has such distortion, that is, the zone line lifting of substrate when being placed on base plate that is smooth, plane.The deviation in the surface of substrate and the face of ideal plane is so large, to such an extent as to this substrate can not be used as the cover glass of smart phone or touch pad.In this embodiment, the thickness of thin glass substrate, in 700 μm or following scope, is preferably less than 550 μm, is particularly preferably and is less than 100 μm.
The maximum deviation of the surface geometry of substrate is represented by A.Deviation A can be 50 μm or more greatly and be even greater than the thickness of substrate dimensionally.This distortion of substrate also can be called the distortion of protrusion.Shown distortion is the one in multiple may distortion, and this distortion makes the application of thin glass substrate become difficulty.The zone line of such as substrate also can to remain in plane and corner angle or outer seamed edge lifting.
Fig. 2 is in the sectional views by the embodiment showing glass workpiece 2 through thin glass substrate that is chemical pre-stressed, that have layer of compensation 20.In order to compensate the distortion of glass workpiece 1 as shown in Figure 1, make substrate 10 be provided with layer of compensation 20, the concave surface that this layer of compensation is applied to substrate cause compression.Select this layer of compensation so ideally, that is, the compression produced by this layer of compensation is so large, to such an extent as to the distortion of substrate is compensated as much as possible or fully.
Therefore, the power that the internal stress due to layer of compensation 20 causes has been resisted the power that caused by the internal stress of substrate and it has been offset completely in the ideal case, thus decreases or fully compensate for distortion.
This layer of compensation 20 of compression that causes by spraying process, preferably can apply by magnetron sputtering method.Select like this temperature of spraying process, power density, pressure and layer thickness to this, make the internal stress of layer of compensation equal the internal stress of substrate, the internal stress of this layer of compensation eliminates the substrate distortion produced.
Fig. 3 with sectional view according to another embodiment showing glass workpiece 3 through chemical pre-stressed, that there is layer of compensation 30 substrate.In order to compensate the distortion of result 1 as shown in Figure 1, make substrate 10 be formed with layer of compensation 30, the convex surface that this layer of compensation is applied to substrate causes tension.Select layer of compensation so ideally, make the tension that produced by this layer of compensation so large, thus the distortion of substrate is compensated as much as possible or fully.The layer of compensation 30 of tension is caused particularly advantageously to apply as liquid coating.
Fig. 4 show in cross section the embodiment of glass workpiece 4, and this glass workpiece has distortion and comprises the substrate 11 with a coating.This substrate 11 is through chemical pre-stressed substrate.Substrate 11 has hard anti-reflection layer system 40, thus avoids less desirable reflection on the surface of a substrate.In order to produce scratch resistance function, anti-reflecting layer system is made to be formed with at least one hard layer in addition.This hard anti-reflection layer system 40 comprises to least two layers, and the refractive index of these two layers is not identical.Layer more than two also can be set one above the other.
Glass workpiece 4 has distortion, that is, have the deviation with flatness and flatness, and this deviation is maximum to be represented with A and can exceed the thickness of substrate.
Fig. 5 show in cross section the embodiment of glass workpiece 5, and this glass workpiece comprises through substrate 11 that is chemical pre-stressed, that have hard anti-reflection layer system 40 and layer of compensation 20.
In order to compensate distortion, make substrate 11 be formed with layer of compensation 20, the concave surface that this layer of compensation is applied to substrate 11 causes compression.Select layer of compensation 20 so ideally, make the compression that produced by this layer of compensation so large, thus the distortion of substrate is compensated as much as possible or fully.
At this, layer of compensation 20 be arranged on substrate 11 with on opposed surface, the surface with hard anti-reflection layer system 40.
Fig. 6 shows substrate 61 with top view.Relate in this embodiment sheet or tabular, the thin glass substrate of rectangle.
Flatness high in meaning of the present invention means, substrate has such geometry under uncharge state, wherein the surface of substrate and the face of plane almost do not have or do not have deviation completely ideally, the face of this plane is parallel to or plane be parallel to substrate surface extend.This deviation can according on a surface of the substrate diagonally B1, B2 interval closely measurement point record.The deviation in the face of these measurement points and ideal plane is also referred to as flexibility.Preferred diagonally this deviation of linear measure longimetry.
Glass workpiece according to the present invention has at least one 100mm, preferred 120mm, particularly preferably the length of side of at least 140mm, thus can be particularly advantageous for the smart phone with 4 inches, 5 inches or 6 inches convention display sizes.
At this, maximum deviation that measure over the entire length along one of them diagonal, that be positioned at measurement point on substrate surface and flatness (flexibility), for being less than 300 μm, being preferably less than 200 μm, and being particularly preferably less than 100 μm.In addition, be preferably less than 80 μm with the maximum deviation of flatness (flexibility), and be very particularly preferably less than 50 μm.
The last embodiment that show in cross section a section according to glass workpiece 7 of the present invention in the figure 7, this glass workpiece comprises substrate 12 and hard anti-reflection layer system 50, and this substrate is through chemical pre-stressed thin glass substrate.
Hard anti-reflection layer system very advantageously can be formed as layer of compensation.This layer system comprises four layers 51,52,53 and 54 altogether.At this, the layer with high index alternates compared with the layer of low-refraction with having.
Particularly advantageously, have and be made up of the silica with aluminium share compared with the layer of low-refraction, wherein the thing mass ratio of aluminium and silicon is greater than 0.05, be preferably greater than 0.08, but the material amount of silicon exceedes the material amount of aluminium, and the layer wherein with high index contains silicide, oxide or nitride.The thing mass ratio of aluminium and silicon is preferably about 0.075 to 0.125, is preferably about 0.1.Because layer 52,54 is mainly containing silica, so these two layers have low-refraction.
Relatively, layer 51,53 be have high index layer and be made up of silicon nitride, it has aluminium share equally.Preferred aluminium is all substantially identical in all layerings with the thing mass ratio of silicon.When transparent hard material layer replaces hard anti-reflection layer system, use above-mentioned material, namely silicon nitride is conducive to transparent hard material layer equally, the aluminium share wherein preferably containing aluminium nitride form.In general and be not limited to illustrated embodiment, transparent hard material layer or there is high index layer also can by particularly containing described aluminium share, the nitrogen oxide of silicon forms.
In order to realize mechanical stability high as far as possible, use the component of mechanically stable as ground floor, i.e. silicon nitride, is formed as thin layer.Be the SiO of adulterated al subsequently
2next layer is the Si of thicker adulterated al
3n
4layer, this layer externally produces resistance.Another is connected in the SiO of the adulterated al in outside
2layer deposits in this wise, makes the antireflection expected become possibility and is compensated the distortion of substrate 12 simultaneously by compression.
This coating structure has been shown to be highly stable and thin glass substrate, the such as borosilicate glass reflectivity in limit of visible spectrum can be reduced to less than 1%, and compensate the distortion of substrate simultaneously like this, flexibility is decreased on the substrate length of 100mm as being less than 50 μm.
At this, the layer thickness on substrate 12 is in the scope of about 10nm to the most about 150nm.According to another embodiment, this layer thickness can be until 500nm.To this, the particularly Si of above-mentioned thicker adulterated al
3n
4layer can be provided with corresponding large layer thickness.At this, the thickness of substrate is in the scope of about 50 μm to maximum 700 μm.
Claims (13)
1. a glass workpiece, described glass workpiece has
-through chemical pre-stressed substrate, described substrate has
-hard anti-reflection layer system or transparent hard material layer and
-opposed layer,
Wherein said substrate has 2mm or following thickness and has the length of at least 100mm at least one direction,
Described hard anti-reflection layer system wherein on the first surface of substrate has to least two layers, and the refractive index of described two layers is not identical,
It is characterized in that, described opposed layer for be applied on the opposed surface of substrate, for reducing at least one layer of compensation of substrate distortion, thus measure on catercorner length along the diagonal on substrate surface, with the maximum deviation of flatness (flexibility) for being less than 300 μm, preferably be less than 200 μm, and be most preferably less than 100 μm.
2. the glass workpiece according to the claims, is characterized in that, described hard anti-reflection layer system or described transparent hard material layer contain nitrogen.
3. the glass workpiece according to any one of the claims, is characterized in that, described hard anti-reflection layer system comprises at least four layers, and the layer wherein with high index alternates compared with the layer of low-refraction with having.
4. the glass workpiece according to any one of the claims, it is characterized in that, described layer of compensation comprises the hard anti-reflection layer system had to least two layers, described anti-reflecting layer system preferably has identical layer material with the hard anti-reflection layer system on described first surface, and particularly preferably described layer of compensation is included in the anti-reflecting layer system of the identical type of anti-reflecting layer system on textural and described first surface.
5. the glass workpiece according to the next item up claim, is characterized in that, makes the refractive index of described layer of compensation adapt to substrate and/or the setting purposes of glass workpiece; And/or
The refractive index of described layer of compensation and the refractive index of described substrate, for being less than 0.3, are preferably less than 0.2.
6. the glass workpiece according to any one of the claims, is characterized in that, the internal stress of described layer of compensation is higher than the internal stress of hard anti-reflection layer system on the first surface.
7. the glass workpiece according to any one of the claims, is characterized in that, described substrate has at least 120mm at least one direction, preferably the length of at least 140mm.
8. the glass workpiece according to any one of the claims, is characterized in that, described layer of compensation comprises the layer containing silica.
9. for the manufacture of the method for the glass workpiece according to any one of the claims, a kind of glass workpiece is wherein provided, described glass workpiece has through chemical pre-stressed substrate, described substrate has hard anti-reflection layer system or transparent hard material layer and an opposed layer, wherein said substrate has 2mm or following thickness and has the length of at least 100mm at least one direction, described hard anti-reflection layer system wherein on the first surface of described substrate has to least two layers, the refractive index of described two layers is not identical
It is characterized in that, described opposed layer for be applied on the opposed surface of described substrate, for reducing at least one layer of compensation of substrate distortion, thus measure on catercorner length along the diagonal on substrate surface, with the maximum deviation of flatness (flexibility) for being less than 300 μm, preferably be less than 200 μm, and be very particularly preferably less than 100 μm.
10. the method according to the next item up claim, is characterized in that, at least one in layer of compensation or these two coatings of anti-reflecting layer system, and preferably these two coatings are all deposited by magnetron sputtering.
11. methods according to claim 9, is characterized in that, the side that the protrusion of described substrate is out of shape applies layer of compensation, and described layer of compensation causes tension over the substrate, reduces distortion thus, preferably fully compensates distortion.
12. for the manufacture of the method for glass workpiece according to any one of aforementioned claim, and wherein said substrate has at least one other layer extraly at least on a side, and described layer in addition comprises anti-finger print layer and/or easy cleaning layer; And/or
After deposition hard anti-reflection layer system and after sedimentary compensation layer, described anti-finger print layer or easy cleaning layer are applied on the surface of described hard anti-reflection layer system.
13. glass workpieces according to any one of the claims are as the purposes of the cover glass of smart phone, touch pad, touch-screen, display screen or display.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102014108060.2 | 2014-06-06 | ||
| DE102014108060.2A DE102014108060A1 (en) | 2014-06-06 | 2014-06-06 | Glass element with a chemically tempered substrate and a compensation layer and method for its production |
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| Publication Number | Publication Date |
|---|---|
| CN105269891A true CN105269891A (en) | 2016-01-27 |
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|---|---|---|---|
| CN201510307319.3A Pending CN105269891A (en) | 2014-06-06 | 2015-06-08 | Glass member with chemically prestressed substrate and compensation layer and manufacturing method thereof |
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| CN (1) | CN105269891A (en) |
| DE (1) | DE102014108060A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111417604A (en) * | 2017-11-29 | 2020-07-14 | 康宁股份有限公司 | Method for producing a coated glass-based component |
| CN113816617A (en) * | 2020-06-19 | 2021-12-21 | 恒颢科技股份有限公司 | Strengthened glass structure and method for making same |
| CN114563883A (en) * | 2022-03-01 | 2022-05-31 | 苏州兴派丽智能科技有限公司 | Tool, tool manufacturing method, detection machine table and manufacturing machine table applying tool manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106102380A (en) * | 2016-08-03 | 2016-11-09 | 南昌欧菲光学技术有限公司 | Glass shell and there is the electronic product of this glass shell |
| DE102020122475A1 (en) | 2020-08-27 | 2022-03-03 | Schott Ag | Element comprising a transparent substrate and a multi-layer anti-wear layer with adapted reflection and method for its production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4619166B2 (en) * | 2005-03-28 | 2011-01-26 | シチズンホールディングス株式会社 | Windshield glass for watches |
| JP2008032949A (en) * | 2006-07-28 | 2008-02-14 | Sony Corp | Antireflection film, heating method of metal film and heating device |
| WO2009041528A1 (en) * | 2007-09-26 | 2009-04-02 | Citizen Holdings Co., Ltd. | Cover glass for watch |
| JP2011149710A (en) * | 2010-01-19 | 2011-08-04 | Seiko Epson Corp | Timepiece cover glass and timepiece |
| WO2013005608A1 (en) * | 2011-07-01 | 2013-01-10 | 旭硝子株式会社 | Float glass for chemical strengthening |
| DE102012213071A1 (en) | 2012-07-25 | 2013-07-11 | Schott Ag | Method for producing toughened substrate e.g. pre-stressed glass substrate used in e.g. smart phone, involves separating substrate along trench provided on two sides of substrate |
-
2014
- 2014-06-06 DE DE102014108060.2A patent/DE102014108060A1/en active Pending
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2015
- 2015-06-08 CN CN201510307319.3A patent/CN105269891A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111417604A (en) * | 2017-11-29 | 2020-07-14 | 康宁股份有限公司 | Method for producing a coated glass-based component |
| US11976005B2 (en) | 2017-11-29 | 2024-05-07 | Corning Incorporated | Methods of making coated glass-based parts |
| CN113816617A (en) * | 2020-06-19 | 2021-12-21 | 恒颢科技股份有限公司 | Strengthened glass structure and method for making same |
| CN114563883A (en) * | 2022-03-01 | 2022-05-31 | 苏州兴派丽智能科技有限公司 | Tool, tool manufacturing method, detection machine table and manufacturing machine table applying tool manufacturing method |
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| Publication number | Publication date |
|---|---|
| DE102014108060A1 (en) | 2015-12-17 |
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Application publication date: 20160127 |