WO2012132328A1 - Verre à bas coefficient de dilatation et verre trempé - Google Patents

Verre à bas coefficient de dilatation et verre trempé Download PDF

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Publication number
WO2012132328A1
WO2012132328A1 PCT/JP2012/001942 JP2012001942W WO2012132328A1 WO 2012132328 A1 WO2012132328 A1 WO 2012132328A1 JP 2012001942 W JP2012001942 W JP 2012001942W WO 2012132328 A1 WO2012132328 A1 WO 2012132328A1
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Prior art keywords
glass
content
low expansion
alkali metal
expansion glass
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PCT/JP2012/001942
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English (en)
Japanese (ja)
Inventor
大正 和田
淳史 倉知
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日本板硝子株式会社
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Priority to JP2013507152A priority Critical patent/JP5890393B2/ja
Publication of WO2012132328A1 publication Critical patent/WO2012132328A1/fr

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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths

Definitions

  • the present invention relates to a low expansion glass and a tempered glass obtained by chemically strengthening the low expansion glass.
  • a borosilicate glass called Pyrex (registered trademark of Corning) is known as the most versatile and inexpensive low expansion glass. This glass is a SiO 2 81% by mass percentage, B 2 O 3 and 13% Al 2 O 3 2%, including 4% Na 2 O, the average linear expansion coefficient of up to 350 ° C. from room temperature to about 33 ⁇ 10 ⁇ 7 / ° C.
  • Low expansion glass is often bonded to silicon by anodic bonding.
  • glass and silicon are brought into contact and heated to about 300 to 450 ° C., while applying a high voltage of about several hundred to 1 kV with silicon as the anode side,
  • the alkali metal ions are moved to the cathode side and electrostatically and chemically strong bonds are formed at the interface between the glass and silicon to bond the two.
  • Patent Document 1 describes a glass for a silicon pedestal containing no alkali metal. It is described that the deterioration of the element due to migration of alkali metal can be prevented as an effect due to the absence of alkali metal.
  • Patent Document 2 describes an anodic bonding glass that does not contain Na 2 O and contains a relatively large amount of Li 2 O. It is described that the anodic bonding between glass and silicon can be performed at a low temperature (less than 300 ° C.) as an effect by containing a relatively large amount of Li 2 O. Moreover, does not contain any Na 2 O, it is described that can suppress the increase in the linear expansion coefficient and volume resistivity of the glass.
  • Patent Document 3 describes a glass that defines the ratio of Li 2 O to Al 2 O 3 .
  • the composition so that the value of (Li 2 O / Al 2 O 3 ) is 0.9 or more, it has a low average linear expansion coefficient while containing a relatively large amount of Li 2 O, and heat It is described that a glass capable of melting at a relatively low temperature can be obtained without devitrification even in the inter-processing.
  • Patent Document 4 describes a composition of low expansion glass suitable for a photoresist mask.
  • Patent Document 1 does not contain an alkali metal. Therefore, the number of ions that move when glass and a silicon wafer are bonded by an anodic bonding method is small. In this case, since the Si—O—Si covalent bond is unlikely to form between silicon and glass, there is a concern that the bonding strength is insufficient. It is also predicted that the joining process will take a long time.
  • glass When using glass as an electronic component, it is important not only that silicon and glass can be reliably bonded by an anodic bonding method, but also the characteristics of the glass itself.
  • One important characteristic of glass is the dielectric loss tangent (tan ⁇ ). As the dielectric loss tangent of glass increases, signal loss (delay) in the high frequency band (mainly the GHz band) increases.
  • the dielectric loss tangent of glass is preferably less than 0.0050, for example, when measured at 25 ° C. and 1 GHz. Corning's glass has a dielectric loss tangent of about 0.0054, and development of glass having a dielectric loss tangent superior to this is expected.
  • the dielectric loss tangent decreases as the alkali metal content decreases.
  • the content of Li 2 O contained in the glass described in Patent Document 3 is adjusted to 1.40% by weight or less
  • the dielectric loss tangent of the glass when measured under the conditions of 25 ° C. and 1 GHz is 0.00. May be less than 0050.
  • Al 2 O 3 is a component that forms a glass skeleton, and is also a component that improves the mobility of an alkali metal by taking four-coordination. Therefore, if the content of Al 2 O 3 is too small, the alkali metal mobility is lowered, and the anodic bondability is deteriorated.
  • Patent Document 4 Since the glass described in Patent Document 4 contains an appropriate amount (1.8 to 3.5% by weight in the examples) of Na 2 O, it is presumed that anodic bonding is possible. However, according to the knowledge of the present inventors, when Na 2 O is used alone, the dielectric loss tangent of the glass tends to be excessive.
  • the present invention has been made paying attention to such a conventional problem, and an object of the present invention is to provide a low expansion glass capable of anodic bonding and having a low dielectric loss tangent.
  • anodic bondability includes not only the bonding strength but also the meaning of ease of anodic bonding. The ease of forming anodic bonding will be described later in detail.
  • alkali metals have the property of increasing the dielectric loss tangent of glass. That is, for glass containing an alkali metal, anodic bondability and dielectric loss tangent are essentially in a trade-off relationship.
  • the present inventors have closely investigated the relationship between the type of alkali metal, the content of alkali metal, and the dielectric loss tangent of glass in the high frequency band (GHz band). As a result, it was found that Li has a lower ability to increase the dielectric loss tangent of glass compared to other alkali metals such as Na and K. As a result, the following present invention has been completed.
  • the present invention Displayed in mol%, SiO 2 : 55 to 75%, B 2 O 3 : 5 to 17%, Al 2 O 3 : 5 to 15%, MgO: 0 to 10%, CaO: 0 to 10%, SrO: 0-5% BaO: 0 to 1%, ZnO: 0 to 6%, Li 2 O: 0.6-4%, Na 2 O: 0 to 1%, K 2 O: 0 to 1%, SnO 2 : 0 to 1% Fe 2 O 3 : 0 to 5%, TiO 2 : 0-30%, and CeO 2 : 0-10%, Including The total content of alkali metal oxides is 5 mol% or less, displayed in mol%, the content of Li 2 O, well above the total content of alkali metal oxides other than Li 2 O, Provided is a low expansion glass having a dielectric loss tangent of less than 0.0050 at measurement conditions of 25 ° C. and 1 GHz.
  • the alkali metal is brought into contact with a molten salt containing a monovalent cation having an ionic radius larger than that of the alkali metal ion contained in the low expansion glass. Ions are exchanged with the monovalent cation to provide a tempered glass having a compressive stress layer formed on the surface.
  • Li 2 O is the most contained as the alkali metal oxide. Accordingly, the dielectric loss tangent of the glass is smaller than when only the same amount of alkali metal oxide other than Li 2 O is contained. Further, (total content) The content of alkali metal oxides but is relatively small, other components such as Al 2 O 3 is properly adjusted. Therefore, even if the content of the alkali metal oxide is small, for example, the mobility of the alkali metal when forming the anodic bonding is sufficiently high. Therefore, the low expansion glass of the present invention has excellent anodic bonding properties. Thus, according to the present invention, it is possible to provide a low expansion glass having not only excellent anodic bonding properties but also low dielectric loss tangent.
  • a tempered glass in which a compression stress layer is formed on the surface by ion-exchange of alkali metal ions contained in the low expansion glass with monovalent cations having a larger ion radius. Can do.
  • SiO 2 is an essential component for forming a glass network.
  • SiO 2 is also a component that enhances the durability, particularly acid resistance, of the glass. Therefore, the content of SiO 2 is too small acid resistance of the glass may be insufficient. Therefore, the lower limit of the content of SiO 2 is 55%.
  • the lower limit of the content of SiO 2 is preferably 60%, more preferably 63%.
  • the upper limit of the content of SiO 2 is 75%.
  • the upper limit of the content of SiO 2 is preferably 72%, and more preferably 70%.
  • the range of the content of SiO 2 can be specified by any combination of these upper and lower limits.
  • B 2 O 3 is an essential component that forms a glass network. If the content of B 2 O 3 is too small, the devitrification temperature is significantly increased, and the meltability of the glass may be significantly decreased. In addition, the productivity of glass may be affected. Therefore, the lower limit of the content of B 2 O 3 is 5%. The lower limit of the content of B 2 O 3 is preferably 7%, and more preferably 9%. On the other hand, if the content of B 2 O 3 is too large, the durability of the glass may be insufficient. Therefore, the upper limit of the content of B 2 O 3 is 17%. The upper limit of the content of B 2 O 3 is preferably 13%. The range of the content of B 2 O 3 can be specified by any combination of these upper and lower limits.
  • Al 2 O 3 is an essential component that plays a role of forming a glass network and a role of modifying the glass network. If the content of Al 2 O 3 is too small, phase separation may occur. Further, as described above, when the content of Al 2 O 3 is too small, the mobility of the alkali metal is lowered, and the anodic bondability may be greatly deteriorated. Therefore, the lower limit of the content of Al 2 O 3 is 5%. The lower limit for the content of Al 2 O 3 is preferably 8%. On the other hand, if the content of Al 2 O 3 is too large, the linear expansion coefficient and the devitrification temperature may be significantly increased. Therefore, the upper limit of the content of Al 2 O 3 is 15%. The upper limit of the content of Al 2 O 3 is preferably 13%, and more preferably 12%. The range of the content of Al 2 O 3 can be specified by any combination of these upper and lower limits.
  • Al 2 O 3 is contained in the low-expansion glass of the present invention more than Li 2 O, regardless of whether it is expressed in mol% or mass%.
  • Alkaline earth metal oxides that is, MgO, CaO, SrO, and BaO are optional components that modify the glass network and are components that improve the meltability of the glass. If the content of the alkaline earth metal oxide is too large, the linear expansion coefficient may be significantly increased. Therefore, the upper limit of the content of MgO is, for example, 10%, preferably 7%, more preferably 5%.
  • the upper limit of the content of CaO is, for example, 10%, preferably 8%, more preferably 7%.
  • the upper limit of the content of SrO is, for example, 5%, preferably 3%, more preferably 2%.
  • the upper limit of the content of BaO is, for example, 1%, preferably 0.5%.
  • the low expansion glass of the present embodiment may not substantially contain BaO.
  • substantially free means not intentionally included unless, for example, it is inevitably mixed with industrial raw materials. Specifically, it means a content of less than 0.1%, preferably less than 0.01%.
  • MgO may be contained, for example, 1% or more, preferably 2% or more.
  • CaO may be contained, for example, 1% or more, preferably 2.5% or more, more preferably 3% or more.
  • the upper limit of the total content of CaO and SrO is, for example, 9%, preferably 7%, more preferably 6%.
  • ZnO ZnO is an optional component having the same effect as the alkaline earth metal oxide, and is generally also a component that improves glass forming ability. When there is too much content of ZnO, devitrification temperature may rise significantly. Therefore, the upper limit of the ZnO content is 6%, preferably 2.5%.
  • the total content of MgO, CaO, SrO, BaO and ZnO is, for example, 5 to 13%, preferably 7 to 13%, more preferably in consideration of the linear expansion coefficient, meltability, anodic bondability, and the like. It may be adjusted to a range of 9 to 11%.
  • the ranges of the contents of MgO, CaO, SrO, BaO and ZnO can be specified by any combination of the above upper limit and lower limit, respectively.
  • Alkali metal oxide is an essential component that improves anodic bonding. At the time of anodic bonding, alkali metal ions move to the cathode, thereby causing a covalent bond between non-crosslinked oxygen ions in the glass and silicon at the interface.
  • the alkali metal oxide is a component that modifies the glass network, and has an effect of appropriately cutting the glass network, lowering the melting temperature of the glass, and keeping the viscosity of the glass melt low. On the other hand, if the content of the alkali metal oxide is too large, the linear expansion coefficient and the dielectric loss tangent may be significantly increased.
  • Li 2 O has a relatively low ability to increase the dielectric loss tangent of glass. Therefore, if Li 2 O is mainly used as the alkali metal oxide, a glass having both excellent anodic bonding properties and low dielectric loss tangent can be provided. Since Li + has a high mobility during anodic bonding, the use of Li 2 O as an essential alkali metal oxide is preferable.
  • the total content of alkali metal oxides is set to 5% or less.
  • the content of Li 2 O is limited to a range of 0.6 to 4%.
  • the content of Li 2 O is expressed in mol% and exceeds the total content of alkali metal oxides other than Li 2 O.
  • the total content of alkali metal oxides is preferably 3% or less.
  • the upper limit of the content of Li 2 O is preferably 3%, more preferably 2%.
  • the lower limit of the content of Li 2 O is preferably 1%.
  • the range of the content of Li 2 O can be specified by any combination of these upper and lower limits.
  • At least one selected from Na 2 O and K 2 O may be contained as an optional component.
  • the upper limit of the content of Na 2 O is, for example, 1%, preferably 0.5%, more preferably 0.25%.
  • the upper limit of the content of K 2 O is, for example, 1%, preferably 0.5%.
  • the low expansion glass of this embodiment may contain 0.05% or more of at least one selected from Na 2 O and K 2 O.
  • the content of Na 2 O and the content of K 2 O are each smaller than the content of Li 2 O.
  • Na 2 O may be contained in the low expansion glass at a ratio of 0.1% or more.
  • K 2 O may be contained in the low expansion glass at a ratio of 0.1% or more.
  • the range of the content of Na 2 O and K 2 O can be specified by any combination of the above upper limit and lower limit, respectively.
  • the ratio of the content of Li 2 O to the total content of Na 2 O and K 2 O can be a value greater than 2.
  • the upper limit of the ratio (Li 2 O / (Na 2 O + K 2 O)) is 80.
  • the content of Li 2 O is 4%, and the content of Na 2 O or K 2 O is 0.05%.
  • the mixed alkali effect is prominent when the ratio of two types of alkali components is 1: 1.
  • the mixed alkali effect is considered to be a phenomenon based on alkali movement.
  • the alkali in the glass only deforms or vibrates, so it is unrelated to the movement of the alkali.
  • SnO 2 Since SnO 2 has a clarification action, it may be contained in the low expansion glass at a ratio of 0.05% or more, preferably 0.1% or more, for example. However, if the SnO 2 content is too large, devitrification and phase separation may occur. Therefore, the upper limit of the content of SnO 2 is, for example, 1%, preferably 0.2%. The range of the content of SnO 2 can be specified by any combination of these upper and lower limits.
  • Fe 2 O 3 , TiO 2 , CeO 2 Fe is present in the glass in the state of Fe 2+ or Fe 3+ .
  • Fe 3+ is a component that improves the ultraviolet absorption characteristics of glass
  • Fe 2+ is a component that improves the heat ray absorption characteristics. Therefore, Fe is not essential, but may be used as a component for adjusting the optical properties of the glass. Moreover, Fe may be inevitably mixed by industrial raw materials.
  • Fe, expressed as Fe 2 O 3 may be contained in the low expansion glass at a ratio of 0.01% or more, preferably 0.5% or more, for example. However, if Fe is excessively contained, the low expansion glass may be excessively colored, or the difficulty in producing the low expansion glass may increase.
  • the upper limit of the Fe content is expressed as Fe 2 O 3 , for example, 5.0%, preferably 2.0%, more preferably 1.0%.
  • the low expansion glass may be processed with a laser.
  • the low expansion glass is required to have a property of absorbing a laser.
  • a small amount of Fe facilitates laser absorption and facilitates processing using a laser, such as drilling.
  • TiO 2 and / or CeO 2 may be contained in the low expansion glass. That is, the low expansion glass of the present embodiment may include at least one selected from the group consisting of Fe 2 O 3 , TiO 2 and CeO 2 as a laser absorption component. Since Fe has a clarification action and is extremely inexpensive, the use of Fe 2 O 3 as a laser absorbing component is preferred.
  • the content of the laser absorbing components Fe 2 O 3 , TiO 2 and CeO 2 ) so that the absorption coefficient of the low expansion glass with respect to a laser having a specific wavelength ⁇ of 535 nm or less is 50 cm ⁇ 1 or less.
  • the absorption coefficient is preferably in the range of 3 to 20 cm ⁇ 1 , more preferably 3 to 10 cm ⁇ 1 .
  • Examples of the laser for processing the low expansion glass include Nd: YAG laser harmonics, Nd: YVO 4 laser harmonics, and Nd: YLF laser harmonics.
  • the harmonic is, for example, a second harmonic, a third harmonic, or a fourth harmonic.
  • the wavelength of the second harmonic of these lasers is in the vicinity of 532 to 535 nm
  • the wavelength of the third harmonic is in the vicinity of 355 to 357 nm
  • the wavelength of the fourth harmonic is in the vicinity of 266 to 268 nm. is there.
  • the lower limit of the content of TiO 2 is, for example, 1%, preferably 3%.
  • the lower limit of the CeO 2 content is, for example, 0.2%, preferably 0.5%.
  • the upper limit of the content of TiO 2 is, for example, 30%, preferably 20%, more preferably 10%.
  • the upper limit of the content of CeO 2 is, for example, 10%, preferably 5%, more preferably 2%.
  • the range of the content of Fe 2 O 3 , TiO 2 and CeO 2 can be specified by any combination of the above upper limit and lower limit, respectively.
  • the absorption coefficient based on these components is represented by “12.5X + Y + 5.9Z”.
  • the maximum value of (X + Y + Z) that satisfies 3 ⁇ (12.5X + Y + 5.9Z) ⁇ 50 is 30 (mol%), and the minimum value is 0.3 (mol%).
  • the low expansion glass of the present invention may consist essentially of the components described above. Moreover, the low expansion glass of this invention does not need to contain substantially components other than an above-described component. Furthermore, the low expansion glass of this invention may consist of an above-described component.
  • a generally known fining agent for example, a chloride such as NaCl, a fluoride such as CaF 2 , arsenous acid, antimony oxide or the like may be added in a small amount to the raw material.
  • the component of the fining agent may remain in the low expansion glass as long as it does not significantly affect the characteristics such as dielectric loss tangent and bonding strength.
  • substances having a large environmental load such as arsenous acid and antimony oxide, are not substantially contained.
  • MEMS Micro Electro Mechanical Systems
  • the use of devices called MEMS produced by making full use of semiconductor technology has been expanded mainly in the fields of automobiles, mobile phones, biochemistry, and the like. Acceleration sensors, pressure sensors, etc. have already been applied to automobiles and the like, and the application range has expanded to optical MEMS, such as optical waveguide sensors and optical switching devices.
  • optical MEMS such as optical waveguide sensors and optical switching devices.
  • the low expansion glass of the present invention can be widely used for applications such as an electronic substrate, an electrically insulating substrate, a pedestal for supporting silicon (silicon wafer).
  • the low expansion glass preferably has a dielectric loss tangent of less than 0.0050 under the measurement conditions of an air temperature of 25 ° C. and a frequency of 1 GHz.
  • the lower limit of the dielectric loss tangent is not particularly limited, but a dielectric loss tangent less than 0.001 is unrealistic.
  • the low expansion glass of the present embodiment has a devitrification temperature in the range of 950 to 1150 ° C., for example, by having the composition in the above range.
  • the devitrification temperature is low, the glass can be produced stably.
  • it is not essential that the devitrification temperature is within the above range.
  • the low expansion glass of this embodiment preferably has an average coefficient of linear expansion in the range of 32 ⁇ 10 ⁇ 7 / ° C. to 40 ⁇ 10 ⁇ 7 / ° C. when measured in the range of 25 to 450 ° C. Yes. If the average linear expansion coefficient is within this range, the problem of residual stress after anodic bonding is unlikely to occur, and the strength of anodic bonding between glass and silicon is easily ensured. In addition, the low expansion glass of the present embodiment is less likely to be warped or damaged due to stress at the bonded portion even when bonded to silicon or the like by a method other than anodic bonding.
  • the low expansion glass of this embodiment is less likely to cause a problem due to thermal stress even when a silicon thin film is formed on the surface and a circuit such as a thin film transistor is further formed.
  • the average linear expansion coefficient can be obtained by measuring the elongation of a sample between 25 ° C. and 450 ° C. with a differential thermal dilatometer and dividing the elongation by the value of temperature change.
  • the low expansion glass of the present invention can be chemically strengthened, and the tempered glass of the present invention can be obtained by chemically strengthening the low expansion glass of the present invention.
  • Chemical strengthening is a technique for forming a compressive stress layer on the glass surface by replacing alkali metal ions contained on the glass surface with monovalent cations having a larger radius.
  • the tempered glass of the present invention can be used, for example, as a circuit board material. Specifically, a through-hole is provided in tempered glass, one surface is bonded to silicon, and a conductive wiring material containing a metal such as copper, aluminum, or silver is connected to silicon through the through-hole from the other surface.
  • a usage pattern for wiring is conceivable. In such a usage pattern, since the metal generally has a large coefficient of linear expansion, there is a possibility that breakage may occur due to the thermal stress difference between the low expansion glass of the present invention and the wiring material. However, according to the tempered glass of the present invention, the risk of breakage due to the thermal stress difference with the wiring material can be reduced by the compressive stress layer formed on the surface. Moreover, if the tempered glass of this invention is used as a glass substrate of the panel part of a touch panel display, for example, since the surface of the tempered glass is strengthened by the compression stress layer, the protective glass of a touch panel display may be made unnecessary.
  • the chemical strengthening of the low expansion glass of the present invention can be performed by bringing the low expansion glass into contact with a molten salt containing a monovalent cation having an ionic radius larger than that of the alkali metal ion contained in the low expansion glass.
  • the alkali metal ion contained in the low expansion glass of the present invention is substituted with a monovalent cation having a larger ion radius, and a compressive stress layer is formed on the surface.
  • lithium ions or sodium ions contained in the low expansion glass of the present invention are replaced with monovalent cations having a larger ion radius.
  • a molten salt of sodium nitrate or potassium nitrate, or a mixed salt thereof can be used as the molten salt.
  • a molten salt of potassium nitrate from the viewpoint of imparting a high compressive stress to the compressive stress layer.
  • the 50% fracture load described later is preferably 1500 gf (gram force) or more, more preferably 1700 gf or more, and further preferably 1800 gf or more.
  • the depth of the compressive stress layer formed on the tempered glass of the present invention is preferably 5 ⁇ m or more.
  • the compressive stress applied to the outermost surface is preferably 200 MPa or more.
  • the lower limit of the content of Al 2 O 3 is 5% as described above, and preferably 8%.
  • CaO and SrO have the ability to bind alkali metals. Therefore, when there is too much content of these, chemical strengthening property may fall. Therefore, the upper limit of the total content of CaO and SrO is, for example, 9%, preferably 7%, more preferably 6%, as described above.
  • the alkali metal oxide is a component that improves chemical strengthening properties.
  • Alkali metal ions contained in the glass derived from the alkali metal oxide are components that improve the glass strength by applying compressive stress to the surface by exchanging with monovalent cations having a larger ion radius. Since Li + easily moves during chemical strengthening, it is preferable to use Li 2 O as an essential component among alkali metal oxides. When the total content of alkali metal oxides and the content of Li 2 O satisfy the above conditions, chemical strengthenability can be ensured. From the viewpoint of improving chemical strengthenability, the content of Li 2 O is preferably 1 to 4%, more preferably 1.2 to 3.5%, and even more preferably 1.5 to 3%.
  • sodium ions have a larger ionic radius than lithium ions, and the compressive stress on the glass surface generated by exchange with potassium ions in the molten salt is smaller than lithium ions. Further, sodium ions do not generate compressive stress when exchanged with sodium ions in the molten salt. The ionic radius of potassium ions is larger than that of sodium ions, and no compression stress is generated by exchange with potassium ions in the molten salt. Potassium ions, on the other hand, lower the compressive stress when exchanged with sodium ions in the molten salt, and in some cases generate tensile stress.
  • the ratio of Li 2 O is greater than 2 in Li 2 O / (Na 2 O + K 2 O).
  • the alkali metal oxide that coexists with Li 2 O is preferably Na 2 O rather than K 2 O.
  • a batch was obtained by weighing and mixing oxides, carbonates, nitrates, sulfates and the like as glass raw materials so that the composition shown in Example 1 of Table 1 was obtained.
  • the obtained batch was put in a platinum crucible and heated in an electric furnace set with an atmospheric temperature of 1400 to 1650 ° C. to melt the batch.
  • the molten glass was kept for 4 to 5 hours in the crucible with proper stirring. Thereafter, molten glass was poured into a carbon or stainless steel mold and gradually cooled to 25 ° C. Thereby, the glass sample of Example 1 was obtained.
  • glass samples of Examples 2 to 23 and Comparative Examples 1 to 9 were obtained.
  • the devitrification temperature of the glass of an Example and a comparative example was measured with the following method. Glass crushed to a particle size of 1.0 to 2.8 mm was placed in a platinum boat and heated in an electric furnace with a temperature gradient (900 to 1400 ° C.) for 24 hours. The devitrification temperature was determined from the maximum temperature of the electric furnace corresponding to the crystal appearance position. The results are shown in Tables 1 to 3. Note that the temperature in the electric furnace is determined in advance, and the glass placed in a predetermined place is heated at a temperature corresponding to the place. The devitrification temperature is a temperature at which crystals start to grow and grow in the molten glass.
  • the measured anodic bonding current does not directly represent the strength of the anodic bonding.
  • those skilled in the art often measure the anodic bonding current as an indicator of anodic bonding properties. This is because a large anodic bonding current means that the mobility of alkali metal is high, which means that anodic bonding can be easily performed and high-strength anodic bonding can be formed.
  • the bonding speed is very slow (anodic bonding process). It takes a long time) and poor bonding may occur.
  • Example 1 The glass samples of Example 1, Example 8, and Example 23 shown in Tables 1 and 2 were cut into a shape of 130 mm ⁇ 70 mm ⁇ 0.7 mm.
  • the cut glass sample was immersed in a molten salt of potassium nitrate at 480 ° C. for 8 hours for chemical strengthening to obtain a strengthened glass sample.
  • the 50% breaking load was measured for the tempered glass sample and the glass sample not subjected to chemical strengthening by the following method.
  • a micro Vickers hardness tester (MVK-G2 manufactured by Akashi Co., Ltd.) is used for any five locations on the surface of the glass sample using a diamond indenter (a square pyramid indenter with a facing angle of 136 °)
  • a 300 gf load was applied for 15 seconds to create a square impression.
  • About the sample glass which added the load it left still for 5 minutes except the load. Thereafter, it was observed with an optical microscope whether cracks were generated on the extended line connecting the center of the square of the indentation and the vertex of the square.
  • the presence or absence of cracks was confirmed at each vertex of the five indentations, and the fracture probability P was determined by dividing the number of cracks generated by the total number of vertices of 20.
  • the load applied to the glass sample was changed to 500 gf, 1000 gf, and 2000 gf, and the fracture probability P of the glass sample with respect to each load was similarly determined.
  • a fracture load with a fracture probability P of 50% was obtained by linear interpolation from the respective fracture probabilities, and was set as the 50% fracture load of the glass sample. The results are shown in Table 4.
  • Example 8 contained 3% Li 2 O and exhibited a dielectric loss tangent of 0.0049.
  • Comparative Example 1 contained 1.5% Na 2 O and exhibited a dielectric loss tangent of 0.0057.
  • Comparative Example 2 contained 1.5% K 2 O and exhibited a dielectric loss tangent of 0.0059. That is, Example 8 exhibited a dielectric loss tangent smaller than those of Comparative Examples 1 and 2 even though it contained twice the molar amount of alkali metal oxide as Comparative Examples 1 and 2. This suggests that Li 2 O can be advantageously used as the alkali metal oxide in order to avoid an excessive increase in the dielectric loss tangent of the glass.
  • Examples 11 and 18 have the same composition except for alkali metal oxides.
  • Example 11 contains 1.5% Li 2 O as the alkali metal oxide.
  • Example 18 contains 1.25% Li 2 O and 0.25% Na 2 O as the alkali metal oxide. That is, the content of the alkali metal oxide of Example 11 is equal to the content of the alkali metal oxide of Example 18. Nevertheless, the dielectric loss tangent of Example 11 was 0.0034, the dielectric loss tangent of Example 18 was 0.0032, and the dielectric loss tangent of Example 18 was 0.0002 smaller than that of Example 11.
  • Examples 11, 13, and 14 have substantially the same composition except for the content of Al 2 O 3 .
  • the anodic bonding current increased. This suggests that Al 2 O 3 has a function of increasing alkali metal mobility.
  • Comparative Example 3 contains 1.5% Li 2 O and 1.5% Na 2 O.
  • Comparative Example 4 contains 1.5% Li 2 O and 1.5% K 2 O. That is, Comparative Examples 3 and 4 each contain the same molar amount of alkali metal oxide as Example 8. And the comparative example 3 showed the dielectric loss tangent of 0.0049. This value is equal to the dielectric loss tangent of Example 8. Comparative Example 4 showed a dielectric loss tangent of 0.0052. This value is smaller than the dielectric loss tangent (0.0059) of Comparative Example 2 containing K 2 O alone as an alkali metal oxide.
  • the absorption coefficients of Examples 1, 2, and 19 to 22 at a wavelength of 355 nm were measured, and were found to be 1.39 cm ⁇ 1 , 1.61 cm ⁇ 1 , 8.77 cm ⁇ 1 , 3.87 cm ⁇ 1 , 3.93 cm ⁇ , respectively. 1 and 6.46 cm ⁇ 1 .
  • the absorption coefficient was calculated according to the following method. A test piece of 20 mm ⁇ 20 mm ⁇ 3 mm was cut out from each glass sample. Using these test pieces, transmittance and reflectance at a wavelength of 355 nm were measured. The absorption coefficient was calculated from the measured transmittance, reflectance, and test piece thickness (3 mm).
  • the tempered glass samples obtained by chemically strengthening the glass samples of Example 1, Example 8 and Example 23 have a considerably larger 50% fracture load than the glass samples not subjected to chemical strengthening. The value is shown. Further, the 50% fracture load of the tempered glass sample obtained by chemically strengthening the glass sample of Example 8 having a Li 2 O content higher than that of Example 1 is the tempered glass obtained by chemically strengthening the glass sample of Example 1. It was larger than that of the sample. This suggests that the strength of the tempered glass as the Li 2 O content in the low-expansion glass is large becomes high. Further, in the tempered glass sample of Example 23, a compressive stress layer depth that was not observed in the tempered glass sample of Example 8 was observed. This suggests that the compressive stress layer is deepened by allowing Na 2 O to coexist with Li 2 O.
  • the low expansion glass and tempered glass of the present invention can be widely used for applications such as an electronic substrate, an electrically insulating substrate, a pedestal for supporting silicon (silicon wafer).

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

Abstract

Le verre à bas coefficient de dilatation ci-décrit comprend, en % en mol, 55 à 75 % de SiO2, 5 à 17 % de B2O3, 5 à 15 % d'Al2O3, 0 à 10 % de MgO, 0 à 10 % de CaO, 0 à 5 % de SrO, 0 à 1 % de BaO, 0 à 6 % de ZnO, 0,6 à 4 % de Li2O, 0 à 1 % de Na2O, 0 à 1 % de K2O, 0 à 1 % de SnO2, 0 à 5% de Fe2O3, 0 à 30 % de TiO2 et 0 à 10 % de CeO2. Sa teneur totale en oxydes de métal alcalin est jusqu'à 5 % en mol, tandis que sa teneur en Li2O est supérieure à la teneur totale en oxydes de métal alcalin autres que Li2O, chaque teneur étant exprimée en termes de % en mol. Le verre à bas coefficient de dilatation selon l'invention manifeste, en outre, une tangente de perte diélectrique, déterminée dans les conditions de 25°C et 1 GHz, inférieure à 0,0050.
PCT/JP2012/001942 2011-03-31 2012-03-21 Verre à bas coefficient de dilatation et verre trempé WO2012132328A1 (fr)

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CN104150765A (zh) * 2013-08-27 2014-11-19 东旭集团有限公司 一种高硅、高铝触摸屏盖板玻璃
CN105502933A (zh) * 2015-12-29 2016-04-20 江苏建达恩电子科技有限公司 用于智能传感器的玻璃管及其制备方法
WO2016129254A1 (fr) * 2015-02-10 2016-08-18 日本板硝子株式会社 Verre pour usinage au laser, et procédé de fabrication de verre perforé mettant en œuvre celui-ci
WO2017217496A1 (fr) * 2016-06-17 2017-12-21 日本板硝子株式会社 Plaque de verre destinée à un traitement au laser
WO2018025883A1 (fr) * 2016-08-05 2018-02-08 旭硝子株式会社 Substrat de verre, dispositif semi-conducteur et dispositif d'affichage
JPWO2017038075A1 (ja) * 2015-08-31 2018-06-14 日本板硝子株式会社 微細構造付きガラスの製造方法
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CN110240419A (zh) * 2019-06-06 2019-09-17 深圳市东丽华科技有限公司 锂铝硅玻璃、锂铝硅化学强化玻璃及其制备方法与应用
JP2020092270A (ja) * 2014-10-03 2020-06-11 日本板硝子株式会社 導電部付ガラス基板
EP3636605A4 (fr) * 2017-06-05 2021-03-10 AGC Inc. Verre trempé
CN112759255A (zh) * 2016-09-13 2021-05-07 Ａｇｃ株式会社 高频器件用玻璃基板和高频器件用电路基板
CN112777931A (zh) * 2021-01-12 2021-05-11 成都光明光电股份有限公司 低介电常数玻璃
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WO2022168963A1 (fr) * 2021-02-05 2022-08-11 日本板硝子株式会社 Composition de verre et fibre de verre, et procédé de production associé
WO2023287499A3 (fr) * 2021-06-01 2023-05-11 Corning Incorporated Compositions de verre ayant une absorption uv améliorée et procédés pour les fabriquer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001072433A (ja) * 1999-09-02 2001-03-21 Asahi Techno Glass Corp 陽極接合用ガラス
JP2010228969A (ja) * 2009-03-27 2010-10-14 Ohara Inc ガラス
JP2012020892A (ja) * 2010-07-13 2012-02-02 Asahi Glass Co Ltd 固体撮像装置用カバーガラス
JP2012036074A (ja) * 2010-07-12 2012-02-23 Nippon Electric Glass Co Ltd ガラス板
JP2012051773A (ja) * 2010-09-02 2012-03-15 Nippon Electric Glass Co Ltd 樹脂複合体基板用ガラス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001072433A (ja) * 1999-09-02 2001-03-21 Asahi Techno Glass Corp 陽極接合用ガラス
JP2010228969A (ja) * 2009-03-27 2010-10-14 Ohara Inc ガラス
JP2012036074A (ja) * 2010-07-12 2012-02-23 Nippon Electric Glass Co Ltd ガラス板
JP2012020892A (ja) * 2010-07-13 2012-02-02 Asahi Glass Co Ltd 固体撮像装置用カバーガラス
JP2012051773A (ja) * 2010-09-02 2012-03-15 Nippon Electric Glass Co Ltd 樹脂複合体基板用ガラス

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JP2020092270A (ja) * 2014-10-03 2020-06-11 日本板硝子株式会社 導電部付ガラス基板
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US20180029924A1 (en) * 2015-02-10 2018-02-01 Nippon Sheet Glass Company, Limited Glass for laser processing and method for producing perforated glass using same
US10717670B2 (en) 2015-02-10 2020-07-21 Nippon Sheet Glass Company, Limited Glass for laser processing and method for producing perforated glass using same
TWI659937B (zh) * 2015-02-10 2019-05-21 日商日本板硝子股份有限公司 雷射加工用玻璃、及使用其之附孔玻璃之製造方法
JPWO2017038075A1 (ja) * 2015-08-31 2018-06-14 日本板硝子株式会社 微細構造付きガラスの製造方法
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US11554983B2 (en) 2016-08-05 2023-01-17 AGC Inc. Glass substrate, semiconductor device, and display device
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JP7415237B2 (ja) 2016-09-13 2024-01-17 Ａｇｃ株式会社 高周波デバイス用ガラス基板と高周波デバイス用回路基板
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