CN110885187A - Alkali-free glass - Google Patents
Alkali-free glass Download PDFInfo
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- CN110885187A CN110885187A CN201911180012.6A CN201911180012A CN110885187A CN 110885187 A CN110885187 A CN 110885187A CN 201911180012 A CN201911180012 A CN 201911180012A CN 110885187 A CN110885187 A CN 110885187A
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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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
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Abstract
The invention provides alkali-free glass, which comprises the following components in percentage by weight: SiO 22：20～60％；B2O3：0～20％；Al2O3: 5-35%; CaO: 10-50%; SrO: 0 to 15 percent; BaO: 0 to 15 percent; MgO: 0 to 15%, wherein CaO/(CaO + MgO + SrO + BaO) is 0.40 to 0.95. Through reasonable component design, the glass obtained by the invention has higher expansion coefficient and meets the application in the field of semiconductor packaging.
Description
Technical Field
The invention relates to glass, in particular to alkali-free glass.
Background
Glass materials have significant advantages over other materials (e.g., metals, crystals, ceramics, etc.) in terms of light transmission properties, chemical properties, mechanical properties, electrical properties, and manufacturing and processing costs, and thus have recently begun to be increasingly used in applications such as semiconductor packaging and semiconductor manufacturing processes. With the integration of semiconductor chip devices becoming higher and higher, carrier material plates are required to prevent the deformation of packaged wafers during the chip packaging process, thereby improving the yield of chip packaging. The glass material has the characteristics of good mechanical stability, good chemical stability, excellent light transmittance, capability of obtaining ultra-large specification at low cost and the like, and is a material with great development potential for semiconductor chip packaging carriers.
When the glass material is used as a packaging material, if the glass material has a high expansion coefficient, laser stripping can be realized conveniently and at low cost after packaging is finished, the process difficulty can be effectively reduced, and the yield of chip packaging is improved, so that development of glass with a high expansion coefficient is crucial to the field of semiconductor sealing.
Disclosure of Invention
The invention aims to solve the technical problem of providing alkali-free glass with a higher expansion coefficient.
The technical scheme adopted by the invention for solving the technical problem is as follows:
(1) alkali-free glass, the composition of which, expressed in weight percent, comprises: SiO 22：20～60％；B2O3：0～20％；Al2O3: 5-35%; CaO: 10-50%; SrO: 0 to 15 percent; BaO: 0 to 15 percent; MgO: 0 to 15%, wherein CaO/(CaO + MgO + SrO + BaO) is 0.40 to 0.95.
(2) The alkali-free glass according to (1), which comprises the following components in percentage by weight: y is2O3：0～25％；ZnO：0～15％；La2O3：0～10％；Gd2O3：0～10％；ZrO2：0～10％；TiO2：0～5％；P2O5: 0 to 5 percent; a clarifying agent: 0 to 2 percent.
(3) Alkali-free glass containing SiO2、Al2O3And an alkaline earth metal oxide as an essential component, wherein CaO/(CaO + MgO + SrO + BaO) is 0.40 to 0.95, and the alkali-free glass has a coefficient of expansion of α20-300℃Is 70X 10-7More than K.
(4) The alkali-free glass according to (3), which comprises the following components in percentage by weight: SiO 22：20～60％；B2O3：0～20％；Al2O3：5～35％；CaO：10～50％；SrO：0～15％；BaO：0～15％；MgO：0～15％；Y2O3：0～25％；ZnO：0～15％；La2O3：0～10％；Gd2O3：0～10％；ZrO2：0～10％；TiO2：0～5％；P2O5: 0 to 5 percent; a clarifying agent: 0 to 2 percent.
(5) The alkali-free glass according to any one of (1) to (4), wherein the glass has a composition satisfying, in terms of weight percent, one or more of the following 4 conditions:
1)B2O3/SiO20.01 to 0.40;
2)Al2O3/SiO20.10 to 0.80;
3)(TiO2+ZrO2)/Al2O30.40 or less;
4)(La2O3+Gd2O3)/Y2O3less than 0.40.
(6) The alkali-free glass according to any one of (1) to (5), which comprises the following components in percentage by weight: SiO 22: 22-55%; and/or B2O3: 1-15%; and/or Al2O3: 7-30%; and/or CaO: 15-45%; and/or SrO: 0 to 10 percent; and/or BaO: 1-10%; and/or MgO: 1-10%; and/or Y2O3: 0 to 20 percent; and/or ZnO: 0 to 10 percent; and/or La2O3: 0-8%; and/or Gd2O3: 0-8%; and/or ZrO2: 0-8%; and/or TiO2: 0 to 3 percent; and/or P2O5: 0 to 3 percent; and/or a clarifying agent: 0 to 1 percent.
(7) The alkali-free glass according to any one of (1) to (6), which has a composition satisfying, in terms of weight percent, one or more of the following 5 conditions:
1)B2O3/SiO20.03 to 0.30;
2)Al2O3/SiO20.15 to 0.70;
3)(TiO2+ZrO2)/Al2O30.30 or less;
4)(La2O3+Gd2O3)/Y2O3less than 0.30;
5) CaO/(CaO + MgO + SrO + BaO) is 0.50-0.90.
(8) The alkali-free glass according to any one of (1) to (7), which comprises the following components in percentage by weight: SiO 22: 25-50%; and/or B2O3: 2-12%; and/or Al2O3: 10-25%; and/or CaO: 20-35%; and/or SrO: 0 to 5 percent; and/or BaO: 2-8%; and/or MgO: 2-8%; and/or Y2O3: 0 to 15 percent; and/or ZnO: 0 to 5 percent; and/or La2O3: 0 to 5 percent; and/or ZrO2: 0 to 5 percent; and/or a clarifying agent: 0 to 0.5 percent.
(9) The alkali-free glass according to any one of (1) to (8), wherein the glass has a composition satisfying, in terms of weight percent, one or more of the following 5 conditions:
1)B2O3/SiO20.05 to 0.25;
2)Al2O3/SiO20.20 to 0.50;
3)(TiO2+ZrO2)/Al2O3is 0.20 or less;
4)(La2O3+Gd2O3)/Y2O3less than 0.20;
5) CaO/(CaO + MgO + SrO + BaO) is 0.60-0.85.
(10) The alkali-free glass according to any one of (1) to (9), which comprises, as components, F: 0 to 5 percent; and/or does not contain TiO2(ii) a And/or does not contain P2O5(ii) a And/or does not contain Gd2O3。
(11) The alkali-free glass according to any one of (1) to (10) having an expansion coefficient of α20-300℃Is 70X 10-7More than K, preferably 75X 10-7More preferably 80X 10 or more,/K-7More than K; and/or a specific elastic modulus of 25 or more, preferably 28 or more, more preferably 30 or more; and/or light transmission rate tau360nmIs more than 60 percent, preferably 70 percentThe content is preferably 80% or more.
(12) The alkali-free glass according to any one of (1) to (11) abovegIs 620 ℃ or higher, preferably 640 ℃ or higher, and more preferably 660 ℃ or higher; and/or a thermal shock cracking resistance temperature of 100 ℃ or higher, preferably 105 ℃ or higher, more preferably 110 ℃ or higher.
(13) Water resistance D of the alkali-free glass according to any one of (1) to (12)WIs 4 or more, preferably 3 or more, more preferably 2 or more; and/or acid resistance DAIs 4 or more, preferably 3 or more.
(14) A sealing material comprising the alkali-free glass according to any one of (1) to (13).
(15) A package carrier made of the alkali-free glass according to any one of (1) to (13).
The invention has the beneficial effects that: through reasonable component design, the glass obtained by the invention has higher expansion coefficient and meets the application in the field of semiconductor packaging.
Detailed Description
The following describes in detail an embodiment of the alkali-free glass of the present invention, but the present invention is not limited to the embodiment described below, and can be carried out with appropriate modifications within the scope of the object of the present invention. Note that, although the description of the duplicate description may be appropriately omitted, the gist of the present invention is not limited to this. In the following, the alkali-free glass of the present invention may be simply referred to as glass.
[ alkali-free glass ]
The ranges of the components of the alkali-free glass of the present invention are explained below. In the present specification, the contents of the respective components are all expressed in terms of weight percentage with respect to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the alkali-free glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is 100%.
Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. The term "and/or" as used herein is inclusive, e.g., "a; and/or B "means A alone, B alone, or both A and B.
< essential Components and optional Components >
The invention relates to an alkali-free glass, i.e. a glass formulation which does not contain alkali metals and compounds thereof (such as Li)2O、Na2O、K2O、Rb2Alkali metal oxides and alkali metal fluorides such as O, LiF, NaF, KF, RbF), etc.).
SiO2The glass is a main network forming body of glass and is a framework for forming the glass, when the content of the glass in the glass is higher than 60%, the melting performance of the glass is reduced, the glass with high internal quality is difficult to obtain, and meanwhile, the expansion coefficient of the glass is rapidly reduced and cannot meet the design requirement. Thus, SiO2The upper limit of the content of (B) is 60%, preferably 55%, more preferably 50%. When SiO is present2When the content of (b) is less than 20%, the chemical stability of the glass is lowered, the devitrification resistance of the glass is rapidly lowered, and at the same time, the density of the glass is rapidly increased, resulting in a decrease in the specific elastic modulus of the glass. Thus, SiO2The lower limit of (B) is 20%, the lower limit is preferably 22%, and the lower limit is more preferably 25%.
The glass of the invention belongs to alkali-free glass, and the melting temperature of the raw materials is high. A large amount of bubbles are easily accumulated in a melting pool in the initial melting stage of glass raw materials, and when the bubbles are accumulated seriously, molten glass overflows from a feeding pool, so that the feeding process and the subsequent homogenizing, clarifying and forming processes are stopped in the continuous melting process. The inventors found a small amount of B through intensive studies2O3The bubble accumulation of the raw materials in the initial melting stage can be greatly reduced, and the smooth operation of the smelting process is facilitated. More importantly, a small amount of B2O3The reduction of the high-temperature viscosity of the glass is promoted, and the high-quality glass can be more easily obtained under the low-temperature condition. But B2O3The amount of (B) exceeds 20%, which tends to increase the erosion of the refractory material by the molten glass during melting, resulting in Na in the refractory material+、K+、Li+When the content of the alkali metal ions in the glass exceeds 0.2%, the alkali metal ions enter the monocrystalline silicon substrate when the glass material is used as a carrier, and a chip circuit is polluted. As a property of the material itself, if B2O3Higher than 20% results in a decrease in the specific elastic modulus and chemical stability of the glass. Thus, B2O3The content of (b) is limited to 0 to 20%, preferably 1 to 15%, more preferably 2 to 12%.
In some embodiments of the invention, when B2O3/SiO2When the content of (A) is in the range of 0.01 to 0.40, preferably 0.03 to 0.30, more preferably 0.05 to 0.25, the glass melting property is optimum, and at the same time, the corrosion to the crucible during melting is small and the alkali metal impurities brought in by melting are small.
Al2O3The glass of the invention can improve the specific elastic rate of the glass and increase the thermal conductivity of the glass, so that the subsequent stripping becomes easy. Further, when Al is present2O3With SiO2When coexisting, an appropriate amount of Al2O3The melting of the glass is promoted, and high-quality glass can be easily obtained under low temperature conditions. If Al is present2O3The content is less than 5%, the specific elastic modulus of the glass is lower than the design target, the mechanical strength of the glass is greatly reduced, and the glass becomes refractory; if the content is more than 35%, the expansion coefficient of the glass is rapidly decreased, the melting property of the glass is deteriorated, and the devitrification is particularly easy. Thus, Al2O3The content of (b) is 5 to 35%, preferably 7 to 30%, more preferably 10 to 25%.
Al2O3And SiO2As two main components of the invention, the ratio of the contents obviously influences the properties of the glass, such as transition temperature, chemical stability (such as water resistance, acid resistance and alkali resistance), and the like. Further, if Al2O3/SiO2When the value of (A) is higher than 0.80, the glass becomesAre particularly refractory; if Al is present2O3/SiO2Below 0.10, the glass transition temperature is greatly reduced and the chemical stability of the glass is reduced. Therefore, to balance the above properties, Al2O3With SiO2Ratio of (A) to (B) Al2O3/SiO2The range of (A) is 0.10 to 0.80, preferably 0.15 to 0.70, and more preferably 0.20 to 0.50.
ZrO2The anti-devitrification ability of the glass can be improved by adding the glass into the glass, and the chemical stability of the glass is enhanced; however, if the content exceeds 10%, the expansion coefficient of the glass is significantly reduced, and the design requirements cannot be met, and the melting property of the glass is also reduced, the high-temperature viscosity of the glass is significantly increased, and infusible substances are likely to appear in the glass. Thus, ZrO2The content is limited to 10% or less, preferably 8% or less, and more preferably 5% or less.
TiO2The addition of the glass can improve the devitrification resistance of the glass, and particularly can improve the specific elastic modulus and the mechanical strength of the glass under the condition that the content of alkaline earth metal oxide exceeds 40 percent. If TiO2The content of (b) exceeds 5%, the ultraviolet transmittance of the glass rapidly decreases, so that the subsequent laser lift-off becomes difficult, and the expansion coefficient of the glass decreases, failing to achieve the design target. Thus, TiO2The content of (b) is 5% or less, preferably 3% or less. In some embodiments, it is further preferred not to add TiO in view of the high transmittance required at 360nm wavelength2。
TiO2、ZrO2、Al2O3The glass of the invention can form a network former, and the expansion coefficient of the glass can be reduced by the components. However, the components added into the glass can improve the crystallization resistance stability of the glass, improve the water resistance, acid resistance and especially alkali resistance stability of the glass, and also contribute to improving the thermal shock resistance stability of the glass. Through research, TiO is found2And ZrO2Sum of Al and2O3the proportional relation of (A) is greatly related to the crystallization resistance stability and alkali resistance of the glass, and further, (TiO) is2+ZrO2)/Al2O3When the value of (A) is more than 0.40, the alkali resistance and devitrification resistance of the glass are lowered. Thus, (TiO)2+ZrO2)/Al2O3The range of (b) is 0.40 or less, preferably 0.30 or less, more preferably 0.20 or less.
CaO, MgO, SrO and BaO belong to alkaline earth metal oxides, and the four oxides are generally considered to have properties almost similar to each other in the prior art and can be partially substituted in a glass system. However, as a result of the intensive studies of the inventors, the above four alkaline earth metal oxides act quite differently to the point that the present invention requires a large expansion coefficient.
For increasing the coefficient of expansion of the glass, CaO is the strongest, BaO being the second, SrO being the second, MgO even lowering the coefficient of expansion under certain conditions. For increasing the specific elastic modulus of the glass, MgO is strongest, CaO is second, and BaO and SrO are weakest. Therefore, the addition of CaO is most advantageous from the viewpoint of increasing the expansion coefficient, and if the addition amount of CaO is less than 10%, the expansion coefficient of the glass does not meet the design requirements; if the amount of CaO added is more than 50%, the stability and devitrification resistance of the glass are sharply decreased. Therefore, the content of CaO is 10 to 50%, preferably 15 to 45%, and more preferably 20 to 35%.
Through a great deal of experimental research of the inventor, the glass has a tendency of instability when the content of CaO in the glass is higher than 15%, and if a small amount of BaO and/or SrO is added, the stability and the anti-devitrification performance of the glass can be greatly improved, so that more CaO can be added into the glass, and the expansion coefficient of the glass is increased. Therefore, when the content of CaO in the glass component is less than 15%, BaO and SrO may not be necessarily added, and when the content of CaO is more than 15%, an appropriate amount of BaO and/or SrO may be added to improve the stability of the glass. If the content of BaO exceeds 15%, the specific elastic modulus and chemical stability of the glass rapidly decrease. Therefore, the content of BaO is 0 to 15%, preferably 1 to 10%, and more preferably 2 to 8%.
SrO functions similarly to BaO, but its ability to increase the expansion coefficient is inferior to that of BaO, and if it exceeds 15%, the expansion coefficient does not meet the design requirements, and the chemical stability of the glass is drastically reduced. Compared with BaO, the raw material cost is higher, so BaO is preferably selected. For the above reasons, the SrO content is 15% or less, preferably 10% or less, and more preferably 5% or less.
The inventors have found that in some embodiments, MgO reduces the coefficient of expansion of the glass and therefore addition of MgO is not desirable for increasing the coefficient of expansion. However, the glass of the present invention has a large coefficient of expansion, and if the glass has poor thermal shock resistance, the glass is easily cracked in a temperature raising and lowering process when used as a carrier. Therefore, based on the angle of improving the thermal shock resistance of the glass, if the addition amount of MgO is less than 1%, the performance of improving the thermal shock resistance is not obvious; if the content is more than 15%, the expansion coefficient of the glass is lower than the design requirement, and the devitrification resistance of the glass is rapidly reduced. Therefore, in the case where the glass has a margin in thermal shock resistance, MgO is preferably not added; if the thermal shock resistance is particularly considered in the design, it may be added in a small amount. Therefore, the MgO content is 0 to 15%, preferably 1 to 10%, more preferably 2 to 8%.
The inventor finds through a large amount of experimental researches that when the CaO/(CaO + MgO + SrO + BaO) value is more than 0.95, the devitrification resistance of the glass is sharply reduced; when the CaO/(CaO + MgO + SrO + BaO) value is less than 0.40, the expansion coefficient of the glass does not meet the design requirements, and the water resistance and acid resistance of the glass are lowered. Therefore, CaO/(CaO + MgO + SrO + BaO) ranges from 0.40 to 0.95, preferably from 0.50 to 0.90, and more preferably from 0.60 to 0.85.
The ZnO added into the glass can improve the chemical stability of the glass, and particularly can improve the thermal shock resistance of the glass under the condition of higher content of alkaline earth metal oxides. However, when the ZnO content is more than 15%, the expansion coefficient of the glass is rapidly reduced, and the glass does not meet the design requirements, and the devitrification resistance of the glass is also reduced. Therefore, the ZnO content is 15% or less, preferably 10% or less, and more preferably 5% or less.
Appropriate amount of Y2O3The specific elasticity and the thermal shock resistance of the glass can be obviously improved by adding the glass into the glass; more importantly, Y is compared with the alkaline earth metal oxide2O3Can obviously reduce the high temperature of the glassViscosity. However, Y2O3If the content of (b) exceeds 25%, the elastic modulus of the glass does not increase basically, the density of the glass increases remarkably, but rather the specific elastic modulus of the glass decreases rapidly, and more importantly, the stability and devitrification resistance of the glass decrease rapidly. Thus, Y in the present invention2O3The content of (B) is limited to 25% or less, preferably 20% or less, and more preferably 15% or less.
Suitable amount of La2O3Added to the glass to replace part Y2O3The high-temperature viscosity of the glass is lowered, but if the content exceeds 10%, the specific modulus of the glass is drastically lowered, and the devitrification resistance of the glass is rapidly lowered. Therefore, La in the present invention2O3The content of (b) is limited to 10% or less, preferably 8% or less, and more preferably 5% or less.
A suitable amount of Gd2O3The addition of the additive into glass can effectively reduce the crystallization temperature of the glass, so that the glass melting becomes easier, especially in Y2O3When the content is higher than 10%, the effect is more obvious. But if Gd2O3When the content exceeds 10%, the glass is particularly likely to be crystallized. Thus, Gd is present in the invention2O3The content of (A) is limited to 10% or less, preferably 8% or less, and more preferably no Gd is added2O3。
In the present invention, Y2O3、La2O3、Gd2O3All have the effect of improving the expansion coefficient of glass, wherein Y is used2O3The effect of raising the expansion coefficient of glass is the weakest, but through the research of the inventor, Y is found in the above three oxides2O3The thermal shock resistance of the glass is enhanced to be strongest, and particularly when the content of the glass is larger, the devitrification resistance of the glass is reduced compared with that of La2O3And Gd2O3More slowly; further, when (La)2O3+Gd2O3)/Y2O3When the value of (A) is less than 0.40, preferably less than 0.30, more preferably less than 0.20, the glass is excellent in devitrification resistance and thermal shock resistance.
P2O5The specific elastic rate of the glass can be improved by introducing the glass into the glass, and the melting performance of the glass is improved; however, if the content exceeds 5%, the glass becomes extremely unstable and even the glass formation is affected. Thus, P2O5The content of (b) is limited to 5% or less, preferably 3% or less, and more preferably not added.
If the content (calculated by weight ratio) exceeds 5%, the volatilization amount of the glass is increased sharply, the glass components become unstable, and streaks are easily generated in the glass. Therefore, the content of F is limited to 5% or less, preferably 3% or less, and more importantly, the fluoride raw material is easily volatilized during the production process, and thus, it is more preferable that F is not added because it puts stress on environmental protection and physical health of operators.
0-2% of clarifying agent can be introduced into the glass to improve the clarifying capacity of the glass and improve the bubble degree of the glass, and the content of the clarifying agent is preferably 0-1%, and more preferably 0-0.5%. The fining agent may comprise Sb2O3、CeO2、SnO2、BaCl2And sulfate. Since CeO2、SnO2And Sb2O3In contrast, the ultraviolet transmittance of the glass is seriously impaired, so that Sb is preferably used in the present invention2O3As a clarifying agent.
< component not to be added >
In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the present invention to improve the effect of visible light transmittance.
Oxides of Th, Cd, Tl, Os, Be and Se, which have been harmful in recent yearsThe chemical substances of (2) tend to be used under control, and therefore, measures for protecting the environment are required not only in the glass production process but also in the processing process and the disposal after the production. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thus, the alkali-free glass contains practically no substances contaminating the environment. Therefore, the alkali-free glass of the present invention can be produced, processed, and discarded without taking special measures for environmental measures. Meanwhile, in order to achieve environmental friendliness, the alkali-free glass of the present invention preferably does not contain As2O3And PbO.
The "no introduction", "no inclusion", "no addition" and "0%" described herein mean that the compound, molecule, element or the like is not intentionally added as a raw material to the glass of the present invention; however, it is also within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the glass, and may be present in small or trace amounts in the final glass.
The properties of the alkali-free glass of the present invention will be described below:
< coefficient of expansion >
The expansion coefficient of the invention is the average expansion coefficient of the glass at 20-300 ℃, which is α20-300℃The test is shown to be carried out according to the method specified in GB/T7962.16-2010.
Coefficient of expansion (α) of the alkali-free glass of the invention20-300℃) Is 70X 10-7More than K, preferably 75X 10-7More preferably 80X 10 or more,/K-7More than K.
< specific ballistic Rate >
The specific elasticity of the invention refers to the ratio of the elastic modulus to the density of the glass, namely: specific elastic modulus/density. The density of the glass is tested according to the method specified in GB/T7962.20-2010; the elastic modulus of glass is also called Young's modulus, and the elastic modulus (E) of glass is calculated by the following formula:
wherein G ═ VS 2ρ
In the formula:
e is the elastic modulus, Pa;
g is shear modulus, Pa;
VTis the longitudinal wave velocity, m/s;
VSis the transverse wave velocity, m/s;
rho is the density of the glass, g/cm3。
The alkali-free glass of the present invention has a specific modulus of 25 or more, preferably 28 or more, more preferably 30 or more, and further preferably 32 or more.
< light transmittance >
The light transmittance of the invention refers to the internal transmittance at 360nm of a glass sample with the thickness of 10mm, and is shown as tau360nmThe test is shown to be carried out according to the method specified in GB/T7962.12-2010.
Light transmittance (. tau.) of the alkali-free glass of the present invention360nm) Is 60% or more, preferably 70% or more, more preferably 80% or more, and further preferably 85% or more.
< transition temperature >
Transition temperature (T) of the glasses according to the inventiong) Testing according to the method specified in GB/T7962.16-2010.
Transition temperature (T) of the alkali-free glass of the present inventiong) Is 620 ℃ or higher, preferably 640 ℃ or higher, more preferably 660 ℃ or higher, and further preferably 700 ℃ or higher.
< stability against Water action >
The water-resistant action stability of the invention is the water-resistant action stability of a glass powder method, and D isWThis means that the water resistance is sometimes referred to simply as "water resistance" and is measured according to the method specified in GB/T17129.
Water resistance (D) of the alkali-free glass of the present inventionW) Is 4 or more, preferably 3 or more, and more preferably 2 or more.
< stability against acid Effect >
The acid-resistant action stability of the invention is the acid-resistant action stability of the glass powder method,with DAThis means, sometimes referred to simply as acid resistance, and is tested according to the method specified in GB/T17129.
Acid resistance of the alkali-free glass of the present invention (D)A) Is 4 or more, preferably 3 or more.
< alkali resistance >
The alkali resistance of the glass was measured according to the test conditions and requirements of ISO 10629 and is expressed as the weight loss of the glass sample.
Processing glass into a test sample with the specification of 30mm multiplied by 2mm, polishing six surfaces, putting the test sample into 2000ml of NaOH solution, wherein the concentration of the NaOH solution is 0.01mol/L, the PH value is 12.0, monitoring the change condition of the PH value of the test solution by using a PH meter in the test process, timely replacing the reaction test solution, and measuring the weight loss of the sample by using an electronic balance after corroding for 100 hours at the temperature of 50 ℃, wherein the weight loss is expressed in mg.
The alkali-free glass of the present invention has a weight loss of less than 20mg, preferably less than 10mg, and more preferably less than 5mg, after the test method described above.
< thermal shock resistance >
The thermal shock resistance of the alkali-free glass is tested by adopting a water cooling method, a glass sample is processed into a wafer with the diameter of 30mm and the thickness of 2mm, and the surface of the wafer is ground. Putting the processed glass wafer into a heating furnace, heating to a preset temperature, preserving heat for 5 minutes from 100 ℃, taking out the glass wafer after the temperature of the glass wafer is uniform, putting the glass wafer into cold water at 10 ℃, increasing the temperature of the heating furnace by 5 ℃ if the glass does not crack, and then carrying out the experiment until the glass wafer cracks in the cold water, wherein the temperature of the heating furnace is recorded as the cracking temperature, and the higher the cracking temperature is, the stronger the thermal shock resistance of the glass is.
The alkali-free glass of the present invention has a thermal shock cracking resistance temperature of 100 ℃ or higher, preferably 105 ℃ or higher, and more preferably 110 ℃ or higher.
The alkali-free glass of the invention can be applied to semiconductor packaging and semiconductor manufacturing process, and can be used for manufacturing packaging materials and/or packaging carriers and the like due to the excellent performance. Specifically, the glass material used as the carrier has a required specification of 700mm × 700mm and requires a low deformation amount. For thin glassThe amount of deformation of the sheet is mainly related to the specific modulus of elasticity of the glass material, which is the ratio of the elastic modulus to the density, and the larger the value, the smaller the amount of deformation of the glass sheet material. In addition, the transition temperature (T) of the carrier glassg) The higher the glass is, the higher the glass is resistant to high temperature processing, and the less easily the glass is deformed in the high temperature processing, especially in the semiconductor processing requiring 500-600 ℃ or higher, the transition temperature of the carrier glass is required to be higher than 600 ℃. Compared with the traditional stripping technology, the ultraviolet laser stripping technology has the advantages of high yield and low cost, but the ultraviolet laser stripping technology requires that a carrier glass material has high transmittance near 360 nm. The carrier glass used for semiconductor packaging has high value, needs to be recycled for dozens of times or even hundreds of times, is cleaned by acid and alkali after each use, and if the glass material has poor water resistance, acid resistance and alkali resistance, the smooth surface of the glass material can be damaged in the cleaning process, so that the service life of the glass material is shortened. More seriously, the carrier glass can contact acid-base chemical reagents in the semiconductor manufacturing process, and if the chemical stability is not good, substances in the glass can be corroded into acid-base solution used in the process, so that the processing solution can be scrapped early, and huge loss is caused. Therefore, as a glass material for a vehicle, it is required to have good water resistance, acid resistance and alkali resistance.
[ production method ]
The manufacturing method of the alkali-free glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace at 1300-1500 ℃ for smelting, the smelting temperature is preferably 4-6 hours, the homogeneous molten glass without bubbles and non-meltable substances is obtained after clarification, stirring and homogenization, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.
Examples
In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.
In this example, alkali-free glasses having compositions shown in tables 1 to 3 were obtained by the above-described method for producing alkali-free glasses. The characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 3. Wherein, B2O3/SiO2The value of (A) is represented by A1, Al2O3/SiO2The value of (A) is represented by A2, (TiO)2+ZrO2)/Al2O3The value of (A) is represented by A3, the value of CaO/(MgO + BaO + SrO + CaO) is represented by A4, and (La)2O3+Gd2O3)/Y2O3Is represented by A5, and the coefficient of expansion (α)20-300℃) Denoted by B1; light transmittance (τ)360nm) Denoted by B2; the specific elastic modulus is represented by B3; water resistance (D)W) Denoted by B4; acid resistance (D)A) Denoted by B5; alkali resistance is represented by B6; the thermal shock cracking resistance temperature is represented by B7; transition temperature (T)g) Indicated with B8.
TABLE 1
TABLE 2
TABLE 3
| Component (wt%) | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 |
| SiO2 | 45.0 | 40.0 | 47.0 | 40.0 | 38.0 | 38.0 | 35.0 | 35.0 | 32.0 | 35.0 |
| B2O3 | 5.0 | 10.0 | 5.0 | 5.0 | 5.0 | 3.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| P2O5 | 0.0 | 0.0 | 0.0 | 0.0 | 1.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| Al2O3 | 9.3 | 9.3 | 7.3 | 9.3 | 9.3 | 10.0 | 13.0 | 11.0 | 13.0 | 13.0 |
| TiO2 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.5 | 0.0 |
| ZrO2 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.3 | 0.1 | 0.1 | 0.1 | 0.1 |
| Y2O3 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 14.7 | 15.7 | 13.2 | 10.7 |
| La2O3 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 2.0 |
| Gd2O3 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 2.0 |
| ZnO | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| MgO | 2.0 | 2.0 | 0.0 | 2.0 | 2.0 | 2.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| CaO | 30.0 | 30.0 | 31.0 | 35.0 | 35.0 | 38.5 | 30.0 | 31.0 | 34.0 | 30.0 |
| SrO | 0.0 | 2.5 | 4.0 | 0.0 | 0.0 | 0.0 | 0.0 | 1.0 | 0.0 | 0.0 |
| BaO | 7.5 | 5.0 | 4.5 | 7.5 | 7.5 | 7.5 | 5.0 | 4.0 | 5.0 | 5.0 |
| Sb2O3 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| CeO2 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| F | 0.0 | 0.0 | 0.0 | 0.0 | 1.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
| A1 | 0.11 | 0.25 | 0.11 | 0.13 | 0.13 | 0.08 | 0.06 | 0.06 | 0.06 | 0.06 |
| A2 | 0.21 | 0.23 | 0.16 | 0.23 | 0.24 | 0.26 | 0.37 | 0.31 | 0.41 | 0.37 |
| A3 | 0.05 | 0.05 | 0.07 | 0.05 | 0.05 | 0.03 | 0.01 | 0.01 | 0.05 | 0.01 |
| A4 | 0.76 | 0.76 | 0.78 | 0.79 | 0.79 | 0.80 | 0.86 | 0.86 | 0.87 | 0.86 |
| A5 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.37 |
| B1(×10-7/K) | 72 | 77 | 70 | 83 | 83 | 88 | 82 | 84 | 86 | 84 |
| B2(％) | 92.5 | 92.1 | 92.2 | 89.9 | 90.2 | 89.7 | 89.4 | 89.0 | 89.1 | 89.3 |
| B3 | 32.10 | 33.10 | 32.57 | 32.80 | 32.60 | 31.93 | 35.80 | 35.11 | 34.90 | 35.64 |
| B4 (class) | 2 | 2 | 2 | 2 | 2 | 2 | 1 | 1 | 1 | 1 |
| B5 (class) | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| B6(mg) | 14.1 | 14.5 | 13.2 | 17.1 | 16.8 | 17.9 | 0.2 | 0.1 | 0.2 | 0.2 |
| B7(℃) | 120 | 115 | 125 | 115 | 115 | 110 | 115 | 115 | 115 | 115 |
| B8(℃) | 707 | 681 | 690 | 683 | 701 | 697 | 715 | 708 | 698 | 728 |
Claims (15)
1. Alkali-free glass, characterized in that its components, expressed in weight percent, contain: SiO 22：20～60％；B2O3：0～20％；Al2O3: 5-35%; CaO: 10-50%; SrO: 0 to 15 percent; BaO: 0 to 15 percent; MgO: 0 to 15%, wherein CaO/(CaO + MgO + SrO + BaO) is 0.40 to 0.95.
2. The alkali-free glass according to claim 1, wherein the glass further comprises, in weight percent: y is2O3：0～25％；ZnO：0～15％；La2O3：0～10％；Gd2O3：0～10％；ZrO2：0～10％；TiO2：0～5％；P2O5: 0 to 5 percent; a clarifying agent: 0 to 2 percent.
3. Alkali-free glass characterized by containing SiO2、Al2O3And an alkaline earth metal oxide as an essential component, wherein CaO/(CaO + MgO + SrO + BaO) is 0.40 to 0.95, and the alkali-free glass has a coefficient of expansion of α20-300℃Is 70X 10-7More than K.
4. The alkali-free glass according to claim 3, wherein the composition comprises, in weight percent: SiO 22：20～60％；B2O3：0～20％；Al2O3：5～35％；CaO：10～50％；SrO：0～15％；BaO：0～15％；MgO：0～15％；Y2O3：0～25％；ZnO：0～15％；La2O3：0～10％；Gd2O3：0～10％；ZrO2：0～10％；TiO2：0～5％；P2O5: 0 to 5 percent; a clarifying agent: 0 to 2 percent.
5. The alkali-free glass according to any one of claims 1 to 4, wherein the composition thereof, expressed in weight percent, satisfies one or more of the following 4 conditions:
1)B2O3/SiO20.01 to 0.40;
2)Al2O3/SiO20.10 to 0.80;
3)(TiO2+ZrO2)/Al2O30.40 or less;
4)(La2O3+Gd2O3)/Y2O3less than 0.40.
6. The alkali-free glass according to any one of claims 1 to 4, wherein the components are expressed in weight percentage, wherein: SiO 22: 22-55%; and/or B2O3: 1-15%; and/or Al2O3: 7-30%; and/or CaO: 15-45%; and/or SrO: 0 to 10 percent; and/or BaO: 1-10%; and/or MgO: 1 to 10 percent(ii) a And/or Y2O3: 0 to 20 percent; and/or ZnO: 0 to 10 percent; and/or La2O3: 0-8%; and/or Gd2O3: 0-8%; and/or ZrO2: 0-8%; and/or TiO2: 0 to 3 percent; and/or P2O5: 0 to 3 percent; and/or a clarifying agent: 0 to 1 percent.
7. The alkali-free glass according to any one of claims 1 to 4, wherein the composition thereof satisfies, in terms of weight percent, one or more of the following 5 conditions:
1)B2O3/SiO20.03 to 0.30;
2)Al2O3/SiO20.15 to 0.70;
3)(TiO2+ZrO2)/Al2O30.30 or less;
4)(La2O3+Gd2O3)/Y2O3less than 0.30;
5) CaO/(CaO + MgO + SrO + BaO) is 0.50-0.90.
8. The alkali-free glass according to any one of claims 1 to 4, wherein the components are expressed in weight percentage, wherein: SiO 22: 25-50%; and/or B2O3: 2-12%; and/or Al2O3: 10-25%; and/or CaO: 20-35%; and/or SrO: 0 to 5 percent; and/or BaO: 2-8%; and/or MgO: 2-8%; and/or Y2O3: 0 to 15 percent; and/or ZnO: 0 to 5 percent; and/or La2O3: 0 to 5 percent; and/or ZrO2: 0 to 5 percent; and/or a clarifying agent: 0 to 0.5 percent.
9. The alkali-free glass according to any one of claims 1 to 4, wherein the composition thereof satisfies, in terms of weight percent, one or more of the following 5 conditions:
1)B2O3/SiO2is 0.05～0.25；
2)Al2O3/SiO20.20 to 0.50;
3)(TiO2+ZrO2)/Al2O3is 0.20 or less;
4)(La2O3+Gd2O3)/Y2O3less than 0.20;
5) CaO/(CaO + MgO + SrO + BaO) is 0.60-0.85.
10. The alkali-free glass according to any one of claims 1 to 4, wherein the composition contains F: 0 to 5 percent; and/or does not contain TiO2(ii) a And/or does not contain P2O5(ii) a And/or does not contain Gd2O3。
11. The alkali-free glass according to any one of claims 1 to 4, wherein the alkali-free glass has an expansion coefficient of α20-300℃Is 70X 10-7More than K, preferably 75X 10-7More preferably 80X 10 or more,/K-7More than K; and/or a specific elastic modulus of 25 or more, preferably 28 or more, more preferably 30 or more; and/or light transmission rate tau360nmIs 60% or more, preferably 70% or more, and more preferably 80% or more.
12. The alkali-free glass according to any one of claims 1 to 4, wherein the transition temperature T of the alkali-free glass isgIs 620 ℃ or higher, preferably 640 ℃ or higher, and more preferably 660 ℃ or higher; and/or a thermal shock cracking resistance temperature of 100 ℃ or higher, preferably 105 ℃ or higher, more preferably 110 ℃ or higher.
13. The alkali-free glass according to any one of claims 1 to 4, wherein the alkali-free glass has a water resistance DWIs 4 or more, preferably 3 or more, more preferably 2 or more; and/or acid resistance DAIs 4 or more, preferably 3 or more.
14. A sealing material comprising the alkali-free glass according to any one of claims 1 to 13.
15. The package carrier is characterized by being made of the alkali-free glass as claimed in any one of claims 1 to 13.
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| WO2023051190A1 (en) * | 2021-09-29 | 2023-04-06 | 成都光明光电股份有限公司 | Glass composition |
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