CN115872615A - Glass material - Google Patents
Glass material Download PDFInfo
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- CN115872615A CN115872615A CN202111153945.3A CN202111153945A CN115872615A CN 115872615 A CN115872615 A CN 115872615A CN 202111153945 A CN202111153945 A CN 202111153945A CN 115872615 A CN115872615 A CN 115872615A
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- glass
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- sio
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- 239000011521 glass Substances 0.000 title claims abstract description 136
- 239000000463 material Substances 0.000 title claims abstract description 68
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 24
- 238000002834 transmittance Methods 0.000 claims abstract description 17
- 230000007704 transition Effects 0.000 claims abstract description 14
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 239000008395 clarifying agent Substances 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 11
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 239000003566 sealing material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 238000013461 design Methods 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 238000004806 packaging method and process Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 23
- 230000008569 process Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 9
- 238000004031 devitrification Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- -1 platinum ions Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention provides a glass material, which comprises the following components in percentage by weight: siO 2 2 ：50～70％；B 2 O 3 ：5～16.5％；Al 2 O 3 :10 to 25 percent; caO:2 to 13% of Al 2 O 3 /B 2 O 3 1.0 to 3.0, and the glass material does not contain an alkali metal oxide. Through reasonable component design, the glass material obtained by the invention has proper thermal expansion coefficient and Young modulus, higher ultraviolet transmittance and transition temperature, meets the requirements of a carrier and packaging in the semiconductor manufacturing process, and is suitable for the field of semiconductor manufacturing.
Description
Technical Field
The invention relates to a glass material, in particular to a glass material which can be used in the field of semiconductor manufacturing.
Background
In the field of semiconductor manufacturing, materials such as metal, ceramic, and single crystal silicon are generally used as substrates for wafers during the manufacturing process, so as to prevent the wafers from being deformed during the processes of photolithography, cleaning, packaging, and the like. Although the substrate material of metal, ceramic and monocrystalline silicon has better mechanical strength and acid-base corrosion resistance, the substrate material is opaque, so a heating stripping process is required in the process of stripping the substrate and the wafer. If a light-transmissive glass material is used as the fabrication substrate, a photo lift-off process may be used. Compared with a heating stripping process, the light stripping process can greatly reduce the process time and the stripping cost, simultaneously avoid the chip wafer from being baked at high temperature, and improve the yield of the chip manufacturing process. The optical lift-off process generally uses ultraviolet laser, which requires the glass substrate material to have a high transmittance to the working wavelength. The prior art contains an alkali metal oxide Li 2 O、Na 2 O、K 2 When the glass of O is used as a carrier, the alkali metal ions Li in the glass + 、Na + 、K + Can enter the monocrystalline silicon substrate to further pollute a chip circuit, and has adverse consequences. On the other hand, the substrate material is generally combined with the resin material, which requires that the thermal expansion coefficient and young modulus of the substrate material are matched with those of the resin material, otherwise, when the chip manufacturing process undergoes high and low temperature changes, the wafer may warp and deform, which results in the chip being discarded, and if the transition temperature of the glass material is too low, the glass deformation may be caused at high temperature.
Disclosure of Invention
For the above reasons, the technical problem to be solved by the present invention is to provide a glass material having suitable thermal expansion coefficient and young's modulus, higher transition temperature and ultraviolet transmittance.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the glass material comprises the following components in percentage by weight: siO 2 2 ：50～70％；B 2 O 3 ：5～16.5％；Al 2 O 3 :10 to 25 percent; caO:2 to 13%, ofMiddle Al 2 O 3 /B 2 O 3 1.0 to 3.0, and the glass material does not contain an alkali metal oxide.
Further, the glass material comprises the following components in percentage by weight: mgO:0 to 8 percent; and/or SrO:0 to 5 percent; and/or BaO:0 to 10 percent; and/or ZnO:0 to 5 percent; and/or Ln 2 O 3 :0 to 5 percent; and/or WO 3 :0 to 5 percent; and/or ZrO 2 :0 to 5 percent; and/or TiO 2 :0 to 5 percent; and/or P 2 O 5 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of Sb as clarifying agent 2 O 3 、CeO 2 、SnO 2 And SnO.
A glass material, the composition of which is expressed in weight percentage, is composed of SiO 2 ：50～70％；B 2 O 3 ：5～16.5％；Al 2 O 3 ：10～25％；CaO：2～13％；MgO：0～8％；SrO：0～5％；BaO：0～10％；ZnO：0～5％；Ln 2 O 3 ：0～5％；WO 3 ：0～5％；ZrO 2 ：0～5％；TiO 2 ：0～5％；P 2 O 5 :0 to 5 percent; a clarifying agent: 0 to 1% of Al 2 O 3 /B 2 O 3 1.0 to 3.0, the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of Sb as clarifying agent 2 O 3 、CeO 2 、SnO 2 And SnO.
Further, the glass material comprises the following components in percentage by weight: al (aluminum) 2 O 3 /B 2 O 3 1.2 to 2.5, preferably Al 2 O 3 /B 2 O 3 1.3 to 2.2; and/or CaO/(BaO + SrO + MgO) is 3.0 to 8.0, preferably CaO/(BaO + SrO + MgO) is 4.0 to 7.0, more preferably CaO/(BaO + MgO)+ SrO + MgO) is 4.5 to 6.0; and/or CaO/SiO 2 0.04 to 0.23, preferably CaO/SiO 2 0.06 to 0.2, more preferably CaO/SiO 2 0.08 to 0.16.
Further, the glass material comprises the following components in percentage by weight: siO 2 2 :54 to 68%, preferably SiO 2 :56 to 65 percent; and/or B 2 O 3 :6 to 15%, preferably B 2 O 3 :7 to 13 percent; and/or Al 2 O 3 :12 to 24%, preferably Al 2 O 3 :14 to 21 percent; and/or CaO:4 to 11%, preferably CaO:5 to 9 percent; and/or MgO: greater than 0 but less than or equal to 6%, preferably MgO:0.5 to 3 percent; and/or SrO:0 to 3%, preferably SrO:0 to 1 percent; and/or BaO:0 to 5%, preferably BaO:0 to 2 percent; and/or ZnO:0 to 3%, preferably ZnO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, preferably Ln 2 O 3 :0 to 1 percent; and/or WO 3 :0 to 3%, preferably WO 3 :0 to 1 percent; and/or ZrO 2 :0 to 3%, preferably ZrO 2 :0 to 1 percent; and/or TiO 2 :0 to 2%, preferably TiO 2 :0 to 1 percent; and/or P 2 O 5 :0 to 2%, preferably P 2 O 5 :0 to 1 percent; and/or a clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of Sb as a clarifying agent 2 O 3 、CeO 2 、SnO 2 And SnO.
Further, the glass material does not contain Ln 2 O 3 (ii) a And/or does not contain WO 3 (ii) a And/or does not contain ZrO 2 (ii) a And/or does not contain TiO 2 Said Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of (a).
Further, the refractive index n of the glass material d Is 1.48 to 1.54, preferably1.49 to 1.53, more preferably 1.50 to 1.52.
Further, the thermal expansion coefficient alpha of the glass material 20/300℃ Is 25X 10 -7 /K～40×10 -7 Preferably 27X 10,/K -7 /K～38×10 -7 More preferably 28X 10,/K -7 /K～36×10 -7 K; and/or transition temperature T g At a temperature of 630 ℃ or higher, preferably 650 ℃ or higher, and more preferably 660 to 750 ℃; and/or an external transmittance tau at 365nm 365nm 70% or more, preferably 80% or more, more preferably 85% or more; and/or stability against acid action D A Is 2 or more, preferably 1; and/or stability against water action D W Is 2 or more, preferably 1; and/or the Young's modulus E is 60 to 85GPa, preferably 65 to 80GPa; and/or a density rho of 3.0g/cm 3 Hereinafter, it is preferably 2.8g/cm 3 Hereinafter, more preferably 2.6g/cm 3 The following.
And the packaging material is made of the glass material.
And the packaging carrier is made of the glass material.
The invention has the beneficial effects that: through reasonable component design, the glass material obtained by the invention has proper thermal expansion coefficient and Young modulus, higher ultraviolet transmittance and transition temperature, meets the requirements of a carrier and packaging in the semiconductor manufacturing process, and is suitable for the field of semiconductor manufacturing.
Detailed Description
The following describes in detail embodiments of the glass material of the present invention, but the present invention is not limited to the embodiments described below, and can be implemented by making appropriate changes within the scope of the object of the present invention. In addition, although the description of the overlapping description may be appropriately omitted, the gist of the present invention is not limited thereto, and the glass material of the present invention may be simply referred to as glass in the following description.
[ glass Material ]
The ranges of the components of the glass material of the present invention are explained below. In the present specification, unless otherwise specified, the contents of the respective components and the total content are all expressed by weight percentage (wt%) relative to the total amount of glass substances in terms of composition of oxides. Here, the "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the glass material composition component of the present invention are decomposed in the melt and converted to oxides, the total weight 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 >
SiO 2 Is one of the main components of the glass of the present invention in which an appropriate amount of SiO is present 2 Can ensure that the glass has higher water resistance and acid resistance, and can realize high ultraviolet transmittance at the same time. If SiO 2 The content of the glass is lower than 50 percent, and the water resistance, the acid resistance and the ultraviolet transmittance of the glass are lower than the design requirements. If SiO 2 The content of (b) is higher than 70%, the melting temperature of the glass is sharply increased, high-quality glass is not easily obtained, and the thermal expansion coefficient of the glass is lower than the design expectation. Thus, siO in the present invention 2 The content of (b) is limited to 50 to 70%, preferably 54 to 68%, more preferably 56 to 65%.
B 2 O 3 The structure of the glass can be converted to a compact direction in the glass, high water resistance and acid resistance are realized, the reduction of the high-temperature viscosity of the glass is promoted, high-quality glass can be obtained more easily under the low-temperature condition, and if the content of the glass is lower than 5%, the effect is not obvious. If B is 2 O 3 The content of (A) is more than 16.5%, and the water resistance and acid resistance of the glass are reduced. Thus, B 2 O 3 The content of (b) is limited to 5 to 16.5%, preferably 6 to 15%, more preferably 7 to 13%.
An appropriate amount of Al 2 O 3 Can be used forThe Young's modulus of the glass is adjusted to increase the thermal conductivity of the glass, and the content of Al is 10% or more in the present invention 2 O 3 To obtain the above-mentioned effect; if the content is more than 25%, the thermal expansion coefficient of the glass rapidly decreases, the melting property becomes poor, and the crystallization is particularly easy. Thus, al 2 O 3 The content of (b) is 10 to 25%, preferably 12 to 24%, more preferably 14 to 21%.
In some embodiments, al 2 O 3 Content of (A) and (B) 2 O 3 Ratio between contents of Al 2 O 3 /B 2 O 3 If it exceeds 3.0, the melting temperature of the glass rises, the transmittance of the glass decreases, the internal quality deteriorates, and Al 2 O 3 /B 2 O 3 If the thermal expansion coefficient is less than 1.0, the glass has a thermal expansion coefficient which is difficult to satisfy the design requirements. Therefore, al is preferable 2 O 3 /B 2 O 3 1.0 to 3.0, more preferably Al 2 O 3 /B 2 O 3 Is 1.2 to 2.5, and Al is more preferable 2 O 3 /B 2 O 3 Is 1.3 to 2.2.
MgO can improve the chemical stability of the glass and adjust the optical constant of the glass, and if the content of MgO exceeds 8%, the thermal expansion coefficient of the glass is reduced, and the design requirements are difficult to meet. Therefore, the content of MgO is 0 to 8%, preferably greater than 0 but less than or equal to 6%, more preferably 0.5 to 3%.
CaO can improve the thermal stability and refractive index of the glass and adjust the thermal expansion coefficient, and in the present invention, the above effect is obtained by containing 2% or more of CaO, preferably 4% or more of CaO, and more preferably 5% or more of CaO. On the other hand, if the content of CaO is more than 13%, the devitrification resistance of the glass is deteriorated and the Young's modulus exceeds the design requirement. Therefore, the content of CaO is 2 to 13%, preferably 4 to 11%, more preferably 5 to 9%.
In some embodiments, the content of CaO and SiO are controlled 2 Ratio between contents of CaO/SiO 2 In the range of 0.04 to 0.23, the desired transition temperature of the glass can be obtained, and the devitrification resistance of the glass can be optimized. Therefore, caO/SiO is preferred 2 0.04 to 0.23, more preferably CaO/SiO 2 0.06 to 0.2, and more preferably CaO/SiO 2 0.08 to 0.16.
BaO can improve the refractive index and the transition temperature of the glass, optimize the stability and the mechanical property of the glass, and if the content of the BaO exceeds 10 percent, the density of the glass is increased, and the chemical stability is poor. Therefore, the content of BaO is 0 to 10%, preferably 0 to 5%, more preferably 0 to 2%.
SrO functions similarly to BaO, and if the content exceeds 5%, the thermal expansion coefficient of the glass does not meet the design requirements, and the chemical stability of the glass is drastically reduced. Therefore, the SrO content is 5% or less, preferably 3% or less, and more preferably 1% or less.
In some embodiments, if the ratio CaO/(BaO + SrO + MgO) between the content of CaO and the total content of BaO, srO and MgO, baO + SrO + MgO exceeds 8.0, the thermal expansion coefficient of the glass hardly reaches the design requirement, and the chemical stability is lowered; if CaO/(BaO + SrO + MgO) is less than 3.0, the melting temperature of the glass increases, and the light transmittance deteriorates. Therefore, caO/(BaO + SrO + MgO) is preferably 3.0 to 8.0, caO/(BaO + SrO + MgO) is more preferably 4.0 to 7.0, and CaO/(BaO + SrO + MgO) is further preferably 4.5 to 6.0.
ZnO can improve chemical stability and reduce thermal expansion coefficient in glass. If the content of ZnO exceeds 5%, the transition temperature of the glass is rapidly reduced, so that the glass is easy to soften and deform in a high-temperature working environment, and the glass device which needs to work in a high-temperature state is fatally influenced. Therefore, the ZnO content is 5% or less, preferably 3% or less, and more preferably 1% or less.
Ln 2 O 3 (Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of) can increase the thermal expansion coefficient and refractive index of the glass, and when the content is too large, the devitrification resistance of the glass is lowered, and the young's modulus and the transition temperature are difficult to meet the design requirements. Thus, ln 2 O 3 Is 5% or less, preferably 3% or less, more preferably 1% or less, and further preferably contains no Ln 2 O 3 。
WO 3 The refractive index and mechanical strength of the glass can be increased, but the light transmittance and transition temperature of the glass are lowered when the content is high. Thus, WO 3 The content of (b) is limited to 5% or less, preferably 3% or less, more preferably 1% or less, and further preferably no WO is contained 3 。
ZrO 2 The devitrification resistance can be improved in the glass, the chemical stability of the glass is enhanced, if the content of the devitrification resistance exceeds 5 percent, the thermal expansion coefficient of the glass is obviously reduced, the design requirement is difficult to achieve, meanwhile, the melting performance of the glass is reduced, the high-temperature viscosity is obviously increased, and infusible substances are easy to appear in the glass. Thus, zrO 2 The content is limited to 5% or less, preferably 3% or less, more preferably 1% or less, and further preferably no ZrO is contained 2 。
TiO 2 The devitrification resistance and the mechanical strength of the glass can be improved. If TiO 2 When the content of (b) exceeds 5%, the ultraviolet transmittance of the glass rapidly decreases, so that the subsequent laser peeling becomes difficult and the thermal expansion coefficient of the glass decreases. Thus, tiO 2 The content of (A) is 5% or less, preferably 2% or less, more preferably 1% or less, and further preferably not containing TiO 2 。
P 2 O 5 Is an optional component which may improve the devitrification resistance of the glass, particularly by reacting P 2 O 5 The content of (A) is 5% or less, and the decrease in chemical stability of the glass can be suppressed. Thus, P 2 O 5 The content of (b) is limited to 5% or less, preferably 2% or less, more preferably 1% or less.
The glass of the invention contains 0 to 1 percent of clarifying agent to improve the clarifying capacity and the bubble degree of the glass, and the content of the clarifying agent is preferably 0 to 0.8 percent, and more preferably 0 to 0.5 percent. The fining agent may comprise Sb 2 O 3 、CeO 2 、SnO 2 And SnO. Since CeO 2 、SnO 2 SnO and Sb 2 O 3 In contrast, the ultraviolet transmittance of the glass is seriously impaired, so that Sb is preferably used in the present invention 2 O 3 As a clarifying agent.
< component which should not be contained >
In recent years, oxides of Th, cd, tl, os, be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. 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. Thereby, the glass becomes practically free from substances contaminating the environment. Therefore, the glass of the present invention can be manufactured, processed, and discarded without taking special measures for environmental countermeasures.
To achieve environmental friendliness, the glasses according to the invention do not contain As 2 O 3 And PbO. Although As 2 O 3 Has the effects of eliminating bubbles and better preventing the glass from coloring, but As 2 O 3 The addition of (b) increases the platinum attack of the glass on the furnace, particularly on the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace. PbO can significantly improve the high-refractivity and high-dispersion properties of the glass, but PbO and As 2 O 3 All cause environmental pollution.
"0%" or "0%" is not included in the present invention, and means that the compound, molecule, element or the like is not intentionally added to the glass of the present invention as a raw material; however, it is within the scope of the present invention that certain impurities or components 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 glass material of the present invention will be described below.
< refractive index >
Refractive index (n) of glass material d ) The test was carried out according to the method specified in GB/T7962.1-2010.
In some embodiments, the refractive index (n) of the glass materials of the present invention d ) Has a lower limit of 1.48, preferably a lower limit of 1.49, more preferably a lower limit of 1.50, a refractive index (n) d ) Upper part ofThe upper limit is 1.54, the upper limit is preferably 1.53, and the upper limit is more preferably 1.52.
< stability against acid Effect >
Stability of the glass Material against acid action (D) A ) (powder method) the test was carried out according to the method prescribed in GB/T17129.
Stability of the acid resistance of the glass Material of the invention (D) A ) Is 2 or more, preferably 1.
< stability against Water Effect >
Stability to Water action of glass materials (D) W ) (powder method) the test was carried out according to the method described in GB/T17129.
Stability to Water action of the glass Material of the invention (D) W ) Is 2 or more, preferably 1.
< coefficient of thermal expansion >
Coefficient of thermal expansion (alpha) of glass material 20/300℃ ) The data at 20-300 ℃ were tested according to the method specified in GB/T7962.16-2010.
In some embodiments, the glass materials of the present invention have a coefficient of thermal expansion (α) 20/300℃ ) Is 25X 10 -7 /K～40×10 -7 Preferably 27X 10,/K -7 /K～38×10 -7 More preferably 28X 10,/K -7 /K～36×10 -7 /K。
< light transmittance >
The light transmittance of the invention refers to the external transmittance at 365nm of a glass sample with the thickness of 10mm, and is shown as tau 365nm It is shown to be tested according to the method specified in GB/T7962.12-2010.
In some embodiments, the glass material of the present invention has an external transmittance (τ) at 365nm 365nm ) Is 70% or more, preferably 80% or more, and more preferably 85% or more.
< transition temperature >
Transition temperature (T) of glass material g ) Testing according to the method specified in GB/T7962.16-2010.
In some embodiments, the glass materials of the present invention have a transition temperature (T) g ) Is 630 ℃ or higher, preferably 650 ℃ or higher, more preferablyIs 660 to 750 ℃.
< Young's modulus >
The Young's modulus (E) of the glass material is calculated by the following formula:
wherein G = V S 2 ρ
In the formula:
e is Young's modulus, pa;
g is shear modulus, pa;
V T is the longitudinal wave velocity, m/s;
V S is the transverse wave velocity, m/s;
rho is the density of the glass, g/cm 3 。
In some embodiments, the glass material of the present invention has a Young's modulus (E) of 60 to 85GPa, preferably 65 to 80GPa.
< Density >
The density (. Rho.) of the glass material was measured according to the method specified in GB/T7962.20-2010.
In some embodiments, the glass material of the present invention has a density (ρ) of 3.0g/cm 3 Hereinafter, it is preferably 2.8g/cm 3 Hereinafter, more preferably 2.6g/cm 3 The following.
The glass material of the present invention has the above excellent properties, and can be widely applied to the fields of packaging of electronic devices, photosensitive devices, and also to the manufacture of glass elements, various devices or instruments, such as imaging devices, sensors, microscopes, medical technologies, digital projection, communications, optical communication technologies/information transmission, optics/lighting in the automotive field, lithography, excimer lasers, wafers, computer chips, and integrated circuits and electronic devices including such circuits and chips, or image pickup devices and apparatuses used in the vehicle-mounted field, monitoring security, and the like. The method can be applied to semiconductor packaging and semiconductor manufacturing process, and is used for manufacturing packaging materials and/or packaging carriers and the like.
[ production method ]
The manufacturing method of the glass material of the invention comprises the following steps: the glass of the invention is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide, fluoride, phosphate, metaphosphate and the like are used as raw materials, the prepared furnace burden is put into a melting furnace at 1400-1600 ℃ for melting after being proportioned by a conventional method, and homogeneous molten glass without air bubbles and undissolved substances is obtained after clarification, stirring and homogenization, and the molten glass is cast in a mould 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, glass materials having compositions shown in tables 1 to 3 were obtained by the above-described glass material production method. 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.
Table 1.
| Example (wt%) | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| SiO 2 | 53.6 | 55.2 | 60.7 | 62.3 | 64.2 | 57.5 | 56.6 |
| B 2 O 3 | 8.2 | 11.45 | 8.7 | 11.7 | 10.48 | 14.3 | 13.1 |
| Al 2 O 3 | 22.5 | 20.6 | 18.4 | 15.4 | 11.5 | 21.5 | 15.6 |
| MgO | 3.6 | 2.5 | 2.1 | 0.4 | 1.7 | 0.8 | 1.2 |
| CaO | 11.5 | 9.6 | 10.0 | 8.5 | 8.0 | 5.8 | 10.4 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 | 2.0 |
| BaO | 0 | 0 | 0 | 1.5 | 0 | 0 | 0 |
| ZnO | 0 | 0 | 0 | 0 | 0 | 0 | 1.0 |
| La 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Gd 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Y 2 O 3 | 0 | 0 | 0 | 0 | 1.0 | 0 | 0 |
| Yb 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| WO 3 | 0 | 0 | 0 | 0 | 1.0 | 0 | 0 |
| ZrO 2 | 0.5 | 0 | 0 | 0 | 0 | 0 | 0 |
| TiO 2 | 0 | 0 | 0 | 0 | 2.0 | 0 | 0 |
| P 2 O 5 | 0 | 0.5 | 0 | 0 | 0 | 0 | 0 |
| Sb 2 O 3 | 0.1 | 0.15 | 0.1 | 0.2 | 0.12 | 0.1 | 0.1 |
| CeO 2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| SnO 2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| SnO | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Is totaled | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Al 2 O 3 /B 2 O 3 | 2.744 | 1.799 | 2.115 | 1.316 | 1.097 | 1.503 | 1.191 |
| CaO/(BaO+SrO+MgO) | 3.194 | 3.84 | 4.762 | 4.474 | 4.706 | 7.25 | 3.25 |
| CaO/SiO 2 | 0.215 | 0.174 | 0.165 | 0.136 | 0.125 | 0.101 | 0.184 |
| n d | 1.5016 | 1.5123 | 1.5087 | 1.5146 | 1.5305 | 1.5106 | 1.5075 |
| α 20/300℃ (×10 -7 /K) | 38 | 28 | 32 | 31 | 35 | 29 | 26 |
| T g (℃) | 675 | 668 | 682 | 675 | 670 | 674 | 665 |
| τ 365nm (％) | 87.4 | 86.5 | 88.0 | 86.6 | 87.1 | 87.2 | 86.8 |
| D A | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 |
| D W | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 |
| E(GPa) | 70.5 | 72.4 | 70.7 | 72.6 | 73.2 | 75.5 | 70.6 |
| ρ(g/cm 3 ) | 2.37 | 2.41 | 2.45 | 2.38 | 2.40 | 2.46 | 2.38 |
Table 2.
| Example (wt%) | 8# | 9# | 10# | 11# | 12# | 13# | 14# |
| SiO 2 | 61.7 | 62.2 | 57.3 | 65.25 | 60.3 | 62.5 | 60.0 |
| B 2 O 3 | 8.7 | 8.4 | 16.5 | 5.9 | 9.7 | 10.5 | 14.1 |
| Al 2 O 3 | 18.2 | 17.2 | 16.87 | 12.2 | 18.0 | 17.2 | 15.7 |
| MgO | 2.5 | 0.6 | 1.4 | 4.0 | 2.2 | 1.3 | 1.4 |
| CaO | 8.8 | 9.3 | 7.8 | 12.5 | 8.6 | 8.4 | 7.2 |
| SrO | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| BaO | 0 | 2.2 | 0 | 0 | 0 | 0 | 0 |
| ZnO | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| La 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 | 1.5 |
| Gd 2 O 3 | 0 | 0 | 0 | 0 | 1.0 | 0 | 0 |
| Y 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Yb 2 O 3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| WO 3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| ZrO 2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| TiO 2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| P 2 O 5 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Sb 2 O 3 | 0.1 | 0.1 | 0.13 | 0.15 | 0.2 | 0.1 | 0.1 |
| CeO 2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| SnO 2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| SnO | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Total up to | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Al 2 O 3 /B 2 O 3 | 2.092 | 2.048 | 1.022 | 2.068 | 1.856 | 1.638 | 1.113 |
| CaO/(BaO+SrO+MgO) | 3.52 | 3.321 | 5.571 | 3.125 | 3.909 | 6.462 | 5.143 |
| CaO/SiO 2 | 0.143 | 0.15 | 0.136 | 0.192 | 0.143 | 0.134 | 0.12 |
| n d | 1.5153 | 1.5146 | 1.5134 | 1.5047 | 1.5214 | 1.5036 | 1.5185 |
| α 20/300℃ (×10 -7 /K) | 35 | 36 | 26 | 30 | 28 | 27 | 36 |
| T g (℃) | 672 | 671 | 680 | 673 | 674 | 670 | 672 |
| τ 365nm (％) | 85.7 | 88.1 | 87.4 | 87.2 | 87.5 | 86.5 | 87.4 |
| D A | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 |
| D W | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 | Class 1 |
| E(GPa) | 74.5 | 72.8 | 73.0 | 75.1 | 78.2 | 72.4 | 72.1 |
| ρ(g/cm 3 ) | 2.42 | 2.46 | 2.32 | 2.35 | 2.42 | 2.41 | 2.47 |
Table 3.
Claims (10)
1. The glass material is characterized by comprising the following components in percentage by weight: siO 2 2 ：50～70％；B 2 O 3 ：5～16.5％；Al 2 O 3 :10 to 25 percent; caO:2 to 13% of Al 2 O 3 /B 2 O 3 1.0 to 3.0, and the glass material does not contain an alkali metal oxide.
2. The glass material according to claim 1, characterized in that it further comprises, in percentages by weight: mgO:0 to 8 percent; and/or SrO:0 to 5 percent; and/or BaO:0 to 10 percent; and/or ZnO:0 to 5 percent; and/or Ln 2 O 3 :0 to 5 percent; and/or WO 3 :0 to 5 percent; and/or ZrO 2 :0 to 5 percent; and/or TiO 2 :0 to 5 percent; and/or P 2 O 5 :0 to 5 percent; and/or a clarifying agent: 0 to 1 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of Sb as clarifying agent 2 O 3 、CeO 2 、SnO 2 And SnO.
3. Glass material, characterized in that its composition, expressed in weight percentage, is represented by SiO 2 ：50～70％；B 2 O 3 ：5～16.5％；Al 2 O 3 ：10～25％；CaO：2～13％；MgO：0～8％；SrO：0～5％；BaO：0～10％；ZnO：0～5％；Ln 2 O 3 ：0～5％；WO 3 ：0～5％；ZrO 2 ：0～5％；TiO 2 ：0～5％；P 2 O 5 :0 to 5 percent; a clarifying agent: 0 to 1% of Al 2 O 3 /B 2 O 3 1.0 to 3.0, the Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of Sb as a clarifying agent 2 O 3 、CeO 2 、SnO 2 And SnO.
4. A glass material according to any one of claims 1 to 3, characterized in that its composition is expressed in weight percentages in which: al (Al) 2 O 3 /B 2 O 3 1.2 to 2.5, preferably Al 2 O 3 /B 2 O 3 1.3 to 2.2; and/or CaO/(BaO + SrO + MgO) is 3.0 to 8.0, preferably CaO/(BaO + SrO + MgO) is 4.0 to 7.0, more preferably CaO/(BaO + SrO + MgO) is 4.5 to 6.0; and/or CaO/SiO 2 0.04 to 0.23, preferably CaO/SiO 2 0.06 to 0.2, more preferably CaO/SiO 2 0.08 to 0.16.
5. A glass material according to any one of claims 1 to 3, characterized in that its composition is expressed in weight percentage, in which: siO 2 2 :54 to 68%, preferably SiO 2 :56 to 65 percent; and/or B 2 O 3 :6 to 15%, preferably B 2 O 3 :7 to 13 percent; and/or Al 2 O 3 :12 to 24%, preferably Al 2 O 3 :14 to 21 percent; and/or CaO: 4E11%, preferably CaO:5 to 9 percent; and/or MgO: greater than 0 but less than or equal to 6%, preferably MgO:0.5 to 3 percent; and/or SrO:0 to 3%, preferably SrO:0 to 1 percent; and/or BaO:0 to 5%, preferably BaO:0 to 2 percent; and/or ZnO:0 to 3%, preferably ZnO:0 to 1 percent; and/or Ln 2 O 3 :0 to 3%, preferably Ln 2 O 3 :0 to 1 percent; and/or WO 3 :0 to 3%, preferably WO 3 :0 to 1 percent; and/or ZrO 2 :0 to 3%, preferably ZrO 2 :0 to 1 percent; and/or TiO 2 :0 to 2%, preferably TiO 2 :0 to 1 percent; and/or P 2 O 5 :0 to 2%, preferably P 2 O 5 :0 to 1 percent; and/or a clarifying agent: 0 to 0.8%, preferably a clarifying agent: 0 to 0.5 percent of Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of Sb as clarifying agent 2 O 3 、CeO 2 、SnO 2 And SnO.
6. Glass material according to any one of claims 1 to 3, characterized in that it does not contain Ln 2 O 3 (ii) a And/or does not contain WO 3 (ii) a And/or does not contain ZrO 2 (ii) a And/or does not contain TiO 2 Said Ln 2 O 3 Is La 2 O 3 、Gd 2 O 3 、Y 2 O 3 、Yb 2 O 3 One or more of (a).
7. The glass material according to any one of claims 1 to 3, wherein the refractive index n of the glass material d Is 1.48 to 1.54, preferably 1.49 to 1.53, more preferably 1.50 to 1.52.
8. The glass material according to any one of claims 1 to 3, wherein the glass material has a coefficient of thermal expansion α 20/300℃ Is 25X 10 -7 /K～40×10 -7 Preferably 27X 10,/K -7 /K～38×10 -7 a/K, more preferably 28X 10 -7 /K～36×10 -7 K; and/or transition temperature T g At a temperature of 630 ℃ or higher, preferably 650 ℃ or higher, more preferably 660 to 750 ℃; and/or an external transmittance τ at 365nm 365nm 70% or more, preferably 80% or more, more preferably 85% or more; and/or stability against acid action D A Is 2 or more, preferably 1; and/or stability against water action D W Is 2 or more, preferably 1; and/or the Young's modulus E is 60 to 85GPa, preferably 65 to 80GPa; and/or a density rho of 3.0g/cm 3 Hereinafter, it is preferably 2.8g/cm 3 Hereinafter, more preferably 2.6g/cm 3 The following.
9. A sealing material comprising the glass material according to any one of claims 1 to 8.
10. A package carrier made of the glass material according to any one of claims 1 to 8.
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