Support plate glass used in semiconductor packaging field and preparation method thereof

Abstract

The invention relates to the field of glass, in particular to carrier plate glass used in the field of semiconductor packaging and a preparation method of the carrier plate glass. The carrier plate glass comprises the following components in percentage by mass: 52 to 73 percent of S O < 2 >, 20 percent of A < 2 > O < 3 >, 10 percent of B < 2 > O < 3 >, 16 percent of Na2O < 2 >, 0 to 30 percent of K2O < 0 >, 0 to 8 percent of MgO < 0 >, 0 to 9 percent of CaO < 0 >, 0 to 9 percent of SrO < 0 >, 0 to 12 percent of BaO < 0 >, 0 to 5 percent of ZnO < 0 >, 1 percent of ZrO < 2 >, 5 percent of Fe < 2 > O < 3 > and 0.1 to 2 percent of clarifying agent. The carrier plate glass has different thermal expansion coefficient values, and the elastic modulus is low and is less than 70.

Description

Technical Field

[0001] The present invention relates to the field of glass, and more particularly, to a carrier glass for semiconductor packaging and a method for preparing the same. Background Art

[0002] With the development of semiconductor devices towards high performance, miniaturization, high integration and high frequency, packaging technology faces increasingly stringent challenges. Traditional packaging materials (such as organic substrates, ceramic substrates) gradually show limitations in some scenarios, such as insufficient thermal stability, high dielectric loss or high cost. As an emerging packaging carrier material, glass has received extensive attention from the academic and industrial circles in recent years due to its unique physical, chemical and mechanical properties. Specifically, the glass core substrate is the key to determining the performance of millimeter-wave devices, and the material is usually required to have good stiffness, chemical stability, weather resistance, as well as high resistivity and low high-frequency dielectric loss. Aluminosilicate glass has higher resistivity, lower dielectric loss and dielectric constant than silicon, as well as a thermal expansion coefficient (CTE) adapted to the device and good rigidity, and can be used to manufacture carriers for larger-size wafer / panel packaging with thinner thickness and smaller roughness.

[0003] However, the current aluminosilicate glass cannot meet the requirements of having different thermal expansion coefficient values and a low elastic modulus. Summary of the Invention

[0004] The present invention provides a carrier glass for semiconductor packaging, which has different thermal expansion coefficient values and a low elastic modulus < 70.

[0005] The present invention is implemented as follows:

[0006] In a first aspect, an embodiment of the present invention provides a carrier glass for semiconductor packaging, the components of which are calculated by mass percentage of oxides and include: SiO2 52 - 73%, Al2O3 0 - 20%, B2O3 0 - 7%, Na2O 2 - 16%, K2O 0 - 30%, MgO 0 - 8%, CaO 0 - 9%, SrO 0 - 9%, BaO 0 - 12%, ZnO 0 - 5%, ZrO2 0 - 1%, Fe2O3 0 - 5% and a clarifying agent 0.1 - 2%.

[0007] Further, in a preferred embodiment of the present invention, the mass content of SiO2 + Al2O3 is 50 - 80%.

[0008] Further, in a preferred embodiment of the present invention, RO / SiO2 < 0.5, where RO represents any one or at least two of MgO, SrO, CaO and BaO.

[0009] Further, in a preferred embodiment of the present invention, calculated by mass percentage of the oxide, the content of SiO2 is 54-68%;

[0010] Preferably, the content of MgO is 0-6%;

[0011] Preferably, the content of B2O3 is 3-9%;

[0012] Preferably, the content of K2O is 0-9%;

[0013] Preferably, the content of Na2O is 10-15%;

[0014] Preferably, the content of Al2O3 is 12-18%.

[0015] Further, in a preferred embodiment of the present invention, at 550 nm of visible light, the light transmittance of the carrier glass is above 90%.

[0016] Further, in a preferred embodiment of the present invention, the transformation point of the carrier glass > 500 °C.

[0017] Further, in a preferred embodiment of the present invention, the elastic modulus of the carrier glass < 70.

[0018] Further, in a preferred embodiment of the present invention, the thermal expansion coefficient of the carrier glass is 60-130.

[0019] Further, in a preferred embodiment of the present invention, the fining agent is SO4 2- , NO3 - , F - , Cl - , SnO2 and Sb2O3, any one or at least two of them.

[0020] Second, an embodiment of the present invention provides a method for preparing a carrier glass for the semiconductor packaging field, including: melting the raw materials for forming the carrier glass at high temperature and then forming.

[0021] The beneficial effects of the present invention are: by using specific raw materials and ratios, the formed carrier glass has different thermal expansion coefficient values, and the elastic modulus is relatively low < 70; and at 550 nm of visible light, the light transmittance is above 90%. Detailed Embodiments

[0022] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not specified by the manufacturer can all be obtained as conventional products through commercial purchase.

[0023] The following specifically describes an embodiment of the present invention, which provides a carrier glass for the field of semiconductor packaging and its preparation method.

[0024] In a first aspect, an embodiment of the present invention provides a carrier glass for the field of semiconductor packaging. In terms of the mass percentage of oxides, its components include: SiO2 52 - 73%, Al2O3 0 - 20%, B2O3 0 - 10%, Na2O 2 - 16%, K2O 0 - 30%, MgO 0 - 8%, CaO 0 - 9%, SrO 0 - 9%, BaO 0 - 12%, ZnO 0 - 5%, ZrO2 0 - 1%, Fe2O3 0 - 5%, and a clarifying agent 0.1 - 2%.

[0025] The carrier glass provided by the embodiment of the present invention has a customizable coefficient of thermal expansion (CTE). By adjusting the composition (such as borosilicate glass, aluminosilicate glass), it can be highly matched with the silicon chip (CTE ≈ 3 ppm / °C), reducing warping and failure caused by thermal stress. It has excellent flatness, and the surface roughness of the glass can be controlled at the nanoscale, suitable for high-precision lithography and microbump processes. High heat resistance: The glass has a high melting point (>600 °C), suitable for high-temperature packaging processes (such as 3D TSV reflow soldering).

[0026] Specifically, SiO2 is the main component that forms silicon-oxygen tetrahedrons and connects to form the glass network structure, which is the basic framework of the glass. The addition amount of SiO2 is 52 - 73%, preferably 54 - 68%. When SiO2 < 52%, the chemical resistance of the glass is poor, and the surface state of the glass deteriorates after being eroded by acid and alkali. The higher the SiO2 content, the greater the degree of connection between silicon-oxygen tetrahedrons, and the higher the chemical stability of the glass. When SiO2 > 73%, the high-temperature viscosity of the glass increases, and the melting temperature increases sharply, which is not conducive to production. Therefore, it is necessary to control its content within a suitable range.

[0027] Al2O3 is easy to form tetrahedral coordination. The [AlO4] tetrahedral coordination can help build a closer network together with the [SiO4] tetrahedrons and is an important component of the glass network structure. It can also make the geometric shape of the glass change very little. The addition amount of Al2O3 is 0 - 20%, preferably 12 - 18%. When the content of Al2O3 exceeds 20%, it is easy to cause the glass to become cloudy or even devitrify. In addition, it will also increase the high-temperature viscosity and the difficulty of melting, which is not conducive to production.

[0028] Na2O is an external oxide of the glass network, Na +It is located in the cavities of the glass structure network. Na2O can provide free oxygen to increase the O / Si ratio in the glass structure, causing bond breakage. Therefore, it is a good flux in the glass components, which can reduce the viscosity of the glass and make the glass easy to melt. It is also an important element for ion exchange in chemical strengthening. At the same time, Na2O will increase the thermal expansion coefficient of the glass, reducing the thermal stability, chemical stability and mechanical strength of the glass. So, too much Na2O cannot be introduced, generally not exceeding 18%. In the embodiments of the present invention, the addition amount of Na2O in the aluminosilicate glass is 2-16%, preferably 10-15%. When the content of Na2O is higher than 16%, the chemical stability of the glass will be reduced. When the content is at least 2%, the melting temperature of the glass can be maintained at a proper level, and considerable ion exchange characteristics can be provided for the glass.

[0029] The function of K2O is similar to that of Na2O. K + has a larger radius than Na + , and the viscosity of potassium glass is greater than that of sodium glass. It can reduce the crystallization tendency of the glass and increase the transparency and gloss of the glass. In the carrier glass provided by the embodiments of the present invention, its content range is 0-30%, preferably 0-9%.

[0030] MgO can moderate the relationship between temperature and viscosity, reducing the devitrification phenomenon of the glass. It improves the meltability, strain point and Young's modulus of the glass, reduces the crystallization tendency and crystallization speed, increases the high-temperature viscosity of the glass, and improves the chemical stability and mechanical strength of the glass. However, when the content of MgO is too high, it will also increase the surface tension of the glass, resulting in difficult melting. In the glass of the present invention, the content range of MgO is 0-8%, preferably 0-6%.

[0031] CaO can improve the chemical stability of the glass, increase the mechanical strength and hardness of the glass, and adjust the thermal expansion coefficient. In the carrier glass provided by the embodiments of the present invention, the content range of CaO is 0-9%.

[0032] BaO is a divalent network modifier oxide, which can increase the refractive index, density, gloss and chemical stability of the glass. A small amount of BaO can accelerate the melting of the glass, but when the content is too much, it will cause secondary bubbles in the clarification. In the carrier glass provided by the embodiments of the present invention, the content range of BaO is 0-12%.

[0033] B2O3 is generally a colorless, transparent, hard and brittle substance (able to scratch glass), with a density of 1.84 g / cm 3 , and a melting point of 600 °C. The density of crystalline boron oxide is 1.805 g / cm 3, with a melting point of 295 °C and a boiling point of 1860 °C, it is soluble in water and alcohol, has strong water absorption, and often exists as a glass network former. B2O3 often exists in two structures, [BO4] and [BO3], in glass. When there is enough free oxygen provided in the glass, boron participates in the network structure in the form of [BO4], playing a role in connecting the network. [BO4] is a tetrahedral structure. When it exists, it can reduce the crystallization tendency of the glass, increase the refractive index of the glass, improve the luster, and enhance the chemical stability and heat resistance; when the content of the network modifier outside the glass composition is low and not enough free oxygen can be provided, boron exists in the form of [BO3] triangular bodies and does not enter the glass network. [BO3] has a chain-like and layered structure. If it gradually increases, the glass will have a lower softening temperature, poorer chemical stability, and a larger expansion coefficient. When the structures of [BO4] and [BO3] transform into each other, obvious changes in certain properties of the glass will occur. Glass science calls this the boron anomaly, that is, there are maxima or minima on the curve of composition and properties. Utilizing the boron anomaly can make the glass meet certain specific requirements. Too high boron content in the glass composition will lead to serious boron volatilization, and cause problems such as unstable glass composition and environmental pollution. In the carrier glass provided by the embodiments of the present invention, the content of B2O3 is 0 - 10%, preferably 3 - 9%.

[0034] ZrO2 not only has the best water and acid resistance, but also has the best alkali resistance. An appropriate amount of ZrO2 helps to improve the chemical durability and hardness of the glass. However, if too much ZrO2 is contained, on the one hand, the devitrification resistance of the glass decreases, and on the other hand, the meltability becomes poor and there is a devitrification tendency, making the forming difficult. In the carrier glass provided by the embodiments of the present invention, the content range of ZrO2 is 0 - 1%.

[0035] Furthermore, the carrier glass provided by the embodiments of the present invention for the semiconductor packaging field has excellent comprehensive performance, which also benefits from the mutual cooperation between the components in the composition, especially when SiO2 + Al2O3 is 50 - 80% and RO / SiO2 < 0.5. Among them, RO represents any one or at least two of MgO, SrO, CaO, and BaO.

[0036] Furthermore, the glass substrate of the carrier glass provided by the embodiments of the present invention for the semiconductor packaging field has a thickness between 1 mm and 2 mm.

[0037] The carrier glass formed by the above materials and ratios has the following advantages:

[0038] (1) At 550 nm of visible light, the light transmittance is above 90%.

[0039] (2) It has a relatively low elastic modulus < 70 and a coefficient of thermal expansion that decreases from high to low (70 - 120), and has stronger flexibility in the later-stage semiconductor manufacturing process, resisting breakage after deformation.

[0040] (3) It has a relatively high working temperature, with a transition point > 500 °C.

[0041] (4) This carrier glass is an environmentally friendly glass system, containing no toxic or harmful substances, conforming to the industry development trend, suitable for production by various forming methods such as float, overflow, and down-draw, suitable for large-scale industrial production, and the prepared glass is applicable to the carrier glass in the semiconductor industry packaging field.

[0042] In a second aspect, an embodiment of the present invention provides a method for preparing a carrier glass for the semiconductor packaging field, including: melting the raw materials for forming the carrier glass at a high temperature and then forming.

[0043] Specifically, weigh silicon-containing compounds, aluminum-containing compounds, sodium-containing compounds, magnesium-containing compounds, potassium-containing compounds, zirconium-containing compounds, boron-containing compounds in proportion, such as any one of carbonates, nitrates, sulfates, and oxides containing the aforementioned elements, etc., and a fining agent. Among them, there is no particular limitation on the specific selection of the fining agent, and it can be SO4 2- 、NO3 - 、F - 、Cl - 、SnO2 and Sb2O3, any one or at least two of them.

[0044] Under heating conditions, the above raw materials are mixed evenly and then subjected to high-temperature melting (1520 - 1680 °C), clarification and homogenization to obtain a homogeneous molten glass without bubbles and undissolved substances. This molten glass is cast in a mold and annealed to obtain an aluminosilicate glass base glass, that is, the carrier glass provided by the embodiment of the present invention. Among them, the large-scale forming techniques used include but are not limited to float method, overflow method, etc.

[0045] The performance of the carrier glass provided by the embodiment of the present invention is detected by the following method:

[0046] The transmittance of the carrier glass applicable to the semiconductor packaging field can be measured by using a spectrophotometer with reference to the standard ISO13468 - 1:1996.

[0047] The coefficient of thermal expansion (α20 / 300 °C) of the carrier glass applicable to the semiconductor packaging field is tested for data at 20 - 300 °C according to the method specified in "GB / T7962.16 - 2010".

[0048] The transformation temperature (Tg) of the carrier glass applicable to the semiconductor packaging field is tested according to the method specified in "GB / T7962.16-2010";

[0049] The hardness of the carrier glass applicable to the semiconductor packaging field is measured by using a Vickers hardness tester with reference to the standard GB / T 16534-2009;

[0050] The density (ρ) of the carrier glass applicable to the semiconductor packaging field is tested according to the method specified in "GB / T7962.20-2010".

[0051] The following specifically describes a carrier glass for the semiconductor packaging field and its preparation method provided by the present invention in conjunction with specific embodiments.

[0052] Examples 1-10

[0053] Examples 1-10 of the present invention and Comparative Examples 1-3 respectively provide a carrier glass for the semiconductor packaging field, and their compositions are shown in Table 1, Table 2 and Table 3 respectively.

[0054] The preparation methods of the carrier glasses provided in the above examples and comparative examples of the present invention are the same, and the only difference lies in the raw material ratios. Specifically, the corresponding raw materials of each component are calculated and weighed, and after being fully stirred and mixed, they are melted, clarified, formed, annealed, cut, etc. to obtain a base glass with a thickness of 1.0 mm. The glass is tested, and the test results are shown in Table 1, Table 2 and Table 3.

[0055] For the glass melted according to the raw materials in Examples 1-5, after testing, the CTE expansion coefficient α20 / 300 (×10 -7 / K) is within the range of 60-80, and the elastic modulus is less than 70, meeting the requirements of the carrier glass in the semiconductor field.

[0056] For the glass melted according to the raw materials in Examples 6-10, after testing, the CTE expansion coefficient α20 / 300 (×10 -7 / K) is within the range of 100-130, and the elastic modulus is less than 70, meeting the requirements of the carrier glass in the semiconductor field.

[0057] For the glass melted according to the raw materials in Comparative Examples 1-3, after testing, the CTE expansion coefficient α20 / 300 (×10 -7 / K) is within the range of 30-40, not meeting the requirements of the carrier glass in the semiconductor field.

[0058] Table 1 Carrier glass of Examples with CTE 60-80 and E < 70

[0059]

[0060] Table 2 Carrier glass of CTE100 - 130, E < 70

[0061]

[0062]

[0063] Table 3 Carrier glass of Comparative Example with CTE30 - 50

[0064]

[0065] It can be seen from Table 1, Table 2 and Table 3 that the glass formed after changing the raw material combination or ratio provided in the embodiments of the present invention cannot meet the requirements of carrier glass and cannot be used as carrier glass, further proving that not any combination or ratio of components can form carrier glass.

[0066] The above is only the preferred embodiment of the present invention and is not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A carrier glass for the field of semiconductor packaging, characterized in that, Its components are calculated by mass percentage of oxides and include: 52 - 73% of SiO₂, 0 - 20% of Al₂O₃, 0 - 10% of B₂O₃, 2 - 16% of Na₂O, 0 - 30% of K₂O, 0 - 8% of MgO, 0 - 9% of CaO, 0 - 9% of SrO, 0 - 12% of BaO, 0 - 5% of ZnO, 0 - 1% of ZrO₂, 0 - 5% of Fe₂O₃ and 0.1 - 2% of clarifying agent.

2. The carrier glass for the semiconductor packaging field according to claim 1, wherein The mass content of SiO₂ + Al₂O₃ is 50 - 80%.

3. The carrier glass for the semiconductor packaging field according to claim 1, wherein RO / SiO₂ < 0.5, where RO represents any one or at least two of MgO, SrO, CaO and BaO.

4. The carrier glass for the semiconductor packaging field according to any one of claims 1-3, characterized in that, Calculated by mass percentage of oxides, the content of SiO₂ is 54 - 68%; Preferably, the content of MgO is 0 - 6%; Preferably, the content of B₂O₃ is 3 - 9%; Preferably, the content of K₂O is 0 - 9%; Preferably, the content of Na₂O is 10 - 15%; Preferably, the content of Al₂O₃ is 12 - 18%.

5. The carrier glass for the field of semiconductor packaging according to any one of claims 1-3, characterized in that At 550 nm of visible light, the light transmittance of the carrier plate glass is above 90%.

6. The carrier glass for the field of semiconductor packaging according to any one of claims 1-3, characterized in that The transformation point of the carrier plate glass > 500 °C.

7. The carrier glass for the semiconductor packaging field according to any one of claims 1-3, characterized in that The elastic modulus of the carrier plate glass < 70.

8. The carrier glass for the field of semiconductor packaging according to any one of claims 1-3, characterized in that, The thermal expansion coefficient of the carrier plate glass is 60 - 130.

9. The carrier glass for the field of semiconductor packaging according to any one of claims 1-3, characterized in that The clarifying agent is SO4 2- , NO3 - , F - , Cl - , any one or at least two of SnO2 and Sb2O3.

10. A method for preparing a carrier glass for the semiconductor packaging field according to claim 1, characterized in that, Including: The raw materials for forming the carrier plate glass are melted at high temperature and then formed.

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