Stacked body and method for manufacturing stacked body

Abstract

A laminate having a glass sheet and a coating layer, the coating layer containing one or more components selected from the group consisting of silicon nitride, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, indium tin oxide, silicon oxide, magnesium fluoride, and calcium fluoride, the ratio (dc / dg) of the thickness dc of the coating layer to the thickness dg of the glass sheet being in the range of 0.05 x 10 －3 ~ 1.2 x 10 －3 , and the radius of curvature r1 of the laminate under a self-weight deflection correction condition being in the range of 10 m to 150 m.

Description

[0001] This application is a divisional application of patent application 201980013998.X (application date: August 16, 2019, invention title: laminate and method for manufacturing laminate). Technical Field

[0002] This invention relates to a laminate and a method for manufacturing a laminate, and more particularly, to a support glass substrate used to support a processing substrate in a semiconductor packaging manufacturing process. Background Technology

[0003] In wafer-level packaging (WLP), a fan-out type WLP has been proposed. In fan-out type WLP, in order to suppress dimensional changes of the processing substrate, it is known to use a glass substrate that supports the processing substrate (Patent Document 1).

[0004] However, in WLP's manufacturing process, such as Figure 1 As shown, processes involving high temperatures, such as the peeling layer lamination process and the resin mold making process, can sometimes cause the substrate to warp due to heat.

[0005] As an improvement to warpage, studies have been conducted on using a support glass substrate with less warpage. However, studies have not yet been conducted on the purpose of counteracting the warpage that occurs during the manufacturing process of the WLP by warping the support glass substrate in the opposite direction to the warpage that occurs in advance during the manufacturing process of the WLP.

[0006] In addition, it is known that warping is generated by coating a thin film on a glass substrate (Patent Document 2), but no technology has been studied to generate warping of the glass plate efficiently with a thinner film.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2017-30997

[0010] Patent Document 2: International Publication No. 2017 / 204167 Summary of the Invention

[0011] Although thickening the coating can easily increase the warpage of the laminate, the manufacturing process of fan-out type WLP can separate the processing substrate from the support substrate by irradiating the release layer with a visible wavelength laser. Therefore, the material and thickness of the coating hinder the transmission of the laser, which becomes a problem.

[0012] In this situation, a support glass substrate material with significant warpage is required while maintaining visible light transmittance.

[0013] The inventors have discovered that the above-mentioned problems have been solved by manufacturing a laminate with a specific warp and structure, and a method for manufacturing a laminate under specific conditions.

[0014] That is, the present invention provides a laminate having a glass plate and a coating, wherein the coating contains one or more components selected from silicon nitride, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, indium tin oxide, silicon oxide, magnesium fluoride, and calcium fluoride, and the ratio of the thickness dg of the glass plate to the thickness dc of the coating is dc / dg = 0.05 × 10⁻⁶. －3 ~1.2×10 －3 The radius of curvature r1 of the above-mentioned laminated body under the self-weight deflection correction condition is 10m to 150m.

[0015] The present invention provides a laminate that maintains visible light transmittance while exhibiting significant warpage. Furthermore, using this laminate as a support glass substrate enables the manufacture of WLPs with high dimensional accuracy. Attached Figure Description

[0016] Figure 1 This is an example of the conventional WLP manufacturing process (up to the peeling off of the support substrate).

[0017] Figure 2 This is one example of a WLP manufacturing process (up to the peeling off of the support substrate) using the laminate of the present invention as a support glass substrate.

[0018] Symbol Explanation

[0019] 10-layer stack

[0020] 11 glass plates

[0021] 12. Thin film (coating) Detailed Implementation

[0022] The laminate and its manufacturing method according to the present invention will be described. It should be noted that, unless otherwise specified, the tilde “~” used to indicate numerical ranges in this specification represents the lower and upper limits of the values ​​described before and after it.

[0023] [Glass Composition]

[0024] Unless otherwise specified, the composition of the glass plate used in the laminate of the present invention can be any known composition with high visible light transmittance. Specifically, a composition with a minimum transmittance (T%) of 60% or more in the wavelength range of 400 nm to 1000 nm can be used.

[0025] Preferred compositions include those expressed as mass percent based on oxides, in the range of SiO2: 40%–70%, B2O3: 0%–15%, MgO: 0%–10%, CaO: 0%–10%, SrO: 0%–13%, BaO: 0%–40%, Na2O: 0%–30%, K2O: 0%–13%, and Al2O3: 0.5%–15%.

[0026] As particularly preferred compositions, examples include those expressed as mass percent based on oxides, in the range of SiO2: 49%–70%, B2O3: 4%–13%, MgO: 0%–0.5%, CaO: 0%–8%, SrO: 0%–8%, BaO: 0%–13%, Na2O: 4%–15%, K2O: 0.1%–13%, and Al2O3: 4%–13%.

[0027] If the composition falls within this range, the visible light transmittance is excellent. Furthermore, in glass compositions with high coefficients of thermal expansion, the effect of warping due to heat treatment is greater, thus the effects of this invention are particularly significant.

[0028] [glass plate]

[0029] Glass sheets are used in the laminates of the present invention. The glass sheets are manufactured, for example, by forming the glass components into a plate of a predetermined shape (e.g., a square or a disc).

[0030] The method of forming the glass plate is not limited; for example, known methods such as float glass, melt glass, and roll-out glass can be used. Furthermore, in this invention, to allow for greater warping of the laminate, it is preferable that the glass plate before coating has a certain degree of warping.

[0031] The ideal warpage of the glass plate before coating is a radius of curvature r0 of 200m to 500m, more preferably 300m to 400m, under the self-weight deflection correction condition (a value corrected to the inherent warpage of the glass wafer. Although "deflection" caused by its own weight occurs under gravity, this value is obtained by excluding it). By keeping the warpage of the glass plate within this range before coating, the coating process, described later, leads to an increase in the warpage of the laminate.

[0032] Glass sheets that meet these conditions can be easily obtained by cutting out portions of warp within that range from raw material sheets manufactured, for example, by float glass.

[0033] The thickness (dg) of the glass plate is preferably 0.3 mm to 3.0 mm. More preferably 0.5 mm to 2.0 mm, and particularly preferably 0.7 mm to 1.2 mm. Within this range, the strength of the laminate is excellent, and the weight is within an acceptable range. In addition, chemically strengthened glass plates can be used.

[0034] [coating]

[0035] In this invention, a coating is formed by applying a thin film to the aforementioned glass plate. The coating contains one or more components selected from silicon nitride, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, indium tin oxide, silicon oxide, magnesium fluoride, and calcium fluoride. Silicon nitride and titanium oxide are preferred because they exhibit excellent visible light transmittance and a good effect on warping the laminate.

[0036] As a coating method, known methods such as sputtering, ion-assisted deposition, and aerosol deposition can be used. Among these, sputtering is preferred because it has an excellent effect on warping the laminate. Furthermore, the coating is applied to the convex side of the aforementioned warped glass plate, thereby increasing the warp of the glass plate.

[0037] The thickness of the coating (dc) is preferably 0.05 μm to 1.2 μm. More preferably 0.1 μm to 1.0 μm, and particularly preferably 0.4 μm to 0.6 μm. Within this range, both large warpage and high visible light transmittance of the laminate can be achieved.

[0038] [Layered Body]

[0039] The laminate of the present invention comprises the aforementioned glass plate and the aforementioned coating. Furthermore, the radius of curvature r1 under self-weight deflection correction conditions is in the range of 10m to 150m, preferably 30m to 100m. Within this range, it is possible to manufacture a WLP with high dimensional accuracy.

[0040] Furthermore, the ratio of the glass plate thickness dg to the coating thickness dc is dc / dg = 0.05 × 10⁻⁶. －3 ~1.2×10 －3 Preferably at 0.4×10 －3 ~0.5×10 －3 Within this range, it is possible to achieve both large warpage and high visible light transmittance of the laminate.

[0041] The thickness of the laminate is preferably 0.3 mm to 3.5 mm. More preferably 0.5 mm to 2.5 mm, and particularly preferably 0.7 mm to 1.3 mm. Within this range, both the strength of the laminate and high visible light transmittance can be obtained.

[0042] In addition, the shape of the laminate is preferably square or disc-shaped.

[0043] This laminate is suitable for use as a support for glass substrates.

[0044] [Manufacturing method of laminated bodies]

[0045] The laminate of the present invention is manufactured by applying the above-described coating to the glass plate. Specific examples of preferred manufacturing methods include... Figure 2 The diagram shows a process in which a thin film (coating) 12 containing one or more components selected from silicon nitride, titanium oxide, aluminum oxide, niobium oxide, zirconium oxide, indium tin oxide, silicon oxide, magnesium fluoride, and calcium fluoride is coated on the convex side of a warped glass plate 11 with a radius of curvature of 200 m to 500 m under self-weight flexural correction conditions. By manufacturing under these conditions, a laminate 10 with a radius of curvature r1 of 10 m to 150 m or less under self-weight flexural correction conditions can be appropriately obtained.

[0046] Example

[0047] The present invention will now be described in detail with reference to embodiments and comparative examples. However, the implementation methods can be appropriately modified as long as the effects of the present invention are achieved.

[0048] <Sample Shape for Evaluation>

[0049] The sample was obtained by coating a disc-shaped glass plate with a diameter of 150 mm (6 inches) and a thickness of 1.0 mm according to the conditions described in Table 1.

[0050] <Measurement Conditions & Evaluation Conditions>

[0051] [Determination of glass plate thickness (dg) and coating thickness (dc)]

[0052] The thicknesses of the glass plate before coating and the laminate after coating were measured using a laser displacement meter (Dyvoce manufactured by Shinzu Seiki Co., Ltd.) at room temperature, and dg and dc were calculated.

[0053] [Radius of curvature (r0, r1) of the glass plate and the laminate]

[0054] The sample was subjected to a laser displacement instrument (Dyvoce manufactured by Kamitsu Seiki Co., Ltd.), and the warpage inherent to the sample was calculated through shape simulation based on the self-weight deflection correction obtained in the two-dimensional difference mode. Furthermore, the radius of curvature was determined from the shape obtained through simulation.

[0055] The radius of curvature of the glass plate before coating under the condition of self-weight deflection correction is set as r0, and the radius of curvature of the glass plate of the laminate after coating under the condition of self-weight deflection correction is set as r1.

[0056] [Evaluation of warping]

[0057] Warpage caused by coating typically increases with coating thickness. Therefore, warpage is evaluated according to R as shown in the following formula. Evaluations A through D are considered acceptable for A, B, and C.

[0058] Formula: R = r1(m) × dc(μm)

[0059] evaluate:

[0060] A: R≤30,

[0061] B: 30 < R ≤ 50

[0062] C: 50 < R < 70

[0063] D: 70≤R

[0064] [Visible light transmittance]

[0065] The lowest transmittance (T%) of the sample at wavelengths of 400-1000 nm is measured using a spectral transmittance meter (V-700, manufactured by Japan Spectrophotometer Co., Ltd.) at room temperature. Evaluation A through C indicates that A or B is acceptable.

[0066] evaluate:

[0067] A: 80% ≤ T,

[0068] B: 60% ≤ T < 80%,

[0069] C: T < 60%

[0070] [Example 1]

[0071] A glass raw material sheet (1000 mm in length and width, 1.4 mm thick) with composition 1 (SiO2: 56.9%, Al2O3: 8.1%, CaO: 2.3%, SrO: 12.3%, BaO: 20.4% by mass) was obtained using the float glass process. A disc-shaped glass plate with a radius of 75 mm (diameter: 150 mm) was cut from the center of the raw material sheet. After chamfering, it was ground using a double-sided grinding machine (Hamai Manufacturing Co., Ltd. 16B-N / F) to adjust the plate thickness (dg) to 1.0 mm. The radius of curvature r0 (based on the float glass process) of this glass plate under self-weight deflection correction conditions is 370 μm.

[0072] Subsequently, a silicon nitride film was formed on the warped convex side of a glass plate using a silicon target via reactive sputtering with a sputtering apparatus (ULVAC SIV-345XYSSS) at a compressive stress of 1 GPa. The coating thickness (dc) was 0.5 μm. The evaluation results are shown in Table 1.

[0073] [Examples 2-7 and Comparative Examples 1-4]

[0074] The conditions are changed to those described in Table 1, and otherwise the same operation is performed as in Example 1.

[0075] The evaluation results are shown in Table 1.

[0076]

[0077] (quality%)

[0078] Composition 1: SiO2: 56.9%, Al2O3: 8.1%, CaO: 2.3%, SrO: 12.3%, BaO: 20.4%

[0079] Composition 2: SiO2: 68.9%, Al2O3: 5.9%, MgO: 4.1%, CaO: 7.3%, Na2O: 14.6%, K2O: 0.2%

[0080] This application claims priority based on Japan Patent Application No. 2018-240262 filed on December 21, 2018, the entire contents of which are incorporated herein by reference.

Claims

1. A laminate comprising a glass plate and a coating, said laminate serving to support a glass substrate, The ratio of the coating thickness dc to the glass plate thickness dg, i.e., dc / dg, is 0.4 × 10⁻⁶. －3 ~1.2×10 －3 Scope The radius of curvature r1 of the laminate under self-weight deflection correction conditions is 54m to 150m. The minimum transmittance for wavelengths in the range of 400nm to 1000nm is above 60%. The coating contains one or more components selected from silicon nitride and titanium oxide. The thickness dc of the coating is 0.4μm to 1.0μm.

2. The laminated body according to claim 1, wherein, The glass used in the glass plate has a composition, by mass percent, in the range of SiO2: 40%–70%, B2O3: 0%–15%, MgO: 0%–10%, CaO: 0%–10%, SrO: 0%–13%, BaO: 0%–40%, Na2O: 0%–30%, K2O: 0%–13%, and Al2O3: 0.5%–15%.

3. The laminate according to claim 1 or 2, wherein, The shape of the stacked body is either square or disc-shaped.

4. A method for manufacturing a laminate according to any one of claims 1 to 3, comprising the following step: coating a thin film containing one or more components selected from silicon nitride and titanium oxide onto the convex side of a warped glass plate having a radius of curvature r0 of 200m to 500m under self-weight flexural correction conditions.

5. The method for manufacturing a laminate according to claim 4, wherein, The coating method is sputtering.

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