High young's modulus glass material and article produced using the glass
Patent Information
- Application Number
- EP2023929256
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-03-29
- Publication Date
- 2026-02-11
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Figure CN2023084820_03102024_PF_FP_ABST
Abstract
Description
High young’s modulus glass material and article produced using the glass
[0001] Specification
[0002] This disclosure generally concerns glasses having a high rigidity. Specifically, this disclosure relates to La2O3 containing glasses.
[0003] In the production of semiconductor chips, glass carrier wafers may be used for various wafer level packaging (WLP) technologies including fan-out WLP. If a glass wafer is used as sensor cover or for Wafer Level Optics (WLO) applications, generally, the glass thickness is restricted due to the requirement of product design, highly automatized processing and tooling, or stack height of miniaturized packages.
[0004] Hence, glass wafers for such applications typical need to be thin (< 2mm) . However, such thin glasses are mechanically flexible and prone to in-process warpage resulting from e.g. thermal expansion mismatch with silicon wafers, compound materials or coatings. To avoid this unwanted effect, one option would be to use thicker glass, which is, due to above mentioned restraints, not feasible. An alternative solution is to increase the stiffness of the glass, by increasing the Young's modulus. Additionally, it is desirable that the glass has a good UV-transmittance for UV-bonding and –debonding. Hence, opaque materials or materials with a high UV-edge transmission are generally not well suited. Further, another desirable feature is the compatibility of the thermal expansion behavior of the glass with other components in a wafer package. Thus, to further improve the in-process compatibility, lowering the coefficient of thermal expansion (CTE) of the glass can help to avoid in-process warpage effects that stem from CTE mismatches, e.g. with silicon wafers.
[0005] Usually, glasses used for above mentioned applications tend to be alkaline-free and have low CTE’s that match the CTE of silicon (~30 -40·107 ℃) . However, Young’s moduli of such glasses are often not particularly high and as such, they are mechanically not very stiff and therefore may not prevent strong warping, if bound to materials with higher or lower CTE.
[0006] US 2021 / 0371326 A1 discloses compositions of glasses and glass ceramics with high content of Y2O3 and TiO2 with high elastic modulus (E > 117 GPa) and hardness. Specifically, a composition is disclosed including 30 mol-%to 60 mol-%SiO2; 15 mol-%to 40 mol-%Al2O3; 5 mol-%to 25 mol-%Y2O3; 5 mol-%to 15 mol-%TiO2; and 0.1 mol-%to 15 mol-%RO, such that RO is a sum of MgO, CaO, SrO, and BaO. However, the crystallization process appears to be complex and the crystallites may affect the optical properties such as light scattering.
[0007] CN 112110645 B discloses a glass composition with high Young’s modulus (E>78GPa) and hardness. The glass contains ZnO, MgO, CaO, SrO, BaO to improve Young’s modulus. However, the glass contains Li2O and Na2O in a range from 5 –14.5 wt-%, with a ratio Li2O / (Li2O+Na2O) being 0.1 -0.4. However, a high content of Li2O is problematic for semi-material processing due to possible diffusion into the semiconductor material. In addition, the glass may be thermally tempered, indicating a high CTE.
[0008] In WO 2013 / 094619 A1, an optical glass with high Abbe number and high refractive index is described, containing 1.0 to 30.0%of B2O3 and 10.0 to 60.0%of La2O3 in wt-%. Examples of the glass have a Boron content of about 12 wt-%and a La2O3 content of around 40 wt-%. There is no disclosure regarding the mechanical properties of the glasses.
[0009] CN 110831908 A discloses support glass substrates for fan out type WLP. The glass types for the support have an average linear thermal expansion coefficient in a temperature range from 30 to 380 ℃ of 30 × 10-7 / ℃ to 55 × 10-7 / ℃ and a Young's modulus of 80 GPa or more. The glass composition contains a total amount of Y2O3 +La2O3 + ZrO2 of up to 20%. Higher contents of these constituents are avoided to maintain devitrification resistance.
[0010] In US2021 / 380469 A1 alkaline-free glasses having a high strain point are described having a composition containing 60 to 74 mol-%of SiO2, 6 to 20 mol-%of Al2O3, 0 to 9 mol-%of B2O3, 1 to 13 mol-%of MgO, 1 to 13 mol-%of CaO, 0 to 7 mol-%of SrO, 0 to 8 mol-%of BaO. Y2O3 + La2O3 are contained in an amount from 0 to 1.0 mol-%, The CTE is in the range from 30·10-7 to 45·10-7 / ℃. The glasses have a high Young’s modulus of 79 GPa or more.
[0011] Similarly, US 2021 / 380465 A1 discloses alkaline-free glasses with Young’s moduli above 78 GPa and a CTE in the range of 30·10-7 to 50·10-7 / ℃. As well, the glasses have a high strain point in order to reduce thermal shrinkage of the glass sheet in a low temperature poly silicon (LIPS) process.
[0012] US 2017 / 327408 A1 describes alkaline-free glass substrates for wafer level packaging having low CTE (in the range of 2 to 4 ppm / ℃ and Young’s moduli of 80 GPa or more for wafer-level packaging applications. The glasses may contain Y2O3 or La2O3 in amounts of 2 mol-%or less.
[0013] WO 2015 / 030013 A1 concerns alkaline-free substrate glasses for various types of displays with a CTE in the range from 30·10-7 to 45·10-7 / ℃ and Young’s moduli of 80 GPa or more. The glasses contain MgO and CaO to achieve high Young’s moduli.
[0014] In US 2021 / 179479 A1 optical glasses with refractive indices (nd) of 1.81 to 2.15, densities of 6.0 g / cm3 or less and SiO2 contents of 5 to 44 mol-%are disclosed. Some glass compositions include glasses containing high La2O3 and TiO2 contents, wherein La2O3 contents are in the range of 3.6 to 27.3 mol-%TiO2 in the range of 5.0 to 33.2 mol-%. However, the glasses have comparably high CTEs and no data of the Young’s modulus are disclosed for the glasses having high La2O3-content.
[0015] US 6555232 B1 concerns titania lanthan aluminosilicate glasses with strain point of > 780 ℃, CTE’s of 20 –60 ·10-7 / ℃ and Young’s modulus exceeding 8.28·l04 MPa. The glasses contain La2O3 together with large quantities of Al2O3 (5 –35 mol-%) and SiO2 in the range of 40 –90 mol-%.
[0016] US 2007 / 042894 A1 describes substrates for liquid crystal displays (LCDs) , solar cells, electronics, microelectronics etc., containing 60 to 88 mol-%of SiO2, 5 to 25 mol-%Al2O3 and rare earth elements according to the sum formula RE2O3 with 2 to 15 mol-%. The glasses have a high strain point and low liquidus temperature.
[0017] The invention aims to provide a glass combining high Young’s modulus with low CTE and suitable UV transmission. A glass article with a high Young’s modulus can reduce in-process warp during the semi-material thinning process or wafer level package (WLP) fabrication, and reduces the warp of finished articles, like glass used as the substrate of wafer level optics (WLO) , filters and sensor covers.
[0018] These requirements are fulfilled by a glass and articles comprising the glass as defined in the independent claims. The dependent claims define further advantageous refinements and embodiments of the invention. Accordingly, a glass is provided having a composition containing both La2O3 in an amount of at least 6.3 mol%, preferably at least 9 mol-%, and WO3 in an amount of at least 0.5 mol-%. A preferred range of the La2O3-content is from 9 mol-%to 20 mol-%, particularly preferred from 9 mol-%to 12 mol-%. The embodiments with a La2O3-content in the above given ranges combine high Young’s modulus with low CTE.
[0019] Further, the constituents of the glass compositions can be adjusted so that the glass has a young’s modulus of at least 85 GPa and a linear coefficient of thermal expansion (CTE) α20 / 300 of at most =7.5·10-6 K-1. Depending on the amounts of the glass components, the CTE may be even considerably lower. According to a refinement, the glass has a CTE α20 / 300 of at most =7·10-6 K-1, preferably at most 6·10-6 K-1, more preferably at most 5·10-6 K-1, most preferred at most 4·10-6 K-1. The low thermal expansion approximately matches the CTE of silicon which reduces warp of a wafer assembly with a silicon wafer and a glass wafer. For this reason, it is also advantageous to adjust the constituents of the glass so that the CTE α20 / 300 on the other hand is at least 2.5 ·10-6 K-1.
[0020] As well, the Young’s modulus may be even higher, preferably more than 90 GPa, more preferred higher than 95 GPa, most preferred more than 100 GPa.
[0021] The Poisson’s ratio of the glass may exceed ν=0.2 or even ν=0.25. Further, the Poisson’s ratio may even exceed ν=0.3, thus rendering the glass rather incompressible.
[0022] The Poisson’s ratio also contributes to the stiffness of the glass. In particular, the anti-warp stiffness of the glass can be very high, thereby reducing the warp, e.g. of a glass wafer produced from the glass. The anti-warp stiffness A is defined as A=E / (1-ν2) , with E denoting the Young’s modulus and ν denoting the Poisson’s ratio. According to a preferred embodiment, the anti-warp stiffness exceeds 88 GPa, preferably exceeds 90 GPa, more preferably is more than 95 GPa. The anti-warp stiffness may even exceed 100 GPa.
[0023] Further characteristics of a glass are the special moduli E / α20 / 300 and E / [ (1-ν) ·α20 / 300] . According to one embodiment, the special modulus E / α20 / 300 of the glass is at least 15·106 GPa·K, preferably at least 20·106 GPa·K, more preferred at least 25·106 GPa·K, most preferred at least 30·106 GPa·K. The special modulus E / [ (1-ν) ·α20 / 300] may be larger than 10·106 GPa·K, preferably larger than 12·106 GPa·K, most preferred larger than 15·106 GPa·K. The latter special modulus is a characteristic for the resistance against biaxial strains caused by temperature variations, e.g. when a wafer assembly with a glass wafer is heated or cooled down.
[0024] Moreover, the glass also can have a high hardness. Specifically, the Vickers hardness HV may exceed 500kg / mm2, preferably 550kg / mm2, or even 600kg / mm2.
[0025] Preferably, the glass has a content of WO3 in an amount of up to 2 mol-%, or, corresponding to a preferred range from 0.5 mol-%to 2 mol-%.
[0026] Further, the glass may contain Nb2O5 to increase Young’s modulus and hardness. A high content of Niobium oxide, however, would also increase the tendency for crystallization and raises the temperature of the softening point. Thus, in one embodiment, the glass contains Nb2O5 in an amount of 3 –5 mol-%. In a refinement, the content may be between 3 mol-%and 4 mol-%.
[0027] Generally, for the glass, the components Ga2O3, BaO, La2O3, WO3, TiO2, ZnO, ZrO2, and Nb2O5 help to increase Young’s modulus. In a preferred embodiment, therefore, the glass has an overall content of the aforementioned constituents from 18 mol-%to 50 mol-%. Particularly effective for raising the Young’s modulus among these constituents are Ga2O3, La2O3, Nb2O5 and WO3. On the other hand, these components also raise the temperature of the softening point. Advantageously, however, a high Young’s modulus may be achieved with a limited content of these components. Specifically, according to one embodiment, the overall content of the components Ga2O3, La2O3, Nb2O5 and WO3 is in the range from 15 mol-%to 25 mol-%, preferably from 16 mol-%to 23 mol-%.
[0028] Further, the glass preferably contains SiO2 in an amount of at least 9 mol-%. B2O3 may advantageously contained in an amount of at least 1 mol-%.
[0029] Advantageously, Y2O3 may be omitted in favor of La2O3 to gain high UV transmittance. Specifically, it is preferred that the content of Y2O3 is less than 0.05 mol-%. In particular, the glass can be free of Y2O3.
[0030] Generally, independent from whether the glass contains Y2O3 or not, the glass has a high transmittance for UV-light. Specifically, the glass may have a transmittance of more than 80%for a glass thickness of 1 mm at a wavelength within a range from 380 nm to 280 nm. The transmittance may also exceed 85 %or even 90 %for at least one wavelength in the range from 380 nm to 280 nm.
[0031] Certain components typically have a negative influence on UV transmittance. The proportions of such components is desirably limited in the glass. Thus, according to a further embodiment, the glass may comprise SnO2, Sb2O3, CeO2, Fe2O3, Co3O4, Cr2O3, Ni2O3, MnO2 in individual amounts of 0 to 0.5 mol%, preferably less than 0.01 mol%.
[0032] TiO2 also tends to reduce UV transmission since its absorbance increases at wavelengths below 400 nm. Thus, in one embodiment, the content of TiO2 is as well limited to 0 to 0.5 mol%, preferably less than 0.01 mol%. However, in another embodiment, the glass may contain a considerable amount of TiO2 since the UV transmittance may be still acceptable in the near-visible range and TiO2 on the other hand is very effective to increase the Young’s modulus. Thus, according to this embodiment, the TiO2-content is in the range from 15 to 28 mol-%, preferably from 16.5 mol%to 20 mol-%.
[0033] Similarly, ZrO2 is effective to increase the stiffness of the glass. Therefore, in one embodiment, the ZrO2-content ranges from 2.8 mol-%to 6.5 mol-%. Preferably, the ZrO2-content is in the range from 5 mol-%to 6.5 mol-%.
[0034] In a preferred embodiment, the glass composition comprises the following constituents: SiO2: 0-70 mol-%; Al2O3: 0 -15 mol-%; B2O3: 0 -40 mol-%; R2O: 0 -4 mol-% (R=Li, Na, K) ; RO: 0 -50 mol-% (R=Mg, Ca, Sr, Ba, Zn) ; R2O3: 0 –60 mol-% (R= Ga, Bi, Y, Sb) , RO2: 0-35 mol-% (R=Ge, Zr, Ti) R2O5: 0-30 mol-% (R=Nb, Ta) ,WO3: 0.5 -10 mol-%.
[0035] Further, a higher SiO2-content is advantageous, inter alia, to lower the coefficient of thermal expansion. According to a preferred embodiment, the content of SiO2 is at least 10 mol-%. It is further preferred to use a glass composition having a SiO2-content of at least 60 mol-%. Preferred ranges of the SiO2-content are from 9 mol-%to 15 mol-%in one embodiment and in a further embodiment from 62 mol-%to 71 mol-%.
[0036] In some preferred embodiments, the glass contains Al2O3 in an amount of 7 –13 mol-%. This component in this compositional range increases the UV-transmittance and the Young’s modulus.
[0037] According to a first, particularly preferred refinement of the above given composition, the glass comprises the following constituents in mol-%:
[0038] SiO2: 60 –70, preferably 64 –68;
[0039] Al2O3: 7 –13, preferably 9 –11;
[0040] B2O3: 1 –4, preferably 2 –3;
[0041] La2O3: 7 –13, preferably 9 –11;
[0042] WO3: 1.5 -2, preferably 1.75 –2;
[0043] Ga2O3: 6 –12, preferably 8 –10.
[0044] Glasses having these constituents exhibit a Young’s modulus of typically higher than 90 GPa and a CTE of typically lower than 5.1 ppm.
[0045] According to a second, preferred embodiment, the glass comprises the following constituents in mol-%: SiO2: 9 –20, preferably 9 –13;
[0046] B2O3: 25 –40, preferably 28 – 35;
[0047] ZnO: 10 –20, preferably 15 –18;
[0048] TiO2: 10 –28, preferably 15 –18;
[0049] La2O3: 11 –17, preferably 12 –16;
[0050] ZrO2: 3 –8, preferably 5 –7;
[0051] Nb2O5: 2 –6, preferably 3 –5;
[0052] WO3: 0.1 -1, preferably 0.3 –0.7.
[0053] In one embodiment, in particular in a refinement of both afore listed compositions with ranges of SiO2 content from 60 to 70 mol-%and from 10 to 20 mol-%, respectively, the glass also contains at least one alkaline earth oxide, preferably BaO. The content is in the range from 0.02 mol-%to 0.1 mol-%. This small admixture may beneficially help to suppress crystallization. However, according to another embodiment, the glass may also be free from alkaline earth oxides (i.e. having a content of less than 0.01 mol%) .
[0054] Further, according to a preferred embodiment, the glass is free from alkali oxides. This means that the total content of alkali oxides like Li2O, Na2O, K2O is less than 0.05 mol-%. This is beneficial to maintain a high Young’s modulus and high hardness of the glass. Further, a low content of alkali oxides avoids contamination of semiconductor devices bonded to the glass. In another embodiment, however, the glass may contain some alkali-oxides to lower the temperature of the softening point and to impede crystallization. According to this embodiment, the total content of alkali oxides is 7 mol-%at most. For example, the glass may contain 6.64 mol-%Li2O. Preferably, if alkali-oxides are contained, then, the minimum content is 0.3 mol-%to provide a beneficial effect. Thus, in this embodiment, the total alkali content may be in the range from 0.3 mol-%to 7 mol-%.
[0055] Further, the glasses according to this disclosure may be free from SnO2. This means that the content of SnO2 preferably is less than 0.05 mol-%. SnO2 may reduce the UV-transmittance. However, according to another embodiment, SnO2 is an effective fining agent and may therefore be used in a quantity from 0.1 mol-%to 1 mol-%.
[0056] This disclosure also concerns articles comprising the glass as described herein. High Young’s modulus glasses as they are subject of this disclosure are advantageous for use in combination with semiconductor carrier wafers, wafer level packages (WLP) , CMOS sensor covers, wafer level optics (WLO) , coating substrates, filter substrates, handheld devices, memory disks and fibers. Thus, an article comprising a glass according to this disclosure may be any of the aforementioned items.
[0057] In particular, the article may be a glass wafer or comprise a glass wafer made from the glass as disclosed herein. The glass article may be a wafer assembly, comprising a glass wafer and a semiconductor wafer, in particular a silicon wafer bonded thereon. The thinner the semiconductor wafers are, the more fragile they become. Bonding silicon wafers to a glass wafer using a removable UV adhesive helps reinforcing the semiconductor wafer and protects them against damage during conventional thinning and post-thinning processes. Thus, the wafer assembly with a glass wafer and a semiconductor wafer may be only temporary to provide an effective way to minimize stress and warp of semiconductor wafers during processing. The temporary adhesive does not damage the wafer surface and peels away without leaving any residue. Semiconductor wafer bonding minimizes issues such as warping, cracking, and edge chipping, leading to higher yields, high throughput, and reduced waste. The key component of the process is to minimize the in-process warp between glass and semi-material. On the other hand, high Young’s modulus glasses as substrates of filters can preserve minimum warpage after coating, when the filters gets thinner and thinner. Thus, in one embodiment, the glass article comprises a coating on a side surface of the glass, in particular, a coating that induces compressive or tensile stress to the glass.
[0058] The bonding may also be permanent so that the glass wafer can be used for packaging electronic semiconductor devices. In another embodiment, as explained above, the glass wafer is used as a carrier for processing the semiconductor wafer. In this embodiment, the glass wafer may be detached from the semiconductor wafer after processing. These embodiments and other details of the invention are further described with reference to the accompanying figures.Brief description of the drawings
[0059] Fig. 1 shows transmission spectra of two examples of high Young’s modulus glasses.
[0060] Fig. 2 shows a wafer assembly with a semiconductor wafer bonded to a glass wafer.
[0061] Detailed description of the drawings
[0062] Fig. 1 shows the transmission curves of two examples of La2O3 containing glasses having a Young’s modulus of at least 85 GPa according to this disclosure. The transmission has been measured with glass specimens having a thickness of 2mm. The UV transmission edge of examples (1) is at 330 nm (line (i) ) . Example (2) shows a UV transmission edge at 360 nm (line (ii) ) . Both examples show a transmission of over 80%at wavelengths above 450 nm, i.e. in the visible range. Example 1 has an even higher transmission, being over 80%for wavelengths above 400 nm.
[0063] The glasses of the examples 1, 2 have the following constituents:
[0064] The Young’s modulus of the glass of example 1 is 95 GPa. The Young’s modulus of example 2 is even higher and amounts to 121 GPa. The CTE of example 2 is 7.1·10-6 K-1 which is still acceptable in combination with silicon wafers. Although the Young’s modulus of the glass of example 1 is 95 GPa and therefore slightly lower than the modulus of example 2, example 1 is particularly suited to connect a silicon device such as a silicon wafer thereto and then process the assembly. This is since the CTE of example 1 is only 4.9·10-6 K-1. Thus, even if the glass may be bent slightly easier than that according to example 2, thermomechanical bending forces during processing are much lower so that warp is substantially avoided.
[0065] Fig. 2 shows an embodiment of an article 1 comprising a glass according to this disclosure. In one embodiment, the article 1 is a glass wafer made from the glass as described herein. However, the article may also comprise additional components. In particular, as in the example of Fig. 2, the article 1 may comprise a wafer assembly 2 with a semiconductor wafer 5, preferably a silicon wafer, bonded to a glass wafer 3. The bond may be permanent or temporary, e.g. a bond with a UV-releasable adhesive. In a variant, a multitude of separate semiconductor devices is bonded to the glass wafer using a permanent or releasable adhesive. One example of this variant is a fan-out wafer level package. Thus, according to one embodiment, the article 1 comprises at least one semiconductor device, which may also be a semiconductor wafer, bonded to the glass wafer 3 with a releasable adhesive, preferably a UV-releasable adhesive.
[0066] Due to different CTE’s of the glass wafer 3 and the semiconductor wafer 5, processing steps which involve heating of the wafer assembly 2 causes thermomechanical strain so that the wafer assembly 2 warps due to the imposed bending forces. Fig. 2 shows the wafer assembly 2 in a warped state. Specifically, in the depicted example, the outer side surface 31 of the glass wafer 3 is convexly bend. This would typically be the case, when the CTE of the glass wafer 3 is higher than the CTE of the semiconductor wafer 5 and the wafer assembly 2 is heated to an elevated temperature after bonding. The warp and its measurement is defined in to SEMI 3D12-0315. According to this standard, the warp is the difference between the most positive and most negative distances of the median surface of a free, unclamped (but gravity-compensated) wafer from a reference plane. Fig. 2 shows an exemplary reference plane close to the outer side face of glass wafer 3 and the maximum positive and negative distances A and B, respectively.
[0067] The warp w of the wafer assembly 2 can be approximated by the following formula:
[0068] In this formula, L denotes the length of the assembly, which is the diameter in case of round wafers. Es denotes the Young’s modulus of the semiconductor wafer and Eg is the Young’s modulus of the glass. tg is the thickness of the glass wafer 3 and ts denotes the thickness of the semiconductor wafer 5. Further, the warp depends on the Poisson’s ratios νg , νs of the glass and of the semiconductor material, respectively. The warp also depends linearly from both the difference of the CTE’s , Δα, and the temperature difference ΔT. For the differences Δα and ΔT, the positive absolute values may be inserted so that the warp has a non-negative value. As is evident from the formula, not only the special modulus E / α20 / 300 is relevant, but also the ratio Eg / Δα, i.e., the ratio of the Young’s modulus of the glass to the difference of the CTE. Thus, in one embodiment, the glass composition is chosen depending to the semiconductor material so that the ratio Eg / Δα is at least 20·106 GPa·K, preferably at least 50·106 GPa·K. Again, Δα is the absolute value of the difference of the linear thermal expansion coefficients (CTE) of the glass and the semiconductor wafer.
[0069] This disclosure also concerns a method for producing a glass wafer, using a glass as described herein. Components of the glass which impose high Young’s modulus besides La2O3 and which may be contained in the glass described here, are Ga2O3, BaO, WO3, TiO2, ZnO, ZrO2, and Nb2O5. Generally, these components may increase the tendency for crystallization. However, high quality glass articles using the glass as disclosed herein can be produced by casting and subsequent cutting and grinding. Although this procedure is slower than drawing methods like down-drawing, floating or overflow-fusion, the method is capable to produce articles with very high flatness and low thickness variations. Thus, in one embodiment, a method for producing a glass article, specifically, for producing a glass wafer is contemplated, the method including the steps of casting a glass block from a glass melt of the glass as described herein, sawing the glass block to cut a glass wafer from the glass block and to finish at least one of the side surfaces of the glass wafer, the finishing preferably including at least one of the steps of lapping and polishing. Although this processing is costly compared to providing a glass sheet with the approximate thickness by a drawing method, a superior flatness and minimal thickness variation can be achieved. Specifically, a glass article such as in particular a glass wafer may have at least one of the following features:
[0070] The roughness Ra of the glass surface is less than 1nm, or even less than 0.8nm;
[0071] The flatness is less than 150 μm, preferably less than 100 μm, or even less than 50 μm for a glass article having a thickness of at least 0.3 mm;
[0072] The total thickness variation (TTV) of the glass article is less than 15μm, preferably less than 10 μm, or even less than 5 μm;
[0073] The warp of the glass article is less than 100 μm, preferably less than 80 μm, or even less than 60μm for a glass article having a lateral dimension of at least 8” , e.g. for a glass wafer having a diameter of 8” or, in case of a square shaped wafer, a side length of 8”.
[0074] Warp and TTV may, e.g., be measured according to SEMI 3D12-0315. Further, SEMI MF1530 defines a test Method for measuring Flatness, thickness, and TTV on silicon wafers by automated non-contact scanning. This method may also be applied to determine flatness, thickness and TTV of a glass wafer according to this disclosure.
[0075] It is clear for a person skilled in the art that the invention as described herein is not limited to specific embodiments and examples. Inter alia, although the preferred method to produce flat or disc or pane shaped glass articles is by casting and subsequent sawing, other methods may be employed as well. For example, if the process is carried out sufficiently fast, a glass article may also be produced by drawing or other methods for producing a glass ribbon from a melt. Thus, although the casting method is preferred for the production of high quality glass wafers, an alternative method may also comprise the step of drawing a glass ribbon from a glass as described herein. Then, glass articles having the desired shape may be cut from the glass ribbon.
[0076] List of reference signs
Claims
1.A glass having a composition containing both La2O3 in an amount of at least 6.3 mol-%and WO3 in an amount of at least 0.5 mol-%, the glass having a young’s modulus of at least 85 GPa, and a linear coefficient of thermal expansion α20 / 300 of at most 7.5·10-6 K-1.2.The glass according to claim 1, having a content of WO3 in an amount of up to 2 mol-%.3.The glass according to claim 1, wherein the content of La2O3 is from 9 mol-%to 20 mol-%, preferably from 9 mol-%to 12 mol-%.4.The glass according to claim 1, comprising at least one of the following features:- the glass has a content of SiO2 of at least 9 mol-%, preferably of at least 60 mol-%,- the glass comprises B2O3 in an amount of at least 1 mol-%,- the glass contains Nb2O5 in an amount of 3 –5 mol-%,- the overall content of the components Ga2O3, La2O3, Nb2O5 and WO3 is in the range from 15 mol-%to 25 mol-%, preferably from 16 mol-%to 23 mol-%- the glass contains TiO2 in an amount from 15 to 28 mol-%, preferably from 16.5 mol%to 20 mol-%.- the content of ZrO2 ranges from 2.8 mol-%to 6.5 mol-%, preferably from 5 mol-%to 6.5 mol-%.5.The glass according to claim 1, wherein the content of Y2O3 is less than 0.05 mol-%, preferably, wherein the glass is free of Y2O3.6.The glass according to claim 1, comprising at least one of the components SnO2, Sb2O3, CeO2, TiO2, Fe2O3, Co3O4, Cr2O3, Ni2O3, MnO2 in individual amounts of 0 to 0.5 mol%, preferably in individual amounts of less than 0.01 mol%.7.The glass according to claim 1, having a transmittance of more than 80 %, preferably more than 85 %, most preferably more than 90 %for a glass thickness of 1 mm at a wavelength within a range from 380 nm to 280 nm.8.The glass according to claim 1, having a glass composition with the following constituents: SiO2: 0-70 mol-%; Al2O3: 0 -15 mol-%; B2O3: 0 -40 mol-%; R2O: 0 -4 mol-% (R=Li, Na, K) ; RO: 0 -50 mol-% (R=Mg, Ca, Sr, Ba, Zn) ; R2O3: 0 –60 mol-% (R= Ga, Bi, Y, Sb) , RO2: 0-35 mol-% (R=Ge, Zr, Ti) R2O5: 0-30 mol-% (R=Nb, Ta) , WO3: 0.5 -10 mol-%.9.The glass according to claim 1, having a composition with the following constituents in mol-%:SiO2: 60 –70, preferably 64 –68;Al2O3: 7 –13, preferably 9 –11;B2O3: 1 –4, preferably 2 –3;La2O3: 7 –13, preferably 9 –11;WO3: 1.5 -2, preferably 1.75 –2;Ga2O3: 6 –12, preferably 8 –10.10.The glass according to claim 1, having a composition with the following constituents in mol-%:SiO2: 9 –20, preferably 10 –13;B2O3: 25 –40, preferably 28 – 35;ZnO: 10 –20, preferably 15 –18;TiO2: 10 –28, preferably 15 –18;La2O3: 11 –17, preferably 12 –16;ZrO2: 3 –8, preferably 5 –7;Nb2O5: 2 –6, preferably 3 –5;WO3: 0.1 -1, preferably 0.3 –0.7.11.The glass according to claim 1, wherein the total content of alkali oxides is 7 mol-%at most.12.The glass according to claim 1, wherein the total content of alkali oxides is less than 0.05 mol-%.13.The glass according to claim 1, having at least one of the following features:- the glass has an anti-warp stiffness A exceeding 88 GPa, preferably exceeding 90 GPa, more preferably exceeding 100 GPa, the anti-warp stiffness being defined as A=E / (1-ν2) , with E denoting the Young’s modulus and ν denoting the Poisson’s ratio- the glass has a Young’s modulus higher than 90 GPa, preferably higher than 95 GPa, most preferred higher than 100 GPa- the glass has a linear coefficient of thermal expansion α20 / 300 of at most 5·10-6 K-1, preferably at most 4·10-6 K-1,- the special modulus E / α20 / 300 of the glass is at least 15·106 GPa·K, preferred at least 25·106 GPa·K, most preferred at least 30·106 GPa·K,- the special modulus E / [ (1-ν) ·α20 / 300] is larger than 10·106 GPa·K, preferably larger than 12·106 GPa·K, most preferred larger than 15·106 GPa·K,- the Vickers hardness HV of the glass exceeds 500kg / mm2, preferably 550kg / mm2, most preferred 600kg / mm2.14.An article (1) comprising a glass according to claim 1.15.The article (1) according to claim 14, wherein the article (1) is a glass wafer (3) or comprises a glass wafer (3) .16.The article (1) according to claim 14, wherein the article (1) comprises a wafer assembly (2) , with a semiconductor wafer (5) attached to a glass wafer (3) .17.The article (1) according to the claim 16, wherein the ratio Eg / Δα is at least 20·106 GPa·K, preferably at least 50·106 GPa·K, wherein Eg is the Young’s modulus of the glass and Δα is the absolute value of the difference of the linear thermal expansion coefficients (CTE) of the glass and the semiconductor wafer.18.The article (1) according to claim 15, having at least one of the following features:- the roughness Ra of the glass surface is less than 1nm, or even less than 0.8nm;- the flatness of the wafer (3) is less than 150 μm, preferably less than 50 μm, wherein the glass article has a thickness of at least 0.3 mm;- the total thickness variation (TTV) of the wafer (3) is less than 15μm, preferably less than 5 μm;- the warp of the wafer (3) is less than 100 μm, preferably less than 60μm, wherein the wafer (3) has a lateral dimension of at least 8” .19.The article (1) according to claim 15, comprising at least one semiconductor device, bonded to the glass wafer (3) with a UV-releasable adhesive.20.A method for producing a glass wafer (3) , using a glass according to claim 1.21.The method according to the preceding claim, the method including the steps of casting a glass block from a glass melt of the glass according to claim 1, sawing the glass block to cut a glass wafer (3) from the glass block and to finish at least one of the side surfaces (31) of the glass wafer (3) , the finishing including at least one of the steps of lapping and polishing.