Lithium aluminosilicate-based crystallized glass and method for manufacturing same

Abstract

The present invention provides a lithium aluminosilicate-based crystallized glass for semiconductors, the lithium aluminosilicate-based crystallized glass comprising a crystalline phase in an amorphous glass matrix, wherein the glass matrix comprises 63.0-75.0 wt% of SiO2, 10.0-16.0 wt% of Li2O, 7.0-18.0 wt% of Al2O3, 0.1-4.0 wt% of K2O, 0.01-1.0 wt% of Na2O, 0.005-0.2 wt% of Ag2O, 0.0025-0.1 wt% of CeO2, 0.2-5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn, or Ba), and 0.02 to 1.0 wt% of a fining agent, and the weight ratio Li2O / (SiO2 + Li2O) satisfies 0.062-0.212. The lithium aluminosilicate-based crystallized glass has a low coefficient of thermal expansion and thus has high material applicability to not only semiconductor glass substrates but also biochips, various sensor components, prove unit / card filters, labs-on-chips, and EUV mirrors.

Description

Lithium aluminosilicate-based crystallized glass and method for manufacturing the same

[0001] The present invention relates to a lithium aluminosilicate-based crystallized glass and a method for manufacturing the same. Specifically, it relates to a SiO2-Li2O-Al2O3-based crystallized glass useful not only as a semiconductor glass substrate but also for biochips, various sensor components, Prove unit / card filters, Lab-on-a-Chip, EUV reflectors, etc., and a method for manufacturing the same.

[0002] Since most materials, including air, absorb EUV light, optical systems applying EUV must be composed of reflective optical systems. Materials for mirrors, which are core components of EUV reflective optical systems, require low surface roughness and high flatness to secure high-efficiency EUV reflective surfaces; therefore, they must possess excellent surface processability and have few internal defects. In particular, low thermal expansion is required to minimize expansion due to temperature changes even under EUV irradiation, so low thermal expansion glass or crystallized glass materials may be considered. EUV (Extreme Ultraviolet) is defined as an electromagnetic wave with a wavelength between X-ray and deep UV (DUV), approximately 10 to 100 nm, and is applied in extreme ultraviolet imaging, spectroscopy, and nanomachining.

[0003] In relation to such low thermal expansion optical materials, lithium aluminosilicate-based (hereinafter, LAS-based) materials have been developed. For example, Korean Patent Publication No. 10-2024-0037860 and No. 10-2023-0158021 describe crystallized glass having specific thermal expansion characteristics.

[0004] The LAS-based crystallized glass described in Korean Patent Publication No. 10-2024-0037860 has a composition comprising SiO2 ≤ 68.5 mol%, Li2O 7 to 9.6 mol%, Al2O3 10 to 22 mol%, ZnO ≤ 1.1 mol% (ZnO + MgO 0.5 to 1.5 mol%), R2O > 0.5 mol% (R2O is Na2O and / or K2O and / or Cs2O and / or Rb2O), a total content of RO(CaO + BaO + SrO) 0.1-6 mol%, and P2O 50-6 mol%, and has a maximum of 0±0.1×10⁻⁶ in the range of 0 to 50 ℃. -6 It is a LAS-based crystallized glass material having an average coefficient of thermal expansion of / K. It is described as being capable of achieving relatively high imaging accuracy in precision parts in EUV lithography.

[0005] The LAS-based crystallized glass described in Korean Patent Publication No. 10-2023-0158021 has a composition comprising SiO2 60 to 71 mol%, Li2O 7 to 9.4 mol%, Al2O3 10 to 22 mol%, ZnO ≤ 0.5 mol% (ZnO + MgO 0.0-0.6 mol%), a total content of R2O (Na2O + K2O + Cs2O + Rb2O) 0.1 to 6.0 mol%, a total content of RO (CaO + BaO + SrO) 0.1 to 6 mol%, and P2O 50.1 to 6.0 mol%, and has a maximum of 0±0.1×10⁻⁶ in the range of 0 to 50 ℃. -6 It is characterized by having an average thermal expansion coefficient of / K, reduced thermal hysteresis at temperatures from 10°C to 35°C, and being easy to manufacture on an industrial scale.

[0006] Regarding another LAS-based crystallized glass material, Japanese Patent Publication No. 2014-091637 describes a LAS-based crystallized glass characterized by containing each component (in terms of oxide) of SiO2, Al2O3, and Li2O, and containing 0.01 to 3% of SnO2 component (in terms of oxide). Specifically, this has a composition comprising 45 to 65 mass% of SiO2, 0.01 to 10 mass% of Li2O, 20 to 30 mass% of Al2O3, 0 to 5 mass% of ZnO, 0 to 5 mass% of CaO, 5 to 15 mass% of P2O, 0 to 5 mass% of MgO, 1 to 10 mass% of TiO2, 1 to 10 mass% of ZrO2, and 0 to 5 mass% of BaO. It is stated here that the proposed LAS-based crystallized glass does not contain arsenic or antimony components, does not contain substances harmful to the environment or human body, has a low average coefficient of thermal expansion, and can be used as a mirror substrate material for next-generation semiconductor manufacturing devices using EUV lithography technology.

[0007] Meanwhile, in semiconductor packages, substrates are used as cores and interposers, and a core substrate is a product in which the core, which serves as the framework, is changed from plastic (resin) to glass. Although the core of a glass core substrate changes from resin to glass, the series of processes involving filling with Ajinomoto Build-up Film (ABF) and insulating layers is similar to the existing method. Glass core substrates have excellent deformation resistance and signal characteristics depending on temperature, making them advantageous for miniaturization and large-area applications. The Young's modulus of glass core substrates is 70 to 80, which is four times the Young's modulus of conventional organic materials (around 20). This means they do not bend easily, have a smooth surface, are suitable for forming microcircuits, and have the advantage of low signal loss.

[0008] Lithium aluminosilicate-based crystallized glass ceramics have low dielectric constant and low dielectric loss, and offer advantages such as ease of large-area fabrication (over 300 mm) and reduced linewidth due to excellent surface flatness, enabling ultra-fine circuit processing.

[0009] Lithium aluminosilicate-based photosensitive glass and crystallized glass are materials with excellent homogeneity, multifunctionality, precision, and light transmittance capable of precise microfabrication; they are manufactured by adding a small amount of photosensitive metal ions to lithium aluminosilicate-based (SiO2-Li2O-Al2O3) glass. When ultraviolet light is irradiated onto photosensitive glass, Ce is produced by the energy 3+ Electrons are emitted, and some are captured by photosensitive ions to become metal atoms. When glass is heat-treated at 450–600 ℃ n (MeO) → (MeO) n A reaction occurs to form a metal colloid (where Me is a metal such as Au, Ag, or Cu). Metal colloid (MeO) in silicate glass containing Li2O n Li2O·SiO2 (lithium metasilicate) crystals, which are highly sensitive to chemical etching, are precipitated using the crystal nucleus. Li2O·SiO2 crystals dissolve easily in HF, and since there is a difference of about 50 times in the dissolution rate compared to the area not irradiated with ultraviolet light, precise etching is possible, enabling micro-machining of the desired size. In addition, through a final heat treatment process, high-performance crystallized glass with desired physical properties (lithium disilicate (Li2Si2O5), lithium aluminosilicate disilicate (LiAlSi2O6), Li3PO4, SiO2, etc.) can be formed.

[0010] Lithium aluminosilicate crystallized glass is being applied or is seeking to be applied to products such as biochips, the fabrication of Intelligent Power Devices (IPDs) including RF components by semiconductor manufacturers, various sensor components, probe unit / card filters, Lab-on-a-Chip (Lab-on-a-Chip) equipment, and EUV reflectors, further increasing the potential for the material's utilization.

[0011] The application of glass substrates is necessary to overcome the limitations of conventional plastic-based semiconductor packaging substrate materials, such as low mechanical strength, low heat resistance, high surface roughness, and high insertion loss in the high-frequency range. Compared to plastic substrates, glass substrates offer superior flatness, making them advantageous for ultra-fine wiring. They also possess the advantage of low electrical loss and are well-suited for large-area implementations because they enable improved reliability by minimizing the coefficient of thermal expansion. Furthermore, as the required surface area for silicon interposers gradually increases, manufacturing costs rise sharply; therefore, glass interposers are being proposed as an alternative due to their ease of implementation.

[0012] Regarding related prior art, Korean Patent No. 1468680 describes a method for forming through-electrodes on an interposer substrate by using a photosensitive glass substrate instead of a silicon substrate as the interposer substrate.

[0013] International Patent Publication WO2015 / 033826 describes a microprocessing process in which microprocessing is performed on a plate-shaped substrate composed of photosensitive glass containing at least silicon oxide and lithium oxide, and a method for manufacturing a silicate ceramic substrate in which the photosensitive glass is crystallized by heat treatment after the microprocessing process, such that the silicate ceramic has a crystallization degree of 95% or more, and the silicate ceramic has a lithium disilicate crystal phase and an α-quartz crystal phase, with the lithium disilicate crystal phase being more numerous than the α-quartz crystal phase. This describes that by crystallizing silicate glass to form a ceramic (polycrystalline) with a very high degree of crystallization and controlling the ratio of crystal phases precipitated by crystallization, a plate-shaped substrate with excellent mechanical properties can be provided even with a thin thickness.

[0014] Japanese Patent Publication No. 2015-040168 describes a method for manufacturing a photosensitive glass substrate by correcting the irradiation position of the energy beam based on the amount of dimensional change of the photosensitive glass caused by the heat treatment, such as the first heat treatment, in a process of irradiating an energy beam onto a photosensitive glass plate-shaped substrate, a crystallization process in which a crystallized portion is obtained by crystallizing the latent fibers through a first heat treatment, and micro-processing by dissolving and removing the crystallized portion to obtain a photosensitive glass substrate. The photosensitive glass exemplified herein is a SiO2-Li2O-Al2O3-based glass, which contains Au, Ag, and Cu as photosensitive components and also contains CeO2 as an enhancing component. The composition is such that, as a specific composition, SiO2 55 to 85 mass%, Al2O3 2 to 20 mass%, and Li2O 5 to 15 mass%, the total of SiO2, Al2O3, and Li2O is contained in an amount of 85 mass% or more relative to the entire photosensitive glass, and Au 0.001 to 0.05 mass%, Ag 0.001 to 0.5 mass%, and Cu2O 0.001 to 1 mass% are photosensitive components, and CeO2 0.001 to 0.2 mass% is contained as a sensitizing component.

[0015] As another technology, Korean Patent Registration No. 1934157 describes a photosensitive glass and a method for manufacturing the same, disclosing a photosensitive glass that reacts more sensitively to UV light irradiation and can be easily crystallized to a higher aspect ratio. Specifically, Si 4+ A responsive photostructuring glass comprising a pair of , one or more crystal agonists, one or more crystal antagonists, and one or more nucleating agents, wherein a. the crystal agonist is Na + , K + and Li + Selected from, and b. the decision antagonist is Al 3+ , B 3+ , Zn 2+ , Sn 2+ and Sb 3+ Selected from, c. The nucleating agent pair comprises cerium, and one or more agents selected from the group consisting of silver, gold, and copper, and Si based on cation % (cat.-%) 4+ The molar ratio of the crystal agonist to the molar ratio is at least 0.3 and at most 0.85, and the glass has a cooling state corresponding to normal cooling from temperature T1 to temperature T2 at a cooling rate K of 10 ℃ / h to 200 ℃ / h, wherein temperature T1 is at least above the glass transition temperature Tg of the glass and temperature T2 is at least 150 ℃ below T1. It is described that such glass is useful in structuring and / or unstructuring for microtechnology, microreaction technology, electronic packaging, microfluidic components, as a FED spacer or as a FED spacer, for biotechnology, as an interposer, or as a 3D structured antenna or 3D structured antenna, and the glass body is also described as being usable as a substrate or glass circuit board in fields such as semiconductors, for example, logic circuits / integrated circuits, memory, etc.

[0016] The present invention aims to provide a lithium aluminosilicate-based crystallized glass for semiconductors having a low coefficient of thermal expansion.

[0017] The present invention also aims to provide a method for manufacturing such lithium aluminosilicate (LAS-based) crystallized glass.

[0018] The present invention also aims to provide a lithium aluminosilicate glass capable of producing a structured product having photosensitivity and a low coefficient of thermal expansion.

[0019] One embodiment of the present invention is a lithium aluminosilicate-based crystallized glass comprising a crystalline phase within an amorphous glass matrix, wherein the glass matrix comprises 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn, or Ba), and 0.02 to 1.0 wt% of a clarifying agent, and satisfies a Li2O / (SiO2+Li2O) weight ratio of 0.062 to 0.212, for use in semiconductors, lithium aluminosilicate-based crystallized glass. Provides glass.

[0020] In a crystallized glass according to a preferred embodiment, the glass matrix may contain 11.0 to 18.0 weight% of Al2O3.

[0021] A crystallized glass according to one embodiment of the present invention may include at least one transition metal selected from the group consisting of La, Y, Pr, Sm, Eu, Tb, Ho, Er, and Tm as an oxidation-reducing agent.

[0022] A crystallized glass according to a preferred embodiment of the present invention may have a crystalline phase comprising lithium metasilicate (Li2SiO3) and Li2O·Al2O3·2xSiO2 (LAS) (where x is an integer from 1 to 4).

[0023] According to the present invention, the average coefficient of thermal expansion (CTE) at 20 ℃ to 300 ℃ is 5.0 × 10 -6 / K to 7.0 × 10 -6 We can provide lithium aluminosilicate-based crystallized glass for semiconductors within the / K range.

[0024] In another embodiment of the present invention, a glass composition comprising 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn, or Ba), and 0.02 to 1.0 wt% of a clarifying agent, satisfying a Li2O / (SiO2+Li2O) weight ratio of 0.062 to 0.212, is melted at at least 1,450 °C for at least 30 minutes, molded in a mold, cooled, and annealed to produce a glass molded article; The present invention provides a method for manufacturing a lithium aluminosilicate-based crystallized glass for semiconductors, comprising the steps of: heat-treating a glass molded article at a set speed for 20 minutes to 4 hours at 330 ℃ to 430 ℃ to produce a glass molded article containing a nucleus; heat-treating the glass molded article containing the nucleus in a first heat treatment at a temperature range of 520 ℃ to 620 ℃; and heat-treating the result of the first heat treatment in a second heat treatment at 630 ℃ to 880 ℃.

[0025] In a method for manufacturing crystallized glass according to a preferred embodiment, the first heat treatment step may be performed at 520 ℃ to 620 ℃ for 10 minutes to 120 minutes.

[0026] In a method for manufacturing crystallized glass according to a preferred embodiment, the step of secondary heat treatment may be performed at 630 ℃ to 880 ℃ for 10 minutes to 120 minutes.

[0027] In another embodiment of the present invention, a semiconductor glass is provided comprising 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02 to 1.0 wt% of a clarifying agent, wherein the Li2O / (SiO2+Li2O) weight ratio satisfies 0.062 to 0.212.

[0028] In an exemplary embodiment of the present invention, a crystallization product obtained by exposing and crystallizing the glass according to the embodiment is provided.

[0029] In a preferred embodiment, the crystallization product may be obtained by undergoing a crystallization heat treatment performed by heat treating exposed glass at a set rate for 20 minutes to 4 hours at 330°C to 430°C to obtain glass containing nuclei, and subsequently heat treating at 520°C to 620°C for 10 minutes to 120 minutes.

[0030] In another exemplary embodiment of the present invention, a structured product is provided by exposing, crystallizing heat treating, and structuring the glass according to the above embodiment.

[0031] In a preferred embodiment, the structured product may be obtained by undergoing a crystallization heat treatment performed by heat treating exposed glass at a set rate at 330 °C to 430 °C for 20 minutes to 4 hours to obtain glass containing nuclei, and subsequently heat treating at 520 °C to 620 °C for 10 minutes to 120 minutes. Additionally, structuring may be performed by etching the crystallization heat-treated product and then performing a secondary heat treatment at 630 °C to 880 °C.

[0032] The structured product according to the present invention may be a lithium aluminosilicate-based crystallized glass comprising a crystalline phase within an amorphous glass matrix, wherein the glass matrix comprises 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02 to 1.0 wt% of a clarifying agent, and the Li2O / (SiO2+Li2O) weight ratio may satisfy 0.062 to 0.212.

[0033] The structured product obtained according to the above embodiments may be useful for components for microtechnology, microreaction technology, electronic packaging, microfluidics, FED spacers, biotechnology, interposers and / or three-dimensional structured antenna applications.

[0034] The lithium aluminosilicate-based crystallized glass according to the present invention can have a low coefficient of thermal expansion and has the advantage of high material versatility for various applications, including semiconductor glass substrates, biochips, various sensor components, Prove unit / card filters, Lab-on-a-Chip, and EUV reflectors.

[0035] In addition, the glass capable of producing such lithium aluminosilicate-based crystallized glass can be used as a photosensitive substrate and, through exposure, crystallization heat treatment and structuring, can be applied as a component for microtechnology, microreaction technology, electronic packaging, microfluidics, FED spacers, biotechnology, interposers and / or 3D structured antenna applications.

[0036] FIG. 1 is a graph of the X-ray diffraction results of LAS-based crystallized glass obtained according to one embodiment of the present invention.

[0037] FIG. 2 is a graph of the coefficient of thermal expansion (CTE) analysis results of LAS-based crystallized glass obtained according to one embodiment of the present invention.

[0038] The foregoing and additional aspects of the present invention will become more apparent through preferred embodiments described with reference to the accompanying drawings. Hereinafter, the present invention will be described in detail so that those skilled in the art can easily understand and reproduce it through such embodiments.

[0039] The present invention provides a lithium aluminosilicate-based crystallized glass for semiconductors comprising a crystalline phase within an amorphous glass matrix, wherein the glass matrix comprises 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02 to 1.0 wt% of a clarifying agent, and the Li2O / (SiO2+Li2O) weight ratio satisfies 0.062 to 0.212.

[0040] In the descriptions above and below, the term "for semiconductors" should be understood to encompass not only various component materials used in the overall process of semiconductor manufacturing, but also various component materials constituting the inspection equipment that performs this.

[0041] In particular, considering the aspect of having a low coefficient of thermal expansion and excellent mechanical properties, the lithium aluminosilicate-based crystallized glass for semiconductors according to the present invention may preferably have a crystalline phase comprising lithium metasilicate (Li2SiO3) and Li2O·Al2O3·2xSiO2(LAS) (where x is an integer from 1 to 4). More preferably, it may comprise Li2O·Al2O3·2xSiO2(LAS) (where x is an integer from 1 to 2).

[0042] The graph of the XRD analysis results for a lithium aluminosilicate-based (hereinafter, LAS-based) crystallized glass according to a preferred embodiment is as shown in FIG. 1.

[0043] In FIG. 1, the crystal phases of the LAS-based crystallized glass for semiconductors according to one embodiment of the present invention are each 2θ LS = 18.741, 26.801 (degree), etc., 2θ LAS Major peaks appear at 22.640, 25.487 (degree), etc., which can be interpreted as lithium metasilicate (LS, Li2SiO3) and Li2O·Al2O3·2xSiO2 (LAS) (where x is an integer from 1 to 2).

[0044] In the description above and below, XRD analysis is understood to be the result of analysis using an X-ray diffraction analyzer (D / MAX-2500, Rigaku, Japan; Cu Kα (40 kV, 60 mA), scan rate: 6° / min, 2θ: 10~60 (degree)).

[0045] Lithium metasilicate is a lithium aluminum silicate-based crystalline phase (which may be abbreviated as LAS) represented by the chemical formula Li2SiO3, which has low chemical and physical durability, but can be converted into lithium disilicate (Li2Si2O5), which has excellent chemical and physical durability, through crystallization at 800°C or higher. Additionally, Li2O·Al2O3·2xSiO2(LAS) (where x is an integer from 1 to 4) is a lithium aluminum silicate-based crystalline phase (which may be abbreviated as LAS), which has excellent chemical and physical durability and has negative expansion characteristics, so a low coefficient of thermal expansion can be achieved when such a crystalline phase is included. Preferably, it may be desirable to include a eucryptite or spodumene crystalline phase as a crystalline phase of Li2O·Al2O3·2xSiO2(LAS) (where x is an integer from 1 to 2).

[0046] These crystalline phases constituting the LAS-based crystallized glass of the present invention enable excellent thermal / mechanical properties and a low coefficient of thermal expansion.

[0047] As described above, the LAS-based crystallized glass according to the present invention may have a glass matrix specifically comprising 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02 to 1.0 wt% of a clarifying agent, and a Li2O / (SiO2+Li2O) weight ratio satisfying 0.062 to 0.212.

[0048] The glass composition undergoes crystal nucleation and crystal growth heat treatment to precipitate a crystalline phase within an amorphous glass matrix, wherein the temperature at which crystal nucleation and growth occur in the aforementioned glass matrix is ​​between 330°C and 880°C. That is, crystal nuclei begin to form at a minimum of 380°C, and crystal growth occurs as the temperature increases; this crystal growth develops into a crystal with excellent strength and a low coefficient of thermal expansion suitable for use as a semiconductor glass substrate at a maximum of 880°C. In other words, since the strength gradually increases from the crystal growth temperature up to a maximum of 880°C, if this crystal growth is realized in a single large-area disk, such LAS-based crystallized glass can be useful as a semiconductor glass substrate.

[0049] The LAS-based crystallized glass of the present invention has an average coefficient of thermal expansion (CTE) of 5.0 × 10⁻⁶ at 20°C to 300°C. -6 / K to 7.0 × 10 -6 It can be within the / K range, which indicates that it possesses low thermal expansion characteristics useful as a semiconductor glass substrate material, considering the coefficient of thermal expansion of semiconductor packaging materials.

[0050] For example, FIG. 2 illustrates the results of a coefficient of thermal expansion analysis for a LAS-based crystallized glass according to one embodiment of the present invention, and from the results, the LAS-based crystallized glass according to the present invention has an average coefficient of thermal expansion (CTE) of 5.0 × 10⁻⁶ at 20°C to 300°C. -6 / K to 7.0 × 10 -6 It can be confirmed that it is within the / K range.

[0051] In the descriptions above and below, the coefficient of thermal expansion was measured using a thermomechanical analyzer (Thermomechanical Analyzer, TMA-60H, SHIMADZU, heating rate: 10 ℃ / min).

[0052] In this regard, another embodiment of the present invention comprises the steps of melting a glass composition comprising 3.0–75.0 wt% SiO2, 10.0–16.0 wt% Li2O, 7.0–18.0 wt% Al2O, 0.1–4.0 wt% K2O, 0.01–1.0 wt% Na2O, 0.005–0.2 wt% Ag2O, 0.0025–0.1 wt% CeO2, 0.2–5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn, or Ba), and 0.02–1.0 wt% of a clarifying agent, satisfying a Li2O / (SiO2+Li2O) weight ratio of 0.062–0.212, at least 1,450 °C for at least 30 minutes, forming and cooling in a mold, and annealing to obtain a glass molded article, and the glass molded article The present invention provides a method for manufacturing a lithium aluminosilicate-based crystallized glass for semiconductors, comprising the steps of: manufacturing a glass molded article containing a nucleus by heat treating at a set speed for 20 minutes to 4 hours at 330 ℃ to 430 ℃; performing a first heat treatment of the glass molded article containing the nucleus in a temperature range of 520 ℃ to 620 ℃; and performing a second heat treatment of the result of the first heat treatment at 630 ℃ to 880 ℃.

[0053] Conventional glass substrates have a very high risk of breakage during transportation, processing, and handling, whereas the glass composition adopted in the present invention is designed to have excellent mechanical properties through secondary heat treatment.

[0054] As a preferred example, the first heat treatment step may be performed at 520 ℃ to 620 ℃ for 10 minutes to 120 minutes, and the second heat treatment step may be performed at 630 ℃ to 880 ℃ for 10 minutes to 120 minutes.

[0055] When the heat treatment method of the present invention described above is used with the glass composition described above, excellent mechanical properties and a low coefficient of thermal expansion can be achieved, which is economically very advantageous because the risk of breakage during transportation, processing, and handling is low.

[0056] For example, a specific embodiment of the present invention first weighs and mixes a glass composition comprising 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02 to 1.0 wt% of a clarifying agent, wherein the Li2O / (SiO2+Li2O) weight ratio satisfies 0.062 to 0.212.

[0057] When Al2O3 is added to silicate glass, it enters tetrahedral sites to act as a glass former, increases viscosity, and reduces ion mobility. Accordingly, if Al2O3 is included in an amount exceeding 18 wt%, its role as a glass former becomes excessive and may cause devitrification, so it is desirable to include it in an amount less than 18 wt%. Additionally, in terms of moldability and glass stability, it may be more desirable to include Al2O3 in an amount of 11 wt% or more. On the other hand, an increase in modifiers such as K2O and Na2O lowers viscosity and increases ion mobility, and when less than 63 weight% of SiO2 is included, viscosity decreases, but glass stability decreases, causing phase separation and devitrification, and the formation of the Li2O·Al2O3·2xSiO2(LAS) (where x is an integer from 1 to 4) crystal phase is insufficient. Therefore, in this respect, a SiO2 / (SiO2+Al2O3) molar ratio of 0.062 to 0.212 may be desirable in providing the lithium aluminosilicate (LAS-based) crystallized glass of the present invention, which includes lithium metasilicate (Li2SiO3) and Li2O·Al2O3·2xSiO2(LAS) (where x is an integer from 1 to 4) as crystal phases.

[0058] Li2CO3 may be added instead of Li2O as a glass composition, and carbon dioxide (CO2), the carbon (C) component of Li2CO3, is released as a gas during the glass melting process. Additionally, K2CO3 and Na2CO3 may be added instead of K2O and Na2O, respectively, in the alkali oxides, and carbon dioxide (CO2), the carbon (C) component of K2CO3 and Na2CO3, is released as a gas during the glass melting process.

[0059] In addition, it may be desirable to include at least one transition metal selected from the group consisting of La, Y, Pr, Sm, Eu, Tb, Ho, Er, and Tm as an oxidation-reduction agent among 17 rare earth elements that have strong oxidation-reduction reactions in the glass composition.

[0060] Mixing is performed using a dry mixing process, such as ball milling. Specifically regarding the ball milling process, the starting materials are loaded into a ball milling machine, and the machine is rotated at a constant speed to mechanically grind and uniformly mix the starting materials. The balls used in the ball milling machine may be made of ceramic materials such as zirconia or alumina, and the balls may all be the same size or at least two different sizes may be used. The ball size, milling time, and rotational speed per minute of the ball milling machine are adjusted considering the target particle size. For example, considering the particle size, the ball size can be set to a range of approximately 1 mm to 30 mm, and the rotational speed of the ball milling machine can be set to a range of approximately 50 to 500 rpm. It is preferable to perform ball milling for 1 to 48 hours, taking into account the target particle size. Through ball milling, the starting materials are ground into fine particles, resulting in a uniform particle size and simultaneous uniform mixing.

[0061] The mixed starting materials are placed in a melting furnace, and the melting furnace containing the starting materials is heated to melt the starting materials. Here, melting means that the starting materials change from a solid state to a liquid state with viscosity. It is desirable for the melting furnace to be made of a material with a high melting point, high strength, and a low contact angle to suppress the phenomenon of the molten material sticking. To this end, it is desirable for the melting furnace to be made of a material such as platinum (Pt), DLC (diamond-like-carbon), or chamotte, or for the surface to be coated with a material such as platinum (Pt) or DLC (diamond-like-carbon).

[0062] It is preferable to perform melting at 1,450°C or higher under atmospheric pressure for at least 30 minutes. If the melting temperature is below 1,450°C, the starting materials may not melt completely; if the melting temperature is excessively high, excessive energy consumption is required, making it uneconomical. Therefore, it is preferable to melt within the temperature range mentioned above. Additionally, if the melting time is too short, the starting materials may not melt sufficiently, and if the melting time is too long, excessive energy consumption is required, making it uneconomical. The heating rate of the melting furnace is preferably about 5 to 50°C / min. If the heating rate is too slow, it takes a long time, reducing productivity, and if the heating rate is too fast, the rapid temperature rise causes a large amount of volatilization of the starting materials, which may result in poor physical properties of the crystallized glass. Therefore, it is preferable to raise the temperature of the melting furnace within the heating rate mentioned above. It is preferable to perform melting in an oxidizing atmosphere such as oxygen (O2) or air.

[0063] The molten material is poured into a designated mold to obtain crystallized glass of a desired shape and size. It is desirable for the mold to be made of a material with a high melting point, high strength, and a low contact angle to suppress the phenomenon of the molten glass sticking. For this purpose, it is made of a material such as graphite or carbon, and it is desirable to preheat to 200 to 300°C to prevent thermal shock before pouring the molten material into the mold.

[0064] As the molten material contained in the molding mold is molded and cooled, it may be desirable to undergo an annealing step after the cooling process, which involves slow cooling from 480°C to 250°C at a set speed for 20 minutes to 2 hours. Undergoing such an annealing step reduces stress variation within the molded product, preferably by eliminating stress, which can have a beneficial effect on controlling the size of the crystal phase and improving the homogeneity of the crystal distribution in the subsequent crystallization step, thereby ultimately enabling the acquisition of the desired LAS-based crystallized glass for semiconductors.

[0065] The speed set here is preferably 2.3 to 14 ℃ / min in terms of sufficient slow cooling.

[0066] In this way, the glass molded product that has undergone the annealing process is transferred to a crystallization heat treatment furnace to nucleate and grow crystals, thereby producing the desired crystallized glass.

[0067] Specifically, first, a glass molded article containing a nucleus can be manufactured by heat treating at a set speed for 20 minutes to 4 hours at 330 ℃ to 430 ℃.

[0068] Next, as described above, a glass molded article containing a nucleus is crystallized by first heat treatment and crystal growth through second heat treatment to obtain a LAS-based crystallized glass with a low coefficient of thermal expansion and excellent mechanical properties.

[0069] The lithium aluminosilicate-based crystallized glass according to the present invention can have a low coefficient of thermal expansion and has the advantage of high material versatility for various applications, including semiconductor glass substrates, biochips, various sensor components, Prove unit / card filters, Lab-on-a-Chip, and EUV reflectors.

[0070] On the other hand, in another example of the present invention, a semiconductor glass can be provided comprising 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02 to 1.0 wt% of a clarifying agent, wherein the Li2O / (SiO2+Li2O) weight ratio satisfies 0.062 to 0.212.

[0071] Such glass is a so-called photosensitive glass, which is a glass containing a photosensitive component and a sensitizing component that undergoes exposure and heat treatment, in which only the exposed portion crystallizes. The crystallized portion has a significantly different dissolution rate with respect to acid compared to the non-crystallized portion. Therefore, by utilizing this property, selective etching can be performed on the photosensitive glass.

[0072] The glass capable of providing LAS-based crystallized glass as described above is a glass containing a photosensitive component and an enhancing component, and can obtain a crystallized product through exposure and crystallization heat treatment, and can obtain a structured product through structuring.

[0073] Specifically, the crystallization heat treatment after exposure can be performed by heat treating at a set rate for 20 minutes to 4 hours at 330 ℃ to 430 ℃ to obtain glass containing nuclei, and subsequently heat treating at 520 ℃ to 620 ℃ for 10 minutes to 120 minutes, thereby obtaining a crystal phase with a different dissolution rate to acid and a non-crystallized portion.

[0074] Next, a structured product can be obtained through structuring, which may involve etching and a secondary heat treatment. The secondary heat treatment is intended to improve the thermal properties and strength of the structured product patterned through etching, and this can be performed by a secondary heat treatment at 630°C to 880°C.

[0075] The product structured in this manner is a lithium aluminosilicate-based crystallized glass comprising a crystalline phase within an amorphous glass matrix, wherein the glass matrix comprises 3.0–75.0 wt% SiO2, 10.0–16.0 wt% Li2O, 7.0–18.0 wt% Al2O, 0.1–4.0 wt% K2O, 0.01–1.0 wt% Na2O, 0.005–0.2 wt% Ag2O, 0.0025–0.1 wt% CeO2, 0.2–5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn, or Ba), and 0.02–1.0 wt% of a clarifying agent, and satisfies a Li2O / (SiO2+Li2O) weight ratio of 0.062–0.212, and is similar to the LAS-based crystallized glass according to the present invention described above. It may be a crystallized glass having crystalline phase characteristics and thermal expansion characteristics.

[0076] The structured product obtained in this way can be useful for components for microtechnology, microreaction technology, electronic packaging, microfluidics, FED spacers, biotechnology, interposers and / or three-dimensional structured antenna applications, but is not limited thereto.

Claims

1. A lithium aluminosilicate-based crystallized glass containing a crystalline phase within an amorphous glass matrix, The glass matrix comprises 3.0–75.0 wt% SiO2, 10.0–16.0 wt% Li2O, 7.0–18.0 wt% Al2O, 0.1–4.0 wt% K2O, 0.01–1.0 wt% Na2O, 0.005–0.2 wt% Ag2O, 0.0025–0.1 wt% CeO2, 0.2–5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn, or Ba), and 0.02–1.0 wt% of a clarifying agent, wherein the Li2O / (SiO2+Li2O) weight ratio satisfies 0.062–0.

212. Lithium aluminosilicate crystallized glass for semiconductors.

2. In claim 1, the glass matrix is ​​characterized by containing 11.0 to 18.0 weight% of Al2O3. Lithium aluminosilicate crystallized glass for semiconductors.

3. The redox agent comprising at least one transition metal selected from the group consisting of La, Y, Pr, Sm, Eu, Tb, Ho, Er, and Tm, characterized in that Lithium aluminosilicate crystallized glass for semiconductors.

4. In claim 1, the crystalline phase is characterized by comprising lithium metasilicate (Li2SiO3) and Li2O·Al2O3·2xSiO2 (LAS) (where x is an integer from 1 to 4). Lithium aluminosilicate crystallized glass for semiconductors.

5. In claim 1, the average coefficient of thermal expansion (CTE) at 20 ℃ to 300 ℃ is 5.0 × 10 -6 / K to 7.0 × 10 -6 Characterized by being within the / K range, Lithium aluminosilicate crystallized glass for semiconductors.

6. A step of preparing a glass molded article by melting a glass composition comprising 3.0~75.0 wt% SiO2, 10.0~16.0 wt% Li2O, 7.0~18.0 wt% Al2O, 0.1~4.0 wt% K2O, 0.01~1.0 wt% Na2O, 0.005~0.2 wt% Ag2O, 0.0025~0.1 wt% CeO2, 0.2~5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02~1.0 wt% of a clarifying agent, satisfying a Li2O / (SiO2+Li2O) weight ratio of 0.062~0.212, at least 1,450 ℃ for at least 30 minutes, molding and cooling in a mold, and annealing; A step of manufacturing a glass molded article containing a nucleus by heat treating at a set speed at 330 ℃ to 430 ℃ for 20 minutes to 4 hours; A step of performing a first heat treatment on a glass molded article containing a core at a temperature range of 520 ℃ to 620 ℃; and A step comprising a second heat treatment of the first heat treatment product at 630 ℃ to 880 ℃, Method for manufacturing lithium aluminosilicate-based crystallized glass for semiconductors.

7. In claim 6, the first heat treatment step is characterized by being performed at 520 ℃ to 620 ℃ for 10 minutes to 120 minutes, Method for manufacturing lithium aluminosilicate-based crystallized glass for semiconductors.

8. In claim 6, the step of secondary heat treatment is characterized by being performed at 630 ℃ to 880 ℃ for 10 minutes to 120 minutes, Method for manufacturing lithium aluminosilicate-based crystallized glass for semiconductors.

9. A semiconductor glass comprising 3.0~75.0 wt% SiO2, 10.0~16.0 wt% Li2O, 7.0~18.0 wt% Al2O, 0.1~4.0 wt% K2O, 0.01~1.0 wt% Na2O, 0.005~0.2 wt% Ag2O, 0.0025~0.1 wt% CeO2, 0.2~5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02~1.0 wt% of a clarifying agent, wherein the Li2O / (SiO2+Li2O) weight ratio satisfies 0.062~0.

212.

10. A crystallization product obtained by exposing and crystallizing the glass according to paragraph 9.

11. A crystallization product according to claim 10, characterized in that the crystallization heat treatment is performed by a method of heat treating exposed glass at a set rate for 20 minutes to 4 hours at 330 ℃ to 430 ℃ to obtain glass containing nuclei, and subsequently heat treating at 520 ℃ to 620 ℃ for 10 minutes to 120 minutes.

12. A structured product obtained by exposing, crystallizing heat treating, and structuring the glass according to paragraph 9.

13. A structured product according to claim 12, characterized in that the crystallization heat treatment is performed by heat treating exposed glass at a set rate at 330 ℃ to 430 ℃ for 20 minutes to 4 hours to obtain glass containing nuclei, and subsequently heat treating at 520 ℃ to 620 ℃ for 10 minutes to 120 minutes.

14. A structured product according to claim 12 or 13, characterized in that the structuring is performed by a method of etching the crystallized heat-treated product and then performing a secondary heat treatment at 630 ℃ to 880 ℃.

15. A structured product according to claim 12, wherein the structured product is a lithium aluminosilicate-based crystallized glass comprising a crystalline phase within an amorphous glass matrix, wherein the glass matrix comprises 3.0 to 75.0 wt% SiO2, 10.0 to 16.0 wt% Li2O, 7.0 to 18.0 wt% Al2O, 0.1 to 4.0 wt% K2O, 0.01 to 1.0 wt% Na2O, 0.005 to 0.2 wt% Ag2O, 0.0025 to 0.1 wt% CeO2, 0.2 to 5.0 wt% of at least one divalent metal oxide represented by MO (where M is Ca, Mg, Sr, Zn or Ba), and 0.02 to 1.0 wt% of a clarifying agent, and the weight ratio of Li2O / (SiO2+Li2O) satisfies 0.062 to 0.

212.

16. The structured product of claim 12, characterized as being for components for applications in microtechnology, microreaction technology, electronic packaging, microfluidics, FED spacers, biotechnology, interposers and / or three-dimensional structured antennas.

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