TW201803824A - Glass processing method containing hydrofluoric acid and an acid having a larger molecular size than that of hydrofluoric acid - Google Patents
Glass processing method containing hydrofluoric acid and an acid having a larger molecular size than that of hydrofluoric acid Download PDFInfo
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Abstract
Description
本發明係關於使用雷射光的玻璃之加工方法。 The present invention relates to a method for processing glass using laser light.
具有複數個微小貫通孔的玻璃基板，例如，可利用於噴墨方式的印刷頭用基板、或兩面配線基板等。貫通孔係通常使用雷射光形成(日本特開2000-61667號公報、日本專利第4672689號公報)。 A glass substrate having a plurality of minute through holes can be used, for example, as a substrate for a print head of an inkjet system, or as a double-sided wiring substrate. The through-hole system is generally formed using laser light (Japanese Patent Laid-Open No. 2000-61667, Japanese Patent No. 4672689).
玻璃與雷射光接觸的部分(變質層)，在加工中具有熱，會因由熱應力所產生的應變而產生龜裂(微龜裂)。藉此，玻璃基板的特性(功能)降低，或玻璃基板變得容易破裂。 The portion of the glass (laser layer) in contact with the laser light has heat during processing, and cracks (microcracks) occur due to strain caused by thermal stress. Thereby, the characteristics (function) of the glass substrate are reduced, or the glass substrate is easily broken.
本發明提供可以使具有貫通孔的玻璃基板的特性提升的玻璃之加工方法。 The present invention provides a glass processing method capable of improving the characteristics of a glass substrate having a through hole.
本發明的一態樣的玻璃之加工方法具備：使用雷射光，在玻璃基板形成貫通孔的步驟；及使用蝕刻液，將前述貫通孔進行濕式蝕刻的步驟。前述蝕刻液包 含氫氟酸、及包含分子尺寸比前述氫氟酸大的酸的第1液體。前述氫氟酸的濃度為4重量%以下。前述第1液體的濃度比前述氫氟酸的濃度高。 One aspect of the glass processing method of the present invention includes a step of forming a through hole in a glass substrate using laser light, and a step of wet etching the through hole using an etching solution. Aforementioned etching solution pack The first liquid containing hydrofluoric acid and an acid having a molecular size larger than that of the hydrofluoric acid. The concentration of the hydrofluoric acid is 4% by weight or less. The concentration of the first liquid is higher than the concentration of the hydrofluoric acid.
根據本發明的話，便能夠提供可以使具有貫通孔的玻璃基板的特性提升的玻璃之加工方法。 According to the present invention, it is possible to provide a glass processing method capable of improving the characteristics of a glass substrate having a through hole.
10‧‧‧玻璃基板 10‧‧‧ glass substrate
11‧‧‧貫通孔 11‧‧‧through hole
12‧‧‧龜裂 12‧‧‧crack
20‧‧‧雷射加工裝置 20‧‧‧laser processing equipment
21‧‧‧雷射振動器 21‧‧‧laser vibrator
22‧‧‧光學系統 22‧‧‧ Optical System
23‧‧‧鏡子 23‧‧‧Mirror
24‧‧‧集光透鏡 24‧‧‧ collection lens
25‧‧‧座台 25‧‧‧ seat
26‧‧‧雷射光 26‧‧‧laser light
30‧‧‧濕式蝕刻裝置 30‧‧‧ Wet Etching Device
31‧‧‧蝕刻處理槽 31‧‧‧etching treatment tank
32‧‧‧超音波產生裝置 32‧‧‧ Ultrasonic generator
33‧‧‧保持機構 33‧‧‧ holding agency
34‧‧‧蝕刻液 34‧‧‧etching solution
S100、S101‧‧‧步驟 S100, S101‧‧‧ steps
D1、D2‧‧‧直徑 D1, D2‧‧‧ diameter
圖1係說明實施形態的玻璃基板之加工方法的流程圖。 FIG. 1 is a flowchart illustrating a method for processing a glass substrate according to an embodiment.
圖2係顯示雷射加工裝置的一例的概略圖。 FIG. 2 is a schematic view showing an example of a laser processing apparatus.
圖3係說明形成了複數個貫通孔的玻璃基板的圖。 FIG. 3 is a view illustrating a glass substrate in which a plurality of through holes are formed.
圖4係濕式蝕刻步驟中所使用的濕式蝕刻裝置的概略圖。 FIG. 4 is a schematic view of a wet etching apparatus used in the wet etching step.
圖5係顯示濕式蝕刻後的貫通孔的一例的剖面圖。 FIG. 5 is a cross-sectional view showing an example of a through hole after wet etching.
圖6係顯示濕式蝕刻前的貫通孔的一例的照片。 FIG. 6 is a photograph showing an example of a through hole before wet etching.
圖7係顯示濕式蝕刻後的貫通孔的一例的照片。 FIG. 7 is a photograph showing an example of a through hole after wet etching.
圖8係說明實施形態的濕式蝕刻的原理的示意圖。 FIG. 8 is a schematic diagram illustrating the principle of wet etching in the embodiment.
圖9係說明本實施形態的濕式蝕刻的蝕刻速率的曲線圖。 FIG. 9 is a graph illustrating an etching rate of the wet etching in the present embodiment.
圖10係說明由超音波產生的氣泡的曲線圖。 FIG. 10 is a graph illustrating bubbles generated by an ultrasonic wave.
圖11係說明比較例的濕式蝕刻的原理的示意圖。 FIG. 11 is a schematic diagram illustrating the principle of wet etching in a comparative example.
圖12係顯示比較例的濕式蝕刻後的貫通孔的一例的照片。 FIG. 12 is a photograph showing an example of a through hole after wet etching in a comparative example.
以下，針對實施形態參照圖式進行說明。但是，圖式係示意或概念的圖式，各圖式的尺寸及比率等不必限於與實物相同。此外，即使是在在圖式彼此間表示相同部分的情況下，也有表示成彼此的尺寸關係、比率互異的情況。特別是，以下所示的數個實施形態係例示供將本發明的技術思想具體化用的裝置及方法，本發明的技術思想不受構成零件的形狀、構造、配置等所限定。又，在以下的說明中，對於具有相同功能及構成的要素賦予相同元件符號，僅在必要的情況下進行重複說明。 Hereinafter, embodiments will be described with reference to the drawings. However, the drawings are schematic or conceptual drawings, and the dimensions and ratios of the drawings are not necessarily the same as the actual ones. In addition, even when the same parts are shown in the drawings, the dimensional relationship and the ratio may be different from each other. In particular, several embodiments shown below illustrate devices and methods for embodying the technical idea of the present invention, and the technical idea of the present invention is not limited by the shape, structure, arrangement, etc. of the constituent parts. In the following description, elements having the same function and configuration are given the same element symbols, and repeated descriptions will be made only when necessary.
圖1係說明本實施形態的玻璃基板之加工方法的流程圖。首先，準備玻璃基板10。玻璃基板10的厚度係例如0.1~1.5mm左右。在本說明書中，表示數值範圍的「~」意指包含其前後數值的範圍。 FIG. 1 is a flowchart illustrating a method for processing a glass substrate according to this embodiment. First, the glass substrate 10 is prepared. The thickness of the glass substrate 10 is, for example, about 0.1 to 1.5 mm. In the present specification, "~" indicating a numerical range means a range including numerical values before and after it.
接著，如圖1所示，使用雷射光在玻璃基板10形成一個或複數個貫通孔(步驟S100)。圖2係顯示雷射加工裝置20的一例的概略圖。雷射加工裝置20具備雷射振動器21、光學系統22(包含鏡子23及集光透鏡24)、及座台25等。 Next, as shown in FIG. 1, one or a plurality of through holes are formed in the glass substrate 10 using laser light (step S100). FIG. 2 is a schematic view showing an example of the laser processing apparatus 20. The laser processing apparatus 20 includes a laser vibrator 21, an optical system 22 (including a mirror 23 and a light collecting lens 24), a table 25, and the like.
座台25保持玻璃基板10。座台25將玻璃基板10加以吸附固定或接著固定。作為吸附固定，例如，可使用真空吸附、或靜電吸附。座台25可以具有使玻璃基板10水平地移動的功能，例如，可以以X-Y座台構成。在此情況下，座台(X-Y座台)25可以利用使用馬達的二軸 移動機構(未圖示)而廣範圍地移動。 The mount 25 holds the glass substrate 10. The base 25 fixes or fixes the glass substrate 10 by suction. As the adsorption fixation, for example, vacuum adsorption or electrostatic adsorption can be used. The base 25 may have a function of horizontally moving the glass substrate 10, and may be configured by, for example, an X-Y base. In this case, the table (X-Y table) 25 can use the two shafts using a motor A moving mechanism (not shown) moves a wide range.
雷射振動器21射出雷射光26。作為雷射，可使用超短波脈衝(例如奈米秒脈衝)的UV(ultraviolet)雷射。作為UV雷射，可使用準分子雷射、或個體雷射等。作為個體雷射，例如，可舉出使用在釔-鋁-石榴石結晶掺雜Nd(釹)的介質的YAG雷射(Nd：YAG雷射)。 The laser vibrator 21 emits laser light 26. As the laser, a UV (ultraviolet) laser with an ultra-short wave pulse (for example, a nanosecond pulse) can be used. As the UV laser, an excimer laser or an individual laser can be used. As the individual laser, for example, a YAG laser (Nd: YAG laser) using a medium doped with Nd (neodymium) in yttrium-aluminum-garnet crystal is mentioned.
鏡子23將來自雷射振動器21的雷射光26反射至玻璃基板10側。集光透鏡24接受來自鏡子23的雷射光26。然後，集光透鏡24對保持在座台25的玻璃基板10集光照射雷射光26。集光透鏡24可以用複數個透鏡構成。雷射光26的集光位置係例如玻璃基板10的雷射光源側的主面或其附近。玻璃基板10被此雷射光26局部地加熱，加熱部分被除去，在玻璃基板10形成貫通孔11。貫通孔11也被稱為貫通玻璃通路(TGV：Through Glass Via)。 The mirror 23 reflects the laser light 26 from the laser vibrator 21 to the glass substrate 10 side. The condenser lens 24 receives laser light 26 from a mirror 23. Then, the light collection lens 24 collects light from the glass substrate 10 held on the pedestal 25 and irradiates the laser light 26. The light collecting lens 24 may be constituted by a plurality of lenses. The light collection position of the laser light 26 is, for example, the main surface on or near the laser light source side of the glass substrate 10. The glass substrate 10 is locally heated by the laser light 26, and the heated portion is removed, and a through hole 11 is formed in the glass substrate 10. The through hole 11 is also called a through glass via (TGV: Through Glass Via).
圖3係說明形成了複數個貫通孔11的玻璃基板10的圖。例如，如圖3所示，對玻璃基板10進行複數次的貫通孔形成步驟，在玻璃基板10形成複數個貫通孔11。貫通孔11的直徑D1係例如10~50μm左右。本說明書中所述的貫通孔的直徑係例如玻璃基板的上表面的尺寸。圖3的玻璃基板10係噴墨方式的印刷頭用基板、兩面配線基板、可用於將複數個IC晶片集結在一個封裝體的多晶片模組(MCM)、或能夠以單一封裝體實現系統層級的功能的系統級封裝(SiP)等的玻璃轉接板(中介基板)的例子。 FIG. 3 is a diagram illustrating a glass substrate 10 in which a plurality of through holes 11 are formed. For example, as shown in FIG. 3, a plurality of through-hole forming steps are performed on the glass substrate 10 to form a plurality of through-holes 11 in the glass substrate 10. The diameter D1 of the through hole 11 is, for example, about 10 to 50 μm. The diameter of the through-hole described in this specification is, for example, the size of the upper surface of a glass substrate. The glass substrate 10 shown in FIG. 3 is a substrate for an inkjet printing head, a double-sided wiring substrate, a multi-chip module (MCM) that can be used to aggregate a plurality of IC chips in a single package, or a single package can be used to achieve a system level An example of a glass interposer (interposer) such as a system-in-package (SiP).
此處，在使用雷射光的貫通孔的形成步驟中，在玻璃基板10的上表面側及底面側且貫通孔11附近產 生複數個龜裂(微龜裂)12。即，使用UV雷射光的貫通孔的形成步驟係熱加工，因此涵蓋加工部分的周邊的廣泛範圍地產生由熱應變所產生的龜裂。 Here, in the step of forming a through hole using laser light, the glass substrate 10 is produced near the through hole 11 on the upper surface side and the bottom surface side. Health multiple cracks (micro cracks) 12. That is, since the formation step of the through-hole using UV laser light is thermal processing, cracks due to thermal strain are generated in a wide range covering the periphery of the processed portion.
然後，如圖1所示，一邊賦予超音波振動一邊進行濕式蝕刻(步驟S101)。濕式蝕刻步驟係例如進行20分鐘左右。圖4係濕式蝕刻步驟中所使用的濕式蝕刻裝置30的概略圖。 Then, as shown in FIG. 1, wet etching is performed while applying ultrasonic vibration (step S101). The wet etching step is performed, for example, for about 20 minutes. FIG. 4 is a schematic view of a wet etching apparatus 30 used in the wet etching step.
濕式蝕刻裝置30具備蝕刻處理槽31、超音波產生裝置32、及保持機構33。向蝕刻處理槽31內供給蝕刻液34。保持機構33為可動式，例如可以保持複數片玻璃基板10。保持機構33係配置在可以將玻璃基板10浸在蝕刻液34的位置。作為玻璃基板10的固定方法，例如，可以將玻璃基板10接著在保持機構33，保持機構33也可以具備挾持玻璃基板10的機構。 The wet etching device 30 includes an etching treatment tank 31, an ultrasonic generation device 32, and a holding mechanism 33. An etching solution 34 is supplied into the etching treatment tank 31. The holding mechanism 33 is movable, and can hold, for example, a plurality of glass substrates 10. The holding mechanism 33 is disposed at a position where the glass substrate 10 can be immersed in the etching solution 34. As a method for fixing the glass substrate 10, for example, the glass substrate 10 may be attached to the holding mechanism 33, and the holding mechanism 33 may include a mechanism for holding the glass substrate 10.
在蝕刻處理槽31內，以浸在蝕刻液34的方式設置超音波產生裝置32。超音波產生裝置32產生超音波，使蝕刻液34發生超音波振動。藉由此超音波振動，在蝕刻液34中產生複數個氣泡，在蝕刻液34中造成空穴(cavitation)。藉此，玻璃基板10的貫通孔11被蝕刻。 An ultrasonic generation device 32 is installed in the etching treatment tank 31 so as to be immersed in the etching solution 34. The ultrasonic generating device 32 generates an ultrasonic wave, and causes the etching solution 34 to generate ultrasonic vibration. Due to this ultrasonic vibration, a plurality of bubbles are generated in the etching solution 34, and cavitation is caused in the etching solution 34. Thereby, the through-hole 11 of the glass substrate 10 is etched.
接著，針對濕式蝕刻步驟中使用的蝕刻液34進行說明。蝕刻液34包含氫氟酸(HF)、硫酸(H2SO4)、及水(H2O)。氫氟酸(HF)的濃度大於0且為4重量%以下。更理想的是，氫氟酸的濃度為1.5重量%以下。硫酸的濃度比氫氟酸的濃度高而為10重量%以上90重量%以下。更理想的是，硫酸的濃度為40重量%以上60重量%以下。具體 而言，蝕刻液34包含0.5重量%左右的氫氟酸、60.0重量%左右的硫酸、及39.5重量%左右的水。 Next, the etchant 34 used in the wet etching step will be described. The etching solution 34 includes hydrofluoric acid (HF), sulfuric acid (H 2 SO 4 ), and water (H 2 O). The concentration of hydrofluoric acid (HF) is more than 0 and 4% by weight or less. More preferably, the concentration of hydrofluoric acid is 1.5% by weight or less. The concentration of sulfuric acid is higher than the concentration of hydrofluoric acid and is 10% by weight to 90% by weight. More preferably, the concentration of sulfuric acid is 40% by weight or more and 60% by weight or less. Specifically, the etching solution 34 contains about 0.5% by weight of hydrofluoric acid, about 60.0% by weight of sulfuric acid, and about 39.5% by weight of water.
玻璃基板10，其主要成分為SiO2(40~70%)，第二多的成分為Al2O3(5~20%)。 The main component of the glass substrate 10 is SiO 2 (40 to 70%), and the second most important component is Al 2 O 3 (5 to 20%).
對玻璃基板10，蝕刻液34中所含的氫氟酸(HF)發生以下所示的3種(1)~(3)的反應。 For the glass substrate 10, the three types of (1) to (3) reactions described below occur in hydrofluoric acid (HF) contained in the etching solution 34.
SiO2+4HF → SiF4+2H2O...(1) SiO 2 + 4HF → SiF 4 + 2H 2 O ... (1)
SiO2+6HF → H2SiF6+2H2O...(2) SiO 2 + 6HF → H 2 SiF 6 + 2H 2 O ... (2)
Al2O3+6HF → 2AlF3+3H2O...(3) Al 2 O 3 + 6HF → 2AlF 3 + 3H 2 O ... (3)
圖5係顯示濕式蝕刻後的貫通孔11的一例的剖面圖。藉由濕式蝕刻步驟，龜裂受到蝕刻，能夠形成幾乎沒有龜裂的貫通孔11。濕式蝕刻後的貫通孔11的直徑D2係例如50~150μm。 FIG. 5 is a cross-sectional view showing an example of the through-hole 11 after wet etching. In the wet etching step, the cracks are etched, and the through holes 11 can be formed with almost no cracks. The diameter D2 of the through-hole 11 after the wet etching is, for example, 50 to 150 μm.
圖6係顯示濕式蝕刻前的貫通孔11的一例的照片。圖6的照片係使用掃描電子顯微鏡(Scanning Electron Microscopy：SEM)拍攝。在圖6的貫通孔11的周圍形成有複數個龜裂。圖6的貫通孔11的直徑為100μm左右。 FIG. 6 is a photograph showing an example of the through hole 11 before the wet etching. The photograph in FIG. 6 was taken using a scanning electron microscope (Scanning Electron Microscopy: SEM). A plurality of cracks are formed around the through hole 11 in FIG. 6. The diameter of the through-hole 11 in FIG. 6 is about 100 μm.
圖7係顯示濕式蝕刻後的貫通孔11的一例的照片。在圖7的貫通孔11的周圍幾乎沒有龜裂，即，可藉由進行本實施形態的濕式蝕刻來完全除去龜裂。 FIG. 7 is a photograph showing an example of the through-hole 11 after wet etching. There are almost no cracks around the through-hole 11 in FIG. 7, that is, the cracks can be completely removed by performing wet etching in this embodiment.
圖8係說明本實施形態的濕式蝕刻的原理的示意圖。圖8的左側係濕式蝕刻前的平面圖，圖8的右側係濕式蝕刻後的平面圖。 FIG. 8 is a schematic diagram illustrating the principle of wet etching in this embodiment. The left side of FIG. 8 is a plan view before wet etching, and the right side of FIG. 8 is a plan view after wet etching.
氫氟酸(HF)係黏度(黏性係數)小，表面張力 小，及分子尺寸小，因此容易侵入龜裂內。另一方面，與氫氟酸相比，硫酸(H2SO4)係黏度大，表面張力大，及分子尺寸大，因此很難侵入龜裂內。又，與氫氟酸混合的酸不限於硫酸，能夠使用具有與氫氟酸相比，黏度較大，表面張力較大，及/或分子尺寸較大的特性的酸。作為滿足這樣的條件的酸，可舉出乙酸、磷酸、或硝酸等。另外，也可以使用滿足上述條件且為酸以外的液體，例如甘油等。 Hydrofluoric acid (HF) series has small viscosity (viscosity coefficient), small surface tension, and small molecular size, so it easily penetrates into cracks. On the other hand, compared with hydrofluoric acid, sulfuric acid (H 2 SO 4 ) has a large viscosity, a large surface tension, and a large molecular size, so it is difficult to penetrate into cracks. Moreover, the acid mixed with hydrofluoric acid is not limited to sulfuric acid, and an acid having characteristics of larger viscosity, larger surface tension, and / or larger molecular size than hydrofluoric acid can be used. Examples of the acid satisfying such conditions include acetic acid, phosphoric acid, and nitric acid. A liquid other than an acid that satisfies the above conditions, such as glycerin, may also be used.
本實施形態的蝕刻液34係硫酸的濃度比氫氟酸的濃度高，蝕刻液34的黏度高。因此，蝕刻液34變得很難侵入龜裂內，能夠抑制龜裂內的蝕刻進行。 The concentration of the sulfuric acid in the etching solution 34 of this embodiment is higher than the concentration of hydrofluoric acid, and the viscosity of the etching solution 34 is high. Therefore, it becomes difficult for the etchant 34 to penetrate into the crack, and the progress of the etching in the crack can be suppressed.
作為蝕刻的原理，氫氟酸離子化，氟(F)離子成為溶解玻璃基板的主體。但是，就使玻璃基板的溶解進行而言，需要氫(H)離子的輔助。氫離子係藉由降低蝕刻液的pH(potential of hydrogen)來輔助玻璃基板的溶解。 As the principle of etching, hydrofluoric acid is ionized, and fluorine (F) ions become the main body that dissolves the glass substrate. However, the dissolution of the glass substrate requires the assistance of hydrogen (H) ions. The hydrogen ion assists the dissolution of the glass substrate by lowering the pH (potential of hydrogen) of the etching solution.
本實施形態係降低氫氟酸的濃度(例如0.5重量%)。在此情況下，在僅有氫氟酸方面，由於輔助玻璃基板的溶解的氫離子少，因此玻璃基板的蝕刻很難進行。但是，本實施形態係蝕刻液包含有硫酸，藉由硫酸所含的氫離子來降低蝕刻液的pH，從而能夠輔助玻璃基板的溶解。 In this embodiment, the concentration (for example, 0.5% by weight) of hydrofluoric acid is reduced. In this case, since only the hydrofluoric acid is used, since there are few dissolved hydrogen ions in the auxiliary glass substrate, the etching of the glass substrate is difficult. However, the etching solution of the present embodiment contains sulfuric acid, and the pH of the etching solution is reduced by the hydrogen ions contained in the sulfuric acid, so that the dissolution of the glass substrate can be assisted.
依照這樣的原理，如圖8所示，不會促進龜裂12內的蝕刻，貫通孔11整體被均勻地蝕刻。藉此，貫通孔11的蝕刻係在龜裂12不被擴大下進行，蝕刻係以貫通孔11整體擴大的方式進行。其結果，幾乎將濕式蝕刻前 的龜裂12除去。又，若氫氟酸的濃度成為4重量%以上，則即使是在向蝕刻液加入氫氟酸以外的成分的情況下，蝕刻也會在龜裂內進行。由此，本實施形態係將氫氟酸的濃度設定為4重量%以下。 According to such a principle, as shown in FIG. 8, the etching in the crack 12 is not promoted, and the entire through hole 11 is uniformly etched. Thereby, the etching of the through-hole 11 is performed without the crack 12 being enlarged, and the etching is performed so that the entire through-hole 11 is enlarged. As a result, the The cracks 12 are removed. In addition, if the concentration of hydrofluoric acid is 4% by weight or more, even when a component other than hydrofluoric acid is added to the etching solution, the etching is performed in the cracks. Therefore, in this embodiment, the concentration of hydrofluoric acid is set to 4% by weight or less.
此外，藉由超音波產生裝置32產生超音波，在蝕刻液34中造成空穴。由空穴所產生的氣泡的直徑，理想的是比貫通孔的直徑小且比龜裂的寬度大。藉此，由空穴所產生的氣泡侵入貫通孔11內，但變得很難侵入龜裂12內。由此，促進貫通孔11的蝕刻，同時能夠抑制龜裂12內的蝕刻。例如，在貫通孔11的直徑為100μm的情況下，氣泡的直徑，理想的是80μm以下。此時的超音波的頻率係設定在28kHz以上。 In addition, the ultrasonic wave is generated by the ultrasonic wave generating device 32, and voids are generated in the etching solution 34. The diameter of the bubbles generated by the holes is preferably smaller than the diameter of the through hole and larger than the width of the crack. As a result, the bubbles generated by the holes penetrate into the through holes 11, but it becomes difficult to penetrate into the cracks 12. Thereby, the etching in the through hole 11 is promoted, and the etching in the crack 12 can be suppressed. For example, when the diameter of the through hole 11 is 100 μm, the diameter of the bubbles is preferably 80 μm or less. The frequency of the ultrasonic wave at this time is set to 28 kHz or more.
圖9係說明本實施形態的濕式蝕刻的蝕刻速率的曲線圖。圖9的橫軸表示處理時間(分鐘)，圖9的縱軸表示蝕刻量(μm)。圖9中使用的蝕刻液包含0.5重量%的氫氟酸、69.3重量%的硫酸、及30.2重量%的水。此蝕刻液的pH小於1。本實施形態的濕式蝕刻能夠實現高蝕刻速率。 FIG. 9 is a graph illustrating an etching rate of the wet etching in the present embodiment. The horizontal axis of FIG. 9 represents the processing time (minutes), and the vertical axis of FIG. 9 represents the etching amount (μm). The etching solution used in FIG. 9 contains 0.5% by weight of hydrofluoric acid, 69.3% by weight of sulfuric acid, and 30.2% by weight of water. The pH of this etchant is less than 1. The wet etching in this embodiment can achieve a high etching rate.
圖10係說明由超音波產生的氣泡的曲線圖。圖10的橫軸表示超音波的頻率(kHz)，圖10的縱軸表示氣泡的直徑(μm)。如圖10所示，藉由將超音波的頻率設定在28kHz以上，能夠形成具有80μm以下的直徑的氣泡。藉此，促進貫通孔11的蝕刻，同時能夠抑制龜裂12內的蝕刻。 FIG. 10 is a graph illustrating bubbles generated by an ultrasonic wave. The horizontal axis of FIG. 10 indicates the frequency (kHz) of the ultrasonic wave, and the vertical axis of FIG. 10 indicates the diameter (μm) of the bubble. As shown in FIG. 10, by setting the frequency of the ultrasonic wave to 28 kHz or more, bubbles having a diameter of 80 μm or less can be formed. Thereby, the etching in the through hole 11 is promoted, and the etching in the crack 12 can be suppressed.
(比較例) (Comparative example)
接著，針對比較例進行說明。圖11係說明比較例的濕式蝕刻的原理的示意圖。圖11的左側為濕式蝕刻前的平面圖，圖11的右側為濕式蝕刻後的平面圖。 Next, a comparative example will be described. FIG. 11 is a schematic diagram illustrating the principle of wet etching in a comparative example. The left side of FIG. 11 is a plan view before wet etching, and the right side of FIG. 11 is a plan view after wet etching.
比較例的蝕刻液，例如，包含4重量%左右的氫氟酸、及96重量%左右的水。即，比較例的蝕刻液不包含氫氟酸以外的酸。 The etching solution of the comparative example contains, for example, about 4% by weight of hydrofluoric acid and about 96% by weight of water. That is, the etching solution of the comparative example does not contain acids other than hydrofluoric acid.
比較例中，氫氟酸(HF)離子化，氟(F)離子溶解玻璃。氫(H)離子降低蝕刻液的pH，輔助由氟離子所產生的玻璃的溶解。比較例的蝕刻液，由於黏度及表面張力低，因此蝕刻液侵入龜裂內。藉此，貫通孔及龜裂被等向性地蝕刻，龜裂被擴大。即，比較例的濕式蝕刻步驟不能除去龜裂。 In the comparative example, hydrofluoric acid (HF) was ionized, and fluorine (F) ions dissolved the glass. Hydrogen (H) ions lower the pH of the etching solution and assist the dissolution of glass produced by fluoride ions. The etching solution of the comparative example has low viscosity and surface tension, and therefore the etching solution penetrates into the cracks. Thereby, the through hole and the crack are etched isotropically, and the crack is enlarged. That is, cracks cannot be removed in the wet etching step of the comparative example.
圖12係顯示比較例的濕式蝕刻後的貫通孔11的一例的照片。如圖12所示，比較例係龜裂會擴大，不能完全除去龜裂。 FIG. 12 is a photograph showing an example of the through-hole 11 after wet etching in a comparative example. As shown in FIG. 12, the cracks of the comparative example were enlarged, and the cracks could not be completely removed.
圖9中，也記載了比較例的曲線圖。圖9中使用的比較例的蝕刻液包含0.5重量%左右的氫氟酸、及99.5重量%左右的水。此蝕刻液的pH為3左右。與本實施形態相比，比較例係蝕刻速率變低。 A graph of a comparative example is also shown in FIG. 9. The etching solution of the comparative example used in FIG. 9 contains about 0.5% by weight of hydrofluoric acid and about 99.5% by weight of water. The pH of this etching solution is about 3. Compared with this embodiment, the comparative example has a lower etching rate.
(效果) (effect)
依以上詳述的方式，本實施形態中，首先，使用雷射光26在玻璃基板10形成貫通孔11。然後，使用蝕刻液34，將貫通孔11進行濕式蝕刻。蝕刻液34包含氫氟酸、分子尺寸比氫氟酸大的硫酸、和水。氫氟酸的濃度為4重量%以下。硫酸的濃度比氫氟酸的濃度高而為10 重量%以上90重量%以下。 As described in detail above, in the present embodiment, first, the through-hole 11 is formed in the glass substrate 10 using the laser light 26. Then, the through-hole 11 is wet-etched using the etching solution 34. The etching solution 34 contains hydrofluoric acid, sulfuric acid having a molecular size larger than that of hydrofluoric acid, and water. The concentration of hydrofluoric acid is 4% by weight or less. The concentration of sulfuric acid is higher than that of hydrofluoric acid and is 10 At least 90% by weight.
由此，根據本發明的話，便能夠將在貫通孔11的周圍所形成的龜裂12除去或幾乎除去。藉此，能夠抑制具有複數個貫通孔11的玻璃基板10的特性(功能)降低。此外，能夠抑制因龜裂12所造成的玻璃基板10破裂。 Thus, according to the present invention, the cracks 12 formed around the through hole 11 can be removed or almost removed. As a result, it is possible to suppress a reduction in characteristics (functions) of the glass substrate 10 having the plurality of through holes 11. In addition, it is possible to suppress cracking of the glass substrate 10 caused by the cracks 12.
此外，藉由使用本實施形態的蝕刻液34，能夠提高蝕刻速率。藉此，能夠縮短濕式蝕刻步驟，因此能夠減低製造成本。 In addition, by using the etching solution 34 of this embodiment, the etching rate can be increased. Thereby, the wet etching step can be shortened, and thus the manufacturing cost can be reduced.
此外，對蝕刻液34施加超音波，在蝕刻液34中造成空穴。另外，為了使由空穴產生的氣泡變得很難侵入龜裂12，將超音波的頻率設定在28kHz以上。藉此，促進貫通孔11的蝕刻，同時能夠抑制龜裂12內的蝕刻。其結果，便可以除去龜裂12。此外，借助空穴，能夠進一步提高蝕刻速率。 In addition, an ultrasonic wave is applied to the etchant 34 to cause holes in the etchant 34. In addition, in order to make it difficult for the bubbles generated by the holes to penetrate the crack 12, the frequency of the ultrasonic wave is set to 28 kHz or higher. Thereby, the etching in the through hole 11 is promoted, and the etching in the crack 12 can be suppressed. As a result, the cracks 12 can be removed. In addition, the etching rate can be further increased by the holes.
本發明不限於上述實施形態，在不脫離其要旨的範圍內，可以將構成要素變形並具體化。另外，上述實施形態中包含有各種階段的發明，能夠藉由1個實施形態中所公開的複數個構成要素的適宜組合、或者是不同實施形態中所公開的構成要素的適宜組合來構成各種發明。例如，即使從實施形態中所公開的全部構成要素削除數個構成要素，也能解決發明所欲解決的課題，在可得到發明的效果的情況下，削除了這些構成要素的實施形態能以發明的形式予以抽出。 The present invention is not limited to the embodiments described above, and the constituent elements may be modified and embodied without departing from the scope of the invention. In addition, the above embodiments include inventions in various stages, and various inventions can be constituted by a suitable combination of a plurality of constituent elements disclosed in one embodiment or a suitable combination of constituent elements disclosed in different embodiments. . For example, even if several constituent elements are deleted from all the constituent elements disclosed in the embodiment, the problem to be solved by the invention can be solved, and when the effect of the invention can be obtained, the embodiment in which these constituent elements are removed can be used The form is extracted.
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| CN112894146A (en) * | 2019-12-04 | 2021-06-04 | 大族激光科技产业集团股份有限公司 | Laser processing method and device for glass substrate through hole |
| CN114643428A (en) * | 2020-12-17 | 2022-06-21 | 钛昇科技股份有限公司 | Method for forming through hole in substrate |
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