TW202043441A - Glass etching solution and glass substrate manufacturing method - Google Patents

Glass etching solution and glass substrate manufacturing method Download PDF

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TW202043441A
TW202043441A TW109104688A TW109104688A TW202043441A TW 202043441 A TW202043441 A TW 202043441A TW 109104688 A TW109104688 A TW 109104688A TW 109104688 A TW109104688 A TW 109104688A TW 202043441 A TW202043441 A TW 202043441A
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etching
glass
glass substrate
etching solution
modified
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TWI832970B (en
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西川晴香
島田和哉
永井忠
三好雄三
冨家夏樹
大小田健太
柏原康宏
齊藤俊介
大山陽照
林篤嗣
福成良介
石垣暢規
元持健
久米貴大
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日商Ｎｓｃ股份有限公司
日商松下電器產業股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/38—Removing material by boring or cutting
    • B23K26/382—Removing material by boring or cutting by boring
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B33/00—Severing cooled glass
    • C03B33/02—Cutting or splitting sheet glass or ribbons; Apparatus or machines therefor
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Surface Treatment Of Glass (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Laser Beam Processing (AREA)

Abstract

To provide a liquid crystal panel manufacturing method capable of minimizing the effects of side etching that accompany etching processes. A glass etching solution according to the present invention is a glass etching solution for etching glass, said solution including at least an etching inhibiting substance which lowers the etching speed of glass and contains at least an alkali or a fluorine complex agent. The etching inhibiting substance preferably generates a reaction product which inhibits an etching reaction by attaching to a modified section which has been modified so as to make glass more readily etchable.

Description

玻璃用蝕刻液及玻璃基板製造方法Etching liquid for glass and glass substrate manufacturing method

本發明係關於用以將玻璃切斷或穿孔的玻璃用蝕刻液、及使用此的玻璃基板製造方法者。The present invention relates to an etching solution for glass for cutting or perforating glass, and a method for manufacturing a glass substrate using the same.

以將玻璃切斷或穿孔的技術而言，存在有各式各樣者。以往大多使用劃線裂片、雷射燒蝕加工、超音波主軸、濕式蝕刻處理等手法。There are various techniques for cutting or perforating glass. In the past, methods such as scribing and splitting, laser ablation processing, ultrasonic spindle, and wet etching processing were mostly used.

在該等手法之中，若採用劃線裂片，難以形成具有帶圓輪廓的玻璃面板。此外，在雷射燒蝕加工中，係容易發生加工速度變慢、或發生因燒蝕殘渣所致之污損等不良情形。在超音波主軸中，係有因加工後的損傷而強度降低的風險，在濕式蝕刻處理中，係難以將加工端面相對主面保持為直角。Among these methods, it is difficult to form a glass panel with a round outline if scribing lobes are used. In addition, in laser ablation processing, the processing speed is likely to slow down, or the ablation residue may cause contamination. In the ultrasonic spindle, there is a risk of strength reduction due to damage after processing. In the wet etching process, it is difficult to maintain the processed end surface at a right angle to the main surface.

因此，在習知技術之中係有採用藉由雷射來使玻璃中應切斷的部位或應穿孔的部位變質之後，利用雷射技術與蝕刻技術之雙方，俾以將該變質部位進行濕式蝕刻處理的手法者(參照例如專利文獻1)。在如上所示之技術中，玻璃中的變質部位比除此之外的部位，蝕刻的速度更快3～5倍左右，結果可將玻璃適當切斷或穿孔。 [先前技術文獻] [專利文獻]Therefore, in the conventional technology, after the part to be cut or the part to be perforated in the glass is deteriorated by laser, the laser technology and etching technology are used to wet the deteriorated part. A method of conventional etching processing (see, for example, Patent Document 1). In the technique shown above, the deterioration of the glass is 3 to 5 times faster than the other parts. As a result, the glass can be appropriately cut or perforated. [Prior Technical Literature] [Patent Literature]

專利文獻1：日本特開2011-124752號公報Patent Document 1: Japanese Patent Application Publication No. 2011-124752

(發明所欲解決之問題)(The problem to be solved by the invention)

但是，在上述之習知技術中，亦因蝕刻在垂直方向及水平方向同樣地進展的性質(等向性)，而有無法獲得所希望的形狀的切剖面或貫穿孔的情形。例如，在切剖面中，厚度方向的中央部大多形成為凸狀。此外，在貫穿孔中，亦相較於兩主面附近的開口徑，離兩主面較遠的厚度方向中央部的內徑較小，剖面視下，大多形成為在厚度方向的中央部具有狹窄部的貫穿孔。However, in the above-mentioned conventional technique, due to the property (isotropy) that the etching progresses in the vertical direction and the horizontal direction equally, there are cases where a cross section or through hole of a desired shape cannot be obtained. For example, in the cross section, the center part in the thickness direction is often formed in a convex shape. In addition, in the through hole, the inner diameter of the center part in the thickness direction farther from the two main surfaces is smaller than the opening diameter near the two main surfaces. In a cross-sectional view, it is often formed to have a central part in the thickness direction. Through hole in the narrow part.

本發明之目的在提供可將濕式蝕刻的等向性的影響抑制為最小限度的玻璃用蝕刻液及玻璃基板製造方法。 (解決問題之技術手段)The object of the present invention is to provide an etching solution for glass and a glass substrate manufacturing method that can minimize the influence of the isotropic properties of wet etching. (Technical means to solve the problem)

本發明之玻璃用蝕刻液係用以蝕刻玻璃(尤其，藉由雷射加工而已被改質為蝕刻容易進展的部分)者。該玻璃用蝕刻液係至少包含使對玻璃的蝕刻速度降低的蝕刻阻礙物質，且為至少含有鹼或氟錯合劑之任一方的蝕刻阻礙物質。The etching solution for glass of the present invention is used to etch glass (especially, a part that has been modified by laser processing to be easily etched). The etching solution for glass contains at least an etching inhibitor that reduces the etching rate of glass, and is an etching inhibitor that contains at least either an alkali or a fluorine complexing agent.

以蝕刻阻礙物質之例而言，列舉氫氧化銨、氫氧化鈉、氫氧化鉀等鹼、或二氧化鈦、氯化鋁、硼酸、二氧化矽等氟錯合劑。Examples of etching inhibitors include alkalis such as ammonium hydroxide, sodium hydroxide, and potassium hydroxide, or fluorine complexing agents such as titanium dioxide, aluminum chloride, boric acid, and silicon dioxide.

因存在如上所示之蝕刻阻礙物質，防止例如氫氟酸等有助於玻璃蝕刻的活性種在玻璃基板的主面附近被消耗。此外，活性種與蝕刻阻礙物質的化合物(例：氟錯合物等)有在移動至遠離玻璃基板的主面的位置之後，放出活性種的情形，結果，活性種容易到達遠離玻璃基板的主面的位置。因此，與玻璃基板的主面呈垂直的方向(例：厚度方向、深度方向)的蝕刻變得容易進展，並且可將與該主面呈平行的方向(例：寬幅方向)的蝕刻抑制為最小限度。Due to the presence of the etching inhibitors as shown above, active species that contribute to glass etching such as hydrofluoric acid are prevented from being consumed near the main surface of the glass substrate. In addition, compounds of active species and etching inhibitors (for example, fluorine complexes, etc.) may release active species after moving to a position away from the main surface of the glass substrate. As a result, the active species easily reach the main surface away from the glass substrate. The location of the face. Therefore, etching in a direction perpendicular to the main surface of the glass substrate (e.g., thickness direction, depth direction) easily progresses, and etching in a direction parallel to the main surface (e.g., width direction) can be suppressed to Minimal.

在上述之玻璃用蝕刻液中，較佳為蝕刻阻礙物質係藉由附著在玻璃中已被改質為容易被蝕刻的改質部而使阻礙蝕刻反應的反應生成物發生。In the above-mentioned etching solution for glass, it is preferable that the etching inhibiting substance adheres to the modified portion of the glass that has been modified to be easily etched to generate a reaction product that inhibits the etching reaction.

上述之含有蝕刻阻礙物質的蝕刻液係被推定阻礙反應的生成物(障礙物(fence))比由氫氟酸與強酸所成的一般蝕刻液更容易附著在切剖面或貫穿孔的內壁。因此，被認為抑制與玻璃基板的主面呈平行的方向(例：寬幅方向)的反應，且僅與玻璃基板的主面呈垂直的方向(例：厚度方向、深度方向)的蝕刻變得較容易進展。實際上，在申請人所實施的實驗中，亦實現了將濕式蝕刻的等向性的影響抑制為最小限度的異向性蝕刻。The above-mentioned etching solution containing an etching inhibitor is a product (fence) that is estimated to hinder the reaction, and it is easier to adhere to the inner wall of the cut section or the through hole than the general etching solution made of hydrofluoric acid and strong acid. Therefore, it is considered that the reaction in the direction parallel to the main surface of the glass substrate (e.g., the width direction) is suppressed, and only the etching in the direction perpendicular to the main surface of the glass substrate (e.g., thickness direction, depth direction) becomes Easier to progress. In fact, in the experiments conducted by the applicant, anisotropic etching that minimizes the effect of wet etching on the isotropic properties was also achieved.

此外，本發明之玻璃基板製造方法係使用上述之玻璃用蝕刻液者。該玻璃基板製造方法係至少包含：改質步驟、及第1蝕刻步驟。在改質步驟中，係以遍及玻璃基板的蝕刻預定位置中的厚度方向而形成能量密度相對較高的焦線的方式，對前述玻璃基板照射雷射光，藉此將蝕刻預定位置改質。在第1蝕刻步驟中，係在改質步驟後，使用玻璃用蝕刻液來蝕刻蝕刻預定位置。In addition, the glass substrate manufacturing method of the present invention uses the above-mentioned etching solution for glass. The manufacturing method of the glass substrate includes at least a modification step and a first etching step. In the modification step, the glass substrate is irradiated with laser light to modify the predetermined etching position by forming a focal line with relatively high energy density throughout the thickness direction of the predetermined etching position of the glass substrate. In the first etching step, after the reforming step, the etching solution for glass is used to etch a predetermined position.

此外，視需要，較佳為在第1蝕刻步驟之後，另外包含：第2蝕刻步驟，其係藉由至少含有氫氟酸的蝕刻液，來蝕刻蝕刻預定位置。第2蝕刻步驟係使用從當初即未含有上述蝕刻阻礙物質的一般的蝕刻液(例：氫氟酸+鹽酸+殘部水)來進行。如上所示之蝕刻液係隨著使氫氟酸濃度增加，亦增加蝕刻速度，因此可視需要而圖求蝕刻處理的短時間化。 (發明之效果)In addition, if necessary, it is preferable to additionally include a second etching step after the first etching step, which is to etch the predetermined position by using an etching solution containing at least hydrofluoric acid. The second etching step is performed using a general etching solution (for example: hydrofluoric acid + hydrochloric acid + residual water) that does not contain the above-mentioned etching inhibitor from the beginning. The etching solution shown above increases the etching rate as the concentration of hydrofluoric acid increases. Therefore, the etching process can be shortened as needed. (Effect of Invention)

藉由本發明，可將濕式蝕刻的等向性的影響抑制為最小限度。According to the present invention, the influence of the isotropy of wet etching can be suppressed to a minimum.

以下使用圖示，說明本發明之液晶面板的製造方法的一實施形態。圖1(A)係顯示本發明之一實施形態之液晶面板10的概略構成。如該圖所示，液晶面板10係構成為陣列基板12及彩色濾光片基板14夾著液晶層等中間層而相貼合。陣列基板12及彩色濾光片基板14的構成係可採用與周知構成相同的構成，因此在此省略說明。Hereinafter, an embodiment of the method of manufacturing a liquid crystal panel of the present invention will be described using drawings. Fig. 1(A) shows a schematic configuration of a liquid crystal panel 10 according to an embodiment of the present invention. As shown in the figure, the liquid crystal panel 10 is configured such that the array substrate 12 and the color filter substrate 14 are laminated with an intermediate layer such as a liquid crystal layer in between. The configurations of the array substrate 12 and the color filter substrate 14 can adopt the same configurations as those of well-known configurations, so the description is omitted here.

陣列基板12係具有設成由與彩色濾光片基板14相貼合的區域延伸出去的電極端子部122。在該電極端子部122係連接複數電氣電路，液晶面板10及該等電氣電路被收納在框體，藉此構成例如圖1(B)所示之智慧型手機100。The array substrate 12 has an electrode terminal portion 122 which is provided so as to extend from a region bonded to the color filter substrate 14. A plurality of electrical circuits are connected to the electrode terminal portion 122, and the liquid crystal panel 10 and the electrical circuits are housed in a housing, thereby constituting, for example, a smartphone 100 as shown in FIG. 1(B).

接著，說明製造液晶面板10的方法之一例。如圖2(A)及圖2(B)所示，一般而言，液晶面板10係被製造為包含有複數此的多倒角用玻璃母材50。接著，藉由將該多倒角用玻璃母材50分斷，可得單個的液晶面板10。Next, an example of a method of manufacturing the liquid crystal panel 10 will be described. As shown in FIG. 2(A) and FIG. 2(B), in general, the liquid crystal panel 10 is manufactured to include a plurality of glass base materials 50 for multiple chamfering. Next, by breaking the multi-chamfer glass base material 50, a single liquid crystal panel 10 can be obtained.

在該實施形態中，為方便起見，說明對6個液晶面板10配置成3行2列的矩陣狀，而且在表面形成有透明性薄膜(ITO膜或有機導電膜等透明性導電膜、或透明保護膜等)17的多倒角用玻璃母材50的處理。但是，多倒角用玻璃母材50所包含的液晶面板10的數量並非為限定於此者，可作適當增減。In this embodiment, for convenience, it is explained that six liquid crystal panels 10 are arranged in a matrix of 3 rows and 2 columns, and a transparent thin film (transparent conductive film such as ITO film or organic conductive film, or Transparent protective film, etc.) 17 for the treatment of the glass base material 50 for multiple chamfering. However, the number of liquid crystal panels 10 included in the glass base material 50 for multiple chamfering is not limited to this, and can be increased or decreased as appropriate.

多倒角用玻璃母材50係首先，如圖3(A)及圖3(B)所示，沿著對應液晶面板10的形狀(輪廓)的形狀切斷預定線，形成改質線20。該改質線20係將藉由例如由皮秒雷射或飛秒雷射等脈衝雷射被照射的光束脈衝(束徑係1～5μm左右)所形成的複數長絲(filament)層進行配列的長絲陣列(參照圖4(A)及圖4(B))。改質線20係例如圖4(A)及圖4(B)所示，呈現具有複數貫穿孔或改質層的孔狀接線狀。改質線20係具有比多倒角用玻璃母材50中的其他部位更容易被蝕刻的性質。當然，改質線20的形狀並非為限定於該形狀者，亦可為呈現除此之外的形狀者。The glass base material 50 for multiple chamfering is first, as shown in FIGS. 3(A) and 3(B), a predetermined line is cut along a shape corresponding to the shape (contour) of the liquid crystal panel 10 to form a modified line 20. The modified line 20 is arranged by multiple filament layers formed by beam pulses (beam diameters of about 1 to 5 μm) irradiated by pulse lasers such as picosecond lasers or femtosecond lasers. Array of filaments (see Figure 4(A) and Figure 4(B)). The modified wire 20 is, for example, as shown in FIGS. 4(A) and 4(B), and has a hole-like wiring shape having a plurality of through holes or modified layers. The modified wire 20 has a property of being more easily etched than other parts in the glass base material 50 for multiple chamfering. Of course, the shape of the modified wire 20 is not limited to this shape, and may exhibit other shapes.

若藉由1個雷射束來同時處理陣列基板12、彩色濾光片基板14、及透明性薄膜17，有在液晶層發生不良情形的可能性。因此，在本實施形態中，係藉由採用如圖3(C)及圖3(D)所示之雷射加工，可抑制如上所示之不良情形的發生。亦即，如圖3(C)所示，若以由陣列基板12側僅在陣列基板12形成改質線20的方式進行焦點調整及強度調整之後照射雷射，能量不易傳達至液晶層近傍即可。在該狀態下，若可藉由施加物理性作用或熱性作用來進行多倒角用玻璃母材50的分斷，雷射加工係在此結束。If the array substrate 12, the color filter substrate 14, and the transparent film 17 are processed at the same time by one laser beam, there is a possibility that defects may occur in the liquid crystal layer. Therefore, in this embodiment, by using the laser processing as shown in FIG. 3(C) and FIG. 3(D), it is possible to suppress the occurrence of the above-mentioned problems. That is, as shown in FIG. 3(C), if the focus adjustment and intensity adjustment are performed so that the modified line 20 is formed only on the array substrate 12 from the side of the array substrate 12 and then the laser is irradiated, the energy is not easily transmitted to the vicinity of the liquid crystal layer. can. In this state, if the glass base material 50 for multiple chamfering can be broken by applying a physical action or a thermal action, the laser processing is ended here.

另一方面，若在該狀態下難以進行多倒角用玻璃母材50的分斷，如圖3(D)所示，這次若以由成為相反側的彩色濾光片基板14側僅在彩色濾光片基板14形成改質線20的方式進行焦點調整及強度調整之後，再照射雷射即可。藉由進行圖3(D)所示之處理，雖然雷射加工的工程數增加，但是可一邊抑制液晶層中的不良情形的發生，一邊輕易進行多倒角用玻璃母材50的分斷。On the other hand, if it is difficult to break the glass base material 50 for multiple chamfers in this state, as shown in FIG. 3(D), if the color filter substrate 14 side is the opposite side, only the color After the focus adjustment and intensity adjustment are performed by the way that the filter substrate 14 forms the modified line 20, the laser can be irradiated. By performing the processing shown in FIG. 3(D), although the number of laser processing steps is increased, it is possible to easily break the glass base material 50 for multiple chamfers while suppressing the occurrence of defects in the liquid crystal layer.

來自皮秒雷射的光束係以適當調整聚光區域為佳。例如，藉由將雷射光的聚光區域調整為不到達中間層，防止因蝕刻處理中的蝕刻液的過度浸透而端子配線腐蝕的情形。For the beam from the picosecond laser, it is better to adjust the focusing area appropriately. For example, by adjusting the condensing area of the laser light so as not to reach the intermediate layer, it is possible to prevent the terminal wiring from corroding due to excessive penetration of the etching solution in the etching process.

在多倒角用玻璃母材50中沿著形狀切斷預定線形成改質線20後，多倒角用玻璃母材50係如圖5(A)及圖5(B)所示，在雙方的主面黏貼具耐蝕刻性的耐蝕刻膜16。在此係採用厚度為50～75μm的聚乙烯，作為耐蝕刻膜16。但是，耐蝕刻膜16的構成並非限定於此。例如，若如聚丙烯或聚氯乙烯或烯烴系樹脂等般為對蝕刻玻璃的蝕刻液具耐性者，亦可適當選擇來採用。After the glass base material 50 for multiple chamfers is cut along the planned line to form the modified line 20, the glass base material 50 for multiple chamfers is shown in FIGS. 5(A) and 5(B). An etch-resistant film 16 with etch resistance is attached to the main surface. Here, polyethylene having a thickness of 50 to 75 μm is used as the etching resistant film 16. However, the structure of the etching resistant film 16 is not limited to this. For example, if it is resistant to an etchant for etching glass, such as polypropylene, polyvinyl chloride, or olefin-based resin, it can be appropriately selected and adopted.

若耐蝕刻膜16的黏貼完成，接著，如圖5(C)所示，沿著與應取出的液晶面板10的形狀相對應的形狀切斷預定線，進行對耐蝕刻膜16照射雷射束。藉由該雷射束的照射，耐蝕刻膜16沿著形狀切斷預定線被去除。接著，沿著形狀切斷預定線，形成耐蝕刻膜16的開口部，結果，與圖3(C)所示之構成同樣地，多倒角用玻璃母材50的改質線20的形成位置露出於外部。When the etching resistant film 16 is pasted, then, as shown in FIG. 5(C), a predetermined line is cut along a shape corresponding to the shape of the liquid crystal panel 10 to be taken out, and the etching resistant film 16 is irradiated with a laser beam . By the irradiation of the laser beam, the etching resistant film 16 is removed along the line to cut the shape. Next, the predetermined line is cut along the shape to form the opening of the etching resistant film 16. As a result, the formation position of the modified line 20 of the glass base material 50 for multiple chamfers is the same as the configuration shown in FIG. 3(C) Exposed to the outside.

若上述雷射加工結束，如圖6所示，多倒角用玻璃母材50係被導入至蝕刻裝置300，施行藉由含有氫氟酸及蝕刻阻礙物質的蝕刻液所為之第1蝕刻步驟，且視需要，施行藉由含有氫氟酸及鹽酸等的一般的蝕刻液所為之第2蝕刻步驟(任意處理)。通常使用含有氫氟酸1～10重量%、鹽酸5～20重量%左右的蝕刻液，且視需要適當併用界面活性劑等，惟在第1蝕刻步驟中，係使一般的蝕刻液另外含有蝕刻阻礙物質。When the above-mentioned laser processing is completed, as shown in FIG. 6, the glass base material 50 for multiple chamfers is introduced into the etching device 300, and the first etching step is performed by an etching solution containing hydrofluoric acid and an etching inhibitor. Furthermore, if necessary, a second etching step (optional treatment) is performed using a general etching solution containing hydrofluoric acid, hydrochloric acid, and the like. Usually, an etching solution containing 1-10% by weight of hydrofluoric acid and 5-20% by weight of hydrochloric acid is used, and surfactants, etc. are appropriately used in combination as necessary. However, in the first etching step, the general etching solution is additionally contained in etching Obstructing substances.

以蝕刻阻礙物質之例而言，列舉氫氧化銨、氫氧化鈉、氫氧化鉀等鹼、或二氧化鈦、氯化鋁、硼酸、二氧化矽等氟錯合劑。蝕刻阻礙物質主要達成減低由氫氟酸與強酸所成的蝕刻液的蝕刻速度(蝕刻率)的作用。通常，氫氟酸濃度或氟濃度、與蝕刻速度具有正相關，伴隨氫氟酸濃度或氟濃度的增加，蝕刻速度會變快。Examples of etching inhibitors include alkalis such as ammonium hydroxide, sodium hydroxide, and potassium hydroxide, or fluorine complexing agents such as titanium dioxide, aluminum chloride, boric acid, and silicon dioxide. The etching inhibitor mainly achieves the effect of reducing the etching rate (etching rate) of the etching solution formed by hydrofluoric acid and strong acid. Generally, the concentration of hydrofluoric acid or the concentration of fluorine has a positive correlation with the etching rate, and as the concentration of hydrofluoric acid or the concentration of fluorine increases, the etching rate becomes faster.

但是，申請人係推測藉由對氫氟酸的物質量，含有0.05～5.00莫耳當量左右的蝕刻阻礙物質，即使提高氫氟酸濃度或氟濃度，亦可將蝕刻速度抑制較低為0.01～3.00μm/min左右，且藉由形成如上所示之狀態，實現將濕式蝕刻的等向性的影響抑制為最小限度的異向性蝕刻。However, the applicant speculates that due to the amount of hydrofluoric acid containing an etching inhibitor of about 0.05 to 5.00 molar equivalent, even if the concentration of hydrofluoric acid or the fluorine concentration is increased, the etching rate can be suppressed to 0.01 to 0.01. About 3.00μm/min, and by forming the state shown above, anisotropic etching can be achieved that minimizes the effect of wet etching on the isotropy.

以氫氟酸與蝕刻阻礙物質的化合物而言，列舉：氟化鈦酸(H2 TiF6 )、氟化銨(NH4 F)、四氟硼酸(HBF4 )、六氟磷酸(HPF6 )、六氟矽酸(H2 SiF6 )、六氟鋁酸(H3 AlF6 )、六氟銻酸(HSbF6 )、六氟砷酸(HAsF6 )、六氟鋯酸(H2 ZrF6 )、四氟鈹酸(H2 BeF4 )、七氟鉭酸(H2 TaF7 )等或該等的鹽，作為至此可適於實現異向性蝕刻者之例。In terms of compounds of hydrofluoric acid and etching inhibitors, examples include fluorinated titanic acid (H 2 TiF 6 ), ammonium fluoride (NH 4 F), tetrafluoroboric acid (HBF 4 ), and hexafluorophosphoric acid (HPF 6 ) , Hexafluorosilicic acid (H 2 SiF 6 ), hexafluoroaluminate (H 3 AlF 6 ), hexafluoroantimonic acid (HSbF 6 ), hexafluoroarsenic acid (HAsF 6 ), hexafluorozirconic acid (H 2 ZrF 6 ), tetrafluoro beryllic acid (H 2 BeF 4 ), heptafluorotantalic acid (H 2 TaF 7 ), etc., or their salts, as examples of those suitable for achieving anisotropic etching so far.

在蝕刻裝置300中，係一邊藉由搬送滾輪來搬送多倒角用玻璃母材50，一邊在蝕刻腔室內，使蝕刻液接觸多倒角用玻璃母材50的單面或雙面，藉此進行對多倒角用玻璃母材50的蝕刻處理。其中，在蝕刻裝置300中的蝕刻腔室的後段，係設有用以沖洗附著在多倒角用玻璃母材50的蝕刻液的洗淨腔室，因此多倒角用玻璃母材50係在蝕刻液被去除的狀態下由蝕刻裝置300被排出。In the etching apparatus 300, the glass base material 50 for multiple chamfers is transported by a conveying roller, while in the etching chamber, the etching solution is brought into contact with one or both sides of the glass base material 50 for multiple chamfers, thereby The etching process of the glass base material 50 for multiple chamfers is performed. Among them, in the back stage of the etching chamber in the etching apparatus 300, there is a cleaning chamber for washing the etching solution adhering to the glass base material 50 for multiple chamfers, so the glass base material 50 for multiple chamfers is used in the etching The liquid is discharged from the etching apparatus 300 in a state where the liquid is removed.

以使蝕刻液接觸多倒角用玻璃母材50的手法之一例而言，列舉如圖7(A)所示，在蝕刻裝置300的各蝕刻腔室302中，對多倒角用玻璃母材50噴射蝕刻液的噴射蝕刻。此外，亦可取代噴射蝕刻，採用如圖7(B)所示，在溢流型的蝕刻腔室304中，一邊接觸溢流的蝕刻液一邊搬送多倒角用玻璃母材50的構成。As an example of a method of contacting the etching solution with the glass base material 50 for multi-chamfering, as shown in FIG. 7(A), in each etching chamber 302 of the etching apparatus 300, the glass base material for multi-chamfering 50 Jet etching with jet etching solution. In addition, instead of jet etching, as shown in FIG. 7(B), in the overflow-type etching chamber 304, the glass base material 50 for multiple chamfers is conveyed while contacting the overflowing etching liquid.

再者，亦可採用如圖7(C)所示，在收納有蝕刻液的蝕刻槽306，浸漬被收納在載體的單數或複數多倒角用玻璃母材50的浸漬式的蝕刻。Furthermore, as shown in FIG. 7(C), immersion etching in which the singular or plural glass base material 50 for multiple chamfers stored in the carrier is immersed in the etching tank 306 containing the etching liquid may be adopted.

在任何情形下，在蝕刻處理中，形狀切斷預定線以厚度方向貫穿，而使多倒角用玻璃母材50不會分斷，乃極為重要。因此，在蝕刻處理中(尤其蝕刻處理的後半部分)，必須減慢蝕刻率，以正確地控制蝕刻量。In any case, in the etching process, it is extremely important that the shape cutting line penetrates in the thickness direction so that the glass base material 50 for multiple chamfers does not break. Therefore, in the etching process (especially the second half of the etching process), the etching rate must be slowed down to accurately control the etching amount.

並非為在蝕刻處理的全體中減慢蝕刻率，若當初一邊採用較快的蝕刻率一邊階段式地減慢，可縮短蝕刻處理的時間。例如，若採用隨著進至蝕刻裝置300的後段而使蝕刻液中的氫氟酸濃度降低的構成即可。It is not to slow down the etching rate in the entire etching process. If the etching rate is initially slowed down step by step while adopting a faster etching rate, the etching process time can be shortened. For example, what is necessary is just to adopt the structure which reduces the hydrofluoric acid concentration in an etching liquid as it progresses to the back stage of the etching apparatus 300.

若多倒角用玻璃母材50通過蝕刻裝置300，改質線20即被蝕刻。在改質線20中，相較於其他部位，蝕刻液更快浸透，沿著該線，玻璃被熔解，藉此，藉由改質線20而容易切斷彩色濾光片基板。此外，即使在雷射照射時發生損傷等，該損傷亦變得容易消失。When the multi-chamfer glass base material 50 passes through the etching device 300, the modified line 20 is etched. In the modified line 20, the etching solution penetrates faster than other parts, and the glass is melted along this line, whereby the color filter substrate can be easily cut by the modified line 20. In addition, even if damage or the like occurs during laser irradiation, the damage easily disappears.

若蝕刻處理結束，原被黏貼的耐蝕刻膜16會被剝離。接著，對多倒角用玻璃母材50，如圖8(A)～圖8(C)所示，進行形成用以去除彩色濾光片基板14中與陣列基板12的電極端子部122相對向的區域的端子部切斷溝30的處理。在該實施形態中，藉由刀輪(輪式切割機)250，在彩色濾光片基板14中與陣列基板12的電極端子部122相對向的區域的內側形成端子部切斷溝30。端子部切斷溝30係沿著端子部切斷預定線形成，俾以去除彩色濾光片基板14中與陣列基板12的電極端子部122相對向的區域。If the etching process is completed, the etching resistant film 16 that was originally pasted will be peeled off. Next, the glass base material 50 for multiple chamfers is formed to remove the color filter substrate 14 facing the electrode terminal portion 122 of the array substrate 12, as shown in FIGS. 8(A) to 8(C). The terminal part of the area cuts the groove 30. In this embodiment, a cutter wheel (wheel cutter) 250 is used to form a terminal part cutting groove 30 on the inner side of a region facing the electrode terminal part 122 of the array substrate 12 in the color filter substrate 14. The terminal part cutting groove 30 is formed along a line to cut the terminal part to remove a region of the color filter substrate 14 that faces the electrode terminal part 122 of the array substrate 12.

若藉由刀輪250所為之端子部切斷溝30的形成結束，移至多倒角用玻璃母材50的分斷及與電極端子部122相對向的區域的去除。在多倒角用玻璃母材50中，藉由雷射的長絲加工，形成改質線20，且藉由將該改質線更進一步蝕刻，僅以些微機械壓力，即可將多倒角用玻璃母材50在改質線20中進行分割。例如，藉由對多倒角用玻璃母材50施加微小的按壓力或拉伸力、或供予微小的超音波振動，如圖9所示，不會污損多倒角用玻璃母材50，即可分斷。When the formation of the terminal cutting groove 30 by the cutter wheel 250 is completed, the process moves to the breaking of the multi-chamfer glass base material 50 and the removal of the region facing the electrode terminal 122. In the glass base material 50 for multi-chamfering, the modified line 20 is formed by laser filament processing, and by further etching the modified line, the multi-chamfering can be made with only slight mechanical pressure. The glass base material 50 is divided in the reforming line 20. For example, by applying a small pressing force or tensile force to the glass base material 50 for multiple chamfers, or applying a small ultrasonic vibration, as shown in FIG. 9, the glass base material 50 for multiple chamfering will not be stained. , It can be broken.

由於未因蝕刻處理而被完全切斷，因此防止發生蝕刻中被分離的液晶面板10端面彼此衝撞而破損等不良情形。此外，亦可照蝕刻處理後的不完全切斷的狀態的多倒角用玻璃母材50的原樣(保持大張的狀態)進行搬運。此外，由於沒有蝕刻液到達電極端子部的情形，因此不需要藉由具耐蝕刻性的罩護劑來保護電極端子部。此外，液晶面板10的端面中的至少中央部以外係被施行蝕刻處理，因此與僅以雷射加工來進行切斷的情形相比較，液晶面板的強度(例如彎曲強度)較高。Since it is not completely cut by the etching process, the end faces of the liquid crystal panel 10 separated during etching are prevented from colliding with each other and being damaged. In addition, the glass base material 50 for multiple chamfers in the incompletely cut state after the etching process may be transported as it is (maintained in a large-sized state). In addition, since the etching solution does not reach the electrode terminal portion, there is no need to protect the electrode terminal portion with an etching-resistant masking agent. In addition, since at least the center portion of the end surface of the liquid crystal panel 10 is etched, the strength (for example, bending strength) of the liquid crystal panel is higher than when cutting is performed only by laser processing.

圖10(A)～圖10(C)係顯示分斷後的液晶面板10的概略構成。如該圖所示，液晶面板10的端面係相對主面形成為大致直角。亦即，可將在板厚的陣列基板12及彩色濾光片基板14的各端面所發生的錐度幅度(圖10(C)中的L1～L4)抑制為大致為零(具體而言為30μm以下)。10(A) to 10(C) show the schematic configuration of the liquid crystal panel 10 after the split. As shown in this figure, the end surface of the liquid crystal panel 10 is formed at a substantially right angle to the main surface. That is, it is possible to suppress the taper width (L1 to L4 in FIG. 10(C)) that occurs on each end surface of the array substrate 12 and the color filter substrate 14 of the plate thickness to approximately zero (specifically, 30 μm) the following).

如上所示，製造液晶面板10時，幾乎不會發生側面蝕刻的影響，因此可設計將液晶面板10彼此近接配置的多倒角用玻璃母材50。另一方面，減小藉由含有蝕刻阻礙物質的蝕刻液所為之處理(第1蝕刻步驟)的比率、且加多藉由含有氫氟酸及鹽酸等的蝕刻液所為之處理(第2蝕刻步驟)的比率，藉此可加大錐度幅度L1～L4的值。若考慮成為必要的端面的形狀或必要的蝕刻率等，而適當調整藉由含有蝕刻阻礙物質的蝕刻液所為之處理的比率即可。As described above, when the liquid crystal panel 10 is manufactured, the influence of side etching hardly occurs. Therefore, it is possible to design the multi-chamfer glass base material 50 in which the liquid crystal panels 10 are arranged close to each other. On the other hand, the ratio of the treatment (first etching step) by the etching solution containing the etching inhibitor substance is reduced, and the treatment by the etching solution containing hydrofluoric acid, hydrochloric acid, etc. (the second etching step) is increased. ) Ratio, which can increase the value of the taper range L1 ~ L4. In consideration of the shape of the necessary end surface, the necessary etching rate, etc., the rate of treatment by the etching solution containing the etching inhibitor substance may be appropriately adjusted.

接著，使用圖11～圖14，說明有關穿孔處理之其他實施形態。圖11係顯示對用以製造具備複數貫穿孔的玻璃中介層的玻璃基板510的加工處理的一步驟。在該實施形態中，製造玻璃中介層時，對玻璃基板510，至少施行改質步驟及蝕刻步驟。Next, using FIGS. 11 to 14, another embodiment of the punching process will be described. FIG. 11 shows a step of processing a glass substrate 510 for manufacturing a glass interposer with a plurality of through holes. In this embodiment, when manufacturing the glass interposer, at least a modification step and an etching step are performed on the glass substrate 510.

玻璃基板510的種類只要是玻璃，並未特別限定，惟如玻璃中介層般，若使用在半導體元件的封裝體，以無鹼玻璃為佳。此係基於若為含鹼玻璃，玻璃中的鹼成分析出，有對半導體元件造成不良影響之虞之故。此外，玻璃基板510的厚度並未特別限定，玻璃基板10係可在例如0.1mm～2.0mm的厚度中適當進行處理。The type of the glass substrate 510 is not particularly limited as long as it is glass. However, like a glass interposer, if it is used in a package of a semiconductor element, alkali-free glass is preferred. This is based on the fact that if it is an alkali-containing glass, the alkali composition in the glass is analyzed, which may cause adverse effects on semiconductor devices. In addition, the thickness of the glass substrate 510 is not specifically limited, For example, the glass substrate 10 can be processed suitably in the thickness of 0.1 mm-2.0 mm.

在改質步驟中，對玻璃基板510中的複數貫穿孔的形成預定位置，由雷射頭512被照射雷射光。該被照射的雷射光係經由用以遍及玻璃基板510的厚度方向而形成能量密度相對較高的焦線的光學系單元514。In the reforming step, the laser head 512 is irradiated with laser light at the predetermined positions where the plurality of through holes in the glass substrate 510 are formed. The irradiated laser light passes through the optical system unit 514 for forming a focal line with a relatively high energy density throughout the thickness direction of the glass substrate 510.

光學系單元514係藉由單一或複數光學要素(透鏡等)所構成，構成為使來自雷射頭512的雷射光，在玻璃基板510的厚度方向朝向具有預定範圍內的長度的雷射光的焦線集束。The optical system unit 514 is composed of a single or multiple optical elements (lenses, etc.), and is configured to focus the laser light from the laser head 512 toward the laser light having a length within a predetermined range in the thickness direction of the glass substrate 510. Wire bundle.

因此，藉由該雷射光被照射至玻璃基板510，玻璃基板510中的貫穿孔形成預定位置遍及厚度方向的全域被改質，例如形成孔隙狀的改質部102。為了在玻璃基板510形成複數改質部102，亦可使用將玻璃基板510在XY平面上移動的載台，亦可使具備有雷射頭512及光學系單元514的雷射加工裝置設置使該等構件以XY方向移動的驅動機構。Therefore, when the laser light is irradiated to the glass substrate 510, the predetermined position for forming the through hole in the glass substrate 510 is modified over the entire thickness direction, for example, a porous modified portion 102 is formed. In order to form a plurality of modified portions 102 on the glass substrate 510, a stage that moves the glass substrate 510 on the XY plane can also be used, or a laser processing device equipped with a laser head 512 and an optical system unit 514 can be installed so that the A drive mechanism that moves components in the XY direction.

雷射光只要可將玻璃基板510的貫穿孔的形成預定位置改質為易被蝕刻的性質，其種類及照射條件並無限制。在該實施形態中，由雷射頭512被照射由短脈衝雷射(例如皮秒雷射、飛秒雷射)被振盪的雷射光，惟亦可使用例如CO2 雷射、UV雷射等。在該實施形態中，以雷射光的平均雷射能量成為約30μJ～300μJ左右的方式進行輸出控制。As long as the laser light can modify the predetermined position of the through hole of the glass substrate 510 to be easily etched, the type and irradiation conditions are not limited. In this embodiment, the laser head 512 is irradiated with laser light oscillated by a short pulse laser (for example, picosecond laser, femtosecond laser), but it is also possible to use CO 2 laser, UV laser, etc. . In this embodiment, the output control is performed so that the average laser energy of the laser light becomes approximately 30 μJ to 300 μJ.

改質步驟之後，將玻璃基板510中形成在貫穿孔形成預定位置的改質部進行蝕刻，藉此將改質部102熔解，且在貫穿孔形成預定位置形成貫穿孔。After the modification step, the modified portion of the glass substrate 510 formed at the predetermined position for forming the through hole is etched, thereby melting the modified portion 102 and forming a through hole at the predetermined position for forming the through hole.

使用圖12(A)～圖12(C)，說明改質步驟及之後的蝕刻步驟。圖12(A)係顯示上述改質步驟。由雷射頭512出射的雷射光係藉由光學系單元514，被聚光在玻璃基板510中的貫穿孔形成預定位置，以貫穿孔形成預定位置的厚度方向形成焦線。光學系單元514係至少具備有例如將雷射光進行擴散的擴散透鏡或進行聚光的聚光透鏡等，例如，可將雷射光以在上述之焦線上的複數點成像的方式進行聚光。Using FIGS. 12(A) to 12(C), the modification step and the subsequent etching step will be described. Figure 12(A) shows the above-mentioned modification step. The laser light emitted from the laser head 512 is focused on the through hole in the glass substrate 510 by the optical unit 514 to form a predetermined position, and a focal line is formed in the thickness direction where the through hole forms the predetermined position. The optical system unit 514 is provided with at least, for example, a diffuser lens that diffuses the laser light, a condenser lens that condenses the light, and the like. For example, the laser light can be condensed so as to form an image at a plurality of points on the aforementioned focal line.

結果，如圖12(B)所示，遍及玻璃基板10的貫穿孔成預定位置中的厚度方向的全域，形成改質部102。改質部102係示出藉由接受來自雷射光的能量，比其他部分更容易被蝕刻的性質。藉由使蝕刻液接觸該改質部102，改質部102被熔解，結果，如圖12(C)所示在貫穿孔形成預定位置形成貫穿孔104。As a result, as shown in FIG. 12(B), the through hole of the glass substrate 10 covers the entire area in the thickness direction in a predetermined position, and the modified portion 102 is formed. The modified part 102 shows the property that it is easier to be etched than other parts by receiving energy from the laser light. By bringing the etching solution into contact with the modified portion 102, the modified portion 102 is melted. As a result, as shown in FIG. 12(C), a through hole 104 is formed at a predetermined position for forming the through hole.

在蝕刻步驟中，如圖13(A)所示，玻璃基板510係被導入至蝕刻裝置520，且藉由含有氫氟酸及鹽酸等的蝕刻液來施行蝕刻處理。在蝕刻裝置520中，係一邊藉由搬送滾輪來搬送玻璃基板510，一邊在蝕刻腔室522內，使蝕刻液接觸玻璃基板510的單面或雙面，藉此進行對玻璃基板510的蝕刻處理。In the etching step, as shown in FIG. 13(A), the glass substrate 510 is introduced into the etching device 520, and an etching process is performed with an etching solution containing hydrofluoric acid, hydrochloric acid, and the like. In the etching device 520, while the glass substrate 510 is conveyed by the conveying roller, the etching solution is brought into contact with one or both sides of the glass substrate 510 in the etching chamber 522, thereby performing an etching process on the glass substrate 510 .

在此係如圖13(B)所示，在蝕刻裝置520的各蝕刻腔室522中，對玻璃基板510進行噴射蝕刻液的噴射蝕刻。以蝕刻液而言，係使用例如氫氟酸1～10重量%、鹽酸5～20重量%、及含有上述蝕刻阻礙物質的蝕刻液。其中，在蝕刻裝置520中的蝕刻腔室522的後段係設有用以沖洗附著在玻璃基板510的蝕刻液的洗淨腔室，因此玻璃基板510係在蝕刻液被去除的狀態下由蝕刻裝置520被排出。Here, as shown in FIG. 13(B), in each etching chamber 522 of the etching apparatus 520, the glass substrate 510 is spray-etched by spraying an etching liquid. As the etching solution, for example, an etching solution containing 1 to 10% by weight of hydrofluoric acid, 5 to 20% by weight of hydrochloric acid, and the aforementioned etching inhibiting substance is used. Among them, the back stage of the etching chamber 522 in the etching device 520 is provided with a cleaning chamber for washing the etching solution attached to the glass substrate 510, so the glass substrate 510 is removed by the etching device 520 in the state where the etching solution is removed. Is discharged.

除了噴射蝕刻液的手法之外，亦可藉由將玻璃基板510浸漬在蝕刻液，使蝕刻液接觸玻璃基板10。但是，若由使蝕刻液浸透至微細貫穿孔的內部的觀點來看，以採用如圖13(A)及圖13(B)所示之噴射蝕刻液的方式為佳。In addition to the method of spraying the etching solution, the glass substrate 510 may be immersed in the etching solution so that the etching solution contacts the glass substrate 10. However, from the viewpoint of allowing the etching liquid to penetrate into the fine through-holes, it is preferable to use the method of spraying the etching liquid as shown in FIGS. 13(A) and 13(B).

藉由將蝕刻液以充分的壓力噴射至玻璃基板510，一般係玻璃基板510的改質部102被適當熔解，如圖12(C)所示在玻璃基板510形成貫穿孔104。在該實施形態中，若以噴射時的吐出壓力為例如0.05Mpa～0.10Mpa、由各噴射噴嘴所噴射的蝕刻液的量為1.25～2.50公升/分鐘左右進行處理，可得較適結果。By spraying the etching liquid to the glass substrate 510 with sufficient pressure, the modified portion 102 of the glass substrate 510 is generally melted appropriately, and the through hole 104 is formed in the glass substrate 510 as shown in FIG. 12(C). In this embodiment, if the discharge pressure during spraying is, for example, 0.05 Mpa to 0.10 Mpa, and the amount of etching liquid sprayed from each spray nozzle is about 1.25 to 2.50 liters/minute, more suitable results can be obtained.

在藉由習知之蝕刻液所為之處理中，依蝕刻液的噴射壓力或濃度或黏度、或改質部102的尺寸，如圖14(A)所示，有形成在中央部具有狹窄部的貫穿孔105的情形。如上所示之貫穿孔105若使用在中介層的用途時，有發生導通不良等不良情形的可能性，因此可謂為不太理想。In the process performed by the conventional etching solution, depending on the spray pressure, concentration, or viscosity of the etching solution, or the size of the modified portion 102, as shown in FIG. 14(A), there is a through hole with a narrow portion formed in the center. The situation of hole 105. If the through hole 105 described above is used for the purpose of an interposer, there is a possibility of poor conduction such as poor conduction, so it is not ideal.

在該實施形態中，藉由適當使用含有蝕刻阻礙物質的蝕刻液，如圖14(B)所示，在玻璃基板510的厚度方向的中央部不易形成狹窄部。 如上所示，藉由使用含有蝕刻阻礙物質的蝕刻液，由於幾乎不會發生起因於濕式蝕刻的等向性的側面蝕刻的影響，因此可形成無狹窄部的貫穿孔。另一方面，減少藉由含有蝕刻阻礙物質的蝕刻液所為之處理(第1蝕刻步驟)的比率，且加多藉由一般的蝕刻液所為之處理(第2蝕刻步驟)的比率，可調整狹窄部的形狀。若考慮成為必要的貫穿孔的形狀或必要的蝕刻率等，而適當調整第1蝕刻步驟及第2蝕刻步驟的比率即可。如上所述，第2蝕刻步驟係任意處理，因此亦可將比率形成為零。In this embodiment, by appropriately using an etching solution containing an etching inhibitor, as shown in FIG. 14(B), it is difficult to form a narrow portion in the center portion of the glass substrate 510 in the thickness direction. As shown above, by using an etching solution containing an etching inhibiting substance, since the effect of isotropic side etching due to wet etching hardly occurs, a through hole without a narrow portion can be formed. On the other hand, it is possible to reduce the ratio of the treatment (first etching step) by an etching solution containing an etching inhibitor and increase the ratio of the treatment (the second etching step) by a general etching solution to adjust the narrowing The shape of the department. In consideration of the shape of the necessary through hole, the necessary etching rate, etc., the ratio of the first etching step and the second etching step may be appropriately adjusted. As described above, the second etching step is an arbitrary process, so the ratio can also be made zero.

採用上述方法所形成的貫穿孔係藉由噴射蝕刻，微裂縫微小化或消滅。因此，不僅可適當保持貫穿孔的形狀，亦有可保持玻璃中介層的強度的優點。此外，在此係說明使用玻璃基板510作為玻璃中介層之例，惟玻璃基板510的用途並非為限定於此。例如，亦可適用於MEMS封裝或適於生命科學的微晶片元件等。The through holes formed by the above method are sprayed and etched to miniaturize or eliminate the micro-cracks. Therefore, not only can the shape of the through hole be properly maintained, but also the strength of the glass interposer can be maintained. In addition, here is an example of using the glass substrate 510 as a glass interposer, but the use of the glass substrate 510 is not limited to this. For example, it can also be applied to MEMS packaging or microchip components suitable for life sciences.

在此，使用圖15，說明上述實施形態中的異向性蝕刻的機制。如該圖所示，氟錯合物(在此係氟化鈦酸)係在化學性的平衡狀態下，伴隨因蝕刻處理所致之氫氟酸的消耗，在遠離玻璃基板的主面的位置，容易放出屬於活性種的氫氟酸。結果，氫氟酸容易到達遠離玻璃基板的主面的位置。因此，與玻璃基板的主面呈垂直的方向(例：厚度方向、深度方向)的蝕刻變得容易進展。Here, the mechanism of anisotropic etching in the above-mentioned embodiment will be explained using FIG. 15. As shown in the figure, the fluorine complex (in this case, fluorinated titanic acid) is in a chemically balanced state, and is located away from the main surface of the glass substrate with the consumption of hydrofluoric acid due to the etching process. , It is easy to release hydrofluoric acid which is an active species. As a result, hydrofluoric acid easily reaches a position away from the main surface of the glass substrate. Therefore, etching in a direction perpendicular to the main surface of the glass substrate (e.g., thickness direction, depth direction) easily progresses.

若在玻璃基板的主面附近，氫氟酸被連續消耗時，進展與玻璃的主面呈平行的方向(例：寬幅方向)的蝕刻，容易發生等向性蝕刻的影響，但是推測出因蝕刻阻礙物質的作用，可將等向性蝕刻的影響抑制為最小限度。If the hydrofluoric acid is continuously consumed near the main surface of the glass substrate, the etching in the direction parallel to the main surface of the glass (e.g., the width direction) progresses, and the effect of isotropic etching is likely to occur. The effect of the etching inhibiting substance can minimize the influence of isotropic etching.

接著，實際上使用實施例，說明本案發明之實施形態之含有蝕刻阻礙物質的玻璃用蝕刻液的作用效果。首先，使用圖16(A)～圖16(D)，說明用以驗證玻璃用蝕刻液的作用效果的實驗手法。如圖16(A)所示，在蝕刻處理之前，首先，雷射光的平均雷射能量以成為約250μJ左右的方式進行輸出控制之後，在厚度200μm左右的玻璃基板形成改質孔。Next, practical examples are used to describe the effect of the etching solution for glass containing an etching inhibitor substance according to the embodiment of the present invention. First, using FIG. 16(A) to FIG. 16(D), the experimental method for verifying the effect of the etching liquid for glass is demonstrated. As shown in FIG. 16(A), before the etching process, first, the average laser energy of the laser light is output controlled so as to be about 250 μJ, and then modified holes are formed in a glass substrate with a thickness of about 200 μm.

接著，以下述表1所示之組成的蝕刻液(40℃)分別進行約40分鐘蝕刻處理。圖16(B)係顯示藉由比較例之蝕刻液進行蝕刻後的玻璃基板，圖16(C)係顯示藉由各實施例之蝕刻液進行蝕刻後的玻璃基板。

Figure 02_image001
Next, the etching process (40 degreeC) of the composition shown in the following Table 1 was performed for about 40 minutes, respectively. FIG. 16(B) shows the glass substrate after etching with the etching solution of the comparative example, and FIG. 16(C) shows the glass substrate after etching with the etching solution of each example.
Figure 02_image001

比較例1之蝕刻液係蝕刻率被調整為1.0μm左右之含有氫氟酸濃度0.90mol/L的蝕刻液。The etching solution of Comparative Example 1 is an etching solution containing a hydrofluoric acid concentration of 0.90 mol/L with an etching rate adjusted to about 1.0 μm.

另一方面，實施例1～實施例6係對氫氟酸，分別添加氫氧化銨、氫氧化鉀、氫氧化鈉、二氧化矽、硼酸、及氯化鋁作為蝕刻阻礙物質的蝕刻液。若添加該等蝕刻阻礙物質，蝕刻速度會降低，因此氫氟酸濃度係分別比比較例1之蝕刻液為更高，俾使蝕刻率成為1.0μm/分鐘左右。On the other hand, Examples 1 to 6 are etching solutions in which ammonium hydroxide, potassium hydroxide, sodium hydroxide, silicon dioxide, boric acid, and aluminum chloride are respectively added to hydrofluoric acid as etching inhibitors. If these etching inhibitors are added, the etching rate will decrease, so the concentration of hydrofluoric acid is higher than that of the etching solution of Comparative Example 1, so that the etching rate will be about 1.0 μm/min.

蝕刻處理後，如圖16(D)所示，計測所形成的孔的寬幅(比較例為W0，實施例為W1)及孔的深度D，將深度的值D除以寬幅的值(W0或W1)而得的值設為「異向性度數」。該異向性度數的值愈大，可謂為愈為實現異向性蝕刻。其中，蝕刻後的玻璃基板的測定係使用光學顯微鏡來進行。After the etching process, as shown in FIG. 16(D), the width of the formed hole (W0 for the comparative example and W1 for the example) and the depth D of the hole were measured, and the value D of the depth was divided by the value of the width ( The value obtained by W0 or W1) is set as the "degree of anisotropy". The larger the value of the degree of anisotropy, the more anisotropic etching is achieved. However, the measurement of the glass substrate after etching was performed using an optical microscope.

如表1所示，以比較例1之蝕刻液所得的異向性度數為3.1。通常，若為等向性蝕刻，異向性度數成為1，惟在此係藉由雷射加工而形成有改質孔，因此即使未添加蝕刻阻礙物質，亦可得大幅超過1的異向性度數。As shown in Table 1, the degree of anisotropy obtained with the etching solution of Comparative Example 1 was 3.1. Normally, in the case of isotropic etching, the degree of anisotropy becomes 1, but here, modified holes are formed by laser processing. Therefore, even if an etching inhibitor is not added, anisotropy greater than 1 can be obtained. degree.

此外，以分別添加有蝕刻阻礙物質的實施例1～實施例6之蝕刻液所得的異向性度數係取得均比以比較例1之蝕刻液所得的異向性度數為更高的值。藉此，可知藉由蝕刻阻礙物質，更進一步實現異向性蝕刻。In addition, the anisotropy system obtained by the etching solutions of Examples 1 to 6 respectively added with the etching inhibiting substance were all higher than the anisotropy system obtained by the etching solution of Comparative Example 1. From this, it can be seen that the anisotropic etching is further realized by the etching inhibiting substance.

在此，使用表2，說明其他實驗結果。

Figure 02_image003
Here, use Table 2 to illustrate other experimental results.
Figure 02_image003

比較例2之蝕刻液係被調整為氫氟酸濃度0.10mol/L的蝕刻液。實施例7～12之蝕刻液係添加相對氫氟酸的物質量為0.10莫耳當量的蝕刻阻礙物質(氫氧化銨、氫氧化鉀、氫氧化鈉、二氧化矽、硼酸、及氯化鋁)而成者。The etching solution of Comparative Example 2 was adjusted to an etching solution with a hydrofluoric acid concentration of 0.10 mol/L. The etching solutions of Examples 7-12 added 0.10 molar equivalent of etching inhibitors (ammonium hydroxide, potassium hydroxide, sodium hydroxide, silicon dioxide, boric acid, and aluminum chloride) with respect to the amount of hydrofluoric acid. Become.

如表2所示，以比較例2之蝕刻液所得的異向性度數為3.0。另一方面，以分別添加有蝕刻阻礙物質的實施例7～實施例12之蝕刻液所得的異向性度數係取得均比以比較例2之蝕刻液所得的異向性度數為更高的值(最大為6.8)。由該表2之實驗結果亦可知藉由蝕刻阻礙物質，更進一步實現異向性蝕刻。As shown in Table 2, the degree of anisotropy obtained with the etching solution of Comparative Example 2 was 3.0. On the other hand, the degree of anisotropy obtained with the etching solutions of Examples 7 to 12 respectively added with an etching inhibitor substance are all higher than the degree of anisotropy obtained with the etching solution of Comparative Example 2. (The maximum is 6.8). It can also be seen from the experimental results in Table 2 that the anisotropic etching is further realized by the etching inhibitor.

上述實施形態的說明應理解全部均為例示，並非為具限制性者。本發明的範圍係藉由申請專利範圍所示，並非為上述之實施形態。此外，在本發明之範圍中係意圖包含與申請專利範圍為均等的涵義、及範圍內的所有變更。It should be understood that all the descriptions of the above-mentioned embodiments are illustrative and not restrictive. The scope of the present invention is shown by the scope of the patent application, not the above-mentioned embodiment. In addition, the scope of the present invention is intended to include the meaning equivalent to the scope of the patent application, and all changes within the scope.

10:液晶面板 12:陣列基板 14:彩色濾光片基板 16:耐蝕刻膜 17:透明性薄膜 20:改質線 30:端子部切斷溝 50:多倒角用玻璃母材 100:智慧型手機 102:改質部 104:貫穿孔 105:貫穿孔 122:電極端子部 250:刀輪 300,520:蝕刻裝置 302,304,522:蝕刻腔室 306:蝕刻槽 510:玻璃基板 512:雷射頭 514:光學系單元10: LCD panel 12: Array substrate 14: Color filter substrate 16: Etching resistant film 17: Transparent film 20: Modification line 30: Terminal cut groove 50: Glass base material for multiple chamfers 100: smart phone 102: Modification Department 104: Through hole 105: Through hole 122: Electrode terminal 250: knife wheel 300,520: Etching device 302, 304, 522: etching chamber 306: Etching slot 510: glass substrate 512: Laser head 514: Optical unit

[圖1]係顯示本發明之一實施形態之液晶面板的概略構成的圖。 [圖2]係顯示包含複數液晶面板的多倒角用玻璃母材的概略構成的圖。 [圖3]係顯示液晶面板製造方法的一實施形態所包含的工程的圖。 [圖4]係顯示液晶面板製造方法的一實施形態所包含的工程的圖。 [圖5]係顯示液晶面板製造方法的一實施形態所包含的工程的圖。 [圖6]係顯示適用於本發明的蝕刻裝置之一例的圖。 [圖7]係顯示適用於本發明的蝕刻處理的變化的圖。 [圖8]係顯示對多倒角用玻璃母材的劃線裂片加工的概略的圖。 [圖9]係顯示被分斷的狀態的多倒角用玻璃母材的概略的圖。 [圖10]係顯示液晶面板的構成的特徵的圖。 [圖11]係說明有關穿孔處理之改質步驟的圖。 [圖12]係說明有關穿孔處理之改質步驟及蝕刻步驟的圖。 [圖13]係顯示有關穿孔處理之蝕刻步驟所使用的裝置的構成例的圖。 [圖14]係說明有關穿孔處理之改質步驟的圖。 [圖15]係用以說明蝕刻阻礙物質的影響的概略圖。 [圖16]係用以說明蝕刻阻礙物質的影響的概略圖。Fig. 1 is a diagram showing a schematic configuration of a liquid crystal panel according to an embodiment of the present invention. [Fig. 2] A diagram showing the schematic configuration of a glass base material for multiple chamfers including a plurality of liquid crystal panels. Fig. 3 is a diagram showing the processes included in one embodiment of a method for manufacturing a liquid crystal panel. Fig. 4 is a diagram showing the processes included in one embodiment of a method of manufacturing a liquid crystal panel. Fig. 5 is a diagram showing the processes included in one embodiment of a method for manufacturing a liquid crystal panel. [Fig. 6] A diagram showing an example of an etching apparatus suitable for the present invention. [Fig. 7] is a diagram showing changes in the etching process applicable to the present invention. [Fig. 8] is a diagram showing the outline of the scribing and splitting of the glass base material for multiple chamfering. Fig. 9 is a diagram showing the outline of a glass base material for multiple chamfering in a divided state. Fig. 10 is a diagram showing the characteristics of the configuration of the liquid crystal panel. [Figure 11] is a diagram illustrating the modification steps related to the punching process. [Fig. 12] A diagram illustrating the modification step and etching step of the perforation process. Fig. 13 is a diagram showing a configuration example of an apparatus used in the etching step of the perforation process. [Figure 14] is a diagram illustrating the modification steps of the punching process. [Fig. 15] A schematic diagram for explaining the influence of the etching inhibiting substance. [FIG. 16] A schematic diagram for explaining the influence of the etching inhibitor substance.

Claims (4)

一種玻璃用蝕刻液，其係用以蝕刻玻璃的玻璃用蝕刻液， 至少包含使對玻璃的蝕刻速度降低的蝕刻阻礙物質，且為至少含有鹼或氟錯合劑之任一方的蝕刻阻礙物質。An etching solution for glass, which is an etching solution for glass used to etch glass, It contains at least an etching inhibiting substance that reduces the etching rate to glass, and is an etching inhibiting substance that contains at least either an alkali or a fluorine complexing agent. 如請求項1之玻璃用蝕刻液，其中，前述蝕刻阻礙物質係藉由附著在玻璃中已被改質為容易被蝕刻的改質部而使阻礙蝕刻反應的反應生成物發生。The etching solution for glass according to claim 1, wherein the etching inhibiting substance adheres to a modified portion of the glass that has been modified to be easily etched, thereby generating a reaction product that inhibits an etching reaction. 一種玻璃基板製造方法，其係使用如請求項1或請求項2之玻璃用蝕刻液的玻璃基板製造方法，其係至少包含： 改質步驟，其係以遍及玻璃基板的蝕刻預定位置中的厚度方向而形成能量密度相對較高的焦線的方式，對前述玻璃基板照射雷射光，藉此將前述蝕刻預定位置改質；及 第1蝕刻步驟，其係在前述改質步驟後，使用前述玻璃用蝕刻液來蝕刻前述蝕刻預定位置。A method for manufacturing a glass substrate, which is a method for manufacturing a glass substrate using an etching solution for glass such as claim 1 or claim 2, which includes at least: The modification step is to irradiate the glass substrate with laser light in a way that a focal line with relatively high energy density is formed throughout the thickness direction of the predetermined etching position of the glass substrate, thereby modifying the predetermined etching position; and The first etching step is to etch the predetermined etching position using the etching solution for glass after the modification step. 如請求項3之玻璃基板製造方法，其中，在前述第1蝕刻步驟之後，另外包含：第2蝕刻步驟，其係藉由至少含有氫氟酸的蝕刻液，來蝕刻前述蝕刻預定位置。The method for manufacturing a glass substrate according to claim 3, wherein after the first etching step, the method further includes a second etching step in which the predetermined etching position is etched by an etching solution containing at least hydrofluoric acid.
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