TWI752149B - Glass substrate with mark and method of making the same - Google Patents

Abstract

The present invention relates to a glass substrate having marks on the surface, and the marks are identification codes, alignment marks, or a part thereof, and the marks are composed of a plurality of dots, and each dot is composed of a plurality of lasers The irradiation marks are formed, and the diameter of the opening of each laser irradiation mark on the surface is in the range of 5 μm to 15 μm, and the depth is in the range of 1 μm to 10 μm.

Description

Glass substrate with mark and method of making the same

The present invention relates to a glass substrate with marks and a manufacturing method thereof.

In recent years, in the manufacturing technology of semiconductor elements and the like, in order to easily identify and manage the semiconductor wafer, a mark such as an identification code is formed on the surface of the semiconductor wafer. In addition, as a method of forming the mark, a technique of irradiating a laser is known. Furthermore, recently, SiC has been attracting attention as a next-generation semiconductor device replacing Si, and therefore, it has been disclosed that a mark is formed by irradiating a laser on the surface of a SiC wafer (for example, Patent Document 1). Prior Art Document Patent Document Patent Document 1: Japanese Patent Laid-Open No. 2012-183549

[Problems to be Solved by the Invention] In recent years, in the semiconductor manufacturing process, the use of glass substrates as members for supporting semiconductor wafers or glass substrates, such as wafers and supporting substrates, has been studied. Glass substrates are rigid and relatively easy to process on smooth surfaces. Therefore, when a glass substrate is used for such a member, the rigidity of the laminated body can be improved, and the positional accuracy can be improved. However, when a glass substrate is used in a semiconductor manufacturing process, it is necessary to give a mark such as an identification code to the glass substrate, similarly to Si wafers and SiC wafers. However, glass is generally transparent, and therefore, there is a tendency that the visibility of the markings is relatively poor compared to opaque, translucent materials such as Si or SiC. In addition, in the case of forming a mark on the surface of a glass substrate by a conventional method such as laser marking on a SiC wafer, due to the difference in the inherent absorption characteristics of the material, the conventional method cannot form sufficient recesses , there is a possibility that the visibility of the mark will deteriorate. On the other hand, if it is intended to increase the output of the laser to improve the visibility of the mark, the possibility of cracking the glass substrate this time increases. The present invention was made in view of such a background, and in the present invention, an object is to provide a glass substrate which has a mark with better visibility and which is deliberately suppressed from cracking. Moreover, in this invention, it aims at providing the manufacturing method of such a glass substrate. [Technical Means for Solving the Problems] In the present invention, there is provided a glass substrate having a mark on its surface, and the mark is a part of an identification code, an alignment mark, or the like, and the mark is formed by a plurality of dots Each point is composed of a plurality of laser irradiation marks, the diameter of the opening of each laser irradiation mark on the surface is in the range of 5 μm to 15 μm, and the depth is in the range of 1 μm to 10 μm. In addition, in the present invention, there is provided a manufacturing method, which is a method of manufacturing a glass substrate having a mark on the surface, and has the step of irradiating a laser on the surface of the glass plate to form a plurality of laser irradiation marks on the surface, the above-mentioned laser The radiation has a wavelength in the range of 500 nm to 570 nm, the above-mentioned plurality of laser irradiation marks constitute dots, and the collection of the above-mentioned dots forms a mark, and the above-mentioned marks are part of identification codes, alignment marks, or the like. The diameter of the opening portion of the scar on the surface is in the range of 5 μm to 15 μm, and the depth is in the range of 1 μm to 10 μm. ADVANTAGE OF THE INVENTION In this invention, the mark with favorable visibility can be provided, and the glass substrate which suppresses cracking intentionally can be provided. Moreover, in this invention, the manufacturing method of such a glass substrate can be provided.

)100 mm～450 mm。於大致矩形狀之情形時，第1基板110之尺寸可列舉100 mm×100 mm～2 m×2 m。 於第1玻璃基板110中，於第1表面112形成有標記130。 此處，於本案中，為了使具有標記130之玻璃基板(例如第1玻璃基板110)之區別變得明確，而將於第1表面112形成標記130之前之玻璃特別稱為「玻璃板」。按照該記載，藉由在玻璃板之第1表面形成標記，而獲得於上述第1表面具有標記130之第1玻璃基板。 標記130亦可為包含例如數字、文字及圖形中之至少一個之識別碼。又，數字、文字及圖形之各者可為一個，亦可為複數個。此種識別碼例如可用於第1玻璃基板110之識別及/或管理。 或者，標記130例如亦可為對準標記。此種對準標記可用於第1玻璃基板110之操作、切割、倒角及貼合等加工時之位置或方向對準等。 再者，之後，將構成標記130之一個數字、文字及圖形特別稱為「標記元件」。 於圖2中，模式性地示出標記130之一例。 如圖2所示，於該例中，標記130係以由12個標記元件132呈直線狀排列成一行而構成之識別碼之形式示出。 但是，標記130並不限於此種態樣。例如，標記130亦可為由各個標記元件132呈非直線狀排列而構成。又，標記130亦可為由各個標記元件132呈直線狀或非直線狀排列2行以上而構成。 標記130之整體尺寸並無特別限制，例如於圖2所示之標記元件132之直線狀排列之情形時，橫向之長度L₁ 為16.43±0.025 mm之範圍，縱向之長度L₂ 為1.624±0.025 mm。再者，於以標記元件132之非直線狀排列構成標記130之情形時，標記130之橫向之長度L₁ 及縱向之長度L₂ 分別規定為假定包含標記130之最小矩形時之該最小矩形之第1邊之長度及第2邊的長度。 構成標記130之各標記元件132係由複數個點所構成。換言之，由複數個點形成一個標記元件132。以下，參照圖3，對該點進行說明。 於圖3中，係將構成標記130之一個標記元件132放大而表示之模式圖。於該例中，標記元件132被視認為數字之「3」。 由圖3可知，標記元件132係藉由合計17個點140之組合而形成。再者，關於數字之「3」以外之標記元件132，亦可藉由縱橫排列複數個點140而形成。 此種點140能夠藉由照射雷射而形成於玻璃板之表面。雷射可使用脈衝雷射，亦可使用連續波雷射。於使用連續波雷射之情形時，較佳為間歇性地使其振盪(脈衝性振盪)。 於圖4中，示出構成標記元件132之一個點140之模式性之放大圖。 如圖4所示，點140係藉由將複數個雷射照射痕150組合而形成。 此處，所謂「雷射照射痕(150)」，係指對玻璃板照射雷射時，於玻璃板之表面產生之凹部。 於圖4之例中，點140構成為具有內側環152及外側環154之大致雙重環。又，內側環152及外側環154係分別藉由將複數個雷射照射痕150排列成圓形而構成。 再者，於所示之例中，於內側環152及外側環154之各者中，相鄰之雷射照射痕150彼此係以相互接觸之方式配置。 然而，構成點140之雷射照射痕150之配置態樣並不限於此。例如，於圖4所示之「雙重環狀」排列中，內側環152或外側環154內之相鄰之雷射照射痕150彼此可為相互非接觸，亦可為一部分重疊。或者亦可為，一部分之相鄰之雷射照射痕150彼此相互非接觸，另一部分之相鄰之雷射照射痕150彼此相互重疊，而另外之雷射照射痕150彼此相互接觸。又，於在點140中，有複數個相鄰之雷射照射痕150彼此相互非接觸之情形時，非接觸之間隔可相同，亦可不同。除此以外亦可具有各種態樣。 再者，點140亦可以雷射照射痕150之大致雙重環狀排列以外之排列而構成。 於圖5～圖9中，模式性地示出點之另一態樣。 於圖5之例中，點140係藉由將複數個雷射照射痕150排列成圓形之螺旋狀(螺旋狀)而形成。於該例中亦為，相鄰之雷射照射痕150彼此可相互接觸，亦可一部分重疊，或者亦可為非接觸。 於圖6之例中，點140係將複數個雷射照射痕150排列成方形之螺旋狀而構成。於圖7之例中，點140係將複數個雷射照射痕150排列成記號(Masu symbol)狀而構成。於圖8之例中，點140係由複數個雷射照射痕150排列成方形框狀而構成。又，於圖9之例中，點140係由複數個雷射照射痕150排列成雙重方形狀而構成。點之態樣並無特別限定，亦可為圓形或方形以外之多邊形狀。又，點亦可為如內部佈滿雷射照射痕般之態樣。 再者，一個點140之尺寸例如可為50 μm×50 μm之範圍，亦可為100 μm×100 μm之範圍，亦可為200 μm×200 μm之範圍。一個點140之尺寸亦可為X軸方向之尺寸與Y軸方向之尺寸不同。 又，構成標記元件132之複數個點140之尺寸可各自互不相同，亦可為相同之值。 於圖10中，模式性地示出於圖4或圖5所示之點140中，相互相鄰之1組雷射照射痕之剖面。於圖10中，示出相互相鄰之第1雷射照射痕150A及第2雷射照射痕150B。 如圖10所示，第1雷射照射痕150A具有形成於第1表面112之第1開口160A及深度d₁ 。關於第1開口160A，自第1表面112之上觀察時為大致圓形，且具有直徑

₁ 。又，第2雷射照射痕150B具有形成於第1表面112之第2開口160B及深度d₂ 。關於第2開口160B，自第1表面112之上觀察時為大致圓形，且具有直徑

₂ 。 再者，直徑

₁ 與直徑

₂ 可互不相同，亦可為相同之值。同樣地，深度d₁ 與深度d₂ 可互不相同，亦可為相同之值。 第1雷射照射痕150A之第1開口160A之中心與第2雷射照射痕150B之第2開口160B之中心之間的距離、即雷射照射痕150之間距P例如可為3 μm～20 μm之範圍，亦可為5 μm～15 μm之範圍。但是，於一個點140中，間距P未必要固定，亦可根據位置而發生變化。 此處，於第1雷射照射痕150A中，第1開口160A之直徑

₁ 為5 μm～15 μm之範圍，深度d₁ 為1 μm～10 μm之範圍。同樣地，於第2雷射照射痕150B中，第2開口160B之直徑

₂ 為5 μm～15 μm之範圍，深度d₂ 為1 μm～10 μm之範圍。 再者，雖於圖中未示出，但圖4及圖5所示以外之雷射照射痕150亦具有與第1及第2雷射照射痕150A、150B大致相同之剖面形態。 因此，更一般而言，第1玻璃基板110具有如下特徵：於例如如圖4或圖5所示之點140中，各雷射照射痕150之第1表面112中之開口160之直徑

為5 μm～15 μm之範圍，深度d為1 μm～10 μm之範圍。 雷射照射痕150之開口160之直徑

較佳為6 μm～12 μm之範圍，更佳為9 μm～11 μm之範圍。 又，雷射照射痕150之深度d較佳為2 μm～10 μm之範圍，更佳為5 μm～11 μm。 於第1表面112形成尺寸包含於此種範圍內之雷射照射痕150之情形時，能夠刻意地抑制於雷射照射痕150之附近產生龜裂之危險性。 又，於以此種尺寸形成雷射照射痕150之情形時，點140之視認性提高，其結果為，能夠獲得具有良好之視認性之標記130。 根據此種效果，於本發明之一實施形態中，能夠提供一種於刻意地抑制龜裂之產生之狀態下將具有良好之視認性之標記配置於第1表面的玻璃基板。 具有此種特徵之第1玻璃基板110例如可應用於半導體元件製造用構件(例如支持基板)、及影像感測器用覆蓋玻璃等。 第1玻璃基板110例如可應用於在穿戴設備、例如帶有投影機之眼鏡、眼鏡型或風鏡型顯示器、虛擬實境擴增實境顯示裝置、虛擬圖像顯示裝置等中使用之玻璃(亦稱為穿戴設備用導光玻璃)等。此外，第1玻璃基板110可應用於小型且攝像視角較廣之攝像玻璃透鏡(亦稱為透鏡用玻璃)等中，以用於車載用攝影機、機器人用視覺感測器等之用途。 (本發明之一實施形態之玻璃基板之製造方法) 其次，參照圖11，對本發明之一實施形態之玻璃基板之製造方法的一例進行說明。 於圖11中，模式性地示出本發明之一實施形態之玻璃基板之製造方法(以下，稱為「第1製造方法」)的流程。 如圖11所示，第1製造方法具有： (i)步驟(步驟S110)，其係準備玻璃板；及 (ii)步驟(步驟S120)，其係對上述玻璃板之表面照射雷射而於上述表面形成複數個雷射照射痕。 以下，對各步驟進行說明。 (步驟S110) 首先，準備玻璃板。玻璃板具有第1表面。 玻璃板之種類並無特別限制。玻璃板例如亦可為石英玻璃或強化玻璃(亦包括化學強化玻璃)。又，本說明書中之玻璃板(玻璃基板)不限於採取玻璃構造者，亦可為名稱一般被稱為玻璃者。例如亦可為藍寶石玻璃。 (步驟S120) 其次，對玻璃板之第1表面照射雷射。 再者，亦可於該雷射照射步驟之前於玻璃板之第1表面設置吸收層。 於玻璃板之第1表面相對平滑之情形時，例如第1表面之算術平均粗糙度Ra未達約0.5 μm之情形時，較佳為設置吸收層。 原因在於：於此種具有「平滑之」第1表面之玻璃板中，存在不充分吸收來自下一步驟S120中所照射之脈衝雷射之能量之傾向。藉由在玻璃板之第1表面設置吸收層，能夠效率良好地吸收脈衝雷射之能量。 吸收層之材料並無特別限制。吸收層例如可由無機材料形成，亦可由有機材料形成。例如作為有機材料，可列舉包含合成樹脂墨水及碳黑等之顏料。作為無機材料，可列舉鋁等金屬材料。 吸收層係藉由例如噴塗法或噴墨法等設置於玻璃基板之第1表面。 但是，吸收層之設置為任意。吸收層只要於雷射照射步驟後適當去除即可。吸收層例如可藉由擦除洗淨(使用海綿及刷之物理性洗淨)、熱處理(退火)、及研磨或使用藥品之溶解而去除。 其次，對玻璃板之第1表面(於具有吸收層之情形時為吸收層)照射雷射。 雷射之照射條件係以如下之方式選定： 於所獲得之雷射照射痕中， ・第1表面中之開口之直徑

成為5 μm～15 μm之範圍， ・深度d成為1 μm～10 μm之範圍。 如上所述，第1表面中之雷射照射痕之開口之直徑

較佳為6 μm～12 μm的範圍。又，雷射照射痕之深度d較佳為2 μm～10 μm之範圍。 為了有效率地形成此種雷射照射痕，雷射較佳為具有600 nm以下之波長，更佳為具有500 nm～570 nm之波長範圍。例如亦可使用波長為532 nm(綠色)之YAG(yttrium aluminum garnet，釔鋁石榴石)雷射(二次諧波)。 再者，雷射照射痕未必要藉由脈衝雷射之1次照射而形成。即，亦可藉由對同一位置複數次照射脈衝雷射而形成一個雷射照射痕。於使用連續波雷射之情形時，不限定於利用間歇性之振盪中之1次照射所進行之形成。亦可對同一複數次照射連續波雷射而形成一個雷射照射痕。 藉由使用此種方法，於第1表面以特定之配置形成複數個雷射照射痕，而構成點。又，藉由將複數個點組合，能夠構成標記元件，進而藉由將複數個標記元件組合，能夠獲得如識別碼或對準標記之標記。 於此種第1製造方法中，照射脈衝雷射時，能夠刻意地抑制於雷射照射痕及附近產生龜裂之危險性。又，於第1製造方法中，由雷射照射痕所構成之點之視認性提高，其結果為，能夠獲得具有良好之視認性之標記。 再者，於玻璃基板形成標記之時點並無特別限定。例如(1)於步驟S110中準備之玻璃板亦可為自玻璃素板切割成所期望之形狀，經過倒角、研削、研磨、洗淨等步驟而成者，且對獲得所期望之品質之玻璃板如步驟S120般形成標記。(2)於步驟S110中準備之玻璃板亦可為切割成所期望之形狀者，且於在步驟S120中形成標記後，進行倒角等各種步驟。(3)步驟S120亦可於倒角、研削、研磨、洗淨等步驟之中途進行。又，亦可不具有切割成所期望之形狀之步驟，而準備最初便具有所期望之形狀之玻璃板。若如(1)之例般，於經過倒角、研削、研磨及洗淨等步驟之後形成標記，則標記之品質不會劣化(因對形成有標記之主表面進行研削或研磨而導致視認性變差等)，故而較佳。進而，於(1)之例之情形時，若於通常之氣體氛圍中實施至步驟S120之前之步驟，於無塵室實施步驟S120之標記形成，則可保持玻璃基板之品質(表面狀態等)，故而較佳。 [實施例] 其次，對實施例進行說明。再者，於以下之說明中，例1～例4係實施例，例5～例6係比較例。 (例1) 藉由以下之方法製造具有標記之玻璃基板。 首先，準備直徑300 mm×厚度0.7 mm之大致圓形狀之無鹼玻璃製之玻璃板(EN-A1：旭硝子股份有限公司製造)。 被雷射照射表面(第1表面)之表面粗糙度(Ra)為約0.45 nm。 其次，於玻璃板之第1表面之形成有標記之位置設置吸收層。吸收層為油性丙烯酸清漆(H62-8808 65)，且藉由噴霧塗佈設置於玻璃板。 其次，對玻璃板之第1表面之吸收層照射脈衝雷射而形成雷射照射痕。又，藉由複數個雷射照射痕之組合而構成點。 於脈衝雷射之照射中，使用刻印裝置(ML9500A：AMADA MIYACHI股份有限公司製)，雷射設為波長532 nm之YGA雷射(二次諧波)。雷射輸出之電流值設為13.0 A。雷射照射痕係藉由對第1表面之同一位置照射4次脈衝雷射而形成。以下，將該同一位置之雷射照射次數稱為「重複次數」。雷射照射痕之間距P係以11 μm為目標。 於圖12中，示出藉由雷射照射痕之組合而獲得之點之一例。該點係以雷射照射痕之雙重環排列而構成。 內側環之尺寸(自一個雷射照射痕之大致中心位置至位於通過內側環之中心點而對向之位置之雷射照射痕之大致中心位置的尺寸)為約42.8 μm，外側環之尺寸(自一個雷射照射痕之大致中心位置至位於通過外側環之中心點而對向之位置之雷射照射痕之大致中心位置的尺寸)為約97.9 μm。 再者，內側環之尺寸係0時、2時及4時之方向上之3點之平均值。同樣地，外側環之尺寸係0時、2時及4時之方向上之3點之平均值。 一個點之縱橫尺寸為約100 μm×約100 μm。 藉由此種方法反覆進行雷射照射，而形成由12個標記元件所構成之標記(參照圖2)。 於所獲得之標記中，橫向之長度L₁ 為約16.4 mm，縱向之長度L₂ 為約1.62 mm。 藉由以上之方法製造具有標記之玻璃基板。 (評價) 對所獲得之玻璃基板實施以下之評價。 (雷射照射痕之測定) 於所獲得之玻璃基板中，對各雷射照射痕之開口之直徑

及深度d進行測定。 雷射照射痕之開口之直徑係以如下之方式進行測定。 利用顯微鏡或雷射顯微鏡觀察雷射照射痕，於圖像上測定雷射照射痕之直徑。再者，於相互最接近之雷射照射痕彼此重疊之情形時，於非重疊部分測定直徑。 測定之結果為，開口之直徑之最小值

_min 為8 μm，最大值

_max 為12 μm。 另一方面，於雷射照射痕之深度之測定中，使用雷射顯微鏡裝置(VK9510：Keyence公司製造)。於該裝置中，可自玻璃基板之表面側起，非破壞式地對雷射照射痕之深度進行測定。 對構成標記之所有雷射照射痕之深度d進行測定，自所獲得之結果求出最大之深度d_max 。 (龜裂之測定) 於所獲得之玻璃基板中，對在第1表面之各標記元件之附近產生之龜裂之數量(總數)進行評價。評價係藉由使用10倍透鏡顯微鏡之目視下之觀察而進行。 (標記之視認性評價) 目視觀察形成於玻璃基板之第1表面之標記。其結果為，將能夠視認出所有標記元件之情形判定為○，將連一部分標記元件亦無法視認之情形判定為×。 (例2～例6) 藉由與例1相同之方法製造具有標記之玻璃基板。 但是，於該等例2～例6中，使脈衝雷射之照射條件(電流值及重複次數)相對於例1之情形發生變化。 使用所獲得之玻璃基板，實施與例1之情形相同之評價。 將各例中之雷射之照射條件及評價結果歸總示於以下之表1。 [表1] 如表1所示，可知於例1～例6之玻璃基板中，標記之視認性均為良好。然而，於例5～例6中，觀測到於標記部分產生龜裂。與此相對，可知於例1～例4中，未產生龜裂。 本案係主張基於在2017年2月15日提出申請之日本專利申請2017-026464號之優先權者，且藉由參照將該日本申請案之全部內容引用於本案中。Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In FIG. 1, the perspective view of the glass substrate (henceforth a "1st glass substrate") which concerns on one Embodiment of this invention is shown typically. As shown in FIG. 1 , the first glass substrate 110 has a first surface 112 and a second surface 114 facing each other. Furthermore, the first glass substrate 110 has a substantially circular shape. However, this is only an example, and the shape of the first glass substrate 110 is not particularly limited. For example, the shape of the first glass substrate 110 may be a substantially circular shape, a substantially rectangular shape (including a substantially square shape), or the like. In addition, the first glass substrate 110 may have a groove, a reference surface, a chamfer, and the like. The size of the first glass substrate 110 is not particularly limited, and in the case of a substantially circular shape, a diameter (

)100mm～450mm. In the case of a substantially rectangular shape, the size of the first substrate 110 may be 100 mm×100 mm to 2 m×2 m. In the 1st glass substrate 110, the mark 130 is formed in the 1st surface 112. Here, in this case, in order to clarify the distinction between the glass substrates having the marks 130 (eg, the first glass substrate 110 ), the glass before the marks 130 are formed on the first surface 112 is specifically referred to as a “glass plate”. According to this description, by forming a mark on the 1st surface of a glass plate, the 1st glass substrate which has the mark 130 on the said 1st surface is obtained. The mark 130 may also be an identification code including at least one of numbers, characters and graphics, for example. In addition, each of numbers, characters, and figures may be one or plural. Such an identification code can be used for identification and/or management of the first glass substrate 110, for example. Alternatively, the mark 130 can also be, for example, an alignment mark. Such alignment marks can be used for position or direction alignment during processing, such as handling, cutting, chamfering, and lamination, of the first glass substrate 110 . Furthermore, hereinafter, one of the numbers, characters and figures constituting the mark 130 will be specifically referred to as a "mark element". In FIG. 2 , an example of the mark 130 is schematically shown. As shown in FIG. 2, in this example, the marking 130 is shown in the form of an identification code formed by 12 marking elements 132 arranged in a line in a straight line. However, the mark 130 is not limited to this aspect. For example, the marker 130 may also be formed by arranging the marker elements 132 in a non-linear shape. In addition, the marker 130 may be constituted by arranging two or more lines of each marker element 132 linearly or non-linearly. The overall size of the marker 130 is not particularly limited. For example, in the case of the linear arrangement of the marker elements 132 shown in FIG. 2 , the horizontal length L ₁ is in the range of 16.43±0.025 mm, and the vertical length L ₂ is 1.624±0.025 mm. Furthermore, when the marker 130 is constituted by the non-linear arrangement of the marker elements 132, the horizontal length L ₁ and the vertical length L _{2 of the} marker 130 are respectively specified as the smallest rectangle assuming the smallest rectangle including the marker 130. The length of the first side and the length of the second side. Each marker element 132 constituting the marker 130 is composed of a plurality of dots. In other words, one marking element 132 is formed by a plurality of dots. This point will be described below with reference to FIG. 3 . In FIG. 3, it is a schematic diagram which enlarges and shows one marking element 132 which comprises the marking 130. As shown in FIG. In this example, the marking element 132 is considered to be the number "3". As can be seen from FIG. 3 , the marking element 132 is formed by a combination of a total of 17 dots 140 . Furthermore, the marking elements 132 other than the numeral "3" can also be formed by arranging a plurality of dots 140 vertically and horizontally. Such dots 140 can be formed on the surface of the glass plate by irradiating a laser. Lasers can use pulsed lasers or continuous wave lasers. When a continuous wave laser is used, it is preferable to oscillate intermittently (pulse oscillation). In FIG. 4, a schematic enlarged view of one of the dots 140 constituting the marking element 132 is shown. As shown in FIG. 4 , the dots 140 are formed by combining a plurality of laser irradiation marks 150 . Here, the so-called "laser irradiation mark (150)" refers to a concave portion formed on the surface of the glass plate when the glass plate is irradiated with a laser. In the example of FIG. 4 , point 140 is configured as a substantially double ring having inner ring 152 and outer ring 154 . In addition, the inner ring 152 and the outer ring 154 are respectively formed by arranging a plurality of laser irradiation marks 150 in a circle. Furthermore, in the example shown, in each of the inner ring 152 and the outer ring 154, the adjacent laser irradiation marks 150 are arranged in contact with each other. However, the configuration of the laser irradiation marks 150 constituting the dots 140 is not limited to this. For example, in the "double ring" arrangement shown in FIG. 4 , the adjacent laser irradiation marks 150 in the inner ring 152 or the outer ring 154 may be non-contact with each other, or may partially overlap. Alternatively, the adjacent laser irradiation marks 150 of a part are not in contact with each other, the adjacent laser irradiation marks 150 of another part are overlapped with each other, and the other laser irradiation marks 150 are in contact with each other. In addition, when there are a plurality of adjacent laser irradiation marks 150 in the point 140 that are not in contact with each other, the non-contact intervals may be the same or different. In addition to this, various forms are also possible. Furthermore, the dots 140 may be formed in an arrangement other than the substantially double annular arrangement of the laser irradiation marks 150 . In FIGS. 5 to 9 , another aspect of the dot is schematically shown. In the example of FIG. 5 , the dots 140 are formed by arranging a plurality of laser irradiation marks 150 in a circular spiral (spiral). Also in this example, the adjacent laser irradiation marks 150 may be in contact with each other, may partially overlap, or may be non-contact. In the example of FIG. 6 , the dots 140 are formed by arranging a plurality of laser irradiation marks 150 in a square spiral shape. In the example of FIG. 7 , the dots 140 are formed by arranging a plurality of laser irradiation marks 150 in a Masu symbol shape. In the example of FIG. 8 , the spot 140 is formed by arranging a plurality of laser irradiation marks 150 in a square frame shape. In addition, in the example of FIG. 9, the spot 140 is comprised by arranging a plurality of laser irradiation marks 150 in a double square shape. The form of the dots is not particularly limited, and may be a circle or a polygon other than a square. In addition, the dot may be in a state as if the inside is covered with laser irradiation marks. Furthermore, the size of one spot 140 may be, for example, in the range of 50 μm×50 μm, or in the range of 100 μm×100 μm, or in the range of 200 μm×200 μm. The size of a point 140 may also be different from the size in the X-axis direction and the Y-axis direction. In addition, the dimensions of the plurality of dots 140 constituting the marking element 132 may be different from each other, or may be the same value. In FIG. 10 , a cross section of a group of laser irradiation marks adjacent to each other is schematically shown at point 140 shown in FIG. 4 or FIG. 5 . In FIG. 10, the mutually adjacent 1st laser irradiation trace 150A and the 2nd laser irradiation trace 150B are shown. As shown in FIG. 10 , the first laser irradiation mark 150A has a first opening 160A formed on the first surface 112 and a depth d ₁ . The first opening 160A is approximately circular when viewed from above the first surface 112 and has a diameter

₁ . Further, the second laser irradiation marks 150B having formed on a first surface 112 of the opening 160B and the second depth d _2. The second opening 160B is approximately circular when viewed from above the first surface 112 and has a diameter

₂ . Furthermore, the diameter

₁ with diameter

₂ may be different from each other or the same value. Similarly, the depth d ₁ and the depth d ₂ may be different from each other, or may be the same value. The distance between the center of the first opening 160A of the first laser-irradiated trace 150A and the center of the second opening 160B of the second laser-irradiated trace 150B, that is, the distance P between the laser-irradiated traces 150 may be, for example, 3 μm to 20 μm The range of μm may also be in the range of 5 μm to 15 μm. However, in one point 140, the pitch P is not necessarily constant, and may vary depending on the position. Here, in the first laser irradiation trace 150A, the diameter of the first opening 160A

₁ is in the range of 5 μm to 15 μm, and the depth d ₁ is in the range of 1 μm to 10 μm. Similarly, in the second laser irradiation mark 150B, the diameter of the second opening 160B

₂ is in the range of 5 μm to 15 μm, and the depth d ₂ is in the range of 1 μm to 10 μm. Furthermore, although not shown in the drawings, the laser irradiation marks 150 other than those shown in FIGS. 4 and 5 also have substantially the same cross-sectional shape as the first and second laser irradiation marks 150A and 150B. Therefore, more generally speaking, the first glass substrate 110 has the following characteristics: for example, in the point 140 shown in FIG. 4 or FIG. 5 , the diameter of the opening 160 in the first surface 112 of each laser irradiation mark 150

It is in the range of 5 μm to 15 μm, and the depth d is in the range of 1 μm to 10 μm. The diameter of the opening 160 of the laser irradiation mark 150

The range of 6 μm to 12 μm is preferable, and the range of 9 μm to 11 μm is more preferable. In addition, the depth d of the laser irradiation marks 150 is preferably in the range of 2 μm to 10 μm, more preferably 5 μm to 11 μm. In the case where the laser-irradiated traces 150 having the size within such a range are formed on the first surface 112 , the risk of cracking in the vicinity of the laser-irradiated traces 150 can be suppressed deliberately. In addition, when the laser irradiation marks 150 are formed in such a size, the visibility of the dots 140 is improved, and as a result, the mark 130 having good visibility can be obtained. According to such an effect, in one Embodiment of this invention, it can provide the glass substrate which arrange|positions the mark which has favorable visibility on the 1st surface in the state which suppressed the generation|occurence|production of a crack intentionally. The first glass substrate 110 having such a characteristic can be applied to, for example, a member for manufacturing a semiconductor element (for example, a support substrate), a cover glass for an image sensor, or the like. The first glass substrate 110 can be applied to, for example, glass used in wearable devices, such as glasses with projectors, glasses-type or goggle-type displays, virtual reality augmented reality display devices, virtual image display devices, and the like (also It is called light guide glass for wearable devices) and so on. In addition, the first glass substrate 110 can be applied to a small imaging glass lens with a wide imaging angle (also referred to as a glass for a lens) or the like, and can be used for in-vehicle cameras, vision sensors for robots, and the like. (The manufacturing method of the glass substrate which concerns on one Embodiment of this invention) Next, referring FIG. 11, an example of the manufacturing method of the glass substrate which concerns on one Embodiment of this invention is demonstrated. In FIG. 11, the flow of the manufacturing method (henceforth "1st manufacturing method") of the glass substrate which concerns on one Embodiment of this invention is shown typically. As shown in FIG. 11 , the first manufacturing method includes: (i) a step (step S110 ) of preparing a glass plate; and (ii) a step (step S120 ) of irradiating the surface of the glass plate with a laser to A plurality of laser irradiation marks are formed on the surface. Hereinafter, each step will be described. (Step S110 ) First, a glass plate is prepared. The glass plate has a first surface. The kind of glass plate is not particularly limited. The glass plate can also be, for example, quartz glass or tempered glass (including chemically tempered glass). In addition, the glass plate (glass substrate) in this specification is not limited to what has a glass structure, and what is generally called glass by name may be sufficient. For example, sapphire glass may also be used. (Step S120 ) Next, the first surface of the glass plate is irradiated with a laser. Furthermore, an absorption layer can also be provided on the first surface of the glass plate before the laser irradiation step. When the first surface of the glass plate is relatively smooth, for example, when the arithmetic mean roughness Ra of the first surface is less than about 0.5 μm, it is preferable to provide an absorption layer. The reason is that in such a glass plate having a "smooth" first surface, the energy from the pulsed laser irradiated in the next step S120 tends to be insufficiently absorbed. By providing the absorption layer on the first surface of the glass plate, the energy of the pulsed laser can be efficiently absorbed. The material of the absorption layer is not particularly limited. The absorption layer may be formed of, for example, an inorganic material or an organic material. For example, the organic material includes pigments including synthetic resin ink, carbon black, and the like. As an inorganic material, metal materials, such as aluminum, are mentioned. The absorption layer is provided on the first surface of the glass substrate by, for example, a spray coating method or an inkjet method. However, the arrangement of the absorption layer is arbitrary. The absorption layer may be appropriately removed after the laser irradiation step. The absorption layer can be removed by, for example, wiping cleaning (physical cleaning using sponges and brushes), heat treatment (annealing), and grinding or dissolution using chemicals. Next, a laser is irradiated on the first surface of the glass plate (in the case of having an absorption layer, an absorption layer). The irradiation conditions of the laser are selected in the following manner: In the obtained laser irradiation marks, ・The diameter of the opening in the first surface

It is in the range of 5 μm to 15 μm, and the depth d is in the range of 1 μm to 10 μm. As mentioned above, the diameter of the opening of the laser irradiation marks in the first surface

Preferably it is the range of 6 micrometers - 12 micrometers. In addition, the depth d of the laser irradiation marks is preferably in the range of 2 μm to 10 μm. In order to efficiently form such laser irradiation marks, the laser preferably has a wavelength of 600 nm or less, and more preferably has a wavelength range of 500 nm to 570 nm. For example, a YAG (yttrium aluminum garnet, yttrium aluminum garnet) laser (second harmonic) with a wavelength of 532 nm (green) can also be used. In addition, it is not necessary for the laser irradiation marks to be formed by one irradiation of the pulsed laser. That is, it is also possible to form one laser irradiation mark by irradiating the same position with the pulsed laser a plurality of times. In the case of using a continuous wave laser, it is not limited to the formation by one shot of intermittent oscillation. It is also possible to irradiate the same continuous wave laser for several times to form a laser irradiation mark. By using such a method, a plurality of laser irradiation marks are formed in a specific arrangement on the first surface to constitute dots. Also, by combining a plurality of dots, a marking element can be formed, and by combining a plurality of marking elements, a mark such as an identification code or an alignment mark can be obtained. In such a first manufacturing method, when the pulsed laser is irradiated, the risk of generating cracks in the laser irradiation marks and the vicinity can be suppressed deliberately. Moreover, in the 1st manufacturing method, the visibility of the dot which consists of laser irradiation marks improves, and as a result, the mark which has favorable visibility can be obtained. In addition, the timing of forming a mark on a glass substrate is not specifically limited. For example (1) The glass plate prepared in step S110 can also be cut from a vitreous plate into a desired shape, and is formed by chamfering, grinding, grinding, cleaning, etc., and it is important to obtain the desired quality. The glass plate is marked as in step S120. (2) The glass plate prepared in step S110 may be cut into a desired shape, and after the mark is formed in step S120, various steps such as chamfering are performed. (3) Step S120 may also be performed in the middle of steps such as chamfering, grinding, grinding, and cleaning. Moreover, you may prepare the glass plate which has a desired shape at first, without the process of cutting into a desired shape. If the mark is formed after the steps of chamfering, grinding, grinding, and cleaning as in the example of (1), the quality of the mark will not be deteriorated (the visibility may be caused by grinding or grinding the main surface on which the mark is formed). deterioration, etc.), so it is better. Furthermore, in the case of the example (1), if the steps before step S120 are performed in a normal gas atmosphere, and the mark formation in step S120 is performed in a clean room, the quality (surface state, etc.) of the glass substrate can be maintained. , so it is better. [Examples] Next, examples will be described. In addition, in the following description, Example 1-Example 4 is an Example, and Example 5-Example 6 is a comparative example. (Example 1) A glass substrate having a mark was produced by the following method. First, a glass plate made of alkali-free glass (EN-A1: manufactured by Asahi Glass Co., Ltd.) having a diameter of 300 mm and a thickness of 0.7 mm was prepared. The surface roughness (Ra) of the laser-irradiated surface (first surface) was about 0.45 nm. Next, an absorption layer is provided at the position where the mark is formed on the first surface of the glass plate. The absorption layer is an oil-based acrylic varnish (H62-8808 65), and is provided on a glass plate by spray coating. Next, a pulsed laser is irradiated to the absorption layer on the first surface of the glass plate to form laser irradiation marks. Moreover, a dot is formed by the combination of a plurality of laser irradiation marks. In the irradiation of the pulsed laser, a marking device (ML9500A: manufactured by AMADA MIYACHI Co., Ltd.) was used, and the laser was set to a YGA laser (second harmonic wave) with a wavelength of 532 nm. The current value of the laser output is set to 13.0 A. The laser irradiation marks were formed by irradiating the same position on the first surface with the pulse laser four times. Hereinafter, the number of times of laser irradiation at the same position is referred to as "the number of repetitions". The distance P between the laser irradiation marks is aimed at 11 μm. In FIG. 12, an example of the point obtained by the combination of laser irradiation marks is shown. The spot is formed by a double ring arrangement of laser irradiated marks. The size of the inner ring (the size from the approximate center position of a laser irradiation mark to the approximate center position of the laser irradiation mark at the position opposite the center point of the inner ring) is about 42.8 μm, and the size of the outer ring ( The dimension from the approximate center position of one laser exposure mark to the approximate center position of the laser exposure trace located at the position facing through the center point of the outer ring) is about 97.9 μm. Furthermore, the size of the inner ring is the average value of 3 points in the direction of 0 o'clock, 2 o'clock and 4 o'clock. Likewise, the dimension of the outer ring is the average value of 3 points in the direction of 0 o'clock, 2 o'clock and 4 o'clock. The vertical and horizontal dimensions of one dot are about 100 μm×about 100 μm. By repeating laser irradiation in this way, a mark composed of 12 marking elements is formed (see FIG. 2 ). In the obtained marks, the length L ₁ in the transverse direction was about 16.4 mm, and the length L _{2 in the} longitudinal direction was about 1.62 mm. The glass substrate with the mark is manufactured by the above method. (Evaluation) The following evaluation was implemented about the obtained glass substrate. (Measurement of laser irradiation marks) In the obtained glass substrate, the diameter of the opening to each laser irradiation mark

and depth d were measured. The diameter of the opening of the laser irradiation marks was measured as follows. Use a microscope or a laser microscope to observe the laser irradiation marks, and measure the diameter of the laser irradiation marks on the image. Furthermore, when the laser irradiation marks closest to each other overlap each other, the diameter is measured at the non-overlapping portion. The result of the measurement is the minimum value of the diameter of the opening

_min is 8 μm, max.

_max is 12 μm. On the other hand, for the measurement of the depth of the laser irradiation marks, a laser microscope apparatus (VK9510: manufactured by Keyence Corporation) was used. In this apparatus, the depth of the laser irradiation marks can be measured nondestructively from the surface side of the glass substrate. The depth d of all the laser irradiation marks constituting the mark was measured, and the maximum depth d _max was obtained from the obtained results. (Measurement of cracks) In the obtained glass substrate, the number (total number) of cracks generated in the vicinity of each marking element on the first surface was evaluated. Evaluation was performed by visual observation using a 10-fold lens microscope. (Evaluation of the visibility of a mark) The mark formed on the 1st surface of a glass substrate was visually observed. As a result, the case where all the marking elements could be visually recognized was determined as ○, and the case where even some of the marking elements could not be visually recognized was determined as ×. (Examples 2 to 6) By the same method as in Example 1, glass substrates with marks were produced. However, in these Examples 2 to 6, the irradiation conditions (current value and number of repetitions) of the pulsed laser were changed from those of Example 1. Using the obtained glass substrate, the same evaluation as in the case of Example 1 was implemented. The irradiation conditions and evaluation results of the laser in each example are collectively shown in Table 1 below. [Table 1] As shown in Table 1, in the glass substrates of Examples 1 to 6, it was found that the visibility of the marks was good. However, in Examples 5 to 6, cracks were observed in the marked portion. In contrast, in Examples 1 to 4, it was found that no cracks occurred. This case claims the priority based on Japanese Patent Application No. 2017-026464 filed on February 15, 2017, and the entire contents of the Japanese application are hereby incorporated by reference.

₁‧‧‧直徑

₂‧‧‧直徑110‧‧‧Glass Substrate 112‧‧‧First Surface 114‧‧‧Second Surface 130‧‧‧Marking 132‧‧‧Marking Components 140‧‧‧Points 150‧‧‧Laser Irradiation Traces 150A‧‧‧Laser Irradiation trace 150B‧‧‧Laser irradiation trace 152‧‧‧Inner ring 154‧‧‧Outer ring 160A‧‧‧Opening 160B‧‧‧Opening d ₁ ‧‧‧ Depth d ₂ ‧‧‧Depth L ₁ ‧‧‧lateral Length L ₂ ‧‧‧ Longitudinal length P‧‧‧Pitch S110, S120‧‧‧Steps

₁ ‧‧‧diameter

₂ ‧‧‧diameter

1 : is a figure which shows typically the perspective view of the glass substrate which concerns on one Embodiment of this invention. It is a figure which shows typically an example of the mark formed in the glass substrate which concerns on one Embodiment of this invention. FIG. 3 is a schematic view showing one of the marking elements (the numeral "3") constituting the marking in an enlarged manner. Figure 4 is a schematic enlarged view of one point constituting the marker element. FIG. 5 is an enlarged view schematically showing another aspect of the dots constituting the marker elements. FIG. 6 is an enlarged view schematically showing still another aspect of the dots constituting the marker elements. FIG. 7 is an enlarged view schematically showing still another aspect of the dots constituting the marker elements. FIG. 8 is an enlarged view schematically showing still another aspect of the dots constituting the marker elements. FIG. 9 is an enlarged view schematically showing still another aspect of the dots constituting the marker elements. FIG. 10 is a diagram schematically showing a cross section of two adjacent laser irradiation marks. FIG. 11 is a diagram schematically showing an example of the flow of the manufacturing method of the glass substrate according to one embodiment of the present invention. FIG. 12 is a photograph showing one point obtained by arranging a plurality of laser irradiation marks in Example 1. FIG.

140‧‧‧points

150‧‧‧Laser irradiation marks

152‧‧‧Inner Ring

154‧‧‧Outer ring

Claims (12)

A glass substrate, which has marks on the surface, and the marks are identification codes, alignment marks, or a part thereof, the marks are formed by a plurality of points, and each point is formed by a plurality of laser irradiation marks The structure is such that the diameter of the opening of each laser irradiation mark on the surface is in the range of 5 μm to 15 μm, and the depth is in the range of 1 μm to 10 μm. The glass substrate of claim 1, wherein in at least one of the above points, the distance between the centers of at least one of the groups of adjacent laser irradiation marks is in the range of 5 μm to 15 μm. The glass substrate of claim 1 or 2, wherein in at least one of the above points, at least one of the groups of adjacent laser irradiation marks are in contact with or overlap with each other. The glass substrate according to claim 1 or 2, wherein at least one of the above-mentioned points is constituted by arranging the plurality of laser-irradiated traces in a double ring shape or a spiral shape. The glass substrate according to claim 1 or 2, wherein the surface roughness Ra of the above-mentioned surface is less than 0.5 μm. The glass substrate according to claim 1 or 2, wherein the surface roughness Ra of the above-mentioned surface is 0.5 μm or more. A manufacturing method, which is a method of manufacturing a glass substrate with a mark on the surface, and has the step of irradiating a laser on the surface of the glass plate to form a plurality of laser irradiation marks on the surface, the laser having a range of 500nm-570nm wavelength, the above-mentioned plural laser irradiation marks constitute points, and the collection of the above-mentioned points forms a mark, and the above-mentioned marks are part of identification codes, alignment marks, or the like, and the diameter of the opening of each laser irradiation mark on the above-mentioned surface is The range of 5μm~15μm, the depth is the range of 1μm~10μm. The manufacturing method of claim 7, wherein the above-mentioned laser is a YAG laser with a wavelength of 532 nm. The manufacturing method of claim 7 or 8, further comprising the step of providing an absorption layer on the surface of the glass plate before the step of forming a plurality of laser irradiation marks on the surface. The manufacturing method of claim 7 or 8, wherein at least one of the above-mentioned points is formed so that the distance between the centers in at least one of the adjacent laser-irradiated marks group is in the range of 5 μm to 15 μm. The manufacturing method of claim 7 or 8, wherein at least one of the above-mentioned points is in at least one of the group of adjacent laser-irradiated traces, and the side where the above-mentioned adjacent laser-irradiated traces contact or overlap each other formula composition. The manufacturing method of claim 7 or 8, wherein in at least one of the above points, the plurality of laser irradiation marks are formed in a double ring or spiral arrangement.

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