201200284 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種半導體裝置貫通電極形成用之玻璃基 板之製造方法。 【先前技術】 為了響應伴隨著高密度安裝化之印刷電路基板之高密度 化之要求，開發有將複數個印刷電路基板積層而成之多層 印刷電路基板。於上述多層電路基板中，於樹脂製之絕緣 層形成被稱為通孔之直徑約為100 μηι以下之微細之貫通 孔，且對其内部實施鍍敷，而將上下積層之印刷電路基板 間之導電層彼此電性連接。 作為更容易地形成上述貫通孔之方法，於專利文獻丨、2 中揭示有經由形成有多個貫通孔之遮罩而對絕緣層照射雷 射光之方法。S忍為根據該方法，可於樹脂製之絕緣層同時 開設複數個貫通孔’因而可更容易地形成多個貫通孔（通 孔）》 又，為了響應1C晶片之小型化、薄型化之要求，近年來 盛行利用晶圓級封裝（WLP，Wafer Level package)技術。 其係可將封裝體尺寸抑制為㈣晶片同等之技術，於形成 有1C之晶圓表面，進行作為半導體封裝體所需之再配線、 焊錫凸塊加工、樹脂密封等，其後藉由切割加卫而使各晶 片單片化。於WLP技術中’通常藉由切割加工而將以樹脂 密封石夕晶®而成者單片化，且近年來就可靠性之方面而 言’開始使用藉由陽極接合技術等而將玻璃接著於矽上 155791.doc 201200284 者。 又’於半導體裝置之小型化、高速化、低消耗電力化之 要求進一步提高的過程中’將包含複數個LSI(Large Scale Integrated circuit ’大型積體電路）之系統收容於}個封裝體 中之系統級封裝（SiP ’ System-in-Package)技術與三維安裝 技術組合的三維SiP技術之開發亦正在發展。此時，打線 接合技術無法與微細之間距對應，因而需要使用貫通電極 之被稱為仲介層（interposer)之中繼基板。 先行技術文獻 專利文獻 專利文獻1:日本專利特開2005-88045號公報 專利文獻2 :曰本專利特開2002-1 26886號公報 【發明内容】 發明所欲解決之問題 如上所述之樹脂製之絕緣層有翹曲或變形等影響，因此 定位精度變差，不適合於高密度安裝用。因此，期望將代 替上述樹脂製絕緣層之材料用於基板材料。 例如’研究有使用矽作為包含貫通電極之仲介層材料。 其原因在於矽可藉由乾式蝕刻而相對容易地進行微細孔加 工。然而，矽為半導體，為了確保絕緣性，必需對貫通孔 之内壁進行絕緣處理。又，預想到上述絕緣處理於今後會 隨著貫通孔之尺寸微細化而變得更難。 因此’要求代替上述樹脂製絕緣層’而使用絕緣性之玻 璃基板。例如，若可於玻璃基板形成複數個微細之貫通 155791.doc 201200284 孔’則可將上述玻璃基板用作仲介層。 然而’有時即便於與在樹脂製之絕緣層形成貫通孔之情 形相同之條件下對玻璃基板照射雷射光，亦極難以於玻璃 基板恰當地形成多個微細之貫通孔。玻璃存在加工性較樹 脂差之可能性。又，玻璃為脆性材料，因此只要未於恰當 之條件下進行雷射加工，則極難以使玻璃基板不產生龜裂 或變形而形成微細之貫通孔。 另一方面，認為若使用濕式蝕刻技術或乾式蝕刻技術， 則亦可於玻璃基板同時形成複數個貫通孔。然而，於此情 形時，有步驟變得複雜，加工時間變長，並且亦產生廢液 處理等問題之可能性。 本發明係鑒於以上問題而完成者，本發明之目的在於提 供一種藉由對玻璃基板照射雷射光，可使玻璃基板不產生 龜裂或變形等而恰當地形成複數個貫通孔之半導體裝置貫 通電極形成用之玻璃基板之製造方法。 解決問題之技術手段 本發明提供以下之半導體裝置貫通電極形成用之玻璃基 板之製造方法。 Π]種半¥體裝置貫通電極形成用之玻璃基板之製造 方法，其包含如下步驟： (1) 準備厚度為〇.〇1 mm〜5 _、si〇2含量為5〇 wt%〜7〇 、 50 C至300 C下之平均熱膨脹係數為1〇χι〇-7/κ〜5〇χ1〇-7/κ 之玻璃基板； (2) 將上述玻璃基板配置於來自準分子雷射光產生裝置 155791.doc 201200284 之準分子雷射光之光程上； (3) 於上述準分子雷射光產生裝置與上述玻璃基板之間 之上述光程上配置不包含貫通開口之遮罩；及 (4) 自上述準分子雷射光產生裝置，沿著上述光程對上 述玻璃基板照射上述準分子雷射光，而於上述玻璃基板形 成貫通孔。 [2] 如[1]之製造方法’其中上述不包含貫通開口之遮罩 包含相對於上述準分子雷射光為透明之基材與設置於該基 材之表面之經圖案化之反射層》 [3] 如[2]之製造方法’其中上述反射層含有選自由 Cr(鉻）、Ag(銀）、A1(鋁）及Au(金）所組成之群中之至少一 種金屬。 [4] 如[2]或[3]之製造方法’其中上述反射層之圖案包含 設置有上述反射層之部分與大致圓形狀之未設置上述反射 層之部分。 [5] 如[1]至[4]中任一項之製造方法，其中照射上述準分 子雷射光之步驟包含將照射通量為1〜2〇 j/cm2之上述準分 子雷射光以上述照射通量（J/cm2)、照射數（次）及上述玻璃 基板之厚度（mm)之乘積成為1，〇〇〇〜3〇,〇〇〇之方式進行照射 的步驟。 [6] 如[1 ]至[5]中任一項之製造方法，其中藉由照射上述 準分子雷射光之步驟’而於上述玻璃基板形成具有 0.1°〜20°之錐角之錐形狀之貫通孔。 [7] 如[1]至[6]中任一項之製造方法，其中上述準分子雷 155791.doc 201200284 射光為KrF雷射、ArF雷射或&雷射中之任一者。 發明之效果 於本發明中，可提供一種藉由對玻璃基板照射雷射光， 可使玻璃基板不產生龜裂或變形等而恰當地形成複數個貫 通孔的半V體裝置貫通電極形成用之玻璃基板之製造方 法0 【實施方式】 以下，藉由圖式對本發明進行說明。 (關於藉由本發明之製造方法所獲得之玻璃基板） 首先最初，對藉由本發明中之半導體裝置貫通電極形成 用之玻璃基板之製造方法所獲得之玻璃基板進行說明。 藉由本發明之製造方法所獲得之半導體裝置貫通電極形 成用之玻璃基板（以下，亦簡稱為「本發明之玻璃基板」） 係厚度為0.01 mm以上且5 mm以下，5〇e>c至3〇〇它下之平均 熱膨脹係數（以下，亦簡稱為「熱膨脹係數」）為l〇xl〇-7/K以 上且5〇Χΐ〇·7/Κ以下者。又，本發明之玻璃基板之Si02含量 處於50 wt%〜70 Wt%之範圍内。 認為有時通常之玻璃基板根據其性狀之不同而無法用作 如上所述之多層電路基板之絕緣層、WLP用玻璃或仲介 層。其原因在於設想到如下情形：將玻璃製絕緣層積層於 矽晶圓上，並將矽晶圓與玻璃製絕緣層接合等時，絕緣層 或WLP玻璃自石夕晶圓剝離，或晶圓龜曲。又，於將破璃用 作仲介層之情形時，由於包含矽之晶片與玻璃製仲介層之 熱膨脹差，而有零件產生翹曲之危險性。 15579I.doc 201200284 與此相對’本發明之玻璃基板之熱膨脹係數處於上述範 圍内。因此’即便將本發明之玻璃基板積層於矽晶圓上， 或反之於本發明之玻璃基板之上部積層包含矽之晶片，亦 難以產生下述情形：於玻璃基板與矽晶圓之間產生剝離， 或者矽晶片發生變形。 尤其’玻璃基板之熱膨脹係數較佳為25 X 1 0·7/Κ以上且 45 χ1〇-7/Κ以下，更佳為3〇χ10-7/Κ以上且4〇xl 〇-7/Κ以下。 於此情形時，可進一步抑制剝離及/或變形《再者，於必 需取付與母板等樹脂基板之匹配之情形時，玻璃基板之熱 膨脹係數較佳為3 5 X 1 0·7/Κ以上。 再者，於本發明中’ 50°C至30(TC下之平均熱膨脹係數 係指使用示差熱膨脹計（TMA)進行測定並根據jIS R3102(1995年度）所求出之值。 本發明之玻璃基板之厚度為〇.〇1 mm以上且5 mm以下。 其原因在於：若玻璃基板之厚度厚於5 mm，則貫通孔之形 成會花費時間’又若未達〇.〇1 mm，則會產生裂紋等問 題。本發明之玻璃基板之厚度更佳為0.02〜3 ，進而較 佳為0.02〜1 mm。玻璃基板之厚度尤佳為〇 〇5爪爪以上且 0.4 mm以下。 本發明之玻璃基板之Si〇2含量為50 wt·5/。以上且70 wt%以 下。若Si〇2含量多於此，則形成貫通孔時，容易於玻璃基 板之背面產生龜裂。進而較佳為Si〇2含量為55 wt%以上且 62 wt%。 已知玻璃之龜裂產生行為於以〇2含量較多之玻璃與較少 155791.doc 201200284 之玻璃中有所不同，Si〇2含量極多之玻璃容易由於與物體 之接觸等而產生圓錐形狀之龜裂。另一方面，Si〇2含量極 少之玻璃容易藉由與物體之接觸等而產生裂紋。因此，可 藉由控制玻璃基板中之Si〇2含量，而變得難以產生裂紋或 龜裂。 本發明之玻璃基板較佳為鹼含有率較低者。具體而言， 鈉（Na)與鉀（K)之合計含量較佳為以氧化物換算計為3.5質 量％以下《若合計含量超過3.5質量％，則熱膨脹係數超過 5〇xl(T7/K之可能性變高。鈉（Na)與鉀（K)之合計含量更佳 為3質量％以下。於將本發明之玻璃基板用於高頻裝置之 情形時’或者於例如以200 μιη以下之間距形成多個5〇 μηι 以下之貫通孔之情形等以極微細之間距形成多個貫通孔之 情形時，玻璃基板尤佳為無鹼玻璃。 此處，所謂無鹼玻璃’係指鹼金屬之總量以氧化物換算 計未達0.1質量°/。之玻璃。 本發明之玻璃基板之2 5 °c、1 MHz下之介電常數較佳為 6以下。又，本發明之玻璃基板之25°c、i mHz下之介電損 失較佳為0.005以下。藉由使介電常數及介電損失較小， 可發揮優異之裝置特性。 作為玻璃基板之具體例，可列舉AN1 〇〇玻璃（旭硝子公 司製造）、EAGLE玻璃（Corning公司製造）、SW玻璃（旭硝 子公司製造）等。該等玻璃基板之熱膨脹係數為丨〇x丨〇-7/κ 以上且5〇χ1〇·7/Κ以下》 ΑΝ1 00玻璃之特徵在於其係熱膨脹係數為3 8 χ丨〇-7/κ之無 155791.doc 201200284 鹼玻璃，Na20與Κ20之合計含量未達0.1 wt%。又，AN100 玻璃之Fe之含量為0.05 wt%。 SW玻璃之熱膨脹係數為36χ10·7/Κ，Na2〇與K20之合計 含量為3 wt %，Fe之含量為50質量ppm。 本發明之玻璃基板包含複數個貫通孔。各貫通孔亦可為 圓形。於此情形時，貫通孔之直徑雖亦根據本發明之玻璃 基板之用途而有所不同’但通常較佳為處於5 μιη〜5〇〇 μιη 之範圍内。關於貫通孔之直徑，於將本發明之玻璃基板用 作如上所述之多層電路基板之絕緣層之情形時，貫通孔之 直徑更佳為0.01 mm〜0.2 mm，進而較佳為0.02 mm〜〇.i mm »又，可採用晶圓級封裝（WLP)技術，將本發明之玻璃 基板積層於晶圓上’而形成用於壓力感測器等之IC晶片， 而此情形時之用以吸入空氣之貫通孔之直徑更佳為〇 .丨〜〇 . 5 mm，進而較佳為〇.2〜〇.4 mm。進而於此情形時，與空氣 孔不同之電極取出用之貫通孔之直徑更佳為〇 〇1〜〇2 mm，進而較佳為〇 〇2〜〇. 1 mm。尤其，於用作仲介層等貫 通電極之情形時，貫通孔之直徑更佳為〇 〇〇5〜〇 〇75 mm， 進而較佳為0.01〜0.05 mm。 再者，如後所述，於本發明之玻璃基板中，有時上述圓 形之貫通孔之於一開口面之直徑與於另一開口面之直徑不 同。於此情形時，所謂「貫通孔之直徑」，係指兩開口面 中之較大者之直徑。 較大者之直徑（di)與較小者之直徑（ds)之比（ds/dl)較佳為 〇’2〜0.99，更較佳為〇.5〜〇 9〇。 '5579l.doc 201200284 於本發明之玻璃基板中，貫通孔之數密度雖亦根據本發 明之玻璃基板之用途而有所不同’但通常為〇1個/mm2〜 10,000個/mm之範圍。於將本發明之玻璃基板用作如上述 說明之多層電路基板之絕緣層之情形時，貫通孔之數密度 較佳為3個/mm2〜10,000個/mm2之範圍，更佳為乃個化爪2〜 100個/mm2之範圍。又，於採用晶圓級封裝體（WLp)技 術，將本發明之玻璃基板積層於晶圓上，而形成用於壓力 感測器·#之1C晶片之情形時，貫通孔之數密度較佳為1個/ mm〜2 5個/mm，更佳為2個/mm2〜10個/mm2之範圍。於用 作仲介層專貫通電極之情形時，貫通孔之數密度更佳為 0.1個/mm2~l，000個/mm2，進而較佳為〇 5個/mm2〜5〇〇個/ mm2 ° 於本發明之玻璃基板中，貫通孔之截面面積亦可自一開 口向另一開口單調遞減。利用圖1對該特徵進行說明。 於圖1中，表示本發明之玻璃基板中所形成之貫通孔之 放大剖面圖之一例。 如圖1所示’本發明之玻璃基板丨包含第1表面la與第2表 面lb。又，玻璃基板丨包含貫通孔5。該貫通孔5係自設置 於玻璃基板1之第1表面la之第1開口 8a貫通至設置於第2表 面1 b之第2開口 8b為止。 貫通孔5之第1開口 8a處之直徑為L1，第2開口 8b處之直 徑為L2。 貫通孔5具有「錐角」α。此處’所謂錐角α，係指玻璃 基板1之第1表面la(及第2表面lb)之法線（圖中之虛線）與貫 15579J.doc -11 · 201200284 通孔5之壁面7所成之角度。 再者’於圖1中’將玻璃基板丨之法線與貫通孔5之右側 之壁面7a所成之角度設為α，於該圖中，玻璃基板！之法線 與貫通孔之左側之面7b所成之角亦同樣為錐角α，通常右 側之錐角α與左側之錐角α表示大致相同之值。右側之錐角 α與左側之錐角α之差亦可有30%左右。 於本發明之玻璃基板中’錐角α較佳為處於〇.丨0〜2〇0之範 圍内。於玻璃基板之貫通孔具有上述錐角α之情形時，採 用打線接合法時，可快速地將金屬線自玻璃基板丨之第丄表 面la側插入至貫通孔5之内部。又，藉此可經由玻璃基板 之貫通孔而將於玻璃基板之上下所積層之印刷電路基板之 導電層彼此更容易且更確實地連接。錐角α尤佳為〇 5。〜1〇。 之範圍。 如後所述，於本發明之玻璃基板之製造方法中，可任意 調整錐角α。 再者，於本申請案中，玻璃基板1之貫通孔5之錐角〇^可 以下述方式求出： 求出玻璃基板1之第i表面la側之開口 8a處之貫通孔5之 直徑L1 ; 求出玻璃基板1之第2表面丨b側之開口 8b處之貫通孔5之 直徑L2 ; 求出玻璃基板1之厚度； 假設於貫通孔5整體，錐角α均一，根據上述測定值而算 出錐角α。 155791.doc •12- 201200284 本發明之玻璃基板之對於準分子雷射光之波長之吸收係 數較佳為3 cm-i以上。於此情形時，貫通孔之形成變得更 容易。為了更有效地吸收準分子雷射光，玻璃基板中之鐵 (Fe)之含有率較佳為2〇質量ppm以上，更佳為〇〇1質量％以 上，進而較佳為〇.〇3質量。/。以上，尤佳為〇 〇5質量％以上。 另一方面，於Fe之含有率較多之情形時，有著色變強，雷 射加工時之位置對準變難之問題。Fe之含有率較佳為〇 2 質量°/〇以下，更佳為〇.丨質量％以下。 本發明之玻璃基板係較佳地用於半導體用裝置構件，更 詳細而言為多層電路基板之絕緣層、晶圓級封裝體、電極 取出用之貫通扎、仲介層等用途。 (關於本發明之玻璃基板之製造方法） 其次，對具有如上所述之特徵之本發明之玻璃基板之製 造方法進行說明。 通常，即便對玻璃板僅照射雷射光，亦難以形成健全之 貫通孔。若提高雷射光之照射通量（能量密度），則雖亦有 時可形成貫通孔，但由於玻璃為脆性材料，故而通常於此 情形時’玻璃產生龜裂或變形。又，若減弱雷射光之照射 通量，則無法形成貫通孔，且根據雷射光之種類或板狀玻 璃之性狀之不同，亦有時會產生龜裂。 本案發明者反覆進行努力研究，發現根據特定之雷射光 與特定之玻璃基板之組合的不同，可使玻璃基板不產生龜 裂而形成包含貫通孔之玻璃基板，從而完成本發明。 即’於本發明中，作為雷射光，選擇準分子雷射光，作 155791.doc 201200284 為玻璃基板，使用厚度為0.01 mm〜5 mm、50°c至300°c下 之平均熱膨脹係數處於1〇χ10·7/Κ〜5〇χ10·7/Κ之範圍内、 Si02含量為50 wt°/〇〜70 wt%者。藉此，可於玻璃基板恰當 地形成微細之複數個貫通孔。 又，本案發明者發現了形成包含貫通孔之玻璃基板時之 合適之照射通量條件。即，若以使照射通量、照射數及板 狀玻璃基板之厚度之乘積成為一定範圍内之方式對玻璃基 板照射準分子雷射光，則可形成更恰當之貫通孔》進而， 藉由調整照射通量，可形成具有所期望之錐角之貫通孔。 以下，參照圖2及圖3，對本發明之玻璃基板之製造方法 進行詳細說明。 於圖2中，表示製造本發明之玻璃基板時所使用之製造 裝置構成圖之一例。 如圖2所示’製造裝置100包含準分子雷射光產生裝置 110、遮罩130及平台140»於準分子雷射光產生裝置no與 遮罩1 3 0之間’配置有複數個反射鏡1 5 0〜1 5 1及均化器 160。又’於遮罩130與平台14〇之間，配置有其他之反射 鏡152及投影透鏡170。 遮罩130不包含貫通開口’且係具有於相對於雷射光為 透明之基材（透明基材）上配置有經圖案化之反射層之構 成。因此’於遮罩130中’於透明基材上設置有反射層之 位可阻斷雷射光’未設置反射層之部位可使雷射光穿 透。 於平台140上配置有成為被加工對象之玻璃基板12〇。藉 15579l.doc 201200284 由二維地或三維地移動平台140 ’可將玻璃基板ι2〇移動至 任意之位置。 於上述製造裝置100之構成中，自準分子雷射光產生裝 置110產生之準分子雷射光190係通過第1反射鏡15〇、均化 器160及第2反射鏡151，入射至遮罩13〇。再者，準分子雷 射光190於通過均化器160時被調整為均一之強度之雷射 光。 如上所述，遮罩130係於相對於雷射光為透明之基材上 具有反射層之圖案。因此，準分子雷射光19〇係以與反射 層之圖案（更詳細而言為未設置反射層之部分）相對應之圖 案自遮罩130輻射。 其後，穿透遮罩130之雷射光19〇藉由第3反射鏡152調整 方向，藉由投影透鏡170縮小投影，而入射至平台j 4〇上所 指示之玻璃基板120上。藉由該雷射光19〇，而於玻璃基板 120同時形成複數個貫通孔。 亦可於玻璃基板120形成貫通孔後，使玻璃基板丨2〇於平 台140上移動，繼而再次對玻璃基板i 2〇照射準分子雷射光 。藉此，可於玻璃基板12〇之表面之所期望之部分形成 所期望之貫通孔。即，於本方法中可採用公知之步進重複 再者，投影透鏡170較佳為可對玻璃基板12〇之表面之加 工區域整體照射準分子雷射光19〇，而一次形成貫通孔。 然而’通常難以獲得可一次形成全部貫通孔之照射通量。 因此，實際上利用投影透鏡170對通過遮罩13〇之準分子雷 155791.doc 15 201200284 射光190進行縮小投影，藉此增加於玻璃基板丨2〇之表面之 準分子雷射光190之照射通量，從而確保為了形成貫通孔 所必需之照射通量。 若藉由利用投影透鏡170之縮小投影’而將於玻璃基板 120之表面之準分子雷射光19〇之戴面面積相對於剛通過遮 罩130後之準分子雷射光19〇之截面面積設為1/1〇，則可將 照射通量設為10倍。藉由使用縮小率為1/1〇之投影透鏡， 將準分子雷射光之截面面積設為1/1〇〇，可將於玻璃基板 120之表面之準分子雷射光之照射通量設為剛自產生裝置 110產生後之準分子雷射光之100倍。 於圖3中，概略地表示本發明之半導體裝置貫通電極形 成用之玻璃基板之製造方法之流程之一例。 如圖3所示，本發明之半導體裝置貫通電極形成用之玻 璃基板之製造方法包含如下步驟： (1) 準備厚度為0.01 mm〜5 mm、Si〇2含量為5〇 wt%~7〇 wt%，50°C至300°C下之平均熱膨脹係數為1〇χ1〇-7/κ〜5〇χ 10_7/Κ之玻璃基板（步驟S110); (2) 將上述玻璃基板配置於來自準分子雷射光產生裝置 之準分子雷射光之光程上（步驟S120); (3) 於上述準分子雷射光產生裝置與上述玻璃基板之間 之上述光程上配置不包含貫通開口之遮罩（步驟sn〇);及 (4) 自上述準分子雷射光產生裝置，沿著上述光程對上 述玻璃基板照射上述準分子雷射光，藉此於上述玻璃基板 形成上述貫通孔（步驟S140)。 155791.doc 201200284 以下，對各步驟進行說明。 (步驟S110) 最初，準備厚度為0.01 mm〜5 mm以下、Si〇2含量為5〇 wt〇/〇 一 7〇 wt%，50°C至30(rc下之平均熱膨脹係數為ι〇χΐ〇_7/κ〜 5 0 X 10 /Κ之玻璃基板。玻璃基板之較佳組成等係如上所 述。 (步驟S120) 繼而，將上述玻璃基板配置於來自準分子雷射光產生裝 置之準分子雷射光之光程上。如圖2所示，亦可將玻璃基 板120配置於平台140上。 作為自準分子雷射光產生裝置Π0所輕射之準分子雷射 光19〇 ,若振盪波長為250 nm以下，則可使用。就輸出之 觀點而言，較佳為KrF準分子雷射（波長為248 nm)、ArF準 分子雷射（193 nm)或&準分子雷射（波長為157 nm)。就操 作與玻璃之吸收之觀點而言，更佳為ArF準分子雷射。 又，作為準分子雷射光19()，於使用脈衝寬度較短者之 隋形時，於玻璃基板丨2〇之照射部位之熱擴散距離變短， 從而可抑制對玻璃基板之熱影響。就該觀點而言，準分子 雷射光190之脈衝寬度較佳為1〇〇 nsec，更佳為5〇以 下’進而較佳為30 nsec以下。 又，準分子雷射光190之照射通量較佳為設為1 J/cm2以 上更佳為没為2 J/cm2以上。若準分子雷射光丨9〇之照射 通量過低，則有無法引起剝蝕之虞，且存在難以於玻璃基 板形成貫通孔之可能性。另一方面，若準分子雷射光190 155791.doc 17 201200284 之照射通量超過20 J/cm2，則有容易於玻璃基板產生龜裂 或裂紋之傾向。準分子雷射光1 90之照射通量之較佳範圍 雖亦根據使用之準分子雷射光190之波段或所加工之玻璃 基板之種類等而有所不同，但於KrF準分子雷射（波長為 248 nm)之情形時’較佳為2〜20 J/cm2。又，於ArF準分子 雷射（波長為193 nm)之情形時，較佳為1〜15 J/cm2。 再者’只要無特別說明，則認為準分子雷射光19〇之照 射通量之值係指於所加工之玻璃基板之表面之值。又，上 述照射通量係指於加工面上使用能量計所測定之值。 (步驟S130) 繼而’於上述準分子雷射光產生裝置11〇與上述玻璃基 板120之間’配置不包含貫通開口之遮罩13〇。 如上所述，遮罩130係藉由於透明基材上形成反射層之 圖案而構成。透明基材只要對於雷射光19〇為透明，則材 質並無特別限定。透明基材之材質係例如亦可為合成石 英、熔融石英、PYREX(註冊商標）、鹼石灰玻璃、無鹼玻 璃、硼矽玻璃等。 另一方面，反射層只要具有有效地阻斷雷射光19〇之性 質’則材質並無特別限定。反射層亦可係例如以鉻、銀、 鋁、及/或金等金屬’或介電質多層膜構成。作為介電質 多層膜，例如可列舉 Si〇2、Ti〇2、Hf02、Ta2〇5、Al2〇3、 Cr203、MgF2、MgO及 Zr02 等。 又’遮罩13〇之大小、遮罩l3〇之反射層圖案之形狀、配 置％並無特別限定。 155791.doc •18· 201200284 (步驟S140) 繼而’經由遮罩130，自準分子帝私止 干刀于田射先產生裝置110對玻 璃基板120照射準分子雷射光19〇。 於對玻璃基板120照射準分子雷射光19〇時，藉由調整準 分子雷射光之重複頻率與照射時間，可調整照射數(照射 數=重複頻率x照射時間）。 較佳為以照射通量(W)、照射數(次)及玻璃基板之厚 度（mm)之乘積成為1000〜30000之方式對玻璃基板12〇照射 準分子雷射光190。 該範圍雖亦取決於玻璃基板120之種類或性狀（尤其推斷 為與玻璃轉移溫度Tg相關），但大體上更佳為 20,000,更佳為2,〇00〜15,000，進而較佳為3〇〇〇〜1〇〇〇〇。 其原因在於：若照射通量與照射數之乘積為上述範圍，則 更難形成龜裂。照射通量較佳為1〜20 J/cm2。 又，若準分子雷射光之照射通量較大，則有錐角α變小 之傾向。反之’若照射通量較小，則有錐角α變大之傾 向。因此，藉由調整照射通量，可獲得具有所期望之錐角 α之貫通孔之玻璃基板。錐角α亦可為0丨。〜2〇。之範圍。 藉由以上之步驟，可製造半導體裝置貫通電極形成用之 玻璃基板。 再者，通常半導體電路製作晶圓大小為6〜8英时左右。 又’於如上所述藉由投影透鏡170進行縮小投影之情形 時’於玻璃基板之表面之加工區域通常為數111111見方左 右。因此，為了對玻璃基板120之加工希望區域整體照射 155791.doc •19· 201200284 準分子雷射光，必需於-個部位之加工結束後，移動準分 子雷射光或移動玻璃基板120。至於為哪一種，較佳為使 玻璃基板12〇相對於準分子雷射光而移動。其原因在於無 需驅動光學系統。 又，若對玻璃基板120照射準分子雷射光，則有時會產 生碎屑（飛散物）。又，若該碎屬堆積於貫通孔之内部，則 有時所加工之玻璃基板之品質或加工率會劣化。因此，亦 可與向玻璃基板之雷射照射之同時，藉由抽吸或吹飛處理 而除去碎屑。 實施例 其次’對本發明之實施例進行說明。 使用圖2所示之製造裝置，按照以下之順序製造包含複 數個貫通孔之玻璃基板。 最初，如圖2所示，配置準分子雷射光之產生裝置n〇。 再者，於準分子雷射光之產生裝置11〇中使用LPX Pro 3〇5 (Coherent公司製造）^該裝置係可產生最大脈衝能：〇 6 J、重複頻率：50 Hz、脈衝寬度：25 ns、產生時之光束大 小：10 mmx24 mm、振盪波長：nm之ArF準分子雷射 光之裝置。 繼而，如圖2所示，將厚度為〇.3 mm、熱膨脹係數為 38χ1〇·7/Κ之玻璃基板120(AN100，旭确子公司製造，Si02 含量為59 wt%)配置於平台140上。玻璃基板120可於平台 140之上表面移動至任意之位置。 繼而’於準分子雷射光之產生裝置110與玻璃基板120之 155791.doc •20· 201200284 間，配置有遮罩130。於圖4中，概略地表示所使用之遮罩 130之構成。 如圖4所不’本實施例中所使用之遮罩n〇係於縱2〇 mrnx榼40 mm、厚度為1.5 mm之合成石英基板132之第1表 面134之一部分包含鉻（Cr)之蒸鍍膜135者。心之蒸鍍膜135 係设置於合成石英基板132之第1表面134之中央之縱1〇 mmx橫24 mm之區域。 又，如圖4之右側所示，Cr之蒸鍍膜135具有將直徑為 0.5 mm之圓形之Cr非蒸鍍部137縱橫二維地排列而成之排 列圖案。Cr非蒸鑛部13 7係縱橫均以1.〇 mm間距，縱向排 列9個，橫向排列23個。201200284 6. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method of manufacturing a glass substrate for forming a through electrode of a semiconductor device. [Prior Art] In order to respond to the demand for higher density of printed circuit boards with high density mounting, a multilayer printed circuit board in which a plurality of printed circuit boards are laminated has been developed. In the multilayer circuit board, a fine through-hole having a diameter of about 100 μm or less is formed in a resin-made insulating layer, and plating is performed on the inside of the insulating layer, and the printed circuit board is laminated between the printed circuit boards. The conductive layers are electrically connected to each other. As a method of forming the through hole more easily, Patent Documents 丨 and 2 disclose a method of irradiating the insulating layer with laser light through a mask in which a plurality of through holes are formed. According to this method, a plurality of through-holes can be simultaneously formed in the insulating layer made of resin, so that a plurality of through-holes (through-holes can be formed more easily), and in response to the request for miniaturization and thinning of the 1C wafer In recent years, wafer level packaging (WLP, Wafer Level package) technology has been widely used. It can suppress the size of the package to (4) the same technology as the wafer, and form the surface of the wafer of 1C, perform rewiring, solder bump processing, resin sealing, etc., which are required for the semiconductor package, and then cut by adding Wei makes each chip singular. In the WLP technology, the resin is sealed by a dicing process, and in recent years, in terms of reliability, the use of anodic bonding technology or the like is followed.矽上155791.doc 201200284. In the process of further increasing the requirements for miniaturization, high speed, and low power consumption of semiconductor devices, a system including a plurality of LSIs (Large Scale Integrated circuit) is housed in one package. The development of three-dimensional SiP technology combined with SiP 'System-in-Package technology and three-dimensional installation technology is also developing. At this time, the wire bonding technique cannot correspond to the fine pitch, and thus it is necessary to use a relay substrate called an interposer using a through electrode. CITATION LIST Patent Literature Patent Literature 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The insulating layer is affected by warpage or deformation, so the positioning accuracy is deteriorated, and it is not suitable for high-density mounting. Therefore, it is desirable to use a material for replacing the above-mentioned resin insulating layer for the substrate material. For example, research has been conducted using ruthenium as a material for a via layer containing a through electrode. The reason for this is that the microporous processing can be performed relatively easily by dry etching. However, in order to ensure insulation, it is necessary to insulate the inner wall of the through hole. Further, it is expected that the above-described insulation treatment will become more difficult in the future as the size of the through holes is made finer. Therefore, it is required to use an insulating glass substrate instead of the above-mentioned resin insulating layer. For example, if a plurality of fine through-holes 155791.doc 201200284 holes can be formed on the glass substrate, the above-mentioned glass substrate can be used as the intermediate layer. However, it is extremely difficult to appropriately form a plurality of fine through holes in the glass substrate even when the glass substrate is irradiated with the laser light under the same conditions as the through hole formed in the resin insulating layer. Glass has the potential to be less processed than the resin. Further, since the glass is a brittle material, it is extremely difficult to form a fine through hole without causing cracks or deformation of the glass substrate as long as the laser processing is not performed under appropriate conditions. On the other hand, it is considered that a plurality of through holes can be simultaneously formed on the glass substrate by using a wet etching technique or a dry etching technique. However, in this case, steps become complicated, processing time becomes long, and there is a possibility that problems such as waste liquid treatment are generated. The present invention has been made in view of the above problems, and an object of the present invention is to provide a semiconductor device through electrode which can appropriately form a plurality of through holes by irradiating laser light onto a glass substrate without causing cracks or deformation of the glass substrate. A method of producing a glass substrate for forming. Means for Solving the Problems The present invention provides a method for producing a glass substrate for forming a through electrode of a semiconductor device. The method for producing a glass substrate for forming a through-electrode device, comprising the following steps: (1) preparing a thickness of 〇.〇1 mm~5 _, and a content of si〇2 of 5〇wt%~7〇 a glass substrate having an average thermal expansion coefficient of from 50 C to 300 C of 1 〇χι -7 / κ 〜 5 〇χ 1 〇 -7 / κ; (2) arranging the glass substrate from the excimer laser light generating device 155791 .doc 201200284 on the optical path of the excimer laser light; (3) arranging a mask not including the through opening in the optical path between the excimer laser light generating device and the glass substrate; and (4) from the above The excimer laser light generating device irradiates the glass substrate with the excimer laser light along the optical path, and forms a through hole in the glass substrate. [2] The method of [1], wherein the mask that does not include the through opening comprises a substrate transparent to the excimer laser light and a patterned reflective layer disposed on a surface of the substrate. [3] The method according to [2] wherein the reflective layer contains at least one metal selected from the group consisting of Cr (chromium), Ag (silver), A1 (aluminum), and Au (gold). [4] The manufacturing method of [2] or [3] wherein the pattern of the reflective layer includes a portion in which the reflective layer is provided and a portion having a substantially circular shape in which the reflective layer is not provided. [5] The manufacturing method according to any one of [1] to [4] wherein the step of irradiating the excimer laser light comprises irradiating the excimer laser light having an irradiation flux of 1 to 2 〇j/cm 2 to the above irradiation The product of the mass (J/cm2), the number of irradiations (times), and the thickness (mm) of the glass substrate described above is 1, 〇〇〇3 〇, and the illuminating step is performed. [6] The manufacturing method according to any one of [1] to [5] wherein the glass substrate is formed into a taper shape having a taper angle of 0.1 to 20° by the step of irradiating the excimer laser light. Through hole. [7] The manufacturing method according to any one of [1] to [6] wherein the excimer laser 155791.doc 201200284 emits light of any one of a KrF laser, an ArF laser or a & laser. According to the present invention, it is possible to provide a glass for forming a through-electrode of a half-V body device in which a plurality of through-holes are appropriately formed by irradiating a glass substrate with laser light without causing cracks or deformation of the glass substrate. Method of Manufacturing Substrate 0 [Embodiment] Hereinafter, the present invention will be described with reference to the drawings. (The glass substrate obtained by the manufacturing method of the present invention) First, the glass substrate obtained by the method for producing a glass substrate for forming a through-electrode of the semiconductor device of the present invention will be described. The glass substrate for forming a through-electrode of the semiconductor device obtained by the production method of the present invention (hereinafter also referred to simply as "the glass substrate of the present invention") has a thickness of 0.01 mm or more and 5 mm or less, and 5 〇e>c to 3 The average coefficient of thermal expansion (hereinafter, also referred to as "thermal expansion coefficient") below it is l〇xl〇-7/K or more and 5〇Χΐ〇·7/Κ or less. Further, the SiO2 content of the glass substrate of the present invention is in the range of 50 wt% to 70 Wt%. It is considered that the usual glass substrate cannot be used as the insulating layer of the multilayer circuit substrate, the glass for WLP or the intermediate layer as described above depending on its properties. The reason for this is that a case where a glass insulating layer is laminated on a germanium wafer and a germanium wafer is bonded to a glass insulating layer, etc., the insulating layer or the WLP glass is peeled off from the stone wafer, or the wafer turtle is conceived. song. Further, in the case where the glass is used as the intermediate layer, there is a risk of warpage of the part due to the difference in thermal expansion between the wafer containing the crucible and the intercalation layer of the glass. 15579I.doc 201200284 In contrast, the thermal expansion coefficient of the glass substrate of the present invention is within the above range. Therefore, even if the glass substrate of the present invention is laminated on a germanium wafer, or vice versa, a wafer containing germanium is laminated on the upper portion of the glass substrate of the present invention, it is difficult to cause peeling between the glass substrate and the germanium wafer. , or the wafer is deformed. In particular, the thermal expansion coefficient of the glass substrate is preferably 25 X 1 0·7/Κ or more and 45 χ1〇-7/Κ or less, more preferably 3〇χ10-7/Κ or more and 4〇xl 〇-7/Κ or less. . In this case, peeling and/or deformation can be further suppressed. Further, when it is necessary to match a resin substrate such as a mother board, the thermal expansion coefficient of the glass substrate is preferably 3 5 X 1 0·7/Κ or more. . Further, in the present invention, '50 ° C to 30 (the average thermal expansion coefficient at TC is a value measured by using a differential thermal dilatometer (TMA) and determined according to JIS R3102 (1995). The glass substrate of the present invention. The thickness is 〇.〇1 mm or more and 5 mm or less. The reason is that if the thickness of the glass substrate is thicker than 5 mm, the formation of the through holes takes time 'if it is less than 〇1 mm, it will be generated. The thickness of the glass substrate of the present invention is more preferably 0.02 to 3, still more preferably 0.02 to 1 mm. The thickness of the glass substrate is preferably 〇〇5 claws or more and 0.4 mm or less. The glass substrate of the present invention. The Si〇2 content is 50 wt·5/ or more and 70 wt% or less. When the Si〇2 content is more than this, when the through-holes are formed, cracks are likely to occur on the back surface of the glass substrate. Further, Si〇 is preferable. 2 The content is 55 wt% or more and 62 wt%. It is known that the cracking behavior of glass is different from the glass with more 〇2 content and the glass of less 155791.doc 201200284, and the content of Si〇2 is extremely high. The glass is easily cracked by a conical shape due to contact with an object, etc. In the surface, the glass having a very small Si〇2 content is liable to be cracked by contact with an object, etc. Therefore, it is possible to prevent cracks or cracks from being generated by controlling the Si〇2 content in the glass substrate. In the case where the total content of sodium (Na) and potassium (K) is preferably 3.5% by mass or less in terms of oxide, the total content of the substrate is preferably 3.5% by mass or less. The coefficient of thermal expansion exceeds 5 〇 xl (the probability of T7/K becomes high. The total content of sodium (Na) and potassium (K) is more preferably 3% by mass or less. In the case where the glass substrate of the present invention is used for a high frequency device In the case where a plurality of through holes of 5 μm or less are formed at a distance of 200 μm or less, for example, when a plurality of through holes are formed at a very fine pitch, the glass substrate is preferably an alkali-free glass. The term "alkali-free glass" means a glass having a total amount of alkali metal of less than 0.1 mass% in terms of oxide. The dielectric constant of the glass substrate of the present invention at 25 ° C and 1 MHz is preferably 6 or less. Further, 25 ° C, i mHz of the glass substrate of the present invention The dielectric loss is preferably 0.005 or less. The dielectric constant and the dielectric loss are small, and excellent device characteristics can be exhibited. Specific examples of the glass substrate include AN1 bismuth glass (manufactured by Asahi Glass Co., Ltd.) and EAGLE. Glass (manufactured by Corning), SW glass (manufactured by Asahi Glass Co., Ltd.), etc. The thermal expansion coefficient of these glass substrates is 丨〇x丨〇-7/κ or more and 5〇χ1〇·7/Κ or less. Features of ΑΝ100 glass It is based on the coefficient of thermal expansion of 3 8 χ丨〇 -7 / κ without 155791.doc 201200284 alkali glass, the total content of Na20 and Κ20 is less than 0.1 wt%. Further, the content of Fe in AN100 glass was 0.05 wt%. The thermal expansion coefficient of the SW glass is 36 χ 10·7 / Κ, the total content of Na 2 〇 and K 20 is 3 wt %, and the content of Fe is 50 mass ppm. The glass substrate of the present invention comprises a plurality of through holes. Each through hole may also be circular. In this case, the diameter of the through hole is also different depending on the use of the glass substrate of the present invention, but it is usually preferably in the range of 5 μm to 5 μm. In the case where the glass substrate of the present invention is used as the insulating layer of the multilayer circuit substrate as described above, the diameter of the through hole is more preferably 0.01 mm to 0.2 mm, and further preferably 0.02 mm to 〇. .i mm »In addition, wafer-level packaging (WLP) technology can be used to laminate the glass substrate of the present invention on a wafer to form an IC wafer for a pressure sensor or the like, and in this case, for inhalation The diameter of the through hole of the air is preferably 〇.丨~〇. 5 mm, and further preferably 〇.2~〇.4 mm. Further, in this case, the diameter of the through hole for electrode extraction different from the air hole is preferably 〇1 to 〇2 mm, and more preferably 〇2 to 〇1 mm. In particular, in the case of being used as a through electrode such as a secondary layer, the diameter of the through hole is more preferably 〇5 to 〇75 mm, and still more preferably 0.01 to 0.05 mm. Further, as will be described later, in the glass substrate of the present invention, the diameter of the through hole of the circular shape may be different from the diameter of the other opening surface. In this case, the "diameter of the through hole" means the diameter of the larger of the two open faces. The ratio (ds/dl) of the larger diameter (di) to the smaller diameter (ds) is preferably 〇'2 to 0.99, more preferably 〇.5 to 〇9〇. '5579l.doc 201200284 In the glass substrate of the present invention, the number density of the through holes is also different depending on the use of the glass substrate of the present invention, but is usually in the range of 〇1/mm2 to 10,000/mm. When the glass substrate of the present invention is used as the insulating layer of the multilayer circuit substrate as described above, the number density of the through holes is preferably in the range of 3 / mm 2 to 10,000 / mm 2 , more preferably a claw 2 to 100 / mm2 range. Moreover, when the glass substrate of the present invention is laminated on a wafer by using a wafer level package (WLp) technology to form a 1C wafer for a pressure sensor, the number density of the through holes is preferably It is 1 / mm to 2 5 / mm, more preferably 2 / mm2 ~ 10 / mm2. In the case where the interlayer is used as a through-electrode, the number density of the through holes is preferably from 0.1/mm2 to 1,000,000/mm2, and further preferably from 〇5/mm2 to 5〇〇/mm2 ° In the glass substrate of the present invention, the cross-sectional area of the through hole may be monotonously decreased from one opening to the other. This feature will be described using FIG. 1. Fig. 1 shows an example of an enlarged cross-sectional view of a through hole formed in a glass substrate of the present invention. As shown in Fig. 1, the glass substrate 本 of the present invention comprises a first surface 1a and a second surface lb. Further, the glass substrate 丨 includes the through holes 5. The through hole 5 is formed from the first opening 8a provided on the first surface la of the glass substrate 1 to the second opening 8b provided in the second surface 1b. The diameter of the first opening 8a of the through hole 5 is L1, and the diameter of the second opening 8b is L2. The through hole 5 has a "taper angle" α. Here, the term "cone angle α" refers to the normal line (the dotted line in the figure) of the first surface la (and the second surface lb) of the glass substrate 1 and the wall surface 7 of the through hole 5 of 15579J.doc -11 · 201200284 In terms of perspective. Further, in Fig. 1, the angle formed by the normal line of the glass substrate and the wall surface 7a on the right side of the through hole 5 is α, and in the figure, the glass substrate! The angle formed by the normal line and the left side surface 7b of the through hole is also the taper angle α, and generally the right side taper angle α and the left side taper angle α indicate substantially the same value. The difference between the taper angle α on the right side and the taper angle α on the left side may also be about 30%. The 'cone angle α' in the glass substrate of the present invention is preferably in the range of 〇.丨0 to 2〇0. When the through hole of the glass substrate has the above-described taper angle α, when the wire bonding method is employed, the metal wire can be quickly inserted into the through hole 5 from the side of the second surface of the glass substrate. Further, the conductive layers of the printed circuit board stacked on the glass substrate can be connected to each other more easily and more reliably via the through holes of the glass substrate. The taper angle α is particularly preferably 〇 5. ~1〇. The scope. As will be described later, in the method for producing a glass substrate of the present invention, the taper angle α can be arbitrarily adjusted. Further, in the present application, the taper angle 贯通 of the through hole 5 of the glass substrate 1 can be obtained as follows: The diameter L1 of the through hole 5 at the opening 8a on the i-th surface la side of the glass substrate 1 is obtained. The diameter L2 of the through hole 5 at the opening 8b on the second surface 丨b side of the glass substrate 1 is obtained. The thickness of the glass substrate 1 is determined. It is assumed that the taper angle α is uniform in the entire through hole 5, and based on the above measured value. Calculate the taper angle α. 155791.doc • 12- 201200284 The glass substrate of the present invention preferably has an absorption coefficient of 3 cm-i or more for the wavelength of excimer laser light. In this case, the formation of the through holes becomes easier. In order to absorb excimer laser light more efficiently, the content of iron (Fe) in the glass substrate is preferably 2 Å by mass or more, more preferably 〇〇 1% by mass or more, and still more preferably 〇. 〇 3 by mass. /. More preferably, it is 5% by mass or more. On the other hand, when the content ratio of Fe is large, the coloring becomes strong, and the alignment at the time of laser processing becomes difficult. The content of Fe is preferably 〇 2 mass ° / 〇 or less, more preferably 〇 丨 mass % or less. The glass substrate of the present invention is preferably used for a device member for a semiconductor, and more specifically, an insulating layer of a multilayer circuit substrate, a wafer-level package, a through-hole for electrode extraction, and an intermediate layer. (Method for Producing Glass Substrate of the Present Invention) Next, a method for producing a glass substrate of the present invention having the above characteristics will be described. In general, even if the glass plate is irradiated with only laser light, it is difficult to form a sound through hole. When the irradiation flux (energy density) of the laser light is increased, the through hole may be formed in some cases. However, since the glass is a brittle material, in general, the glass is cracked or deformed. Further, if the irradiation flux of the laser light is weakened, the through hole cannot be formed, and cracks may occur depending on the type of the laser light or the properties of the plate glass. The inventors of the present invention have conducted intensive studies and found that the glass substrate can be formed into a through-hole without causing cracks depending on the combination of the specific laser light and the specific glass substrate. That is, in the present invention, as the laser light, excimer laser light is selected as 155791.doc 201200284 as a glass substrate, and the average thermal expansion coefficient at a thickness of 0.01 mm to 5 mm and 50 ° c to 300 ° c is 1 〇. Χ10·7/Κ~5〇χ10·7/Κ, the SiO2 content is 50 wt ° / 〇 ~ 70 wt%. Thereby, a plurality of fine through holes can be appropriately formed on the glass substrate. Further, the inventors of the present invention have found suitable irradiation flux conditions for forming a glass substrate including through holes. In other words, when the glass substrate is irradiated with excimer laser light so that the product of the irradiation flux, the number of irradiations, and the thickness of the plate-like glass substrate is within a certain range, a more appropriate through-hole can be formed, and further, the irradiation can be adjusted. Through the flux, a through hole having a desired taper angle can be formed. Hereinafter, a method of manufacturing a glass substrate of the present invention will be described in detail with reference to Figs. 2 and 3 . Fig. 2 shows an example of a configuration of a manufacturing apparatus used in the production of the glass substrate of the present invention. As shown in FIG. 2, the manufacturing apparatus 100 includes an excimer laser light generating device 110, a mask 130, and a platform 140» between the excimer laser light generating device no and the mask 130, and a plurality of mirrors 15 are disposed. 0 to 1 5 1 and homogenizer 160. Further, between the mask 130 and the stage 14A, other mirrors 152 and projection lenses 170 are disposed. The mask 130 does not include a through opening ‘and has a patterned reflective layer disposed on a substrate (transparent substrate) that is transparent with respect to laser light. Therefore, the position of the reflective layer disposed on the transparent substrate in the mask 130 blocks the laser light. The portion where the reflective layer is not provided allows the laser light to penetrate. A glass substrate 12A to be processed is placed on the stage 140. The glass substrate ι2 can be moved to any position by moving the platform 140' two-dimensionally or three-dimensionally by means of 15579l.doc 201200284. In the configuration of the manufacturing apparatus 100 described above, the excimer laser light 190 generated by the excimer laser light generating device 110 passes through the first mirror 15A, the homogenizer 160, and the second mirror 151, and enters the mask 13〇. . Further, the excimer laser light 190 is adjusted to a uniform intensity of the laser light as it passes through the homogenizer 160. As described above, the mask 130 is patterned with a reflective layer on a substrate that is transparent with respect to the laser light. Therefore, the excimer laser light 19 is radiated from the mask 130 in a pattern corresponding to the pattern of the reflective layer (more specifically, the portion where the reflective layer is not provided). Thereafter, the laser light 19 through the mask 130 is adjusted by the third mirror 152, and is projected by the projection lens 170 to be incident on the glass substrate 120 indicated on the stage j 4 . A plurality of through holes are simultaneously formed in the glass substrate 120 by the laser light 19 。. After the through holes are formed in the glass substrate 120, the glass substrate 2 is moved over the stage 140, and then the glass substrate i 2 is irradiated with excimer laser light. Thereby, a desired through hole can be formed in a desired portion of the surface of the glass substrate 12A. That is, in the present method, a known step repeat can be employed. Further, the projection lens 170 preferably irradiates the entire processing area of the surface of the glass substrate 12 with the excimer laser light 19 〇, and forms the through hole at a time. However, it is often difficult to obtain an irradiation flux that can form all of the through holes at one time. Therefore, the projection lens 170 is actually used to reduce the projection of the excimer laser 155791.doc 15 201200284 by the mask 13 , thereby increasing the illumination flux of the excimer laser light 190 on the surface of the glass substrate 丨 2 〇 2 . Thereby ensuring the flux of radiation necessary to form the through holes. The cross-sectional area of the excimer laser light 19 将于 on the surface of the glass substrate 120 relative to the area of the excimer laser light 19 刚 just after passing through the mask 130 is set by using the reduced projection ' of the projection lens 170'. 1/1〇, the irradiation flux can be set to 10 times. By using a projection lens having a reduction ratio of 1/1 ,, the cross-sectional area of the excimer laser light is set to 1/1 〇〇, and the irradiation flux of the excimer laser light on the surface of the glass substrate 120 can be set to just 100 times the excimer laser light generated by the generating device 110. Fig. 3 is a view schematically showing an example of a flow of a method for producing a glass substrate for forming a through electrode of a semiconductor device of the present invention. As shown in FIG. 3, the method for manufacturing a glass substrate for forming a through electrode of the semiconductor device of the present invention comprises the following steps: (1) preparing a thickness of 0.01 mm to 5 mm and a Si〇2 content of 5 〇 wt% to 7 〇wt. %, a glass substrate having an average thermal expansion coefficient of from 50 ° C to 300 ° C of 1 〇χ 1 〇 -7 / κ 〜 5 〇χ 10 _ 7 / ( (step S110); (2) arranging the above glass substrate from an excimer a path of the excimer laser light of the laser light generating device (step S120); (3) arranging a mask not including the through opening in the optical path between the excimer laser light generating device and the glass substrate (step And (4) the excimer laser light generating device irradiates the glass substrate with the excimer laser light along the optical path to form the through hole in the glass substrate (step S140). 155791.doc 201200284 The following describes each step. (Step S110) Initially, the thickness is prepared to be 0.01 mm to 5 mm or less, the content of Si〇2 is 5 〇wt〇/〇-7 〇wt%, and the average thermal expansion coefficient under rc is ι〇χΐ〇 _7/κ~5 0 X 10 / Κ glass substrate. The preferred composition of the glass substrate is as described above. (Step S120) Then, the glass substrate is placed on the excimer laser from the excimer laser light generating device. As shown in Fig. 2, the glass substrate 120 can also be disposed on the platform 140. The excimer laser light 19, which is lightly emitted by the self-excimer laser light generating device Π0, has an oscillation wavelength of 250 nm. The following can be used. From the viewpoint of output, it is preferably a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (193 nm) or an excimer laser (wavelength of 157 nm). From the viewpoint of handling and absorption of glass, it is more preferably an ArF excimer laser. Also, as the excimer laser light 19(), when the shape of the pulse having a shorter pulse width is used, the glass substrate is 丨2〇. The thermal diffusion distance of the irradiated portion is shortened, so that the thermal influence on the glass substrate can be suppressed. The pulse width of the excimer laser light 190 is preferably 1 〇〇 nsec, more preferably 5 Å or less, and further preferably 30 nsec or less. Further, the irradiation flux of the excimer laser light 190 is preferably set to 1 J/cm 2 or more is more preferably 2 J/cm 2 or more. If the irradiation flux of the excimer laser beam 9 过 is too low, there is a possibility that the ablation cannot be caused, and there is a possibility that it is difficult to form a through hole in the glass substrate. On the other hand, if the irradiation flux of the excimer laser light 190 155791.doc 17 201200284 exceeds 20 J/cm 2 , there is a tendency that cracks or cracks are likely to occur on the glass substrate. Excimer laser light 1 90 The preferred range of the amount varies depending on the wavelength of the excimer laser light 190 used or the type of the glass substrate to be processed, but is preferably in the case of a KrF excimer laser (wavelength of 248 nm). It is 2 to 20 J/cm 2 , and in the case of an ArF excimer laser (wavelength of 193 nm), it is preferably 1 to 15 J/cm 2 . Further, as long as there is no special explanation, it is considered to be excimer laser light. The value of the irradiation flux of 19〇 refers to the value of the surface of the processed glass substrate. Further, the irradiation flux is a value measured by an energy meter on the processing surface (step S130), and then 'between the excimer laser light generating device 11A and the glass substrate 120' is disposed without a through opening. The mask 130 is configured by forming a pattern of a reflective layer on the transparent substrate as described above. The transparent substrate is not particularly limited as long as it is transparent to the laser light 19 。. The material may be, for example, synthetic quartz, fused silica, PYREX (registered trademark), soda lime glass, alkali-free glass, borosilicate glass or the like. On the other hand, the material of the reflective layer is not particularly limited as long as it has the property of effectively blocking the laser light 19'. The reflective layer may be formed, for example, of a metal such as chromium, silver, aluminum, and/or gold or a dielectric multilayer film. Examples of the dielectric multilayer film include Si〇2, Ti〇2, Hf02, Ta2〇5, Al2〇3, Cr203, MgF2, MgO, and Zr02. Further, the size of the mask 13 、 and the shape and arrangement % of the reflective layer pattern of the mask 13 are not particularly limited. 155791.doc •18·201200284 (Step S140) Then, the glass substrate 120 is irradiated with the excimer laser light 19 by the self-exortion of the self-existing singularity of the first generation device 110 via the mask 130. When the excimer laser light 19 is applied to the glass substrate 120, the number of irradiations (number of irradiations = repetition frequency x irradiation time) can be adjusted by adjusting the repetition frequency of the pseudo-molecular laser light and the irradiation time. Preferably, the glass substrate 12 is irradiated with excimer laser light 190 such that the product of the irradiation flux (W), the number of irradiations (times), and the thickness (mm) of the glass substrate is 1000 to 30,000. The range depends on the type or properties of the glass substrate 120 (especially inferred to be related to the glass transition temperature Tg), but is generally more preferably 20,000, more preferably 2, 〇00 to 15,000, and still more preferably 3 〇〇. 〇~1〇〇〇〇. This is because if the product of the irradiation flux and the number of irradiations is in the above range, it is more difficult to form cracks. The irradiation flux is preferably from 1 to 20 J/cm 2 . Further, if the irradiation flux of the excimer laser light is large, the taper angle α tends to be small. On the other hand, if the irradiation flux is small, the taper angle α becomes larger. Therefore, by adjusting the irradiation flux, a glass substrate having a through hole having a desired taper angle α can be obtained. The taper angle α can also be 0丨. ~2〇. The scope. According to the above steps, a glass substrate for forming a through-electrode of a semiconductor device can be manufactured. Furthermore, the semiconductor circuit fabrication wafer size is usually about 6 to 8 inches. Further, when the projection lens 170 is used for the reduction projection as described above, the processing area on the surface of the glass substrate is usually about 111111 square. Therefore, in order to irradiate the entire desired region of processing of the glass substrate 120 with 155791.doc • 19· 201200284 excimer laser light, it is necessary to move the quasi-molecular laser light or the moving glass substrate 120 after the processing of the respective portions is completed. As to which one, it is preferable to move the glass substrate 12 〇 with respect to the excimer laser light. The reason is that there is no need to drive the optical system. Further, when the glass substrate 120 is irradiated with excimer laser light, debris (scattering matter) may be generated. Further, if the shredded material is deposited inside the through hole, the quality or processing rate of the processed glass substrate may be deteriorated. Therefore, it is also possible to remove the debris by suction or blowing treatment while irradiating the laser to the glass substrate. EXAMPLES Next, examples of the invention will be described. Using the manufacturing apparatus shown in Fig. 2, a glass substrate including a plurality of through holes was produced in the following order. Initially, as shown in Fig. 2, a device for generating excimer laser light is disposed. Further, LPX Pro 3〇5 (manufactured by Coherent) is used in the excimer laser light generating device 11A. The device can generate a maximum pulse energy: 〇6 J, repetition frequency: 50 Hz, pulse width: 25 ns. , the beam size at the time of generation: 10 mm x 24 mm, oscillation wavelength: nm ArF excimer laser light device. Then, as shown in FIG. 2, a glass substrate 120 (AN100, manufactured by Asahi Kasei Co., Ltd., having a SiO 2 content of 59 wt%) having a thickness of 〇.3 mm and a thermal expansion coefficient of 38χ1〇·7/Κ was disposed on the platform 140. . The glass substrate 120 can be moved to an arbitrary position on the upper surface of the stage 140. Then, a mask 130 is disposed between the excimer laser light generating device 110 and the glass substrate 120 between 155791.doc • 20·201200284. In Fig. 4, the configuration of the mask 130 used is schematically shown. As shown in FIG. 4, the mask used in the present embodiment is a portion of the first surface 134 of the synthetic quartz substrate 132 having a longitudinal 2〇mrnx榼40 mm and a thickness of 1.5 mm, which contains chromium (Cr). Coating 135. The vapor deposited film 135 of the core is disposed in a region of the center of the first surface 134 of the synthetic quartz substrate 132, which is 1 mm in length and 24 mm in width. Further, as shown on the right side of Fig. 4, the vapor deposited film 135 of Cr has a circular pattern in which circular Cr non-vapor-deposited portions 137 having a diameter of 0.5 mm are arranged two-dimensionally. The Cr non-steamed portion 13 7 is vertically and horizontally arranged at a pitch of 1.〇 mm, arranged in a longitudinal direction of nine, and arranged in a lateral direction by 23.
Cr之蒸鍍部135可反射99_9%之ArF準分子雷射光。另一 方面’ Cr非蒸鍍部137可使92°/。之ArF準分子雷射光穿透。 繼而，於遮罩130與玻璃基板120之間，配置有投影透鏡 170。投影透鏡170係焦距為1 〇〇 mm之透鏡，且以與光程上 之遮罩130之距離為11〇〇 mm，與玻璃基板120之加工面（未 與平台140接觸之表面）之距離為11〇 mm之方式而配置。於 此情形時’投影透鏡170之縮小率成為1/1〇，將縮小為1/1〇 之遮罩圖案投影於玻璃基板120上。即，自準分子雷射光 之產生裝置110以10 mm><24 mm之光束大小所產生之準分 子雷射光190係以於到達玻璃基板120之加工面之時間點， 縮小為1.0 mmx2.4 mm之光束大小（面積比=1/1〇〇)。 再者，對玻璃基板120實施雷射加工之前，藉由能量計 測定於玻璃基板120之加工面之準分子雷射光190之照射通 155791.doc •21- 201200284 量。其結果，照射通量係將由於光束傳送系統之損失等而 減少之部分與由於光束縮小而提高之部分相加而最大為i i J/cm2左右。 使用上述製造裝置’對玻璃基板120之加工面照射準分 子雷射光190。再者’進行照射時’藉由衰減器調整雷射 光190’以使於玻璃基板120之加工面之照射通量成為$ J7cm 〇 藉由雷射光190之照射’而於玻璃基板12〇同時形成 9x23=207個貫通孔。直至貫通為止之照射時間為78秒。所 獲得之各貫通孔之直徑為約50 μηι ’間距為約丨〇〇 μηι。 又，貫通孔之數密度為86個/mm2。 根據自雷射光190之照射開始至於玻璃基板12〇形成貫通 孔為止之照射時間’求出照射數。於本實施例中，所使用 之準分子雷射光之重複頻率為50 Hz’直至貫通為止之照 射時間為78秒’因而計算出照射數為3900次（78秒x5〇次 =3900次）。 加工後之玻璃基板120係於外觀上未看到龜裂或變形。 又’玻璃基板120上亦幾乎未發現殘留應力。 如上所述，於本發明中，藉由對玻璃基板照射雷射光而 同時形成複數個貫通孔，因而可容易地製造半導體裝置貫 通電極形成用之玻璃基板。又，所獲得之玻璃基板係積層 於石夕晶圓上’即便與其進行接合，亦難以與矽晶圓剝離。 進而’預想到於用作仲介層時，難以產生變形等問題，從 而發揮優異之裝置特性。 155791.doc •22· 201200284 詳細地且參照特定之實施態樣說明了本發明，但業者應 明白於不脫離本發明之精神與範圍之狀態下可施加各種變 更或修正。 本申凊案係基於2010年4月20日申請之日本專利出願 2010-097226者，並將其内容作為參照引用於此。 產業上之可利用性 本發明之方法係用作如下玻璃基板之製造方法：較佳地 用於半導體用裝置構件，更詳細而言為多層電路基板之絕 緣層、晶圓級封裝體、電極取出用之貫通孔、仲介層等用 途。 【圖式簡單說明】 圖1係本發明之玻璃基板中之貫通孔之放大剖面圖。 圖2係概略地表示本發明之製造方法中所使用之製造裝 置之一構成之圖。 圖3係概略地表示本發明之製造方法之流程之圖。 圖4係概略地表示實施例中所使用之遮罩之俯視圖。 【主要元件符號說明】 1 ' 12〇 玻璃基板 la 第1表面 lb 第2表面 1 C 壁面 5 貫通孔 7、7a、7b 壁面 8a 第1開口 155791.doc -23- 201200284 8b 第2開口 100 製造裝置 110 準分子雷射光之產生裝置 130 遮罩 132 合成石英基板 134 合成石英基板之第1表面 135 蒸鍍膜 137 Cr非蒸鍍部 140 平台 150〜152 反射鏡 160 均化器 170 投影透鏡 190 準分子雷射光 LI 貫通孔之第1開口之直徑 L2 貫通孔之第2開口之直徑 S110〜S140 步驟 α 錐角 155791.doc -24-The vapor deposition portion 135 of Cr can reflect 99 to 9% of ArF excimer laser light. On the other hand, the Cr non-evaporation portion 137 can be 92 ° /. The ArF excimer laser light penetrates. Then, a projection lens 170 is disposed between the mask 130 and the glass substrate 120. The projection lens 170 is a lens having a focal length of 1 〇〇 mm, and the distance from the mask 130 on the optical path is 11 〇〇 mm, and the distance from the processed surface of the glass substrate 120 (the surface not in contact with the platform 140) is Configured in 11 〇mm mode. In this case, the reduction ratio of the projection lens 170 is 1/1 〇, and the mask pattern reduced to 1/1 投影 is projected on the glass substrate 120. That is, the excimer laser light 190 generated by the excimer laser light generating device 110 with a beam size of 10 mm >< 24 mm is reduced to 1.0 mm x 2.4 at the time of reaching the processing surface of the glass substrate 120. Beam size of mm (area ratio = 1/1 〇〇). Further, before the laser processing of the glass substrate 120, the amount of the excimer laser light 190 measured on the processing surface of the glass substrate 120 by the energy meter is 155791.doc • 21 - 201200284. As a result, the irradiation flux is increased by a portion which is reduced by the loss of the beam transfer system or the like, and is increased by a portion which is increased by the reduction of the beam, and is at most about i i J/cm 2 . The processed surface of the glass substrate 120 is irradiated with the pseudo-laser laser light 190 using the above-described manufacturing apparatus. Further, when the irradiation is performed, the laser light 190' is adjusted by the attenuator so that the irradiation flux of the processed surface of the glass substrate 120 becomes $J7cm, and the irradiation of the laser light 190 is simultaneously formed on the glass substrate 12? = 207 through holes. The irradiation time until the penetration was 78 seconds. The diameter of each of the through holes obtained is about 50 μηι ′ and the pitch is about 丨〇〇 μηι. Further, the number density of the through holes was 86/mm2. The number of irradiations is determined based on the irradiation time from the irradiation of the laser light 190 to the formation of the through holes in the glass substrate 12A. In the present embodiment, the repetition frequency of the excimer laser light used was 50 Hz' until the irradiation time was 78 seconds, and thus the number of irradiations was calculated to be 3,900 times (78 seconds x 5 times = 3,900 times). The processed glass substrate 120 was not cracked or deformed in appearance. Further, almost no residual stress was observed on the glass substrate 120. As described above, in the present invention, by irradiating the glass substrate with laser light and simultaneously forming a plurality of through holes, the glass substrate for forming a semiconductor device through the electrode can be easily manufactured. Further, the obtained glass substrate is laminated on the Shihwa wafer. Even if it is bonded to it, it is difficult to peel off from the tantalum wafer. Further, when it is expected to be used as a secondary layer, it is difficult to cause problems such as deformation, and thus excellent device characteristics are exhibited. 155791.doc • 22· 201200284 The present invention has been described in detail with reference to the specific embodiments thereof, and it is understood that various changes or modifications may be made without departing from the spirit and scope of the invention. The present application is based on Japanese Patent Application No. 2010-097226, filed on Apr. INDUSTRIAL APPLICABILITY The method of the present invention is used as a method of manufacturing a glass substrate which is preferably used for a device member for a semiconductor, more specifically, an insulating layer of a multilayer circuit substrate, a wafer level package, and an electrode removal Use for through holes, intermediate layers, etc. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an enlarged cross-sectional view showing a through hole in a glass substrate of the present invention. Fig. 2 is a view schematically showing the configuration of one of the manufacturing apparatuses used in the production method of the present invention. Fig. 3 is a view schematically showing the flow of the manufacturing method of the present invention. Fig. 4 is a plan view schematically showing a mask used in the embodiment. [Description of main component symbols] 1 '12-inch glass substrate la First surface lb Second surface 1 C Wall surface 5 Through-holes 7, 7a, 7b Wall surface 8a First opening 155791.doc -23- 201200284 8b Second opening 100 Manufacturing apparatus 110 Excimer laser light generating device 130 Mask 132 Synthetic quartz substrate 134 Synthetic quartz substrate first surface 135 Evaporation film 137 Cr non-vapor deposition portion 140 Platform 150 to 152 Mirror 160 Homogenizer 170 Projection lens 190 Excimer thunder The diameter L2 of the first opening of the through-light LI through hole The diameter of the second opening of the through hole S110 to S140 Step α Cone angle 155791.doc -24-