1358396 嚴格的標準，而要求高等級的潔淨度。而且除了表面的潔淨 度之外，亦要求在玻璃內部不能存在有氣泡'紋路、結晶， 並防止鈾等異物的混入。再者爲了與各種的封裝良好的封閉 接著’要求要與封裝材料具有相近的熱膨脹係數。而且，此 種玻璃亦要求具有經過長時間表面等級亦不會降低的優良耐 候性，以及低密度而能夠輕量化。 再者，於CCD用途方面’如在玻璃蓋中含有放射線元素 如鈾（U)或钍（Th)的話，容易由玻璃放射出α射線，由於此放 射線多的話將會引起軟誤記(soft error)，因此要求盡量不要含 有鈾、钍。因此’其對策是在製造CCD玻璃蓋之際，採用高 純度的原料，並且以放射性同位素少的耐火物或白金形成用 以熔融原料之熔融爐的內壁。例如是，下述專利文獻1〜3， 係提出減少放射性同位素，並降低α射線放出量的固態攝影 元件封裝用玻璃蓋。 專利文獻1 :日本專利第2660891號公報 專利文獻2:日本早期公開專利平6-211539號公報 專利文獻3:日本早期公開專利平7_21 1539號公報 如上所述，固態攝影元件封裝用玻璃蓋的使用量，由於 用途的拓廣以及影像資料利用的開展而急遽的增加。然而， 由於以往的固態攝影元件封裝用玻璃蓋是以下述的方法製 作，表面等級不佳，而且不適於大量生產。亦即是，在製作 固態攝影元件封裝用玻璃蓋的場合’首先於熔融爐將玻璃原 料熔融，並進行脫泡•紋路以均質化後’將玻璃熔融液注入 鑄模內以澆鑄成形，或是將玻璃熔融液於延伸板上連續的引 出，形成一定的形狀。其次，藉由將所得的玻璃成形體（玻璃 鑄錠）徐冷，將此些以一定厚度切下以得到切塊後，並將其表 13146pif.doc/008 6 1358396 面施以硏磨加工以得到一定厚度的大塊板狀玻璃，將此玻璃 以一定尺寸進行細切加工。依此，雖然對固態攝影元件封裝 用玻璃蓋的透光面的兩面施加硏磨加工，然而由於硏磨而會 在表面形成無數的細微凹凸（微小傷痕）。另一方面近年來固態 攝影元件係謀求高畫質化、小型化，伴隨著高畫質化、小型 化而具有每1個元件的受光量減少的傾向，並且硏磨玻璃蓋 之透光面所形成的細微凹凸會使得入射光容易散射，使得一 部分的元件的受光量不足，此結果將會具有元件發生誤動作 的疑慮。 而且，如果在固態攝影元件封裝用玻璃蓋中混入異物或 氣泡，在表面附著灰塵的話’無法得到良好的顯示影像’由 於此爲玻璃蓋的致命缺陷’在玻璃蓋出貨前一定會進行影像 檢查。但是，如上所述的’在玻璃蓋的透光面形成有無數的 細微凹凸，在影像檢查之時’玻璃蓋的透光面的凹凸照射光 會造成照射光折射’明可見部份與暗可見部份會混合’無法 正確的檢測有無異物或灰塵。 而且，對玻璃蓋的透光面’經由非常精密且長時間的研1 磨加工，可以使凹凸變得更小’然而’此等精密硏磨不適合 大量生產，爲了因應遽增的需要’必須大幅度的增設設備° 再者，此精密加工是藉由具備人工皮革的回轉硏磨加工機’ 邊供應在水中分散有氧化鈽等游離硏磨粒的硏漿邊進行’然 而，因硏磨產生的玻璃粉會進入人工皮革中’於人工皮革的 一部分形成凸起部。因爲此玻璃粉所形成之人工皮革的凸起 部，在硏磨時會削取玻璃蓋的表面’而成爲形成局部溝槽的 原因。然.後，由於此種溝槽具有比較廣、淺的形狀’在以電 子儀器檢查的影像檢查步驟中會被忽略’而此種的玻璃蓋裝 13146pif.doc/008 7 1358396 載在固體攝影裝置的話，在顯示影像中會產生黑紋。而且作 爲游離硏磨粒使用的氧化鈽中含有摻質Th，在硏磨後如果未 將附著於玻璃上的氧化鈽完全去除的話，亦可能成爲α射線 的來源。 如上所述之損及生產性的精密硏磨，或是進行所產生的 對固態攝影元件的惡影響，受限於進行硏磨，而爲某個程度 上無法避免的問題。 【發明內容】 鑑於上述的課題，本發明的目的是提供一種半導體封裝 用玻璃蓋，藉由使其透光面不需進行硏磨就呈平滑狀態，能 夠消除伴隨硏磨產生的各種問題。 爲了解決上述的課題’本發明的半導體封裝用玻璃蓋， 其特徵爲具有無硏磨面的透光面，表面粗糙度(11幻爲10ηπι以 下。此處「R_a」爲在Jis Β0601-1994中定義的算數平均粗糙 度(arithmetical mean roughness)。 而且’本發明的半導體封裝用玻璃蓋，其特徵爲使用下 拉(down draw)法或是浮(float)法成形，透光面的表面粗糙度(Ra) 爲l.Onm以下。 而且’本發明的半導體封裝用玻璃蓋，其特徵爲於質量％ 含有 Si02 52〜70%、Al2〇3 5〜20% ' B2〇3 5 〜20%、鹼土類金 屬氧化物4〜30%、ZnO 0〜5%的基本組成，實質上不含有鹼 金屬氧化物’於溫度範圍30〜380度。C的平均熱膨脹係數爲30 〜85x 1(T7/°C，液相溫度的玻璃黏度爲105.2 dPa . s以上。 而且’本發明的半導體封裝用玻璃蓋，其特徵爲於質量％ 含有 Si02 58〜75%、Al2〇3 0.5 〜15%、B2〇3 5 〜20%、鹼金屬 氧化物1〜20%、鹼土類金屬氧化物0〜20°/。' ZnOO〜10% 13146pif.doc/008 8 1358396 的基本組成，於溫度範圍30〜380度。c的平均熱膨膜係數爲30 〜85x 10.7/°C，液相溫度的玻璃黏度爲1〇5·2 dPa · s以上。 而且，本發明的半導體封裝用玻璃蓋的製造方法，在至 少由耐火物形成內壁的熔融槽內投入玻璃原料’熔融之後使 用下拉法或是浮法成形爲板狀。 由於本發明的半導體封裝用玻璃蓋具有無硏磨面的透光 面，且表面粗糙度(Ra)爲l.Onm以下’能夠抑制入射光散射所 引起的元件誤動作，並能夠於影像檢查正確的檢測有無異物 或灰塵，並防止如同黑條紋等的顯示不良。而且，由於能夠 省略精密加工的步驟，能便宜且大量的生產，再者由於不需 要硏磨而未使用游離硏磨粒，能夠防止氧化鈽所導致的α射 線放出。 而且，如依照本發明的半導體封裝用玻璃蓋的製造方法 的話，能夠容易的製造鉑粒子少、於透光面無硏磨面、表面 粗糙度(Ra)爲l.Onm以下的半導體封裝用玻璃蓋。 【實施方式】 本發明的半導體封裝用玻璃蓋’其特徵爲具有無硏磨面 的透光面’表面粗糙度(Ra)爲l.Onm以下。此種表面品位高的 玻璃蓋’可以使用下拉法或是浮法成形。作爲下拉法，適合 使用溢流下拉法或是狹縫下拉法’然而，特別是在使用溢流 下拉法的％口 ’由於玻璃的表面爲自由表面，不會艇其他構 件接觸’藉由控制其熔融條件與成形條件，能夠得到具有所 希望的厚度（於半導體封裝用玻璃蓋的場合，〇 〇1〜〇 7mm)， S表面平滑性的板玻璃而較佳。亦即是，如採用溢流下 拉法的話，由於表面（透光面）不需硏磨加工，能夠得到平滑的 表面’ ft形成因硏磨造成的微小傷痕，能夠製造表面粗糖 13146pif.doc/008 9 1358396 度(Ra)爲1·〇 nm以下、0.5 nm以下、甚至0.3 nm以下的玻璃 蓋。依此玻璃蓋的透光面的表面粗糙度(Ra)愈小’因玻璃蓋表 面粗糙度的透光面的散射光所引起的元件誤動作之發生率降 低，而且提昇檢測異物等的影像檢查的精度。尙且’表面粗 糙度（Ra)是用以表示表面平滑性的品位’能夠使用基於JIS B0601的實驗方法以進行測量。 而且，作爲浮法，係能夠在將熔融玻璃供給至還原氣體 環境中的熔融金屬錫浴上以成形爲板狀的方法’或是在支撐 體上供應熔融玻璃的方法，在支撐體與玻璃之間’介由蒸汽 _ 膜形成劑汽化的蒸汽膜薄層互相滑動以成形爲板狀的方法（請 參照日本早期公開發明平9-295819號、日本早期公開發明 2001-192219號）。尙且，由於藉由浮法形成之玻璃蓋與藉由下 法形成之玻璃蓋相較之下，其表面品位較差，較佳爲因應需 要施加表面加工。但是，即使於此場合，由於硏磨時間短， 因此能夠盡可能的減少生產性的降低，亦能夠盡可能的減少 由A硏磨所產生之對固態攝影元件的壞影響。 而且，本發明的半導體封裝用玻璃蓋，液相溫度的玻璃 . 黏度(液相黏度)在1〇5·2 dPa . S以上的話，在玻璃中不易產生 鲁 失去透明物，可以藉由下拉法成形。亦即是將Si〇2-Al203-B203-R0(或是R20)系的玻璃基板以下拉法成形的場合，成形 部分的玻璃黏度大約等於105 () dPa · S。因此，玻璃的液相黏 度在105 e dPa . S附近，或是在其以下的話，成形的玻璃中容 易產生失去透明物。在玻璃中產生失去透明物的話由於會損 及透光性，而無法使用於玻璃蓋。依此在使用下拉法形成玻 璃蓋的場合，較佳爲使玻璃的液相黏度盡可能的高，作爲半 導體封裝用玻璃蓋，液相黏度需要在1〇5_2 dPa · s以上。液相 13146pif.doc/008 10 1358396 黏度較佳爲在l〇5_4dPa ，以上，更佳馬在105.8 dPa · s以上。 而且’本發明的半導體封裝用玻璃蔓，藉由使溫度範圍3〇 〜380度。C的平均熱膨脹係數爲3〇〜85χ 1(m：，即使使用有 機樹脂或是低融點玻璃所形成的黏接材料的氧化錦封裝(約7〇 X HTVt：)或各種旨_裝，在內部不會產生應變，以及經 態膨膜縫， 較佳爲 35〜80x 10·7/^：，更佳爲 50〜75χ 10·7/Τ：。 而且，本發明的半導體封裝用玻璃蓋，藉由使^射線放 出量限制爲〇‘〇1 c/cm2.hr，能夠達成降低〇射線所引起的固 體攝β兀件的軟故g己。爲了使α射線放出量限制爲〇.〇 1 c/cm2 . hr以下，防止混入來自原料或是熔融爐的雜質，較佳爲將玻 璃中U量抑制在10 ppb以下’ Th量抑制在20 ppb以下。由 於隨著固體攝影元件的高畫素化、小型化而容易產生〇；射線 所引起的軟誤記’玻璃蓋的α射線較佳爲0.005 c/cm2 . hr以 下’更佳爲0.003 c/cm2 . hr以下。而且，u量爲5 ppb以下，1358396 Strict standards, while requiring a high level of cleanliness. In addition to the cleanliness of the surface, it is also required that bubbles do not exist in the interior of the glass, and that foreign matter such as uranium can be prevented from entering. Furthermore, in order to be well sealed with various packages, it is required to have a thermal expansion coefficient similar to that of the packaging material. Moreover, such a glass is also required to have excellent weather resistance which is not deteriorated over a long period of time, and low density and light weight. Furthermore, in the case of CCD use, if a glass element contains a radioactive element such as uranium (U) or yttrium (Th), it is easy to emit α-rays from the glass, and since this radiation is large, soft error will be caused. Therefore, it is required to try not to contain uranium or plutonium. Therefore, the countermeasure is to use a high-purity raw material in the production of a CCD glass cover, and to form an inner wall of a melting furnace for melting a raw material with a refractory or a platinum having a small radioisotope. For example, Patent Documents 1 to 3 below propose a glass cover for solid-state imaging element packaging which reduces radioactive isotope and reduces the amount of α-ray emission. Patent Document 1: Japanese Patent No. 2660891 Patent Document 2: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 6-211539. The amount is rapidly increasing due to the expansion of the use and the development of the use of image data. However, since the conventional glass cover for solid-state photographic element packaging is produced by the following method, the surface grade is not good and it is not suitable for mass production. In other words, when manufacturing a glass cover for solid-state imaging device packaging, the glass raw material is first melted in a melting furnace, defoamed, and textured to be homogenized, and then the glass melt is poured into a mold to be cast, or The glass melt is continuously drawn out on the extension plate to form a certain shape. Next, by extruding the obtained glass formed body (glass ingot), the cut pieces were cut to a certain thickness to obtain a dicing, and the surface of the table 13146pif.doc/008 6 1358396 was subjected to honing processing. A large piece of plate glass having a certain thickness is obtained, and the glass is subjected to fine cutting processing in a certain size. According to this, although honing processing is applied to both surfaces of the light-transmissive surface of the cover glass for solid-state imaging device packaging, numerous fine irregularities (small flaws) are formed on the surface due to honing. On the other hand, in recent years, solid-state imaging devices have been designed to achieve high image quality and miniaturization, and the amount of light received per element has been reduced with high image quality and miniaturization, and the light-transmissive surface of the glass cover has been honed. The fine concavities and convexities formed cause the incident light to be easily scattered, so that the amount of light received by a part of the components is insufficient, and this result may have a concern that the components malfunction. In addition, if foreign matter or air bubbles are mixed in the glass cover for solid-state photographic element packaging, and dust is attached to the surface, 'good display image cannot be obtained'. This is a fatal defect of the glass cover. Image inspection will be performed before the glass cover is shipped. . However, as described above, 'there are numerous fine concavities and convexities formed on the light-transmissive surface of the glass cover. At the time of image inspection, the concave-convex illumination of the light-transmissive surface of the glass cover causes the illumination light to refract. Some will mix 'cannot correctly detect the presence of foreign matter or dust. Moreover, the translucent surface of the glass cover can be made smaller by a very precise and long-term grinding process. However, such precision honing is not suitable for mass production, and it must be large in order to cope with the increase. In addition, this precision machining is carried out by a rotary honing machine equipped with artificial leather while supplying a slurry of free honing particles such as cerium oxide dispersed in water. However, due to honing The glass powder will enter the artificial leather' part of the artificial leather to form a raised portion. Since the convex portion of the artificial leather formed by the glass frit is cut at the surface of the glass cover during honing, it becomes a cause of forming a partial groove. However, since such a groove has a relatively wide and shallow shape 'will be ignored in the image inspection step by electronic inspection', such a glass cover 13146pif.doc/008 7 1358396 is carried in a solid-state imaging device. If it is displayed, black lines will appear in the displayed image. Further, the cerium oxide used as the free cerium abrasive grains contains the dopant Th, and if the cerium oxide adhered to the glass is not completely removed after honing, it may become a source of α rays. The above-mentioned precision honing that impairs productivity, or the adverse effects on the solid-state photographic elements produced, is limited to the problem of honing, which is an unavoidable problem. SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a glass cover for a semiconductor package which can be smoothed without honing, and can eliminate various problems associated with honing. In order to solve the above-mentioned problem, the glass cover for semiconductor package of the present invention is characterized in that it has a light-transmissive surface having no honing surface, and the surface roughness (11 illusion is 10 ηπι or less. Here, "R_a" is in Jis Β0601-1994 The arithmetic mean roughness of the semiconductor package of the present invention is characterized by the use of a down draw method or a float method to form a surface roughness of the light transmissive surface ( Ra) is not more than 1.Onm. Further, the glass cover for semiconductor package of the present invention is characterized in that it contains SiO 2 52 to 70%, Al 2 〇 3 5 to 20% 'B2 〇 3 5 〜 20%, and alkaline earth type in mass%. The basic composition of metal oxide 4~30%, ZnO 0~5%, substantially does not contain alkali metal oxide' in the temperature range of 30~380 degrees. The average thermal expansion coefficient of C is 30~85x 1 (T7/°C, The glass viscosity at the liquidus temperature is 105.2 dPa·s or more. Further, the glass cover for semiconductor package of the present invention is characterized in that it contains SiO 2 58 to 75%, Al 2 〇 3 0.5 〜 15%, and B 2 〇 3 5 〜 20%, alkali metal oxide 1~20%, alkaline earth metal oxide 0~20°/ The basic composition of ZnOO~10% 13146pif.doc/008 8 1358396 is in the temperature range of 30~380 degrees. The average thermal expansion coefficient of c is 30~85x 10.7/°C, and the glass viscosity of liquid phase temperature is 1〇. In addition, in the method for producing a glass cover for a semiconductor package of the present invention, the glass raw material is poured into a melting tank in which at least the refractory is formed into an inner wall, and is melted into a sheet by a down-draw method or a float method. The glass cover for semiconductor package of the present invention has a light-transmissive surface without a honing surface, and has a surface roughness (Ra) of less than 1.Onm, which can suppress component malfunction caused by incident light scattering, and can perform image inspection. Properly detect the presence of foreign matter or dust, and prevent display defects such as black streaks. Moreover, since the steps of precision machining can be omitted, it can be produced inexpensively and in large quantities, and since no honing is required without using honing, It is possible to prevent the emission of α-rays due to cerium oxide. Further, according to the method for producing a glass cover for a semiconductor package according to the present invention, it is possible to easily produce a small amount of platinum particles on the light-transmitting surface. A glass cover for a semiconductor package having a surface roughness (Ra) of not more than 1.Onm. [Embodiment] The glass cover for semiconductor package of the present invention is characterized in that the surface of the light-transmissive surface having a honing surface is rough. The degree (Ra) is less than 1.Onm. The glass cover with a high surface quality can be formed by a down-draw method or a float method. As a down-draw method, it is suitable to use an overflow down-draw method or a slit-down method. In the % port of the overflow down-draw method, since the surface of the glass is a free surface, the other members of the boat are not in contact. By controlling the melting conditions and the molding conditions, it is possible to obtain a desired thickness (for the glass cover for semiconductor packaging) In the case of 〇〇1 to 〇7 mm), it is preferable to use a smooth glass plate. In other words, if the overflow down-draw method is used, since the surface (transparent surface) does not need to be honed, a smooth surface can be obtained to form a small scratch caused by honing, and the surface raw sugar can be manufactured 13146pif.doc/008 9 1358396 degrees (Ra) is a glass cover of 1 〇 nm or less, 0.5 nm or less, or even 0.3 nm or less. The smaller the surface roughness (Ra) of the light-transmissive surface of the glass cover, the lower the incidence of component malfunction due to the scattered light of the light-transmissive surface of the surface roughness of the glass cover, and the improvement of image inspection for detecting foreign matter and the like. Precision. Further, 'surface roughness (Ra) is a grade used to indicate surface smoothness' can be measured using an experimental method based on JIS B0601. Further, as the float method, a method of forming a molten metal in a molten metal tin bath in a reducing gas atmosphere, or a method of supplying molten glass on a support, in a support and a glass A method in which a thin film of a vapor film vaporized by a vapor-film forming agent is slid to each other to form a plate shape (refer to Japanese Laid-Open Patent Publication No. Hei 9-295819, Japanese Laid-Open Publication No. 2001-192219). Moreover, since the glass cover formed by the float method is inferior in surface quality as compared with the glass cover formed by the lower method, it is preferred to apply surface processing as needed. However, even in this case, since the honing time is short, the decrease in productivity can be reduced as much as possible, and the adverse effect on the solid-state imaging element caused by the A honing can be reduced as much as possible. Further, in the glass cover for semiconductor package of the present invention, the viscosity of the glass at a liquidus temperature (liquidus viscosity) is 1〇5·2 dPa·s or more, and it is difficult to cause a loss of transparency in the glass, and it is possible to use a down-draw method. Forming. That is, when a glass substrate of Si〇2-Al203-B203-R0 (or R20) is formed by the following drawing, the glass viscosity of the molded portion is approximately equal to 105 () dPa · S. Therefore, if the liquid viscosity of the glass is in the vicinity of 105 e dPa·s or below, the formed glass is liable to lose the transparency. If the loss of transparency occurs in the glass, it may not be used for the glass cover due to damage and light transmission. In the case where the glass lid is formed by the down-draw method, it is preferred to make the liquid phase viscosity of the glass as high as possible. As a glass cover for a semiconductor package, the liquidus viscosity needs to be 1 〇 5 2 dPa · s or more. The liquid phase 13146pif.doc/008 10 1358396 preferably has a viscosity of l〇5_4dPa or more, and more preferably a horse of 105.8 dPa·s or more. Further, the glass vine for semiconductor package of the present invention has a temperature range of 3 〜 to 380 °. C has an average coefficient of thermal expansion of 3 〇 to 85 χ 1 (m: even if an organic resin or a low-melting glass is used to form a bonding material of a oxidized metal package (about 7 〇 X HTVt:) or various purposes, The inside does not generate strain, and the warp slit, preferably 35 to 80 x 10 · 7 / ^:, more preferably 50 to 75 χ 10 · 7 / Τ: Moreover, the glass cover for the semiconductor package of the present invention, By limiting the amount of emission of the ray to 〇'〇1 c/cm2.hr, it is possible to reduce the softness of the solid-state 兀 兀 caused by the x-ray. In order to limit the amount of α-ray emission to 〇.〇1 Below c/cm2.hr, it is preferable to prevent the impurities from the raw material or the melting furnace from being mixed, and it is preferable to suppress the U amount in the glass to 10 ppb or less. The amount of Th is suppressed to 20 ppb or less. Due to the high pixel of the solid-state imaging element. It is easy to produce flaws due to miniaturization; soft misunderstanding caused by rays. The α-ray of the glass cover is preferably 0.005 c/cm 2 . The following hr is more preferably 0.003 c/cm 2 · hr or less. Moreover, the amount of u is 5 ppb. the following,
Th量爲10 ppb以下，較佳U量爲4 ppb以下，Th量爲8 ppb 以下。尙且與Th相比之下，U容易放出〇：射線因此U的容許 量與Th的容許量相比之下較小。 而且，本發明的半導體封裝用玻璃蓋，其玻璃的密度爲2.55 g/cm3以下（較佳爲2.45 g/cm3以下），鹼溶出量爲l.Omg以下（較 佳爲0.1 mg以下，更佳爲〇.〇1 mg以下）的話，特別是適用裝 載於戶外使用的攜帶用電子機器的用途。亦即是’由於數位 照相機、數位攝影機、行動電話、個人數位助理（PDA)等的機 器’具有於戶外使用的狀況，要求輕量而適於攜行’且具有 高耐候性。因此，對於用於此些用途的固體攝影元件用蓋玻 璃，在輕量的特性之外，必須具有安定的耐候性，以及即使 13146pif.doc/008 11 1358396 在戶外的嚴苛環境下使用亦不會使表面品位降低的特性。因 此’特別是此種用途使用的玻璃蓋，較佳爲藉由降低密度而 輕量化，且降低鹼溶出量以提昇耐候性。 而且’本發明的半導體封裝用玻璃蓋，厚度較佳爲0.05 〜0.7 mm。厚度大的話透過率降低且機器的輕量化、薄型化 困難而較爲不佳。而且厚度過薄的話，實用強度不足且大塊 板狀玻璃的撓曲變大而造成操作困難。較佳的厚度爲0.1〜0.5 mm，更佳的厚度爲0.1〜0.4 mm。 而且’本發明的半導體封裝用玻璃蓋，其楊氏率65 GPa 以上，更佳爲67 GPa以上。楊氏率表示在玻璃蓋上施加一定 之外力的狀況下的容易變形程度。楊氏率大的話則不易變形。 玻璃蓋的楊氏率愈高，能夠防止直接施加於玻璃蓋的直接壓 力，其結果能夠防止元件的損傷。 而且，本發明的半導體封裝用玻璃蓋，其比楊氏率（楊氏 率/密度）爲27 Gpa/g . cm·3的話，由於能夠滿足輕量且不易 變开^的特性，特別是適用於攜帶用電子機器所使用的固體攝 影元件用玻璃蓋。由此觀點觀之，固態攝影元件用玻璃蓋的 比楊氏率較佳爲盡可能的大，且較佳爲28 Gpa/g . cm_3以上。籲 而且，本發明的半導體封裝用玻璃蓋，其維氏硬度爲500 以上的話由於在表面不易形成傷痕而較佳。其理由在於如果 在電子機器的組裝步驟或搬運步驟時對表面造成微小傷痕的 話’由於在裝載於固體攝影元件後的影像檢查步驟會產生不 良。因此維氏硬度較佳爲520以上。 於本發明中，考量到耐候性的話，較佳爲於質量％含有Si02 52〜70%、Al2〇3 5〜20%、B203 5〜20%、鹼土類金屬氧化物4 〜30%、ZnO 〇〜5%的基本組成，實質上不含有鹼金屬氧化物。 13146pif.doc/008 12 1358396 具有此組成的玻璃盍，由於其驗溶出重未滿0.01 mg，耐候性 優良，即使長時間使用外觀品位不會降低的優點。尙且，於 本發明中的「實質未含有」，意味著其成分的含有量未滿2〇〇〇 ppm。而且鹼溶出量可藉由使用基於JIS R3502的實驗方法以 測量。 上述之構成玻璃蓋的各成分的限制理由係說明如下。 si〇2爲成爲構成玻璃之骨骼的主成分，並具有提昇玻璃 耐候性的效果，然而過多的話，具有玻璃的高溫黏度上升， 且熔融性惡化的同時，液相黏度變高的傾向。依此，Si02的 含量爲52〜70%，較佳爲53〜67%，更佳爲55〜65%。 αι203爲提高玻璃的耐候性與液相黏度的成分，過多的言舌’ 具有玻璃的高溫黏度上升，且熔融性惡化的同時，液相霍占胃 變高的傾向。依此，A1203的含量爲5〜20%，較佳爲8〜19% ’ 更佳爲10〜18°/。。 B2o3爲發揮融劑的作用，降低玻璃的黏性，改善溶融;丨'生 的成分。再者，其爲用以提高液相黏度的成分。但是’ B2G3 過多的話玻璃的耐候性具有降低的傾向。依此，B2〇3 胃 爲5〜20%，較佳爲6〜15%，更佳爲7〜13%。 鹼土類金屬氧化物(MgO、CaO、SrO、BaO)，在提昇玻璃 的耐候性的同時，降低玻璃的黏性，而爲改善熔融性的成分’ 然而過多的話，玻璃具有在容易失去透明的同時密度上升@ 傾向。依此，鹼土類金屬氧化物的含量爲4〜30%，較佳爲5 〜20%，更佳爲6.〜16%。 特別是CaO，是比較容易入手的高純度原料，是顯著改 善玻璃的熔融性以及耐候性的成分。CaO的含量小於1·5%的 場合，上述效果小，反之超過15%的場合，耐候性降低。爲 13146pif.doc/008 13 1358396 了達成更安定的品位，CaO的含量較佳爲2〜12°/。，更佳爲3 〜10% 0 而且’由於BaO與SrO顯著的使玻璃的密度上升，在玻 璃密度低的場合，將各別的含量限制在I2%、10%以下，再者 較佳爲將兩者含量的合計量限制爲6.5〜13%。而且，由於BaO 與SrO容易在原料中含有放射性同位元素，在希望降低〇射 線的場合，兩者含量的合計量限制爲8.5%以下，較佳爲3%以 下，更佳爲1.4以下％。The Th amount is 10 ppb or less, preferably the U amount is 4 ppb or less, and the Th amount is 8 ppb or less. Moreover, compared with Th, U is easy to emit 〇: ray, so the tolerance of U is smaller than the allowable amount of Th. Further, the glass cover for a semiconductor package of the present invention has a glass density of 2.55 g/cm3 or less (preferably 2.45 g/cm3 or less), and an alkali elution amount of 1.0 mg or less (preferably 0.1 mg or less, more preferably In the case of 〇.〇1 mg or less, it is particularly suitable for use in portable electronic devices that are used outdoors. That is, a machine such as a digital camera, a digital camera, a mobile phone, a personal digital assistant (PDA), etc., which is used outdoors, is required to be lightweight and suitable for carrying, and has high weather resistance. Therefore, for the cover glass for solid-state photographic elements used for such applications, it is necessary to have stable weather resistance in addition to the lightweight characteristics, and even if 13146pif.doc/008 11 1358396 is used in an outdoor harsh environment. A property that reduces the surface quality. Therefore, it is preferable that the glass cover used in such a use is lightweight by reducing the density, and the amount of alkali elution is lowered to improve the weather resistance. Further, the glass cover for semiconductor package of the present invention preferably has a thickness of 0.05 to 0.7 mm. When the thickness is large, the transmittance is lowered, and the weight and thickness of the machine are difficult, which is not preferable. Further, if the thickness is too thin, the practical strength is insufficient and the deflection of the bulk plate glass becomes large, which causes difficulty in operation. A preferred thickness is 0.1 to 0.5 mm, and a more preferred thickness is 0.1 to 0.4 mm. Further, the glass cover for a semiconductor package of the present invention has a Young's modulus of 65 GPa or more, more preferably 67 GPa or more. The Young's ratio indicates the degree of easy deformation under the condition that a certain external force is applied to the cover glass. If the Young's rate is large, it will not be easily deformed. The higher the Young's rate of the glass cover, the direct pressure applied to the glass cover can be prevented, and as a result, the damage of the element can be prevented. Further, the glass cover for a semiconductor package of the present invention has a specific Young's ratio (Young's ratio/density) of 27 GPa/g·cm·3, and is particularly suitable for use because it can satisfy the characteristics of being lightweight and difficult to change. A glass cover for a solid-state imaging element used in portable electronic equipment. From this point of view, the specific Young's ratio of the glass cover for a solid-state imaging element is preferably as large as possible, and is preferably 28 GPa/g.cm_3 or more. Further, in the glass cover for a semiconductor package of the present invention, when the Vickers hardness is 500 or more, it is preferable that the surface is less likely to be scratched on the surface. The reason is that if the surface is slightly scratched during the assembly step or the carrying step of the electronic device, the image inspection step after loading on the solid-state imaging element may be defective. Therefore, the Vickers hardness is preferably 520 or more. In the present invention, in consideration of weather resistance, it is preferable to contain 52% to 70% of SiO2, 5 to 20% of Al2?, 5 to 20% of B203, 4 to 30% of alkaline earth metal oxide, and ZnO by mass%. The basic composition of ~5% does not substantially contain an alkali metal oxide. 13146pif.doc/008 12 1358396 A glass crucible having this composition has an excellent weather resistance because it is less than 0.01 mg in weight, and has an advantage that the appearance quality does not decrease even if it is used for a long period of time. Further, "substantially not contained" in the present invention means that the content of the component is less than 2 〇〇〇 ppm. Further, the amount of alkali elution can be measured by using an experimental method based on JIS R3502. The reason for limiting the components constituting the glass cover described above is as follows. Si 〇 2 is a main component of the skeleton constituting the glass and has an effect of improving the weather resistance of the glass. However, if the temperature is too high, the high-temperature viscosity of the glass is increased, and the meltability is deteriorated, and the liquid viscosity tends to be high. Accordingly, the content of SiO 2 is 52 to 70%, preferably 53 to 67%, more preferably 55 to 65%. Αι203 is a component that improves the weather resistance and liquid viscosity of glass. Too many words have a high temperature viscosity of glass, and the meltability is deteriorated, and the liquid phase tends to become high in the stomach. Accordingly, the content of A1203 is 5 to 20%, preferably 8 to 19% Å, more preferably 10 to 18 °/. . B2o3 acts as a melting agent to reduce the viscosity of the glass and improve the melting; Further, it is a component for increasing the viscosity of the liquid phase. However, when the amount of B2G3 is too large, the weather resistance of the glass tends to decrease. Accordingly, the B2〇3 stomach is 5 to 20%, preferably 6 to 15%, more preferably 7 to 13%. Alkaline earth metal oxides (MgO, CaO, SrO, BaO), while improving the weather resistance of the glass, reduce the viscosity of the glass, and improve the meltability of the component. However, if the glass is excessive, the glass tends to lose transparency. Density rises @ tendencies. Accordingly, the content of the alkaline earth metal oxide is 4 to 30%, preferably 5 to 20%, more preferably 6. to 16%. In particular, CaO is a highly pure raw material which is relatively easy to handle, and is a component which remarkably improves the meltability and weather resistance of the glass. When the content of CaO is less than 1.5%, the above effect is small, and if it exceeds 15%, the weather resistance is lowered. A more stable grade is achieved for 13146 pif.doc/008 13 1358396, and the CaO content is preferably 2 to 12 °/. More preferably, it is 3 to 10% 0 and 'Because BaO and SrO significantly increase the density of the glass, when the glass density is low, the respective contents are limited to I2% and 10% or less, and more preferably The total amount of both is limited to 6.5 to 13%. Further, since BaO and SrO are likely to contain a radioactive ectopic element in the raw material, when it is desired to reduce the enthalpy, the total amount of both is limited to 8.5% or less, preferably 3% or less, more preferably 1.4 or less.
ZnO係改善玻璃的熔融性，具有抑制b203或鹼土類金屬 氧化物由熔融玻璃中揮發的效果，然而含量過多的話，由於 玻璃容易失去透明且密度上升而較爲不佳。因此，其含量的 上限爲5%以下，較佳爲3%以下，更佳爲1以下％。 然而，含有鹼金屬氧化物(Na20、K20、Li20)的話，由於 從玻璃中溶出的鹼溶出量增加，耐候性降低之故其含量較佳 爲抑制在未滿0.2%。爲了達成更安定的耐候性，鹼金屬氧化 丄 物的含量較佳爲未滿0.1%，更佳爲未滿0.05%。 而且，玻璃中的鹼金屬氧化物少的話，具有抑制用以封 合封裝之黏著劑劣化的優點。亦即是，固態攝影元件封裝用 的玻璃蓋，多使用有機樹脂(例如環氧樹脂）以進行黏著’如果 玻璃蓋中含有鹼成分的話，鹼成分會徐徐的溶出到黏著劑中。 由於環氧樹脂等有機樹脂具有由於鹼成分而降低黏著強度的 特性，因而容易徐徐的降低玻璃蓋與封裝之間的黏著強度。 其結果，兩者之間產生間隙，且玻璃蓋會剝離’從而無法達 到所期望之保護固態攝影元件的效果。 而且，於本發明中，特別在考慮到製造面，於質量％含有 Si02 58〜7ς%、Al2〇3 0.5〜15%、B2〇3 5 〜20% ' 驗金屬氧化 13146pif.doc/008 14 1358396 物1〜20%、鹼土類金屬氧化物0〜20%、ZnO 0〜10%的基 本組成，具有此種組成的玻璃蓋，其熔融性提昇，液相黏度 容易調整。 構成上述玻璃蓋之各成分的限定理由如下所述。ZnO improves the meltability of the glass and has an effect of suppressing the volatilization of b203 or an alkaline earth metal oxide from the molten glass. However, if the content is too large, the glass tends to lose transparency and the density is increased, which is not preferable. Therefore, the upper limit of the content is 5% or less, preferably 3% or less, more preferably 1 or less. However, when an alkali metal oxide (Na20, K20, or Li20) is contained, the amount of alkali eluted from the glass is increased, and the weather resistance is lowered, so that the content is preferably suppressed to less than 0.2%. In order to achieve more stable weatherability, the content of the alkali metal cerium oxide is preferably less than 0.1%, more preferably less than 0.05%. Further, if the amount of alkali metal oxide in the glass is small, there is an advantage that the deterioration of the adhesive for sealing the package is suppressed. That is, the glass cover for encapsulating the solid-state imaging element is usually made of an organic resin (e.g., epoxy resin) for adhesion. If the glass cover contains an alkali component, the alkali component is slowly eluted into the adhesive. Since an organic resin such as an epoxy resin has a property of lowering the adhesive strength due to an alkali component, it is easy to gradually reduce the adhesion strength between the glass cover and the package. As a result, a gap is formed between the two, and the cover of the glass is peeled off, so that the desired effect of protecting the solid-state imaging element cannot be achieved. Further, in the present invention, in particular, in consideration of the production surface, the mass% contains SiO 2 58 to 7 %, Al 2 〇 3 0.5 to 15%, and B 2 〇 3 5 to 20% ' metal oxide 13146pif.doc/008 14 1358396 The basic composition of the material 1 to 20%, the alkaline earth metal oxide 0 to 20%, and the ZnO 0 to 10%, and the glass cover having such a composition, the meltability is improved, and the liquidus viscosity is easily adjusted. The reason for limiting the components constituting the above glass cover is as follows.
Si02爲成爲構成玻璃之骨骼的主成分，並具有提昇玻璃 耐候性的效果，然而過多的話，具有玻璃的高溫黏度上升， 且熔融性惡化的同時，液相黏度變高的傾向。依此，Si02的 含量爲58〜75%，較佳爲58〜72%，更佳爲60〜70%，最佳 爲 60〜68.5%。Si02 is a main component of the skeleton constituting the glass, and has an effect of improving the weather resistance of the glass. However, if the amount is too high, the high-temperature viscosity of the glass increases, and the meltability deteriorates, and the viscosity of the liquid phase tends to increase. Accordingly, the content of SiO 2 is 58 to 75%, preferably 58 to 72%, more preferably 60 to 70%, most preferably 60 to 68.5%.
Al2〇3爲提高液相黏度必須的成分，過多的話，具有玻璃 的高溫黏度上升，且熔融性惡化的傾向。依此，Al2〇3的含量 爲0.5〜15%，較佳爲1.1〜12%，更佳爲3.5〜12%，最佳爲6 〜11%。 b203爲發揮融劑的作用，降低玻璃的黏性，改善熔融性 的成分。再者，其爲用以提高液相黏度的成分。但是，：B2〇3 過多的話玻璃的耐候性具有降低的傾向。依此，b203的含量 爲5〜20%，較佳爲9〜18%，更佳爲11〜18%，最佳爲12〜 18%。 鹼金屬氧化物(Na20、K20、Li20)爲降低玻璃黏度、改善 熔融性的同時，有效的調整熱膨脹係數與液相黏度的成分， 然而量多的話會顯著的使玻璃的耐候性惡化。依此，鹼金屬 氧化物的含量爲1〜20%，較佳爲5〜18%，更佳爲7〜13%。 特別是Na20在熱膨脹係數的調整上具有大的效果，而且 K20在提昇液相黏度上具有大的效果。因此，倂用Na20、K20 的話，能夠一邊維持高液相黏度，一邊調整熱膨脹係數。依 此，Na20的含量較佳爲〇.1〜11%，Κ20的含量較佳爲〇.1〜 13146pif.doc/008 15 1358396 的話，由於玻璃容易失去透明且密度上升’因此，Zn〇的含 量的限制在10%以下’較佳爲9%以下，更佳爲6以下％ ° 再者，於本發明中’在上述成分以外’在不損及玻璃特 性的範圍內，能夠含有P2〇5、Y2〇3、Nb203、La203等成分5% 以下，各種澄淸劑3%以下。淸澄劑例如是可以使用SB203、 Sb205、F2、（:12、C、S03、Sn02 或是 Al、Si 等的金屬粉末的 1種或兩種以上。 由於As203能夠在廣泛的溫度範圍（1300〜1700°C的程度） 內產生澄淸氣體，以往此種澄淸劑係被廣泛的應用’然而由 於容易在原料中含有放射線同位元素。尙且的毒性非常的強， 在玻璃製造步驟中以及廢玻璃的處理時會造成環境污染的問 題。依此必須實質的不含有As2〇3。而且，由於Pb〇、CdO的 毒性亦強，必須避免使用。再者，SB203、Sb205亦與As203 — 樣爲具有優良澄淸效果的成分，然而，由於其毒性亦強，較 佳爲盡可能不要含有。 依此，在本發明之Si02-Al20rB20rR0系玻璃的場合， 澄淸劑成分的比例較佳爲SB203、Sb205的合計量爲0.05〜 2.0% ’ F2、Cl2、C、S03、Sn02 的合計量爲 0,1 〜3·0°/〇(特別是 Cl2 爲 0.005 〜1.0%，311〇2爲 0.01 〜1.0%)。而且，在 Si〇2_ Al2〇3-B2〇3_RO系玻璃的場合，爲了使熔融性優良，其比例較 佳爲 SB203、Sb205 的合計量爲 0.2%，F2、Cl2、C、s〇3、Sn〇2 的合計量爲0.1〜3.0%。 而且，FhO3亦可以作爲澄淸劑使用，然而爲了便玻璃著 色’其含量限制爲500 ppm以下，較佳爲300 ppm以下，更 佳爲200 ppm以下。Ce〇2亦可以作爲澄淸劑使用，然而爲了 將玻璃著色，其含量爲2%以下，較佳爲1%以下，更佳爲〇 7% 13146pif.doc/008 17 1358396 以下。Ti02具有改善玻璃的耐候性，並降低高溫黏度的效果， 但是由於會助長FhO3所致的著色，多量含有的話並不佳。但 是，Fe2〇3在200 ppm以下的話，能夠含有至5%。Zr〇2爲提 昇耐候性的成分，然而由於容易含有放射性同位元素，其含 量爲0〜2% ’較佳爲0〜0.5% ’更佳爲5〇〇 ppm以下。 本發明的半導體封裝用玻璃蓋，藉由具有上述的基本組 成，並採用高純度原料與雜質不易混入的熔融環境，而能夠 精密的控制 U、Th、Fe203、PbO、Ti02、Mn02、Zr02 等的含 量。特別是會影響在紫外線附近透過率的Fe2〇3、Pb〇、Ti〇2、 Mn〇2 ’能夠將之個別管理在1〜loo ρρηι的等級，造成α射線 所致的CCD元件的軟誤記的u、Th，個別管理在1〜10 ppb 的等級。尙且，CCD容易因爲α射線產生軟誤記，今日希望 由玻璃盖的α射線放出量未滿0.005 c/cm2. hr，CMOS的場合， 不易產生α射線引起的軟誤記，由玻璃蓋的射線放出量未 滿0.5 c/cm2 · hr亦可以使用。因此，在製作CMOS用玻璃蓋 的場合，並非一定要使用高純度原料，而且熔融時之降低U、 Th的混入亦無必要。 其次’以一個範例說明α射線放出量少的半導體封裝用 玻璃蓋的製造方法。 首先’準備能夠形成具有所希望組成玻璃的玻璃原料調 合物。玻璃原料使用U、Th等雜質少的高純度原料。更具體 而言，使用U與Th的含量各5 ppb以下的高純度原料。其次， 將調合的玻璃原料投入熔融槽熔融。熔融槽可使用鉑容器（包 含鈾铑容器），然而由於容易在玻璃中混入白金粒子，較佳爲 至少熔融槽的內壁（天頂、側面、底面）以U、Th含量少的耐 火物製作。具體而言，由於氧化鋁耐火物（例如氧化鋁質電鑄 13146pif.doc/008 18 1358396 磚）或石英耐火物(例如是矽block)不易腐蝕，而且能夠使U、 Th含量各在1 ppm以下，u、Th向玻璃的溶出量低而較佳。 其次，於澄淸槽進行熔融玻璃的均質化(脫泡.去除紋路）。此 澄淸槽能夠以耐火物或白金製作。尙且，一般的氧化錯耐火 物’在具有非常優良耐腐蝕性的反面，由於具有多量的放射 線同位元素，在使用上必須避免，然而如將氧化锆耐火物中 的雜質降低，且將U、Th含量降低至1 ppm以下的話，將其 作爲熔融槽的內壁使用，能夠製造出α射線放出量少的半導 體封裝用玻璃蓋。 其後’均質化的玻璃以下拉法成形爲板狀，得到所希望 厚度的板狀玻璃。下拉法可以使用溢流下拉法或是狹縫下拉 法。依此得到的板狀玻璃以一定的尺寸進行細切加工，並視 需要進行整平加工以製作玻璃蓋。 以下基於實施例說明本發明的封裝用玻璃蓋。 圖1所示爲實施例半導體封裝用玻璃蓋10。此半導體封 裝用玻璃蓋10,係爲具備有與板厚度方向相對向的第1透光 面1 〇a以及第2透光面10b，構成邊緣的側面i〇c的板狀玻璃。 此玻璃蓋10的尺寸爲14x 16x 0.5 mm，第1透光面l〇a以及 第2透光面i〇b爲無硏磨面，其表面粗糙度(Ra)的其中任一爲 0.5nm以下。而且雖然於圖式中省略側面i〇c具有平整的形狀。 其次，對於上述半導體封裝用玻璃蓋的製造方法與其性 能的評價試驗的結果進行說明。 板狀玻璃的最初製造步驟，爲製作—邊5〇〇mm以上的大 塊板狀玻璃的步驟。如上所述，形成表面品位優良的板狀玻 璃，最好是使用溢流下拉法。溢流下拉法，如圖2所示，是 由耐火物所形成的簷溝11使熔融玻璃12流動，由簷溝11的 13146pif.doc/〇〇s 1358396 兩側溢出的熔融玻璃12於簷溝U的底部融合，形成板狀而 向下方移動的方法。依此方法的話，由於熔融玻璃的自由表 面形成板狀玻璃的表裡面，能夠得到平滑性優良的大塊板狀 玻璃13。而且，藉由控制熔融條件與成形條件，能夠容易形 成厚度〇.〇5〜0.7 mm ’表面粗糖度(Ra) 1.0 nm以下的大塊板狀 玻璃。依此，能夠製作不需對大塊板狀玻璃13的表面硏磨， 僅以一定大小進行細切加工的半導體封裝用玻璃蓋。 此大塊板狀玻璃的細切方法，可使用機械切割或是雷射 切割。雷射切割首先使用熱加工雷射切斷裝置，在大塊板狀 玻璃的一側的面上，以雷射光束移動速度180± 5mm/sec或是 ® 220± 5mm/sec，雷射出力120± 5W，或是160± 5W的條件， 進行切割至約板厚方向之約20%厚度，加工爲棋盤眼狀。其 $如圖3的槪念所示的，對於大塊板狀玻璃13的加工面13a， 由其相反側以動作方向Μ移動金屬製的線狀頭14,同時藉由 於大塊板狀玻璃13的加工面13a側以模具（圖式省略)押壓， 於头塊版狀13的加工面13a施加應力以進行切割。依此進行 切斷，則得到沿著形成於棋盤眼狀的預定線分割的短冊狀的 板狀玻璃。依此押壓切割的短條狀玻璃的板狀玻璃，個別利 籲 用真空鉗（圖示省略）搬運至至下一個步驟。然後，將短條狀板 狀玻璃再次進行切割加工，以得到具有一定尺寸的玻璃蓋。 表1所示爲Si02-Al203-B203-R0系玻璃構成之本發明的 封裝用玻璃蓋的實施例(試樣No. 1〜5)。 13146pif.doc/008 20 1358396 表1 (質量％) 樣本No 組成 1 2 3 4 5 Si02 59.0 63.0 58.0 59.0 59.0 ΑΙΑ 15.0 16.0 16.0 15.0 17.0 β2〇3 10.0 10.0 8.0 10.0 8.0 MgO 一 —— 1.0 1.0 3.0 CaO 6.0 8.0 4.0 5.0 4.0 SrO 5.0 1.0 2.0 3.0 8.0 BaO 3.0 1.0 10.0 6.0 — ZnO 1.0 —— -— —— —— N^O —— —— —— — 一 K20 一 一 — 一 一 Li20 一 —— —— —— 一 Sb203 1.0 1.0 1.0 1.0 1.0 鹼溶出量 (mg) <0.01 <0.01 <0.01 <0.01 <0.01 密度(g/cm3) 2.49 2.38 2.55 2.49 2.51 楊式率(Gpa) 77 70 70 68 77 比楊式率 (Gpa/g*cm3) 28 29 27 27 31 維式硬度 600 580 590 570 610 熱膨脹係數 [30-380。。] (X 1〇-7/°〇 38 33 37 37 37 液相溫度(°C) 1065 1105 1030 1055 1130 液相黏度 (dPa . s) 6.0 6.0 6.7 6.1 5.2 α射線放出 量(c/cm2 · hr) 0.0076 0.0035 0.0156 0.0108 0.0075 將表1的玻璃試樣，如下述的進行製作。首先，將如表1 13146pif.doc/008 21 1358396 中組成所調製的高純度玻璃原料投入鉑铑坩鍋中，在具有攪 拌功能的電熔爐以攝氏1600度、20小時的條件熔融。其次， 將此熔融玻璃在碳板上流出並徐冷以製作玻璃樣本，並且調 查各特性。 如表1所明示的，無論是哪一個玻璃，鹼溶出量非常少， 而且密度、楊氏率、比楊氏率、維氏硬度、熱膨脹係數，能 夠滿足半導體封裝用玻璃蓋所要求的條件。而且，由於液相 溫度在1130°C以下，液相黏度爲1〇5·2 dPa 以上，耐失去透 明性優良。 而且，表2、3所示爲Si02-Al203-B203-R20系玻璃所形成 之本發明的封裝用玻璃蓋的實施例(樣本No. 6〜17)。 13146pif.doc/008 22 1358396 表2 (質量％) 樣本No 組成 6 7 8 9 10 11 Si02 68.8 65.8 68.4 68.3 68.8 67.8 ΑΙΑ 7.0 8.0 5.2 7.5 7.0 8.0 BA 13.1 13.1 1.09 13.1 13.1 13.1 MgO 一 0.4 一 一 — 一 CaO 2.2 0.6 3.2 — 0.6 0.6 SrO ___ 一 一 一 一 一 BaO 一 —— 一 — 一 一 ZnO 一 1.2 0.9 一 — 一 NajO 6.7 8.6 5.6 8.9 6.7 8.6 K20 1.9 2.0 5.7 1.9 3.5 1.6 Li20 一 _. 一 — 一 一 Ti02 一 — — 一 一 — Sb203 0.3 0.3 0.3 0.3 0.3 0.3 Cl 一 — — 一 一 — Sn02 一 — — 一 — 一 S〇3 一 —— __ 一 一 一 Fe203 30ppm 30ppm 30ppm 30ppm 30ppm 30ppm U(ppb) 4 未測量 未測量 未測量 未測量 4 Th(ppb) 2 未測量 未測量 未測量 未測量 2 熱膨脹係數 (x l〇-7/°C) 55.8 62.8 64.9 62.0 59.0 60.4 密度(g/cm3) 2.35 2.37 2.42 2.36 2.35 2.35 黏度應變點 ro 535 517 536 518 514 520 徐冷點(。〇 571 554 576 561 558 561 軟化點rc) 765 743 760 755 760 754 104(°C) 1119 1091 1093 1077 1102 1087 103(°C) 1345 1301 1292 1282 1316 1300 102-5(〇C) 1500 1456 1434 1434 1471 1455 液相溫度 rc) 884 728 882 817 822 未失去透 明 液相黏度 (dPa * s) 5.9 7.9 5.8 6.6 6.6 未失去透 明 α射線放出 量(c/cm2 · hr) 0.0020 0.0022 0.0021 0.0021 0.0020 0.0021 23 13146pif.doc/008 1358396 表3 (質量％) 樣本No 組成 12 13 14 159 16 17 SiO? 66.5 68.8 66.8 65.8 66.9 68.3 ai,〇3 8.0 7.0 7.0 8.0 7.5 7.0 β7ο, 13.1 12.0 13.1 13.1 13.1 13.1 MgO 一 — — _ 一 — CaO 0.6 2.2 2.2 0.6 2.2 0.6 SrO 一 —— — — 一 0.8 BaO —— —— 一 — — 0.8 ZnO 1.6 一 — 一 一 一 Na,0 7.9 6.7 8.6 8.6 6.2 6.7 K20 2.0 3.0 2.0 2.0 3.0 2.4 Li20 一 一 — 一 0.5 — Ti02 1.6 Sb203 0.3 0.3 0.3 0.3 — 一 Cl 一 —— — 一 0.2 一 Sn02 0.3 0.3 S〇3 _ —— 一 一 一 lOOpprn Fe203 30ppm 30ppm 30ppm lOppm 30ppm 30ppm U(ppb) 未測量 未測量 4 4 未測量 未測量 Th(ppb) 未測量 未測量 2 2 未測量 未測量 熱腿係數 (x i〇 r〇 59.9 59.1 62.8 61.4 60.6 55.8 密度(g/cm3) 2.36 2.37 2.39 2.36 2.36 2.33 黏度應變點 ro 509 531 530 510 527 521 徐冷點Γ〇 552 574 568 552 568 561 軟化點(。C) 752 764 745 · 744 759 761 104(°C) 1106 1117 1059 1086 1095 1109 103(°C) 1331 1341 1261 1306 1306 1333 1025(〇C) 1483 1494 1401 1461 1454 1486 液相溫度 rc) 未失去透· 明 867 855 822 842 853 液相黏度 (dPa · s) 未失去透 明 6.1 5.9 6.4 6.3 6.2 ^射線放出 量(c/cm2 · hr) 0.0021 0.0021 0.0021 0.0021 0.0023 0.0030 13146pif.doc/008 24 1358396 表2、3中的各玻璃試樣’如下述的進行製作。 首先，將如表中組成所調製的高純度玻璃原料，投入鉑 铑、氧化錯、石英的其中之一種所製作的坩鍋中，在具有攪 拌功能的電熔爐以攝氏1550度、6小時的條件熔融，並將此 熔融玻璃在碳板上流出’將此板玻璃徐冷以得到玻璃樣本。 如表所明確表示的’各玻璃試料滿足熱膨脹係數、密度、 α射線放出量滿足半導體用玻璃蓋的要求，且由於1〇2.5 dPa· s相當的黏度爲1500°C以下其熔融性優良，由於液相黏度爲 105·8 dPa，s以上耐失去透明性優良。 尙且，表中的鹼溶出量是基於JIS R3502測量。密度以公 知的阿基米德法測量。楊氏率以鐘紡(股）製非破壞彈性測量裝 置（KI-11)，計算出藉由共振法測量的楊氏率與密度。維氏硬 度基於JIS Z2244-1992測量。熱膨脹係數係使用膨脹計測量30 〜380°C溫度範圍內的平均熱膨脹係數。液相溫度係將各別粉 碎爲300〜500；czm的粒徑’將此置入鉑船中，並與溫度匹配 爐中保持8小時，以顯微鏡進行觀察，測量見到玻璃試樣內 部失去透明（結晶異物）的最高溫度，此溫度作爲液相溫度。而 且，液相溫度時的玻璃的黏度作爲液相黏度。No. 11、12的 玻璃試樣，不會失去透明，特別是具有優良的耐失去透明性。 U、Th的含量，係藉由ICP-MASS測量。而且，應變點以及 徐冷點係依據ASTM C336-71的方法測定，軟化點係依據 C338-93 的方法測量。104 dPa · S、103 dPa · S 以及 102 5 dPa · S，藉由周知的白金球上升法求得。102·5 dPa · S溫度係測量 高溫黏度爲1〇2·5泊相當的溫度，此値愈低的話熔融性愈優良。 α射線放出量使用超低等級α射線測量裝置（住友化學公司製 LACS-400M)以進行測量。 13146pif.doc/008 25 !358396 而且，將表1〜3的第No. 1、6、11、14以及15的玻璃 試料於實驗熔融槽（氧化鋁耐火物)熔融，以溢流下拉法形成厚 度〇·5 mm的板狀，其表面不進行硏磨，以雷射切割進行細切 加工，製作縱尺寸14 mm、橫尺寸16 mm的玻璃蓋。 而且，爲了進行比較，將構成試樣No. 1之玻璃的原料容 溶於上述的實驗熔融槽後，以800x 300x 300 mm的尺寸澆鑄 成形，藉由鋼絲鋸切斷，加工爲板厚1.5mm的板狀。其後， 將此板狀玻璃的兩面以回轉硏磨機施以精密硏磨加工以形$ 大塊板狀玻璃(厚度〇·5 mm)，以雷射切割進行細切加工，製 作縱尺寸14 mm、橫尺寸16 mm的玻璃蓋。 依此製作的各玻璃蓋的表裡的透光面（第1透光面與第2 透光面）的表面粗糙度（Ra)，以探針式表面粗糙測量機 Talystep(Tayler-Hobson社製)進行測量，其結果如表4所示。 表4 試樣No. 1 6 11 14 15 比較例 表面粗糙度 (Ra) 第1透光面 第2透光面 0.15nm 0.20nm 0.20 nm 0.15 nm 0.23 nm 0.19 nm 0.20 nm 0.18 nm 0.18nm 0.16 nm 0.56 nm 0.95 nm 如表4所明確表示的，實施例的玻璃蓋，無論是第1透 光面或第2透光面的表面粗糙度(Ra)爲0.23 rnn以下，具有極 爲良好的平滑面，而比較例的玻璃蓋，即使是施加精密硏磨 加工，其表面粗糙度（Ra)爲〇_56以上。而且，各玻璃蓋的透 光面以原子力顯微鏡(AFM)觀察，於比較例的玻璃蓋，於其全 部表面形成有無述的微小傷痕，而於實施例的玻璃蓋，認定 13146pif.doc/008 26 1358396 沒有此種傷痕。 產業h可利甩 本發明的封裝用玻璃蓋適用於固體攝影元件封裝用玻璃 蓋’此外亦適用於封裝雷射二極體等的各種半導體封裝的玻 璃蓋。而且’此玻璃蓋於30〜38(TC的溫度範圍之平均熱膨脹 係數爲30〜85x 10_7/°C，除了氧化鋁封裝之外，對於以樹脂、 錫金屬、姑合金、組合金、36Ni-Fe合金、42 Ni-Fe合金、45Ni-Fe 合金、46Ni-Fe合金、52Ni-Fe合金製作的各種封裝，能夠以 有機樹脂或低融點玻璃進行封裝。 【圖式簡單說明】 圖1所繪示爲實施例的半導體封裝用玻璃蓋的斜視圖。 圖2所繪示爲使用溢流下拉法以形成板狀玻璃的方法的 說明圖。 圖3所繪示爲使用雷射切割對大塊板狀玻璃進行細切加 工的方法。 【圖式標示說明】 10 :半導體封裝用玻璃蓋 1.0a :第1透光面 10b :第2透光面 10c :側面 11 :簷溝 12 :熔融玻璃 13 :大塊板狀玻璃 13a :加工面 14 :線狀頭 Μ :動作方向 13146pif.doc/008 27Al2〇3 is a component which is necessary for increasing the viscosity of the liquid phase. When the amount is too large, the high-temperature viscosity of the glass increases and the meltability tends to deteriorate. Accordingly, the content of Al2〇3 is from 0.5 to 15%, preferably from 1.1 to 12%, more preferably from 3.5 to 12%, most preferably from 6 to 11%. B203 is a component that acts as a melting agent to reduce the viscosity of the glass and improve the meltability. Further, it is a component for increasing the viscosity of the liquid phase. However, if the amount of B2〇3 is too large, the weather resistance of the glass tends to decrease. Accordingly, the content of b203 is 5 to 20%, preferably 9 to 18%, more preferably 11 to 18%, most preferably 12 to 18%. The alkali metal oxides (Na20, K20, and Li20) are components which effectively adjust the thermal expansion coefficient and the liquidus viscosity while lowering the viscosity of the glass and improving the meltability. However, if the amount is large, the weather resistance of the glass is remarkably deteriorated. Accordingly, the alkali metal oxide is contained in an amount of from 1 to 20%, preferably from 5 to 18%, more preferably from 7 to 13%. In particular, Na20 has a large effect on the adjustment of the coefficient of thermal expansion, and K20 has a large effect on the viscosity of the liquid phase. Therefore, when Na20 or K20 is used, the coefficient of thermal expansion can be adjusted while maintaining the viscosity of the high liquid phase. Accordingly, the content of Na20 is preferably 〇1 to 11%, and the content of Κ20 is preferably 〇.1 to 13146pif.doc/008 15 1358396, since the glass is liable to lose transparency and increase in density. Therefore, the content of Zn 〇 The limit is 10% or less, preferably 9% or less, more preferably 6 or less. Further, in the present invention, 'beyond the above components', P2〇5 can be contained in a range that does not impair the glass characteristics. The components such as Y2〇3, Nb203, and La203 are 5% or less, and various types of chopping agents are 3% or less. For example, one or two or more kinds of metal powders such as SB203, Sb205, F2, (:12, C, S03, Sn02 or Al, Si, etc. can be used as the clarifying agent. Since As203 can be used in a wide temperature range (1300~) At a temperature of 1700 ° C, a sulphur gas is produced in the past. In the past, such a sputum agent was widely used. However, it is easy to contain a radioisotope in a raw material. The toxicity is very strong, and it is in the glass manufacturing step and waste. The treatment of glass will cause environmental pollution. Therefore, it is essential that it does not contain As2〇3. Moreover, since Pb〇 and CdO are also highly toxic, they must be avoided. Furthermore, SB203 and Sb205 are also like As203. The component having an excellent clarification effect, however, is also highly toxic, and is preferably not contained as much as possible. Accordingly, in the case of the SiO 2 -Al 20r B 20 rR0 glass of the present invention, the proportion of the chopping agent component is preferably SB 203. The total amount of Sb205 is 0.05 to 2.0%. The total amount of F2, Cl2, C, S03, and Sn02 is 0,1 to 3·0°/〇 (especially, Cl2 is 0.005 to 1.0%, and 311〇2 is 0.01 to 1.0). %). Also, in Si〇2_ Al2〇3-B2 In the case of the 3_RO-based glass, in order to improve the meltability, the ratio of SB203 and Sb205 is preferably 0.2%, and the total amount of F2, Cl2, C, s〇3, and Sn2 is 0.1 to 3.0%. FhO3 can also be used as a clarifying agent. However, in order to color the glass, the content is limited to 500 ppm or less, preferably 300 ppm or less, more preferably 200 ppm or less. Ce〇2 can also be used as a chelating agent, however In order to color the glass, the content thereof is 2% or less, preferably 1% or less, more preferably 〇7% 146 13146pif.doc/008 17 1358396 or less. Ti02 has an effect of improving the weather resistance of the glass and lowering the high temperature viscosity, but It is not preferable because it can promote the coloring caused by FhO3. However, when Fe2〇3 is 200 ppm or less, it can be contained to 5%. Zr〇2 is a component that improves weather resistance, but it is easy to contain radioactive isotope. The content is 0 to 2% 'preferably 0 to 0.5%', more preferably 5 〇〇 ppm or less. The glass cover for semiconductor package of the present invention has the above basic composition and uses high-purity raw materials and impurities. Melting ring that is difficult to mix in , and can precisely control the content of U, Th, Fe203, PbO, Ti02, Mn02, Zr02, etc. In particular, Fe2〇3, Pb〇, Ti〇2, Mn〇2' which affect the transmittance near the ultraviolet ray can be The individual management is at the level of 1 to loo ρρηι, and u and Th which cause soft mis-recording of the CCD element due to α-ray are individually managed at a level of 1 to 10 ppb. Moreover, the CCD is prone to soft mis-recording due to alpha rays. Today, it is desirable that the amount of α-ray emission from the glass cover is less than 0.005 c/cm2. hr. In the case of CMOS, soft mis-recording due to alpha rays is less likely to occur, and the radiation from the glass cover is released. The amount is less than 0.5 c/cm2 · hr can also be used. Therefore, in the case of producing a glass cover for CMOS, it is not always necessary to use a high-purity raw material, and it is not necessary to reduce the mixing of U and Th during melting. Next, a method of manufacturing a glass cover for a semiconductor package in which the amount of α-ray emission is small will be described by way of an example. First, it is prepared to form a glass raw material composition having a desired composition of glass. As the glass raw material, a high-purity raw material having less impurities such as U and Th is used. More specifically, a high-purity raw material having a content of U and Th of 5 ppb or less is used. Next, the blended glass raw materials are put into a melting tank to be melted. A platinum container (including a uranium-tantalum container) can be used for the melting tank. However, since it is easy to mix the platinum particles in the glass, it is preferable that at least the inner wall (the zenith, the side surface, and the bottom surface) of the melting tank is made of a fire-resistant material having a small U and Th content. Specifically, alumina refractories (for example, alumina-based electroformed 13146pif.doc/008 18 1358396 brick) or quartz refractories (for example, 矽block) are not easily corroded, and U and Th contents can be made less than 1 ppm each. It is preferable that the amount of elution of u and Th into the glass is low. Next, homogenization of the molten glass (defoaming and removal of the grain) is carried out in the Chengyu tank. This Chengyu tank can be made of refractory or platinum. Moreover, the general oxidized fault refractory 'in the reverse side with very good corrosion resistance, due to having a large amount of radiation isotope, must be avoided in use, however, if the impurities in the zirconia refractory are lowered, and U, When the Th content is reduced to 1 ppm or less, it is used as an inner wall of the melting tank, and a glass cover for semiconductor package having a small amount of α-ray emission can be produced. Thereafter, the homogenized glass is formed into a plate shape by a pulling method to obtain a plate glass having a desired thickness. The pulldown method can use the overflow pulldown method or the slit pulldown method. The sheet glass obtained in this way is subjected to fine cutting processing in a certain size, and is subjected to leveling processing as needed to produce a glass cover. The glass cover for packaging of the present invention will be described below based on examples. Fig. 1 shows a glass cover 10 for an embodiment of a semiconductor package. The glass cover 10 for semiconductor encapsulation is a plate-shaped glass having a first light-transmissive surface 1a and a second light-transmissive surface 10b facing the thickness direction of the sheet, and forming a side surface i〇c of the edge. The size of the glass cover 10 is 14 x 16 x 0.5 mm, and the first light transmitting surface 10a and the second light transmitting surface i〇b are boring surfaces, and any of the surface roughness (Ra) is 0.5 nm or less. . Moreover, although the side surface i〇c is omitted in the drawing, it has a flat shape. Next, the results of the above-described method for producing a glass cover for a semiconductor package and its performance evaluation test will be described. The initial production step of the sheet glass is a step of producing a large sheet glass having a side of 5 mm or more. As described above, it is preferable to use an overflow down-draw method to form a plate-shaped glass having an excellent surface quality. The overflow down-draw method, as shown in Fig. 2, is a trench 11 formed by a refractory material to cause the molten glass 12 to flow, and the molten glass 12 overflowing from both sides of the 13146pif.doc/〇〇s 1358396 of the trench 11 is in the trench. The bottom of U is fused to form a plate shape and moves downward. According to this method, since the free surface of the molten glass forms the front surface of the sheet glass, the large sheet glass 13 excellent in smoothness can be obtained. Further, by controlling the melting conditions and the molding conditions, it is possible to easily form a large plate glass having a thickness of 〇5 to 0.7 mm Å and having a surface roughness (Ra) of 1.0 nm or less. According to this, it is possible to produce a glass cover for a semiconductor package which does not need to be honed on the surface of the large plate glass 13 and is subjected to fine cutting only by a predetermined size. The fine cutting method of the large plate glass can be mechanical cutting or laser cutting. Laser cutting first uses a hot-processed laser cutting device to achieve a laser beam moving speed of 180 ± 5 mm/sec or ® 220 ± 5 mm/sec on one side of a large piece of sheet glass, with a laser output of 120. ± 5W, or 160 ± 5W, cut to about 20% thickness in the direction of the plate thickness, and processed into a checkerboard eye shape. As shown in the commemoration of FIG. 3, the machined surface 13a of the large plate glass 13 is moved from the opposite side to the wire-shaped head 14 made of metal in the direction of movement, and by the large plate glass 13 The side of the machined surface 13a is pressed by a mold (not shown), and stress is applied to the machined surface 13a of the head block 13 to perform cutting. When the cutting is performed in this manner, a sheet-like glass having a short book shape which is divided along a predetermined line formed in the shape of the checkerboard eye is obtained. The sheet glass of the cut strip glass is pressed accordingly, and the vacuum is clamped (not shown) to the next step. Then, the short strip-shaped plate glass is again subjected to cutting processing to obtain a glass cover having a certain size. Table 1 shows examples (sample Nos. 1 to 5) of the glass cover for packaging of the present invention comprising SiO 2 -Al 2 O 2 -203 - R0 glass. 13146pif.doc/008 20 1358396 Table 1 (% by mass) Sample No Composition 1 2 3 4 5 Si02 59.0 63.0 58.0 59.0 59.0 ΑΙΑ 15.0 16.0 16.0 15.0 17.0 β2〇3 10.0 10.0 8.0 10.0 8.0 MgO 1 - 1.0 1.0 3.0 CaO 6.0 8.0 4.0 5.0 4.0 SrO 5.0 1.0 2.0 3.0 8.0 BaO 3.0 1.0 10.0 6.0 — ZnO 1.0 ———————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————— — A Sb203 1.0 1.0 1.0 1.0 1.0 Alkali dissolution (mg) <0.01 <0.01 <0.01 <0.01 <0.01 Density (g/cm3) 2.49 2.38 2.55 2.49 2.51 Poplar rate (Gpa) 77 70 70 68 77 Ratio of Yang type (Gpa/g*cm3) 28 29 27 27 31 Victorian hardness 600 580 590 570 610 Thermal expansion coefficient [30-380. . ] (X 1〇-7/°〇38 33 37 37 37 Liquidus temperature (°C) 1065 1105 1030 1055 1130 Liquid viscosity (dPa.s) 6.0 6.0 6.7 6.1 5.2 α-ray emission (c/cm2 · hr 0.0076 0.0035 0.0156 0.0108 0.0075 The glass sample of Table 1 was prepared as follows. First, the high-purity glass raw material prepared as shown in Table 1 13146pif.doc/008 21 1358396 was put into a platinum crucible. The electric melting furnace having the stirring function was melted at 1600 ° C for 20 hours. Secondly, the molten glass was discharged on a carbon plate and quenched to prepare a glass sample, and various characteristics were investigated. As shown in Table 1, Which glass, the amount of alkali elution is very small, and the density, Young's ratio, Young's ratio, Vickers hardness, and thermal expansion coefficient can satisfy the conditions required for the glass cover for semiconductor packaging. Moreover, since the liquidus temperature is 1130°. C or less, the liquidus viscosity is 1 〇 5·2 dPa or more, and is excellent in loss of transparency. Further, Tables 2 and 3 show the glass cover for packaging of the present invention which is formed of SiO 2 -Al 203-B 203-R20 glass. Example (Sample No. 6 to 17). 13146pi F.doc/008 22 1358396 Table 2 (% by mass) Sample No Composition 6 7 8 9 10 11 Si02 68.8 65.8 68.4 68.3 68.8 67.8 ΑΙΑ 7.0 8.0 5.2 7.5 7.0 8.0 BA 13.1 13.1 1.09 13.1 13.1 13.1 MgO 0.41 -1 CaO 2.2 0.6 3.2 — 0.6 0.6 SrO ___ One to one BaO one — one—one ZnO one 1.2 0.9 one — one NajO 6.7 8.6 5.6 8.9 6.7 8.6 K20 1.9 2.0 5.7 1.9 3.5 1.6 Li20 One _. A Ti02 - one - one - Sb203 0.3 0.3 0.3 0.3 0.3 0.3 Cl - one - one - Sn02 one - one - one S〇3 one - __ one by one Fe203 30ppm 30ppm 30ppm 30ppm 30ppm 30ppm U (ppb) 4 Not measured Not measured Not measured Not measured 4 Th(ppb) 2 Not measured Not measured Not measured Not measured 2 Thermal expansion coefficient (xl〇-7/°C) 55.8 62.8 64.9 62.0 59.0 60.4 Density (g/cm3) 2.35 2.37 2.42 2.36 2.35 2.35 Viscosity strain point ro 535 517 536 518 514 520 Xu cold point (. 〇571 554 576 561 558 561 Softening point rc) 765 743 760 755 760 754 104 (°C) 1119 1091 1093 1077 1102 1087 103 (°C) 1345 1301 1292 1282 1316 1300 102-5 (〇C) 1500 1456 1434 1434 1471 1455 Liquid temperature rc) 884 728 882 817 822 No loss of transparent liquid viscosity (dPa * s) 5.9 7.9 5.8 6.6 6.6 No loss of transparent alpha ray release (c/cm2 · hr) 0.0020 0.0022 0.0021 0.0021 0.0020 0.0021 23 13146pif .doc/008 1358396 Table 3 (% by mass) Sample No Composition 12 13 14 159 16 17 SiO? 66.5 68.8 66.8 65.8 66.9 68.3 ai, 〇3 8.0 7.0 7.0 8.0 7.5 7.0 β7ο, 13.1 12.0 13.1 13.1 13.1 13.1 MgO A – _ I—CaO 0.6 2.2 2.2 0.6 2.2 0.6 SrO ——— — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Li20 一一—一0.5 — Ti02 1.6 Sb203 0.3 0.3 0.3 0.3 — One Cl ——— One 0.2 One Sn02 0.3 0.3 S〇3 —— —— One to one lOOpprn Fe203 30ppm 30ppm 30ppm lOppm 30ppm 30ppm U(ppb) Not measuredNot measured 4 4 Not measured Unmeasured Th(ppb) Not measured Not measured 2 2 Unmeasured unmeasured hot leg coefficient (xi〇r〇59.9 59.1 62.8 61.4 60.6 55.8 Density (g/cm3) 2.36 2.37 2.39 2.36 2.36 2.33 Viscosity strain Point ro 509 531 530 510 527 521 Xu cold point Γ〇 552 574 568 552 568 561 softening point (. C) 752 764 745 · 744 759 761 104 (°C) 1106 1117 1059 1086 1095 1109 103 (°C) 1331 1341 1261 1306 1306 1333 1025 (〇C) 1483 1494 1401 1461 1454 1486 Liquid temperature rc) · Ming 867 855 822 842 853 Liquid viscosity (dPa · s) No loss of transparency 6.1 5.9 6.4 6.3 6.2 ^ Ray release (c/cm2 · hr) 0.0021 0.0021 0.0021 0.0021 0.0023 0.0030 13146pif.doc/008 24 1358396 Table 2 Each of the glass samples '3' was produced as follows. First, the high-purity glass raw material prepared as shown in the table is put into a crucible made of one of platinum rhodium, oxidized mist, and quartz, and is subjected to an electric melting furnace having a stirring function at a temperature of 1550 degrees Celsius for 6 hours. Melting and flowing the molten glass on a carbon plate 'cool the plate glass to obtain a glass sample. As shown in the table, 'each glass sample satisfies the requirements of the thermal expansion coefficient, density, and α-ray emission amount to satisfy the glass cover for semiconductors, and the viscosity is 1 1500 dPa·s, and the viscosity is 1500 ° C or less. The liquid viscosity is 105·8 dPa, which is excellent in loss of transparency above s. Further, the amount of alkali elution in the table is measured based on JIS R3502. The density is measured by the well-known Archimedes method. Young's rate is calculated by the non-destructive elastic measuring device (KI-11) manufactured by Zhongfang (stock), and the Young's rate and density measured by the resonance method are calculated. The Vickers hardness is measured based on JIS Z2244-1992. The coefficient of thermal expansion is measured by using a dilatometer to measure the average coefficient of thermal expansion in the temperature range of 30 to 380 °C. The liquidus temperature will be pulverized to 300~500; the particle size of czm will be placed in a platinum boat and kept in a temperature-matched oven for 8 hours. Observed by a microscope, the measurement will see the interior of the glass sample lose transparency. The highest temperature of (crystalline foreign matter), which is the liquidus temperature. Moreover, the viscosity of the glass at the liquidus temperature is taken as the liquid phase viscosity. The glass samples of No. 11 and 12 did not lose transparency, and in particular, they had excellent resistance to loss of transparency. The contents of U and Th were measured by ICP-MASS. Further, the strain point and the quenching point were measured in accordance with the method of ASTM C336-71, and the softening point was measured in accordance with the method of C338-93. 104 dPa · S, 103 dPa · S and 102 5 dPa · S, obtained by the well-known platinum ball rising method. 102·5 dPa · S temperature measurement The high temperature viscosity is a temperature equivalent to 1 〇 2·5 poise. The lower the enthalpy, the better the meltability. The amount of α-ray emission was measured using an ultra-low-grade α-ray measuring device (LACS-400M manufactured by Sumitomo Chemical Co., Ltd.). 13146pif.doc/008 25 !358396 Further, the glass samples of Nos. 1, 6, 11, 14 and 15 of Tables 1 to 3 were melted in an experimental melting tank (alumina refractory), and thickness was formed by an overflow down-draw method.板·5 mm plate shape, the surface is not honed, and the laser cutting is performed by laser cutting to produce a glass cover with a vertical dimension of 14 mm and a horizontal dimension of 16 mm. Further, for comparison, the raw material of the glass constituting the sample No. 1 was dissolved in the above-mentioned experimental melting tank, cast in a size of 800 x 300 x 300 mm, and cut into a sheet thickness of 1.5 mm by a wire saw. Plate shape. Thereafter, both sides of the plate glass were subjected to precision honing by a rotary honing machine to form a large piece of plate glass (thickness 〇·5 mm), and finely cut by laser cutting to produce a vertical size of 14 Glass cover with mm and horizontal dimensions of 16 mm. The surface roughness (Ra) of the light-transmissive surface (the first light-transmissive surface and the second light-transmitting surface) in the surface of each of the glass covers produced in this manner was probe-type surface roughness measuring machine Talystep (Tayler-Hobson) The measurement was carried out, and the results are shown in Table 4. Table 4 Sample No. 1 6 11 14 15 Comparative Example Surface Roughness (Ra) 1st Transmissive Surface 2nd Transmissive Surface 0.15nm 0.20nm 0.20 nm 0.15 nm 0.23 nm 0.19 nm 0.20 nm 0.18 nm 0.18nm 0.16 nm 0.56 Nm 0.95 nm As clearly shown in Table 4, the glass cover of the example has an extremely smooth surface, regardless of the surface roughness (Ra) of the first light-transmissive surface or the second light-transmissive surface of 0.23 rnn or less. The glass cover of the comparative example had a surface roughness (Ra) of 〇_56 or more even when precision honing was applied. Further, the light-transmissive surface of each of the glass covers was observed by an atomic force microscope (AFM), and the glass cover of the comparative example was formed with minute scratches on the entire surface thereof, and the glass cover of the example was identified as 13146 pif.doc/008 26 1358396 No such scars. INDUSTRIAL APPLICABILITY The glass cover for packaging of the present invention is suitable for a glass cover for solid-state imaging device packaging, and is also applicable to a glass cover for packaging various semiconductor packages such as a laser diode. And 'this glass cover is 30~38 (the average thermal expansion coefficient of the temperature range of TC is 30~85x 10_7/°C, except for the alumina package, for resin, tin metal, gu alloy, combination gold, 36Ni-Fe Various packages made of alloy, 42 Ni-Fe alloy, 45Ni-Fe alloy, 46Ni-Fe alloy, and 52Ni-Fe alloy can be packaged with organic resin or low melting point glass. [Simplified illustration] Figure 1 Fig. 2 is an explanatory view showing a method of forming a sheet glass using an overflow down-draw method. Fig. 3 is a view showing a large plate shape using a laser cutting method. Method for fine-cutting glass. [Illustration of pattern designation] 10: Glass cover for semiconductor package 1.0a: First light-transmissive surface 10b: Second light-transmissive surface 10c: Side surface 11: Trench 12: Molten glass 13: Large Plate-shaped glass 13a: machined surface 14: linear head Μ: action direction 13146pif.doc/008 27