TW200842116A

TW200842116A - Cover glass for solid state imaging device and method for manufacturing the cover glass

Info

Publication number: TW200842116A
Application number: TW096151486A
Authority: TW
Inventors: Hiroaki Nakahori; Daisuke Okawa; Masahiro Yodogawa
Original assignee: Nippon Electric Glass Co
Priority date: 2007-01-05
Filing date: 2007-12-31
Publication date: 2008-11-01
Also published as: TWI393687B; CN101553926B; KR101413499B1; JP2008187170A; JP5347267B2; CN101553926A; KR20090101207A; WO2008081828A1

Abstract

This invention provides a cover glass for a solid state imaging device, which is less likely to undergo the separation of a covering film provided on the cover glass on its light transparent face, can realize satisfactory bonding area and bonding strength to a substrate, has a high level of mechanical strength and a high level of optical properties, and stable chemical properties, and has a high level of cleanness, and a method for manufacturing the cover glass.; A cover glass (10) for a solid state imaging device is characterized in that it comprises a thin sheet formed of an inorganic oxide glass, the thin sheet has two light transparent faces (11, 12) opposed to the sheet thickness direction, a covering film (C1, C2) is provided on at least one of the light transparent faces (11, 12), the outer peripheral end face of the cover glass (10) is formed of faces (13, 14) cut by a laser beam, and the covering film (C1, C2) has been formed before the laser beam cutting.; The method for manufacturing the cover glass comprises the step of melting a glass raw material mixture, the step of molding the molten glass into a sheet glass (G), the step of forming a covering film (C1, C2) on at least one of two light transparent faces (11, 12) of the sheet glass (G) (film forming step), the step of applying a laser beam to the sheet glass with the covering film (light application step), and the step of dividing the sheet glass subjected to the laser beam application step into small glass pieces.

Description

200842116 九、發明說明：【發明所屬之技術領域】本發明係關於-種作為使光線透過收納有固態攝像元件之封裝的窗材而配設、用以保護固態攝像元件之玻璃蓋及[Technical Field] The present invention relates to a glass cover which is provided as a window material for allowing light to pass through a package in which a solid-state image sensor is housed, and for protecting a solid-state image sensor.

其製造方法。 I • 【先前技術】 ' 固11攝像元件除了隸在掃描器或傳真機（fax machine) 垂等中所使用的消耗電力較低之cis(Contact Image Sens〇r， #接觸式影像感測器）之用途外，亦可藉由於行動電話或 PHS(Personal Handyphone System，個人手機系統）等小型 f訊終端設備等上搭載有數位攝影機，而實現更多樣化之高性能。就用於上述用途之固態攝像元件而言，大致分為 CCD(Charge Coupled Device，電荷耦合元件）與cm〇s(亦稱作 c〇mplementary Metal 〇xide ⑽互補金氧半導體）。1990年代，CCD以顯著高像素化等為首的各修種欧此付取得了較大進步，近年來，亦藉由對克服了技術性課題而促進其用於各種用途中。 • 就作為輸入如此之固態攝像元件之圖像資訊之窗材而使用的玻璃盖而言，伴隨固態攝像元件之發展而逐步克服了 ' 各種課題。且正在不斷努力嘗試減少玻璃才反中所含有等貴金屬、耐火物等之各種微細異物、或者附著於玻璃表面之灰塵、垃圾或微粒等。專利文獻1中揭示有：為了對破璃盍之表面及内面加以區分地檢測出附著於玻璃蓋表面垃圾，而使用有組合有垂直照明與斜光照明之檢查裝 128130.doc 200842116 置。因玻璃蓋表面垃圾之附著可作為雜訊而被檢測出，故對於要求高精度圖像之固態攝像元件而言，該玻璃蓋表面之垃圾之檢測較為重要。又，專利文獻2中，為了減少因玻璃蓋中所含有之鈾（u)或钍（Th)等放射性同位元素所引起之α射線之產生量，而提供有放射性同位元素之含量較少之玻璃組成。因α射線會導致固態攝像元件所拍攝之圖像中產生被稱作白斑之缺陷，因此，解決了上述問題。進而，專利文獻3中揭示有如下發明：藉由將具有特定組成之薄玻璃板成形品之側面形狀限定為特定之形狀，則可實現高強度、高化學耐久性。專利文獻4中揭示有如下發明：藉由限定-個面上預先形成有被覆膜之固態攝像元件用玻璃蓋之被覆膜之端緣部的形狀，可減少因被覆膜邊緣部所引起之玻璃蓋之缺陷。專利文獻1:日本專利特開2〇〇〇_295639號公報專利文獻2·日本專利特開平7-215733號公報專利文獻3:日本專利特開2〇〇 ‘ 221541號公報專利文獻4 ·曰本專利特開2〇〇6-14〇458公報【發明内容】發明所欲解決之問題 ☆然而，至今所完成之發明+，於以穩定品質供給更高性能之固態攝像元件用玻璃蓋該方面還存在問題。使態攝像元件之電子設備’進行了各種技術革新，除了功1 方面亦要求其尺寸或形狀等輕薄短小化。因此，伴隨固：攝像7G件之輕薄短小化，亦必須要求固態攝像元件用坡璃 128130.doc 200842116 蓋輕薄短小化，從而開發出滿足上述條件之製品。然而，因小型化或薄型化之急速發展，至今所完成之對固態攝像 T件用玻璃蓋之各種改良或發明中，尚未能充分實現穩定地供給固態攝像元件。具體而言，作為對固態攝像元件用之玻璃蓋之要求，有如下：即使減小收納有固態攝像元件之封裝之外形尺寸，亦能滿足玻璃蓋與封裝基板不會剝離之充分高之接著強度，且即使增大收納於封裝中之固態攝像元件之面積，亦具有可充分收納於封裝内之模穴部面積，另一方面可實現與封裝基板間之充分接著強度的接著部面積，^而可實現優良之品質與性能。進而’除了如上述般要求封裝或玻璃蓋輕薄短小之外， 2要求各種波長之光線透過之玻璃板表面具有用以實現所需透射率之高潔淨度、且具有高化學耐久性，而且，即使係厚度尺寸或透光面之面積較小之玻璃蓋，亦會妨礙實際使用之強度。即使厚度尺寸或透光面之面積等較小’尤其是就伴隨行動電話等各種行動裝置之顯著發展而搭載於如上述般之精密機器之固態攝像元件而' 在會對穩定機械強度造成威脅之表面傷痕或碎片專各種表面缺陷，料受職讀擊之情料，亦會產生由上述原因所引起之玻璃蓋易破碎之致命性問題: 險1此’對於用作封裝或玻璃蓋之玻璃板而言，& 有南於先前之精密加工精度與較高之形狀品質。二口心攝像7G件用破璃蓋而言，有時會藉由於其透光面被 128130.doc 200842116 所需之膜而加以使用，於玻璃表面形成有被覆膜之狀態下之固態攝像元件用玻璃蓋的潔淨度，亦會引起如下門題. 膜後之處理歷程之情況，會出現膜周緣容易剝離而之微細剝離物會浮游而附著於玻璃蓋表面等問題， :而，對於經成膜之固態攝像元件用玻璃蓋之潔淨度而 a ’重要課題在於實現高品質。 ,,因此，本發明者們實施了上述專利文獻4中之發明，僅對專利文獻4中之不充分之古品壬k ^ 刀之方面，重新研究其製造步驟， :覆研究可更有效地製造、且具有穩定品質之經成膜的固恶攝像元件用玻璃蓋。亦即’#於上述狀況’本發明者們的課題在於提供一種 :態攝像元件用玻璃蓋及其製造方法：因用作高像素之固態攝像S件之透光窗用途之玻璃蓋係加工精度優良且形狀品質較高之玻璃板材，故而，覆蓋於玻璃蓋之透光面之被覆膜難以容易地剝離，且與基板具有充分的接著面積與接著強度，玻璃板端面之加工品質亦優良，從而，具有高機械強度與高光學性能、進而是敎之化學性能，且潔淨度較高。解決問題之技術手段本發明之固態攝像it相玻璃蓋係無機氧化物玻璃製之薄板狀之固態攝像元件用玻璃蓋，於在板厚方向上相對向之兩個透光面之至少-面上具有被覆膜，玻璃蓋之外周端面係由已藉由雷射切斷之面構成’讀覆膜形成於雷射切斷之前。 128130.doc 200842116 此處，所謂無機氧化物玻璃製之薄板狀之㈣攝像元件用玻璃蓋係指，以覆蓋固態攝像元件之封裝之整個面之方式而用於固態攝像元件用途之玻璃蓋，且該玻璃蓋由按照無機元素之氧化物換算之質量百分比來表示玻璃組成之玻帛而組成。又，所謂於在板厚方向上相對向之兩個透光面之至少一面上具有被覆膜係表示，於在板厚方向上相對向之兩個呈大致矩形狀之透光面的兩個面上具有薄膜狀之被籲 I膜，或者任-個面上具有薄膜狀之被覆_。所謂玻璃蓋之外周端面由藉由雷射而切斷之面構成係指，呈矩形狀之外形的四個邊之任一面均藉由照射雷射進行切斷加工而形成。而且，所謂被覆膜係於雷射切斷之前予以成膜係指，藉由被覆膜之成膜而形成於至少一面上之被覆膜形成於雷射切斷之前。關於覆蓋於在板厚方向上相對向之兩個透光面之至少一面上之被覆膜（簡稱為薄膜），對其材質或厚度、構成等並 φ 未加以特別限制，可根據需要而採用任意者。亦即，就被復膜而σ ，可覆蓋紅外線反射膜（或者紅外線截止過濾 _ 膜）、抗反射膜（亦稱作AR膜）、無反射膜、導電膜、抗靜 ’ 電膜、低通濾波器、高通濾波器、帶通濾波器、遮蔽膜、 " 強化膜、或者保護膜等。尤其是紅外線反射膜，因CCD之紅外線區域之靈敏度較高，故可藉由抑制其入射至紅外線之兀件而使固態攝像元件之圖像接近肉眼所觀察到之圖像，故而較佳。就被覆兩個透光面之被覆膜之種類而言，可相同亦可不同。又，亦可將具有不同功能之異種被覆膜 128130.doc •10- 200842116 積層於1個面上。當麸，、、為了達成相同目的，對積層被覆、、之積層數未加以限定，可增加至2層、3層、4層、$ 進而亦可形成為具有1〇層、2〇層、層、⑽層等任竟層數之多層構造。 “ 就上述被覆膜而言，其被覆膜之具體材質可為如下之各種例如可使用具有如下組成者：二氧化石夕（Si02)、三氧化一鋁（Ah〇3)、二氧化锆（Zr〇2卜五氧化二鈕（或者 Tamala)(Ta2〇5)、五氧化二錕⑽办）、三氧化二鑭 (U2〇3)、三氧化二釔（丫2〇3)、氧化鎂（Mg〇)、二氧化铪 (Hf〇2)、二氧化二鉻（Chh)、二氟化鎂迚2)、三氧化鉬 (Mo03)、三氧化鎢（w〇3)、二氧化鈽（Ce〇2)、二氧化釩 (vo2)、四氧化鈦锆（ZrTi〇4)、硫化鋅（21^)、冰晶石 (Na3AlF6)、錐冰晶石（NasAl3Fi4)、三氟化釔（γΡ3)、二氟化鈣（CaF2)、三氟化鋁（AiF3)、二氟化鋇（BaF2)、氟化鋰 (UF)、三氟化鑭（LaF3)、三氟化釓（GdF3)、三氟化鏑 (DyFO、三氟化鉛（|>|^3)、二氟化锶（8]^2)、含銻之氧化錫 (ΑΤΟ)膜、氧化銦-锡膜（IT0膜）、以〇2與Al2〇3之多層膜、 SiOx-TiOx 系多層膜、Si02-Ta205 系多層膜、Si〇x-La〇x_ TiOx系列之多層膜、Ιη2〇3_Υ2〇3固溶體膜、氧化鋁固溶體膜、金屬薄膜、膠體粒子分散膜、聚甲基丙烯酸曱醋膜 (PMMA(poIymethyl methacrylate)膜）、聚碳酸醋膜 (PC(polycarbonate)膜）、聚苯乙烯膜、或者甲基丙烯酸甲酯-苯乙烯共聚膜、聚丙烯酸酯膜等之組成。又，關於被覆膜之形成方法，只要係可實現特定之表面 328130.doc 11 200842116 精度、功能且不會增加製造所需之費用之方法即可，並無特別限定，可採用各種方法。例如濺鍍法、真空蒸鍍法、或者熱 CVD(chemieal 法、雷射CVD法、 (molecular beam epitaxy)法）、離子電鍍法、雷射剝離法 vapor deposition，化學氣相沈積）電漿CVD法、分子束磊晶法（mbe 有機金屬化學氣相沈積法（M〇CVD，Its manufacturing method. I • [Prior Art] 'Solution 11 image sensor is a low-cost cis (Contact Image Sens〇r, #contact image sensor) used in scanners or fax machines. In addition, it is possible to achieve a more diverse high performance by mounting a digital camera on a small mobile terminal such as a mobile phone or a PHS (Personal Handyphone System). The solid-state image pickup device used for the above-mentioned applications is roughly classified into a CCD (Charge Coupled Device) and a cm〇s (also referred to as a c〇mplementary Metal 〇xide (10) complementary oxy-semiconductor). In the 1990s, CCDs made significant progress in various types of cultivation, such as significantly high pixelation. In recent years, they have also been promoted for various uses by overcoming technical problems. • As for the glass cover used as the window material for inputting image information of such a solid-state image sensor, the various problems have been gradually overcome with the development of the solid-state image sensor. In addition, we are constantly striving to reduce the amount of fine foreign matter such as precious metals and refractories contained in glass, or dust, garbage, or particles adhering to the surface of glass. Patent Document 1 discloses that in order to detect the adhesion to the surface of the glass cover by distinguishing between the surface and the inner surface of the glass crucible, an inspection apparatus 128130.doc 200842116 in which vertical illumination and oblique illumination are combined is used. Since the adhesion of the surface of the glass cover can be detected as noise, it is important to detect the garbage on the surface of the glass cover for a solid-state image sensor that requires a high-precision image. Further, in Patent Document 2, in order to reduce the amount of α-rays caused by radioactive isotope such as uranium (u) or thorium (Th) contained in the cover glass, glass having a lower content of radioactive isotope is provided. composition. The above problem is solved because alpha rays cause defects in the image captured by the solid-state image sensor to be called white spots. Further, Patent Document 3 discloses an invention in which the side shape of a thin glass sheet molded article having a specific composition is limited to a specific shape, thereby achieving high strength and high chemical durability. Patent Document 4 discloses that the shape of the edge portion of the coating film of the glass cover for a solid-state image sensor for which a coating film is formed in advance is limited, and the edge portion of the coating film can be reduced. The defect of the glass cover. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 7-215733. Patent Document 3: Japanese Patent Laid-Open No. 2 221541 Patent Publication No. 2-6-14〇458 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION ☆ However, the invention completed so far has been in the field of providing a glass cover for a solid-state image sensor having higher performance with stable quality. There is a problem. Various electronic innovations have been made in the electronic device of the image pickup device, and in addition to the work, the size and shape thereof are required to be light and thin. Therefore, in order to reduce the weight and thickness of the 7G device, it is necessary to require the solid-state image sensor to be light and thin, and to develop a product that satisfies the above conditions. However, in the various improvements or inventions for the glass cover for solid-state image pickup devices, the solid-state image pickup device has not yet been sufficiently stably supplied due to the rapid development of miniaturization or thinning. Specifically, as a requirement for a glass cover for a solid-state image sensor, it is possible to satisfy a sufficiently high bonding strength that the glass cover and the package substrate are not peeled off even if the size of the package in which the solid-state image sensor is housed is reduced. Moreover, even if the area of the solid-state image sensor housed in the package is increased, the area of the cavity portion that can be sufficiently accommodated in the package can be achieved, and the area of the adhesion portion with sufficient adhesion strength between the package substrate and the package substrate can be realized. Excellent quality and performance. Further, in addition to requiring the package or the glass cover to be light and thin as described above, 2 the surface of the glass plate through which light of various wavelengths is required has high cleanliness to achieve desired transmittance and high chemical durability, and even A glass cover having a small thickness or a light-transmissive surface may also impede the strength of actual use. Even if the thickness is small or the area of the light-transmissive surface is small, in particular, it is mounted on a solid-state image sensor of a precision machine as described above with the remarkable development of various mobile devices such as mobile phones, and it poses a threat to stable mechanical strength. Surface flaws or debris Dedicated to various surface defects, which are expected to cause damage to the glass cover caused by the above reasons: Risk 1 This is for a glass plate used as a package or glass cover. In terms of &, there is a previous precision machining accuracy and higher shape quality. In the case of a two-portion 7G piece with a broken glass cover, a solid-state image pickup element in a state in which a coating film is formed on a glass surface by a film which is required for the light-transmissive surface to be used by 128130.doc 200842116 is sometimes used. The cleanliness of the glass cover also causes the following problems. In the case of the treatment process after the film, there is a problem that the peripheral edge of the film is easily peeled off and the fine peeling material floats and adheres to the surface of the glass cover, etc. The cleanliness of the glass cover for the solid-state image sensor of the film is a key issue in achieving high quality. Therefore, the inventors of the present invention have carried out the invention of the above-mentioned Patent Document 4, and have re-examined the manufacturing steps only in respect of the insufficient artifacts in Patent Document 4, and the research on the cover can be more effective. A glass cover for a solid-film image sensor that has been produced and has a stable quality. In other words, the inventors of the present invention have an object of providing a glass cover for a state of the image sensor and a method for manufacturing the same: a glass cover processing precision for use as a light-transmitting window for a solid-state image pickup S of a high pixel Since the glass sheet having excellent shape and high quality is difficult to be easily peeled off, the coating film covering the light-transmissive surface of the glass cover has sufficient adhesion area and adhesion strength to the substrate, and the processing quality of the end surface of the glass sheet is also excellent. Therefore, it has high mechanical strength and high optical properties, and is further chemical, and has a high degree of cleanliness. MEANS FOR SOLVING THE PROBLEMS The solid-state imaging phase-in-glass cover of the present invention is a glass cover for a thin-plate solid-state image sensor made of inorganic oxide glass, at least in the plane of the two opposite light-transmissive surfaces in the thickness direction. The coating film is provided, and the outer peripheral end surface of the glass cover is formed by the surface cut by the laser. The reading film is formed before the laser cutting. 128130.doc 200842116 Here, the glass cover for the image sensor of the thin plate of the inorganic oxide glass is used for the glass cover of the solid-state image sensor for covering the entire surface of the package of the solid-state image sensor. The glass cover is composed of a glass composition of a glass composition in terms of a mass percentage in terms of an oxide of an inorganic element. Further, at least one of the two light-transmissive surfaces facing each other in the thickness direction has a coating film, and two of the two substantially transparent light-transmissive surfaces are opposed to each other in the thickness direction. The film has a film-like I film, or a film-like coating on any one surface. The outer peripheral end surface of the glass cover is formed by a surface cut by laser, and any one of the four sides of the rectangular outer shape is formed by cutting by laser irradiation. Further, the coating film is formed by forming a film before the laser cutting, and the coating film formed on at least one surface by the film formation of the coating film is formed before the laser cutting. The coating film (referred to as a film) covering at least one of the two light-transmissive surfaces facing each other in the thickness direction is not particularly limited in terms of material, thickness, configuration, and the like, and may be used as needed. Any one. That is, it is laminated and σ can cover the infrared reflective film (or infrared cut filter _ film), anti-reflective film (also known as AR film), non-reflective film, conductive film, anti-static film, low pass Filters, high-pass filters, bandpass filters, masking films, " reinforced films, or protective films. In particular, since the infrared ray reflection film has high sensitivity in the infrared ray region, it is preferable to suppress the image of the solid-state image sensor from being incident on the image observed by the naked eye by suppressing the incident on the infrared ray. The type of the coating film covering the two light transmitting surfaces may be the same or different. Further, a dissimilar film 128130.doc •10- 200842116 having different functions may be laminated on one surface. When the bran, and the same purpose are used, the number of layers of the laminated coating is not limited, and may be increased to 2 layers, 3 layers, 4 layers, and further formed to have 1 layer, 2 layers, layers. , (10) layer, etc., the multilayer structure of the number of layers. "For the above-mentioned coating film, the specific material of the coating film may be as follows. For example, a composition having the following composition: SiO 2 (SiO 2 ), aluminum arsenide (Ah 〇 3 ), and zirconia may be used. (Zr〇2 Bu pentoxide oxide (Tamala) (Ta2〇5), bismuth pentoxide (10), bismuth trioxide (U2〇3), antimony trioxide (丫2〇3), magnesium oxide (Mg〇), cerium oxide (Hf〇2), chromium dioxide (Chh), magnesium difluoride bismuth 2), molybdenum trioxide (Mo03), tungsten trioxide (w〇3), cerium oxide ( Ce〇2), vanadium dioxide (vo2), zirconium tetraoxide (ZrTi〇4), zinc sulfide (21^), cryolite (Na3AlF6), cone cryolite (NasAl3Fi4), lanthanum trifluoride (γΡ3), Calcium difluoride (CaF2), aluminum trifluoride (AiF3), barium difluoride (BaF2), lithium fluoride (UF), barium trifluoride (LaF3), barium trifluoride (GdF3), trifluoride镝 (DyFO, lead trifluoride (|>|^3), bismuth difluoride (8)^2), antimony-containing tin oxide (yttrium) film, indium oxide-tin film (IT0 film), 2 multilayer film with Al2〇3, SiOx-TiOx multilayer film, SiO2-Ta205 multilayer film, Si〇x-La〇x_ Ti Ox series multilayer film, Ιη2〇3_Υ2〇3 solid solution film, alumina solid solution film, metal film, colloidal particle dispersion film, polymethyl methacrylate film (PMMA (poIymethyl methacrylate) film), polycarbonate a composition of a film (PC (polycarbonate) film), a polystyrene film, or a methyl methacrylate-styrene copolymer film, a polyacrylate film, etc. Further, as for the method of forming the coating film, a specific method can be realized. Surface 328130.doc 11 200842116 The method of precision and function without increasing the cost required for manufacturing is not particularly limited, and various methods such as sputtering, vacuum evaporation, or thermal CVD (chemieal method, Laser CVD method (molecular beam epitaxy), ion plating, laser deposition, chemical vapor deposition, plasma CVD, molecular beam epitaxy (mbe organometallic chemical vapor deposition (M) 〇CVD,

Chemical VaP〇r Depositi〇n)等化學氣相沈積法（或 cvd 法）、進而是溶膠-凝膠法、旋轉塗佈法或絲網印刷之塗佈法、或者電鑛法等液相成長法，均可作為形成本發明之被覆膜之方法而採用。其中，該等方法中，尤其是CVD法能夠以低溫形成密著性優良之被覆膜’可適應於各種被膜，適於化合物之被膜形成，因此係較佳之方法。關於固態攝像it件用玻璃蓋之材質，只要滿足所需光學 {•生此，即可使用任一種材質。例如，適合使用硼矽酸玻璃、石英玻璃、無鹼玻璃、鋁矽酸鹽玻璃、實質無鈾與钍之玻璃、磷酸鹽玻璃、鈉鈣玻璃、高折射率玻璃、或者高軟化點玻璃等各種玻璃材質。口作為藉由雷射切斷固態攝像元件用玻璃蓋之外周端面之方法，例如藉由二氧化碳氣體雷射形成第一加工面，接著二以使藉由二氧化碳氣體雷射照射而形成之第一加工面之刖端為支點的方式，向支點之正下方施加彎曲應力進行㈣’藉此形成第二加工面。此處，第一加工面之形成係藉由如下所述而完成：於覆蓋有被覆膜之透光面之表面，以光束強度分布為±5%以内之輸出條件，照射光束點形狀 128130.doc 200842116 如此，新生成為橢圓、大致矩形狀、直線狀、三角形狀之二氧化碳氣體雷射且以等速度直線驅動，藉此，於相當於光束驅動部位之形成有被膜之玻璃板之玻璃表面與形成於該表面之被膜之兩者上形成切口，對該部位之被膜進行蒸發或者切斷，於玻璃板之剖面方向形成特定深度之切口之表面成為第一加工面。Chemical vapor deposition (or cvd method) such as Chemical VaP〇r Depositi〇n), further sol-gel method, spin coating method or screen printing coating method, or liquid phase growth method such as electromineral method Both can be employed as a method of forming the coating film of the present invention. Among these methods, in particular, the CVD method is capable of forming a coating film having excellent adhesion at a low temperature, which is suitable for various coating films, and is suitable for formation of a film of a compound, and is therefore a preferred method. For the solid-state camera, the material of the glass cover is used as long as it meets the required optics. For example, it is suitable to use borosilicate glass, quartz glass, alkali-free glass, aluminosilicate glass, substantially uranium-free glass, phosphate glass, soda lime glass, high refractive index glass, or high softening point glass. Glass material. The port is a method of cutting a peripheral end surface of a glass cover for a solid-state image sensor by laser, for example, forming a first processed surface by a carbon dioxide gas laser, and then performing a first processing formed by a carbon dioxide gas laser irradiation. In the manner in which the end of the face is a fulcrum, a bending stress is applied directly under the fulcrum to perform a fourth working surface. Here, the formation of the first processing surface is accomplished by: illuminating the beam spot shape 128130 on the surface of the light transmissive surface covered with the coating film with an output condition of within ±5% of the beam intensity distribution. Doc 200842116 In this way, the new element is an elliptical, substantially rectangular, linear, triangular-shaped carbon dioxide gas laser that is linearly driven at a constant speed, thereby forming a glass surface and forming a glass plate corresponding to the light beam driving portion. A slit is formed in both of the coatings on the surface, and the film of the portion is evaporated or cut, and the surface of the slit having a specific depth in the cross-sectional direction of the glass sheet becomes the first processed surface.

*本發明之固態攝像元件用玻璃蓋係無機氧化物玻璃製之薄板狀之固態攝像元件用玻璃蓋，於在板厚方向上相對向之兩個透光面之至少一面上具有被覆臈，玻璃蓋之外周端面由已藉由雷射切斷之面構成，從而可簡化步驟且有效地製造，因此較佳。又二本發明之固態攝像元件用玻璃蓋的特徵在於：其係無機氧化物玻璃製之薄板狀之固態攝像元件用玻璃蓋，於在板厚方向上相對向之兩個透光面之至少—面上具有被覆臈’被覆膜之外周端固著於透光面。此處，所謂本發明之固態攝像元件用玻璃蓋係無機氧化物玻璃製之薄板狀之固態攝像元件用玻璃蓋，於在板厚方向上相對向之兩個透光面之至少一面上具有被覆臈，被覆膜之外周端固著於透光面係指，透光面上之被覆膜於外周端部以高溫受到加熱’膜之邊緣料化，藉此，被覆膜難以剝離且成為牢固地接合之狀態。因此，可減少因膜剝離而產生之灰塵或異物等，且可抑制因灰塵或異物附著而產生之不良的產生數。又，除上述之外，本發明之固態攝像元件用玻璃蓋中， 128130.doc 200842116 若被覆膜係抗反射膜，則可實現玻璃蓋之可視透過率達到充分高之透射率值的性能。此處，所謂被覆膜係抗反射膜係指，藉由將具有折射率小於藉由玻璃之組成而決定之玻璃之折射率的透明被膜附於玻璃之表面，可減少反射光且可增加透過玻璃蓋之光線之光量。作為構成抗反射膜之膜之材料，可適當採用Ti〇2、In the glass cover of the solid-state image sensor of the present invention, the glass cover for a solid-state image sensor of a thin plate-shaped inorganic oxide glass has a coating on at least one of the two light-transmissive surfaces in the thickness direction. The outer peripheral end surface of the cover is constituted by the surface which has been cut by the laser, so that the steps can be simplified and efficiently manufactured, which is preferable. Further, the glass cover for a solid-state image sensor of the present invention is characterized in that it is a glass cover for a solid-state image sensor having a thin plate shape made of inorganic oxide glass, and at least two of the two light-transmissive surfaces in the thickness direction are - The outer surface of the coating having the coating 臈' coating is fixed to the light transmitting surface. Here, the glass cover for a solid-state image sensor having a thin plate shape made of a glass cover-based inorganic oxide glass for a solid-state image sensor of the present invention has a coating on at least one of two light-transmissive surfaces in the thickness direction.臈, the outer peripheral end of the coating film is fixed to the light-transmitting surface, and the coating film on the light-transmitting surface is heated at a high temperature at the outer peripheral end portion, and the edge of the film is materialized, whereby the coating film is difficult to peel off and becomes Firmly engaged. Therefore, it is possible to reduce dust, foreign matter, and the like which are generated by peeling of the film, and it is possible to suppress the number of occurrences of defects caused by adhesion of dust or foreign matter. Further, in addition to the above, in the glass cover for a solid-state image sensor of the present invention, 128130.doc 200842116, if the film is an antireflection film, the transmittance of the glass cover can be sufficiently high to obtain a transmittance value. Here, the coating film-based anti-reflection film means that a transparent film having a refractive index lower than a refractive index of glass determined by the composition of the glass is attached to the surface of the glass, thereby reducing reflected light and increasing transmission. The amount of light from the glass cover. As a material constituting the film of the antireflection film, Ti 〇 2 can be suitably used.

CaF2、Si〇2、a12〇3、Mgs2、Zr〇2、Ni〇、或者 Μ@2 等與上述相同之材質。又除上述之外，本發明之固態攝像元件用玻璃蓋，若被覆臈之外周端藉由利用有雷射切斷之加熱而固定於透光面，則具有被膜及玻璃之端部彼此牢固之構造，因此可抑制玻璃盡端部之缺陷夕吝4 、產生。又，成為於切斷面之玻璃表面並未形成有較大之凹凸 #仏丄〇卸之狀悲，该較大凹凸面係於採用使用有先前之化學钱刻等製造方法時會產生，因此，無 H 了方式來⑦相態攝像元件，#，無須使將收納固悲攝像元件之各種部件盥玻葚 Μ /、坡离衰接耆日守所使用之部分之面積增大為必要以上。進而，不易產生由該切斷面之凹凸所引起之灰塵、或者剝離物等，定之品質。寺口此所製造之玻璃蓋具有穩八7隊上述之外 ^ 一桊發明之固態攝像元件用玻璃蓋，若被覆膜係光學薄膜，且内，則容1 _至100 _之範圍 π 幻合易實現光學性銥 .. 此方面與用途相對應之所需類型。此處，所謂被覆膜係光學寻暝且膜厚處於0.01 μπι至 128130.doc 200842116 100 μιη之範圍内係指，覆蓋於在板厚方向上相對向之兩個透光面之兩個面上的被覆膜之板厚方向之厚度尺寸處於 IxlO·8 m至lxl〇-4 m之範圍内。若膜厚超過0·01 μιη至100 μχη之範圍，則有時會出現難以充分實現透射率等光學性能達到所需要求，因此，較好的是覆蓋於本發明之固態攝像元件用玻璃蓋之被覆膜之膜厚為0,01 μιη至100 μιη之範圍内。CaF2, Si〇2, a12〇3, Mgs2, Zr〇2, Ni〇, or Μ@2 are the same materials as described above. In addition, the glass cover for a solid-state image sensor of the present invention has a glass cover which is fixed to the light-transmissive surface by heating by laser cutting, and has an end portion of the film and the glass. The structure can therefore suppress the defects at the end of the glass. Moreover, since the surface of the glass on the cut surface is not formed with a large unevenness, the large uneven surface is generated when a manufacturing method such as the previous chemical money is used. There is no H method to the 7-phase image sensor, #, and it is not necessary to increase the area of the parts to be used for storing the solid image sensor, and the area of the part used by the slope. Further, it is difficult to produce dust or a peeling object caused by the unevenness of the cut surface, and the quality is determined. The glass cover made by the temple mouth has a stable glass cover of the 7th team. The glass cover for the solid-state image sensor of the invention is one of the inventions. If the film is an optical film and is inside, the range of _ to 100 _ is π Easy to achieve optical 铱.. This aspect corresponds to the type of use required. Here, the coating film is optically searched and the film thickness is in the range of 0.01 μm to 128130.doc 200842116 100 μm, which means covering both faces of the two translucent surfaces in the thickness direction. The thickness dimension of the thickness direction of the coating film is in the range of IxlO·8 m to lxl〇-4 m. When the film thickness is in the range of from 0. 01 μm to 100 μχη, it may be difficult to sufficiently achieve optical performance such as transmittance, and therefore it is preferable to cover the glass cover for a solid-state image sensor of the present invention. The film thickness of the coating film is in the range of 0,01 μm to 100 μm.

又，除上述之外，本發明之固態攝像元件用玻璃蓋，若玻璃蓋之外周端面之凹部深度為3〇 μηι以下，且凹部長度為500 μιη以下，則即使於受到較大衝擊之情形時，玻璃蓋亦不容易破損，因此，不會對保護固態攝像元件之功能造成影響，因此較佳。此處，所謂玻璃蓋之外周端面之凹部.深度為3〇 μιη& 下，且凹部長度為㈣以下係指，於因玻璃蓋端面之表面的龜裂或碎片而削去表面之一部分的狀態之情形時，該凹部之深度尺寸為30 μιη以下，沿著端邊之凹部之長度尺寸為500 μιη以下。使用圖1對玻璃蓋之外周端面之品質加以更具體地說明。圖1係固態攝像it件之立體圖，圖1 + 1表示固態攝像元件用玻璃蓋’ 2表示玻璃板之端面，3表示玻璃板之第一透光'，4表示玻璃板之第二透光面，5表示第一加工面， 6表示第二加X面’ C1表示形成於破璃板之第—透光面之被膜’ C2表示形成於玻璃板之第二透光面之被膜，g表示玻璃板H示«板端面之凹部之脊線方向長度尺寸， 128130.doc -15- 200842116 Η表示玻璃板端面之凹部之玻璃板厚度方向之深度尺寸， L表示玻璃板端面之凹部之玻璃板透光面方向之深产尺寸。所謂脊線係指，例如第一透光面與第—加工二線，或者第二透光面與第二加工面之分界線。圖1中，所明玻璃蓋之外周端面之凹部深度係指，玻璃板端面之凹部之玻璃板厚度方向之深度尺寸Η及玻璃板端面之凹部之玻璃板透光面方向之深度尺寸l中之較大的尺寸口此任尺寸之值均為3〇㈣以下且玻璃板端面之凹部之邊方向長度尺寸貨為5〇〇 μιη以下。於玻璃蓋之外周端面之凹部深度超過3〇之情形時，尤其是於玻璃蓋受到衝擊性外力等之情形時，玻璃蓋之強度會明顯減料’塗佈於玻璃蓋表面之被覆膜之端，以具有超過30 μΐη2凹凸之凹部部位為基點而容易剝離，因Z 不理想，又，於凹部長度為超過5〇〇之情形時，亦會存在與凹部深度同樣之強度問題、或具有會發現被覆膜容易剝離之現象之傾向，因此不理想。作為以玻璃蓋之外周端面之凹部深度為3〇以下、且凹部長度為500 μπι以下之方式而進行玻璃蓋加工的加工方法，有各種加工方法，例如可藉由選擇雷射加工時之雷射之諸條件，尤其是雷射功率條件或雷射移動速度、進而是雷射束徑之縮小光圈，而減小於雷射加熱時所產生之凹部等凹凸之產生率或其尺寸。又，關於雷射照射面之内面，能以儘量對玻璃面施加均等按壓力之方式，且以使玻璃板之固定角度與按壓力之施加方向不產生偏差之方式，降低 128130.doc -16- 200842116 機械性動作之誤差且進行精密動作。又，除上述之外，本私明 _ ^月之固態攝像元件用玻璃蓋中，包括藉由按麼之割斷择作 ’、而形成之第二加工面在内之凹部缺陷尺寸之值大於包括雷鼾估田射知射而形成之第一加工面在内之凹部深度之值的固離摄德攝像兀件用玻璃蓋的比例占9成以上。亦即’若對10 〇〇片之罝乃 < 具有凹部之玻璃蓋進行調查，則包含藉由按壓之割斷操作而丨 <卡并向I成之弟二加工面在内的凹部In addition, in the glass cover for a solid-state image sensor of the present invention, when the depth of the concave portion of the peripheral end surface of the glass cover is 3 μm or less and the length of the concave portion is 500 μm or less, even when subjected to a large impact. The glass cover is also not easily broken, and therefore, it does not affect the function of protecting the solid-state image sensor, and therefore is preferable. Here, the recessed portion of the outer peripheral end surface of the cover glass has a depth of 3 〇 μηη and amp; and the length of the recessed portion is (4) or less, which is a state in which one part of the surface is cut off due to cracks or chips on the surface of the end surface of the cover glass. In this case, the recess has a depth dimension of 30 μm or less, and the length of the recess along the end side is 500 μm or less. The quality of the outer peripheral end face of the cover glass will be more specifically described using Fig. 1. 1 is a perspective view of a solid-state imaging device, and FIG. 1 + 1 shows a glass cover '2 for a solid-state imaging element, an end surface of the glass plate, 3 a first light transmission of the glass plate, and 4 a second light-transmissive surface of the glass plate. 5 denotes a first processed surface, 6 denotes a second plus X face 'C1 denotes a film formed on the first light-transmissive surface of the glass plate' C2 denotes a film formed on the second light-transmissive surface of the glass plate, and g denotes glass The plate H indicates the length dimension of the ridge line direction of the concave end of the plate end, 128130.doc -15- 200842116 Η indicates the depth dimension of the thickness direction of the glass plate in the concave portion of the end face of the glass plate, and L indicates the transparency of the glass plate in the concave portion of the end face of the glass plate. The deep production size in the face direction. The ridge line means, for example, a boundary between the first light-transmissive surface and the first-processed second line, or the second light-transmissive surface and the second processed surface. In Fig. 1, the depth of the concave portion of the outer peripheral end surface of the glass cover is defined by the depth dimension of the thickness direction of the glass plate in the concave portion of the end face of the glass plate and the depth dimension l of the direction of the transparent surface of the glass plate of the concave portion of the end face of the glass plate. The larger size port has a value of 3 〇 (four) or less and the length of the concave portion of the end face of the glass plate is 5 〇〇 μηη or less. When the depth of the concave portion of the peripheral end surface of the glass cover exceeds 3 ,, especially when the glass cover is subjected to an impact external force or the like, the strength of the glass cover significantly reduces the coating of the coating film applied to the surface of the glass cover. The end is easily peeled off with a concave portion having more than 30 μΐη2 unevenness. Since Z is not ideal, when the length of the concave portion exceeds 5 ,, there is also the same strength problem as the depth of the concave portion, or there is a The tendency of the coating film to be easily peeled off is found, which is not preferable. There are various processing methods for performing a glass cover processing such that the depth of the concave portion on the outer peripheral end surface of the glass cover is 3 Å or less and the length of the concave portion is 500 μm or less. For example, laser light can be selected by laser processing. The conditions, in particular, the laser power conditions or the laser moving speed, and further the reduced aperture of the laser beam diameter, are reduced by the incidence of concavities and the like of the recesses or the like which are generated when the laser is heated. Further, regarding the inner surface of the laser irradiation surface, it is possible to reduce the 128130.doc -16- by applying an equal pressing force to the glass surface as much as possible, so that the fixed angle of the glass plate does not deviate from the direction in which the pressing force is applied. 200842116 Error in mechanical action and precise operation. Further, in addition to the above, in the glass cover for the solid-state image sensor of the present invention, the value of the defect size of the concave portion including the second processed surface formed by cutting the cut is selected to be larger than The ratio of the depth of the concave portion of the first processed surface formed by the Thunder estimator is tens of more than 90%. In other words, if the glass cover with a concave portion is inspected, the glass cover with the concave portion is included, and the concave portion is cut by the pressing operation, and the concave portion is formed by the card and the processing surface of the I.

缺陷尺寸之值大於包含第一 3 ^ 加工面在内之凹部缺陷尺寸之值的玻璃蓋有900片以上。關於外周端面之凹部深度之各處之尺寸值的測量，可使用附屬於立體顯微鏡或電子顯微鏡等之尺寸測量器或雷射尺寸測量機器等來測量。又，除上述之外，本發明之固態攝像元件用玻璃蓋，若固態攝像元件係CCD或CM〇s，則於用作搭載於行動電話或數位攝影機等圖像記錄裝置上之薄型的光半導體元件之别表面窗玻璃之情形時，亦可實現穩定之品質。所謂固態攝像元件為CCD或CM〇s，係表示於半導體基板上二維地排列並集成具有光電轉換與電荷儲存功能之像素群而成的攝像元件，即固態攝像元件，係被稱作ccd (charge couple device，電荷耦合元件）或者 CM〇s (Complementary Metal-Oxide-Semiconductor，互補金氧半導體）之影像感測器。又，除上述之外，本發明之固態攝像元件用破璃蓋，若以氧化物換算之質量百分比表示，無機氧化物玻璃製之薄 128130.doc -17· 200842116 板狀玻璃之組成中含有：56〜70%之Si〇2、〇 5〜i8%之 Al2〇3、5〜20% 之 b2〇3、ο.!〜2〇% 之 R〇 (R〇=Mg〇+Ca〇+The glass cover having a value of the defect size larger than the value of the defect size of the recess including the first 3^-machined surface has 900 or more. The measurement of the dimensional value of the depth of the concave portion of the outer peripheral end surface can be measured by a size measuring device attached to a stereo microscope or an electron microscope or a laser size measuring machine or the like. In addition, the glass cover for a solid-state image sensor of the present invention is used as a thin optical semiconductor mounted on an image recording apparatus such as a mobile phone or a digital camera, if the solid-state image sensor is CCD or CM〇s. Stable quality can also be achieved when the component is in the case of a surface glazing. The solid-state imaging device is a CCD or a CM〇s, and is an image pickup device in which a pixel group having a photoelectric conversion and a charge storage function is two-dimensionally arranged and integrated on a semiconductor substrate, that is, a solid-state image pickup device, which is called a ccd ( Charge couple device, or CM〇s (Complementary Metal-Oxide-Semiconductor) image sensor. Further, in addition to the above, the glass cover for a solid-state image sensor of the present invention is expressed by a mass percentage in terms of oxide, and the composition of the sheet glass of the inorganic oxide glass is 128130.doc -17· 200842116. 56~70% of Si〇2, 〇5~i8% of Al2〇3, 5~20% of b2〇3, ο.!~2〇% of R〇(R〇=Mg〇+Ca〇+

Zn〇+Sr0+Ba0)、〇〜9% 之 Zn〇、以及卜跳之制（M2〇= LiW+Nae+LO)，則除了折射率或透過率等所需之光學性能外，亦具有較高之财水性及硬度，又，藉由使玻璃炼融而成形為玻璃板之情形時亦容易進行成形操作，且可達到成形尺寸之精度優良之品質。此處’所謂以氧化物換算之f量百分比表示，無機氧化物玻璃製之薄板狀玻璃之組成中含有：56〜7〇%之⑽、 0.5〜18%之Al2〇3、5〜鳩之b2〇3、〇卜鳩之r〇㈣=Zn〇+Sr0+Ba0), 〇~9% of Zn〇, and 跳之 (M2〇= LiW+Nae+LO), in addition to the required optical properties such as refractive index or transmittance, The water and hardness of the high-yield material are also easily formed by molding the glass into a glass plate, and the quality of the molded size can be improved. Here, 'the percentage of the amount of f in terms of oxide, the composition of the thin plate glass made of inorganic oxide glass contains: 56 to 7 % (10), 0.5 to 18% of Al 2 〇 3, 5 to b b2 〇3, 〇卜鸠之r〇(4)=

MgO+CaO+Zn0+Sr0+Ba〇)、〇〜9%之211〇、以及 η州之 M2〇 (M2〇=U2〇+Na2〇+K2〇)係指，作為固態攝像元件用玻璃蓋之構成成分，以氧化物換算表示來表述玻璃中所含有之成刀之丨月形時，二氧化矽（亦稱作siiica)為％至7〇質量 %，三氧化二鋁（亦稱作8111〇1111&)為〇 5至18質量。，三氧化二删為5至2〇質量％，氧化鎂（亦稱作magnesia)、氧化約（亦稱作Ca—、氧化鋅（或者亦稱作Chinese white)、氧化銘以及氧化鋇之總量為0.U2〇質量％，氧化辞為9質量。A以下’氧化鐘（亦稱作lithia)1化鈉以及氧化鉀之總量為i 至1 8質量％。關於固態攝像元件用玻璃蓋之組成範圍為如此之限定範圍之原因，以下依序說明。玻璃組成中之Si〇2(二氧化石夕，silica)成分係構成玻璃之原子級尺度之網狀構造之骨架的主要成分，當其含量小於 128130.doc -18- 200842116 56貝里％日寸，產生由玻璃表面之化學耐久性而引起之問題。的危險性會增大，因此不理想。又，若其含量超過70質量則為了使玻璃成為均質之狀態而進行溶解從而獲得均質之玻璃蓋，必須具有費用較高之玻璃熔融設備。 • 玻璃組成中之Al2〇3(三氧化二铭，alumina)成分，係用一 R使玻璃之網狀構造穩定化之必需成分，同時當將玻璃自無機原料以高溫加熱熔融而成為熔融玻璃時，具有提高玻鲁璃化反應之初期之熔融性的作用，因此係較佳之一成分。又，該Α12〇3成分亦對玻璃之化學耐久性之提高有效。然而，當Al2〇3之含量小於〇·5質量％時，難以實現溶融時之初期熔解性之提高或成形後之化學耐久性之提高。又，若 Alz〇3之含量超過18質量％，則提高熔解性之效能會降低，亦會成為使玻璃熔融時之熔解性惡化之要因，玻璃之失透 k南而谷易生成結晶等，因此不理想。根據上述觀點， Ah〇3之含量更好的是15質量％以下。 • 玻璃組成中之β2〇3(三氧化二硼）成分，係具有使加熱玻璃％之玻璃之熔融溫度降低且提高玻璃熔融時之熔解性能 , 之作用的成分。然而，該玻璃組成系中，含有5質量％以上才可發揮該效果，因此較佳。另一方面，若Β2〇3超過2〇 ’ 貝里/〇’則來自熔融時之熔融玻璃質地表面之硼酸成分之療♦里^:多’結果，使熔融玻璃成形為玻璃物品後，會成為玻璃物品中之不均質之原因，且亦會對玻璃物品之化學耐久性造成影響，因此不理想。關於玻璃組成中之MgO(氧化鎂）成分、CaO(氧化鈣）、 128130.doc •19· 200842116MgO+CaO+Zn0+Sr0+Ba〇), 〇~9% of 211〇, and η州's M2〇(M2〇=U2〇+Na2〇+K2〇) means a glass cover for a solid-state image sensor When the constituent component is expressed in terms of oxide, the cerium oxide (also referred to as siiica) is % to 7 〇 mass%, and aluminum oxide (also referred to as 8111 时) when expressed in the form of oxides. 1111 &) is 〇 5 to 18 mass. , trioxide is deleted to 5 to 2% by mass, magnesium oxide (also known as magnesia), oxidation (also known as Ca-, zinc oxide (or also known as Chinese white), oxidation and total amount of antimony oxide It is 0.U2〇% by mass, and the oxidation is 9 mass. The total amount of sodium oxide and potassium oxide of the 'oxidation clock (also called lithia) below A is i to 18% by mass. The reason why the composition range is such a limited range is as follows. The Si〇2 (silica dioxide) component in the glass composition is the main component of the skeleton of the network structure of the atomic scale of the glass. The content is less than 128130.doc -18- 200842116 56 Berry% of the day, causing problems caused by the chemical durability of the glass surface. The risk will increase, so it is not ideal. Also, if the content exceeds 70 mass, then When the glass is made homogeneous and dissolved to obtain a homogeneous glass cover, it is necessary to have a high-cost glass melting equipment. • Al2〇3 (alumina) in the glass composition is made of a glass. Mesh structure At the same time, when the glass is heated and melted from the inorganic material at a high temperature to become molten glass, the glass has an effect of improving the initial meltability of the glass transition reaction, and therefore it is preferably one component. The component 3 is also effective for improving the chemical durability of the glass. However, when the content of Al2〇3 is less than 5% by mass, it is difficult to achieve an improvement in initial meltability at the time of melting or an increase in chemical durability after molding. When the content of Alz〇3 exceeds 18% by mass, the efficiency of improving the meltability is lowered, and the meltability at the time of melting the glass is deteriorated. The glass is devitrified and the valley is likely to form crystals. According to the above viewpoint, the content of Ah〇3 is more preferably 15% by mass or less. • The β2〇3 (boron trioxide) component in the glass composition has a melting temperature of the glass which heats the glass of % and is improved. The component which acts on the melting property when the glass is melted. However, it is preferable that the glass composition system contains 5% by mass or more to exhibit the effect, and therefore, it is preferable. 3 more than 2 〇 'Berry / 〇' is derived from the treatment of the boric acid component on the surface of the molten glass at the time of melting. The result is that after the molten glass is formed into a glass article, it becomes an inhomogeneity in the glass article. The reason is also affecting the chemical durability of glass articles, so it is not ideal. About the composition of MgO (magnesium oxide) in glass composition, CaO (calcium oxide), 128130.doc •19· 200842116

Zn〇(氧化鋅）成分、Sr0(氧化锶）成分以及BaO(氧化鋇）成刀之、& i而5 ’该等成分中之任一成分均係使玻璃之耐水性或熔解性、進而是折射率、透射率、硬度等各種物性值滿足預期之性能時所需者。然而，若該等成分之總量值小於〇· 1貝里0/〇，則較多情況下無法充分實現所需之功能。又若"亥總1超過20質量％，則較多情況下會對玻璃之耐候性或熔融時之料性造成影響。又，就玻璃之機械強度而言，若超過20質量％則會產生問題，因此不理想。玻璃組成中之Zn〇成分，係藉由添加於玻璃中而顯著改口如下性此之成分，即，可提高成形為玻璃板後之玻璃板表面長時間維持化學耐久性或玻璃表面之耐劃傷性，若以質量％表示之添加量超過9%，則當然會使化學耐久性劣化，因此不理想。玻璃組成中作為鹼金屬元素之氧化物而表示之Li2〇(氧化鋰）成分、Na2〇(氧化鈉）成分以及1〇(氧化鉀）成分之總里為了實施與被覆膜之加熱時之應力調整、或補償因與固態攝像元件之封裝框體之膨脹收縮所產生之熱應力，而將玻璃蓋之線熱膨脹係數設為特定之範圍，藉此，具有實見相對於知加至玻璃盍之熱負荷而具有穩定性能的作用，因此係有用之成分。而且，若該等成分之總量為i質量％以上，則可與無鹼玻璃明顯地區分，玻璃之熔融作業中無須如無鹼玻璃般需花費較大勞力，即可容易實現使線熱膨脹係數較大地變動之效果。然而，若超過丨8質量％，則合對玻璃之化學耐久性、尤其是玻璃表面之耐水性造成影 128l30.doc -20- 200842116 響’因此不理想。又，本發明之固態攝像元件用玻璃蓋1無機氧化物玻璃係無鹼玻璃，則有利於實現構成固態攝像元件封裝後之車父南之耐候性。此處，所謂無機氧化物玻璃係無鹼玻璃係指，實質上不含鹼金屬元素成分之U、Na、κ之玻璃。此處，所謂實質上不含有係指，作為玻璃組成中之鹼金屬元素之Na(鈉卜 K(鉀）、Li(鋰）等元素以氧化物換算之總量計算，為❹^質置％以下者。亦即，關於本發明之固態攝像元件用玻璃蓋，根據其用途而採用所需之玻璃組成，若即使在當存在玻璃物品中所含有之鹼成分會阻礙玻璃表面之經時耐候性之相關功能、且玻璃熔融作業時需要花費勞力之情形時，亦可貝現與此相應的實際效益，則較佳。而且，此時，可使用不§有驗金屬元素之組成、所謂無鹼玻璃組成來作為玻璃蓋之組成，將本發明用於無鹼玻璃，藉此可實現所需之功能。作為在上述情況下可採用之無鹼玻璃之組成，於以氧化物換异表示來表述玻璃中所含有之各成分之情形時，較好的是以質量％表示，以〇2為53〜61%，Al2〇3為〇.7〜2〇%， Β2〇3 為 6〜16%，R〇為 2〜28% (RO=MgO+BaO)，JO (j0== CaO+SrO)為my/。，玻璃中之⑽基含量為5〇 ppm〜7〇〇 ppm之範圍内。此處’關於無鹼玻璃之組成，以質量％表示，若以〇2小於53% ’則具有化學耐久性會降低之傾向，另一方面，若 128130.doc -21 - 200842116Zn〇 (zinc oxide) component, Sr0 (yttria) component, and BaO (yttria) are formed into a knife, & i and 5', and any of these components is such that the glass is water-resistant or meltable, and further It is required when various physical properties such as refractive index, transmittance, and hardness satisfy the expected performance. However, if the total value of these components is less than 〇·1 Berry 0/〇, the required function cannot be fully realized in many cases. Further, if the total amount of "Hai" is more than 20% by mass, the weather resistance of the glass or the material property at the time of melting may be affected in many cases. Further, when the mechanical strength of the glass exceeds 20% by mass, problems occur, which is not preferable. The Zn 〇 component in the glass composition is remarkably modified by being added to the glass, that is, the surface of the glass plate formed into a glass plate can be maintained for a long time to maintain chemical durability or scratch resistance of the glass surface. When the amount added by mass% exceeds 9%, the chemical durability is naturally deteriorated, which is not preferable. In the glass composition, the Li2〇 (lithium oxide) component, the Na2〇 (sodium oxide) component, and the 1〇 (potassium oxide) component, which are represented by the oxide of the alkali metal element, are used to perform stress heating with the coating film. Adjusting or compensating for the thermal stress generated by the expansion and contraction of the package frame of the solid-state image sensor, and setting the coefficient of thermal expansion of the glass cover to a specific range, thereby realizing the fact that it is added to the glass crucible The heat load has a function of stability and is therefore a useful component. Further, if the total amount of the components is i% by mass or more, it can be clearly distinguished from the alkali-free glass, and it is easy to realize the coefficient of thermal expansion of the wire without requiring a large labor force such as alkali-free glass in the melting operation of the glass. The effect of a large change. However, if it exceeds 丨8% by mass, the chemical durability of the glass, especially the water resistance of the glass surface, causes a shadow of 128l30.doc -20-200842116, which is not preferable. Further, the glass cover 1 of the solid-state image sensor of the present invention, the inorganic oxide glass-based alkali-free glass, is advantageous in realizing the weather resistance of the south of the vehicle after the solid-state image sensor is packaged. Here, the inorganic oxide glass-based alkali-free glass means a glass of U, Na, or κ which does not substantially contain an alkali metal element. Here, the term "substantially does not contain a finger", and the elements such as Na (sodium, K (potassium), and Li (lithium)) which are alkali metal elements in the glass composition are calculated as the total amount of the oxide, and are In other words, the glass cover for a solid-state image sensor of the present invention adopts a desired glass composition depending on the use thereof, and if the alkali component contained in the glass article is present, the weather resistance of the glass surface is hindered. When the related functions and the labor required for the glass melting operation are required, the actual benefits corresponding to the present may be preferred, and in this case, the composition of the metal element may be used, and the so-called alkali-free The glass composition is used as a composition of a glass cover, and the present invention is applied to an alkali-free glass, whereby a desired function can be achieved. As a composition of the alkali-free glass which can be used in the above case, it is expressed by an oxide-differential expression. In the case of each component contained in the glass, it is preferably expressed by mass%, 〇2 is 53 to 61%, Al2〇3 is 〇.7 to 2〇%, and Β2〇3 is 6 to 16%, R〇 is 2~28% (RO=MgO+BaO), JO (j0== C aO+SrO) is my/., the content of the (10) group in the glass is in the range of 5〇ppm~7〇〇ppm. Here, the composition of the alkali-free glass is expressed by mass%, and if 〇2 is less than 53% 'There is a tendency to reduce chemical durability, on the other hand, if 128130.doc -21 - 200842116

Si〇2超過61%，且不含有鹼金屬元素，從而备曰現如下情形：熔融玻璃之黏性會增大，因此容易 — X +岣質之熔融狀態，難以以廉價之製造原價來形成均質之 /寻坡璃板，因此不理想。又’關於無驗玻璃之組成，以質量％表 Α12〇3處於 0.7〜20〇/〇之範圍内，可調合耐電性等之玻璃之電氣性能及化學性能，因此較佳。Si〇2 exceeds 61% and does not contain an alkali metal element, so that the viscosity of the molten glass is increased, so that it is easy to melt the X + enamel, and it is difficult to form a homogenization at a low cost. It is not ideal. Further, it is preferable that the composition of the non-inspective glass is in the range of 0.7 to 20 Å/〇 in terms of mass% of 〇12〇3, and the electrical properties and chemical properties of the glass such as electric resistance can be adjusted.

關於玻璃組成中之Mg〇與BaO之總量，以皙旦。一貝里A表不，處於2〜28〇/〇之範圍内時，於成形後之耐藥品性、熱膨脹係數、以及避免熔融時自熔融玻璃析出結晶之方面_俨 ” 關於玻璃組成中之CaO與SrO之總量，以皙旦0/士一貝里/〇表示，處於0·1〜15%之範圍内，可使成形後之耐薬品性、熱膨脹係數、或者低溫黏性等性質處於最佳狀態，因此較佳。玻璃組成中之1〇3係可提高玻璃之熔解性之成分，於該玻璃組成系中，以質量％表示，含有6%以上可發揮該效果’因此較佳。另一方面，以質量％表示，若Β2〇二過 16%，則熔融時之蒸發量增多，玻璃容易變得不均質，因此不理想。、關於玻璃組成中之ΟΗ基含量，藉由紅外分光光度計測量紅外線區域之透過率，藉此可使其含量特定，^於“ ppm〜700 ppm之範圍内，可將溫度高於玻璃之ι〇4· sec之熔融玻璃之黏性設為適當黏性值，而關於利用各種之成形方法所成形之玻璃表面，可獲得組成均質且具有平滑表面狀態的玻璃之成形體，因此較佳。 128130.doc -22- 200842116 又，本發明之固態攝像元件用玻璃蓋之組成，於各玻璃組成中’糟由採用高純度原料與其所配備之熔融環境，可精確控制 u(鈷）、Th(鼓）、Ra(鐘）、Fe2〇3、pb〇、Ti〇2、斷〇2、Zr〇2等雜質之含量，尤其是對固態攝像元件用玻璃盍之紫外線附近之透過率造成影響之Fe203、Pbo、 • 2 Mn〇2叙好的疋分別以1〜100 ppmi級別來進行管理。又，關於成為α射線之CCD等軟性錯誤之原因的u、 Th Ra，可分別以〇1〜1〇卩心之級別來進行管理。而且，藉由上述管理，固態攝像元件用玻璃蓋之α射線放出量必須為0.5 c/cm2 · hr以下。本發明之固態攝像元件用玻璃蓋之製造方法包括：於耐熱性容器内熔融玻璃原料混合物之步驟；使所獲得之熔融玻璃成形為玻璃板之步驟；於該玻璃板之兩個透光面中之至少一面上形成被覆膜之成膜步驟；將雷射射出至在兩個透光面中之至少一面上具有被覆膜之附被覆膜之玻璃板之射出步驟；以及，將射出步驟後之玻璃板分割為小片之玻璃之步驟，根據該方法，就玻璃蓋之任一端面而言，其形狀品質或外觀品質均優良，可獲得不易產生碎片或龜裂等構造缺陷之兩面附膜之狀態的薄玻璃板。此處，所謂包括：於耐熱性容器内熔融玻璃原料混合物之步驟，使所獲得之溶融玻璃成形為玻璃板之步驟；於該玻璃板之兩個透光面中之至少一面上形成被覆膜之成膜步驟’將雷射射出至在兩個透光面中之至少一面上具有被覆膜之附被覆膜之玻璃板之射出步驟；以及將射出步驟後之 128130.doc -23- 200842116 玻璃板分割為小片之玻璃之步驟，係如下所述者。亦即勺括如下步驟··於具有财熱性之陶竟製之爐壁的玻璃炫= 或具有耐熱性之白金等貴金屬製之玻璃熔融坩堝中，使ςRegarding the total amount of Mg 〇 and BaO in the glass composition, it is 皙。. One Berry A does not, in the range of 2 to 28 〇 / ,, the chemical resistance after molding, the coefficient of thermal expansion, and the prevention of crystallization from the molten glass during melting _ 俨" About the CaO in the glass composition The total amount of SrO and the total amount of SrO, expressed in the range of 0·1 to 15%, can be such that the properties such as heat resistance, thermal expansion coefficient, or low temperature viscosity after forming are at the maximum. In the glass composition, the 1〇3 system can improve the melting property of the glass, and in the glass composition system, it is expressed by mass%, and it is preferable to contain 6% or more. On the other hand, it is represented by mass %, and if Β2〇 is over 16%, the amount of evaporation during melting increases, and the glass tends to be uneven, which is not preferable. The thiol content in the glass composition is determined by infrared spectrophotometry. The transmittance of the infrared region is measured, so that the content can be made specific. In the range of "ppm to 700 ppm, the viscosity of the molten glass having a temperature higher than that of the glass of ι 4 sec can be set to an appropriate viscosity. Value, and about using various things The method of forming the glass surface, and a homogeneous composition is obtained having a smooth surface state of molded glass, and therefore preferred. 128130.doc -22- 200842116 Further, the composition of the glass cover for the solid-state image sensor of the present invention can accurately control u (cobalt) and Th (by using a high-purity raw material and a molten environment thereof) in each glass composition. The content of impurities such as drums, Ra (clock), Fe2〇3, pb〇, Ti〇2, broken 〇2, Zr〇2, etc., especially the Fe203 which affects the transmittance near the ultraviolet ray of the glass crucible for solid-state imaging elements. , Pbo, • 2 Mn〇2 are well managed and managed on a scale of 1 to 100 ppmi. Further, u and Th Ra, which are causes of soft errors such as CCDs for α rays, can be managed at levels of 〇1 to 1 respectively. Further, according to the above management, the amount of α-ray emission from the glass cover for the solid-state image sensor must be 0.5 c/cm 2 · hr or less. The method for producing a glass cover for a solid-state image sensor of the present invention comprises the steps of: melting a glass raw material mixture in a heat-resistant container; and forming the obtained molten glass into a glass plate; and in the two transparent surfaces of the glass plate a film forming step of forming a coating film on at least one side; an emitting step of emitting a laser beam to a glass sheet having a coating film having a coating film on at least one of the two light transmitting surfaces; and an ejection step According to the method, the glass sheet is divided into a small piece of glass, and according to the method, the shape quality or the appearance quality of the end surface of the glass cover is excellent, and a double-sided film which is less likely to cause structural defects such as chips or cracks can be obtained. A thin glass plate in the state of the state. Here, the method includes: a step of melting a glass raw material mixture in a heat resistant container, a step of forming the obtained molten glass into a glass plate; and forming a coating film on at least one of the two light transmissive surfaces of the glass plate a film forming step of: ejecting a laser to an exiting step of a glass sheet having a coating film on at least one of the two light transmissive surfaces; and 128130.doc -23- 200842116 after the ejecting step The step of dividing the glass sheet into small pieces of glass is as follows. That is, the following steps are included in the glass melting enamel of the noble metal such as the heat-resistant ceramics or the glass-melting enamel made of precious metals such as platinum having heat resistance.

融玻璃熔融而形成均質之狀態；將藉由該步驟所獲得之均質狀悲之熔融玻璃，利用成形裝置成形為具有特定之板^ 之玻璃板；於在所成形之玻璃板之板厚方向上相對向之= 個透光面之至少-側之面上形成特定材f之被覆膜；對在被覆膜形成步驟中所獲得之至少一面上形成有膜的玻璃板之透光面照射雷射光’藉此於玻璃板上殘留有料用以藉由雷射光分斷之預備龜裂線的照射痕；進而藉由重複對‘ 備龜裂線實施分割操作，而將經雷射照射後之兩面附膜之玻璃板分斷為容積小於原來玻璃板溶容積之玻璃板。關於在耐熱性容器内中熔融玻璃原料混合物之步驟，只要可於具有絲融玻化之物理操作、亦即攪摔操; 或發泡等之操作機構之環境下使麵均質化，料使用用以加熱為熔融玻璃之加熱機構或裝置之尺寸、或者裝置之外形為任意者。衣又，關於使所獲得之熔融玻璃成形為玻璃板之步驟，只要係可使透光面之成形精度為特定精度之方法，則可採用任意成形方法。例如，可係對藉由鑄襞成形所獲得之塊材進行切片而形成玻璃板之方法…亦可採用利用有金屬錫浴之浮法，進而是下拉成形法等各種成形方法。關於在該玻璃板之兩個透光面令之至少一面上形成被覆臊之成膜步驟，只要係可藉由適當之方法使上述各種被覆】28l30.d〇c -24- 200842116 膜材料形成為薄膜狀，則可採用任意方法。關於將雷射射出至在兩個透光面之至少一面上具有被覆膜之附被覆膜之玻璃板之射出步驟，只要藉由以特定之輸出條件對被復膜與玻璃板之兩者照射縮小了輸出值的雷射光，藉此可於玻璃板上產生直線狀之預備龜裂線，則可採用利用任意之方法照射雷射光的方法。又，所謂將射出步驟後之玻璃板分割為小片之玻璃之步驟，只要可藉由對具有預備龜裂線之玻璃板進行特定之重複操作，而對預備龜裂線之龜裂前端施加拉伸力，以將工個玻璃板分斷為2個以上之較小容積之玻璃板，則可採用任意方法。本發明之固態攝像元件用玻璃蓋之製造方法的特徵在於：使溶融玻璃成形為玻璃板之步驟中，使炼融玻璃以同速度向下方延伸成形後冷卻固化為玻璃板。可連續形成板之厚度尺寸精度或玻璃板透光面之面精度較高之狀態的玻璃板。此處’所謂於使㈣玻璃成形為玻璃板之步驟中使溶融玻离向下方延伸成形後冷卻固化為玻璃板係指，使用採用有向下方延伸成形之成形機構之裝置而成形為玻璃板，利用所需之成形方法成形為高溫狀態之熔融玻璃時，經由具有輥等耐熱構造之裝置’對熔融破璃施加延伸力使之延伸’藉此可利用實現特定之表面精度、板厚、板面積之方法來成形。例如，作為延伸成形之方法，具體而言有：槽下拉成形法、溢出下拉成形法（或者炫化法）、滾壓成形 128l30.doc -25- 200842116 法、彳K拉成形法等藉由成形機構而丹叩成形為玻璃板形狀的方法。除上述之外，本發明之固能蘊# _ U心攝像凡件用玻璃蓋之製造方法’若分割為小片之玻璃之步驟係切割步驟，則以沿著預先形成之用以分斷之預備龜裂線而形成為正確形狀的方式，進行分斷、或者分割，從而可獲得具有較高尺寸精度之玻璃板小片，因此較理想。The molten glass is melted to form a homogeneous state; the homogeneous molten glass obtained by the step is formed into a glass plate having a specific plate by a forming device; in the direction of the thickness of the formed glass plate a coating film of a specific material f is formed on at least a side surface of at least one of the light transmissive surfaces; and a light transmissive surface of the glass plate on which at least one surface obtained in the coating film forming step is formed is irradiated with a light The illuminating light is used to leave the illuminating marks on the glass plate for the preparation of the cracking line by the laser light; and the two sides after the laser irradiation are repeated by repeating the dividing operation of the prepared cracking line. The glass plate with the film is divided into a glass plate having a smaller volume than the original glass plate. The step of melting the glass raw material mixture in the heat-resistant container is as long as the surface can be homogenized in an environment having a physical operation of silk-melting, that is, a stirring operation, or an operation mechanism such as foaming. Any of the dimensions of the heating mechanism or device heated to the molten glass, or the outside of the device. Further, in the step of forming the obtained molten glass into a glass plate, any molding method may be employed as long as the molding precision of the light-transmitting surface is made to be a specific precision. For example, a method of forming a glass sheet by slicing a block obtained by casting a crucible may be employed. Various forming methods such as a float method using a metal tin bath and a down draw method may be employed. Regarding the film forming step of forming a coating on at least one of the two light-transmissive surfaces of the glass sheet, the above-mentioned various coatings can be formed into a film material by a suitable method as 28l30.d〇c -24- 200842116 In the case of a film, any method can be employed. The step of ejecting the laser to the glass sheet with the coating film having the coating film on at least one of the two light transmissive surfaces, as long as the composite film and the glass sheet are both subjected to specific output conditions. By irradiating the laser light whose output value is reduced, a linear pre-crack line can be generated on the glass plate, and a method of irradiating the laser light by any method can be employed. Further, the step of dividing the glass sheet after the injection step into small pieces of glass may be performed by applying a stretching operation to the cracked tip of the preliminary crack line by repeating a specific operation on the glass sheet having the preliminary crack line. The force can be any method by dividing the glass plate into two or more smaller volume glass plates. In the method for producing a glass cover for a solid-state image sensor of the present invention, in the step of forming the molten glass into a glass plate, the molten glass is stretched downward at the same speed and then solidified into a glass plate. The glass sheet can be continuously formed in a state in which the thickness dimensional accuracy of the sheet or the surface of the glass sheet is high. Here, in the step of forming the (four) glass into a glass plate, the molten glass is stretched downward and molded, and then cooled and solidified into a glass plate, and the glass plate is formed by using a device having a molding mechanism extending downward. When the molten glass is formed into a high-temperature state by a molding method required, a device having a heat-resistant structure such as a roll is used to apply an extension force to the molten glass to extend it, thereby realizing specific surface precision, plate thickness, and plate area. The method to form. For example, as a method of the extension molding, specifically, a groove drawing forming method, an overflow drawing forming method (or a blipping method), a roll forming method 128l30.doc -25-200842116, a 彳K-drawing method, and the like are formed by forming The mechanism and the method of forming a glass plate shape. In addition to the above, the method of manufacturing the glass cover for the solid-state image of the present invention, if the step of dividing into a small piece of glass is a cutting step, is prepared along the pre-formed portion for cutting. It is preferable that the crack line is formed into a correct shape and is divided or divided to obtain a small piece of glass plate having high dimensional accuracy.

所謂分割為小片之玻璃之步驟係折斷步驟係指，自具有預備龜裂線之附膜之玻璃板之背面，將特定之按壓力施加至附膜之玻璃板，藉此使附膜之玻璃板料，對預備龜裂線之龜裂前端施加適度拉伸力，結果，重複將—片兩面附膜之玻璃板分斷為2片附膜之玻璃板的操作，將μ附膜之玻璃板細分割為複數片小片之附膜之玻璃板的步驟。作為附膜之玻璃板，可僅於雷射照射面、亦即施加按壓力之面之背侧面附膜，又’亦可於兩面附膜，只要最終成為兩面附膜模之狀態即可，但關於製造效率方面，較好的是兩面預先附膜之玻璃板。 /於折斷操作’必須注意不要因對經分割之各個玻璃板施加多餘的應力或衝擊，而導致玻璃板上產生碎片或損傷等缺’ X ’亦必須充分留意使折斷時所產生之微細粉塵不會附著於玻璃板表面。發明之效果 “（1)如上所述，本發明之固態攝像元件用玻璃蓋，係無機乳化物玻璃製之薄板狀之固態攝像元件用玻璃蓋，於在 128l30.doc -26- 200842116 板厚方向上相對向之兩個透光面之至少一面上具有被覆膜，玻璃盍之外周端面由已藉由雷射切斷之面而構成，被覆膜形成於雷射切斷之前，因此，覆蓋於玻璃蓋之透光面之被覆膜對玻璃板之結合力增強，從而玻璃板與被覆膜之界面成為具有高機械強度、硬度之狀態，容易實現被覆膜不易剝離。 (2)又，本發明之固態攝像元件用玻璃蓋，若為無機氧The step of dividing into a small piece of glass means that the breaking step means applying a specific pressing force to the glass plate of the attached film from the back surface of the glass plate having the film of the preliminary crack line, thereby making the glass plate attached to the film The material is applied with a moderate tensile force to the cracked front end of the preliminary crack line. As a result, the operation of dividing the glass sheet on both sides of the film into two glass sheets with a film is repeated, and the glass sheet of the μ attached film is thin. The step of dividing into a glass plate attached to a plurality of small pieces. As the glass plate attached to the film, the film may be attached only to the laser-irradiated surface, that is, the back side to which the pressing surface is applied, and the film may be attached to both sides as long as the film is finally formed on both sides, but As for the manufacturing efficiency, a glass plate having a film attached to both sides is preferred. / In the breaking operation 'Be careful not to apply excessive stress or impact to the divided glass plates, resulting in the occurrence of debris or damage on the glass plate. 'X ' must also pay full attention to the fine dust generated when breaking Will adhere to the surface of the glass plate. (1) As described above, the glass cover for a solid-state image sensor of the present invention is a glass cover for a solid-state image sensor having a thin plate shape made of inorganic emulsion glass, and is in the thickness direction of 128l30.doc -26- 200842116 At least one of the two opposite light-transmissive surfaces has a coating film, and the outer circumferential end surface of the glass crucible is formed by a surface that has been cut by a laser, and the coating film is formed before the laser cutting, so that the coating is covered. The bonding force of the coating film on the light-transmissive surface of the glass cover is enhanced to the glass plate, so that the interface between the glass plate and the coating film has a state of high mechanical strength and hardness, and the coating film is easily peeled off easily. A glass cover for a solid-state image sensor of the present invention, if it is an inorganic oxygen

^匕物破璃製之薄板狀之固態攝像元件用玻璃蓋，則於在板厚方向上相對向之兩個透光面之至少一面上具有被覆臈，且被覆膜之外周端固著於透光面，則可降低於玻璃板之端面邛中產生之各種缺陷之產生率，從而具有高品質。 ▲ (3)又，本發明之固態攝像元件用玻璃蓋，若被覆膜係抗反射臈，則可成為充分提高特定之波段範圍内玻璃蓋之 :射率的狀態，因&，可使充分之光量入射至固態攝像元件，使固態攝像元件之性能達到如所設計般之優良品質。々二而本發明之固態攝像元件用玻璃蓋，若被覆膜之稭由利用雷射切斷之加熱而固著於透光面，則雷射 + " $成有較大之凹凸，因此，可縮小玻璃蓋與用U收納固態攝像料70件之陶以基板之接著面積，即使減積亦可實現充分高之接著強度…即使收納於封裝外形固態攝！元件之面積增大，亦無須使元件之模〜”、員者増大’而藉由使封裝之收納有固態攝像、八邛之面積增大即可解決上述問題。 (5)又，本發明之固態攝像元件用玻璃蓋，若被覆膜係 128130.doc -27- 200842116 光學薄膜，且膜厚處於0.01 0111至1〇〇 μηι之範圍内，則可調整膜厚以將各種光學性能賦予附膜之玻璃板。 ⑹又，本發明之固態攝像元件用玻璃i，若玻璃蓋之外周端面之凹部深度為3() μπ1以下，且凹部長度為谓_ 以下則可抑制形成於玻璃蓋表面之被膜易於剝離之問題，或者玻璃蓋本身之機械強度降低之問題。A glass cover for a solid-state image sensor of a thin plate-shaped thin plate has a coating on at least one of two light-transmissive surfaces in a thickness direction, and the outer peripheral end of the coating is fixed to The light-transmissive surface can reduce the generation rate of various defects generated in the end face of the glass plate, thereby having high quality. (3) In addition, the glass cover for a solid-state image sensor of the present invention can be used to sufficiently improve the state of the glass cover in a specific wavelength range, and the film cover can be made to have an anti-reflection coating. A sufficient amount of light is incident on the solid-state imaging element, so that the performance of the solid-state imaging element is as good as designed. Further, in the glass cover for a solid-state image sensor of the present invention, if the straw of the coating film is fixed to the light-transmitting surface by heating by laser cutting, the laser + " $ has a large unevenness, so It can reduce the glass cover and the back area of the ceramic substrate with 70 pieces of solid-state imaging material stored in U. Even if the product is reduced, it can achieve a sufficiently high bonding strength... even if it is stored in the package shape solid-state photo! The area of the component is increased, and the above problem can be solved by making the package of the solid-state imaging and the area of the gossip increased without enclosing the component. (5) Further, the present invention A glass cover for a solid-state image sensor, if the film is a film of 128130.doc -27- 200842116, and the film thickness is in the range of 0.01 0111 to 1 〇〇μηι, the film thickness can be adjusted to impart various optical properties to the film. (6) In addition, in the glass i for the solid-state image sensor of the present invention, if the depth of the concave portion of the peripheral end surface of the glass cover is 3 () μπ1 or less, and the length of the concave portion is _ or less, the film formed on the surface of the glass cover can be suppressed. The problem of easy peeling, or the problem of reduced mechanical strength of the glass cover itself.

广本發明之固態攝像元件用玻璃蓋，I固態攝像元件係CCD或CMOS，則可具有機械性能穩定之品質，該機械性能亦能適應純厚尺寸較小之目g攝像元件用玻璃蓋，該固態攝像元件用玻璃蓋搭載於用於搭載於資訊行動裝置等時所需之薄型固態攝像元件上。 (8)進而本發明之固態攝像元件用玻璃蓋中，若以氧化物換算之質量百分比表*，錢氧化物玻璃製之薄板狀玻璃之組成含有：56〜70%之Si〇2、〇·5〜18%之Al2〇3、5〜2〇% 之 B2O3、0.1 〜20%之 R〇 (R〇=Mg〇+CaO+ZnO+SrO+BaO)、〇〜9%之Zn0、以及卜腦之^^ (M2〇=Li2〇+Na2〇+K2〇)，則可增加可見光範圍之透過率性能或耐水性、耐酸性等化學耐久性能，而且可形成作為輕量化之目標的密度充分低之玻璃材料，進而，可成為具有相應硬度之材質，因此，可構成具有輕量且穩定之強度性能之玻璃蓋。 (9)本發明之固態攝像元件用玻璃蓋之製造方法包含以下步驟：於耐熱性容器内熔融玻璃原料混合物之步驟；使所獲得之熔融玻璃成形為玻璃板之步驟；於該玻璃板之兩個透光面之至少一面上形成被覆膜之成膜步驟；將雷射射 128130.doc -28- 200842116 至兩個透光面之至少一面上具有被覆膜之附被覆臈之玻璃板之射出步驟；以及，將射出步驟後之玻璃板分割為小片之玻璃之步驟，因此’無須構築用以將玻璃板細分為小片狀之切斷後分別使被覆膜形成為小片狀玻璃板之情形時般的複雜步驟，即可有效地實現玻璃板之製造。 ⑽又，本發明之固態攝像元件用玻璃蓋之製造方法中’若使溶融玻璃成形為玻璃板之步驟係使溶融玻璃向; 乙伸成形後冷卻固化為玻璃板’則藉由適當管理作為母材之玻璃板之起伏等表面品f，可高速實施能滿足顧客之尺寸精度之要求的溶融玻璃之精密成形，藉由實現高製造效率而可Λ現付合市場要求之品質與價格。 (11)又，本發明之固態攝像元件用玻璃蓋之製造方法，若分割為小片之玻璃之步驟係折斷步驟，則分割為小片之玻璃之步驟不會成為複雜步驟，因此可容易地進行管理，亦可容易地檢測出缺陷之存在，從而可作為良品率較高之步驟。【實施方式】以下，根據實施例，就本發明之固態攝像元件用玻璃蓋與其製造方法加以詳細說明。實施例1 圖2(A)表不本發明之固態攝像元件用玻璃蓋之立體圖，圖2(B)表示其局部放大剖面圖。圖2中，10表示固態攝像元件用玻璃蓋，u表示與玻璃板G之厚度方向相對向之兩個透光面中的第—透光面，a 128130.doc -29- 200842116 表示與^透光面叫目對向之第二透光面，u表示玻璃板側周之第一加工面，14表示玻璃板側周之第二加工面，C1 表示覆蓋於第-透光面之被膜，⑽示覆蓋於第二透光面之被膜。The glass cover for a solid-state image sensor of the present invention, and the solid-state image sensor of the present invention, CCD or CMOS, can have a mechanically stable quality, and the mechanical property can also be adapted to a glass cover for a camera element having a small thickness and a small thickness. The glass cover for a solid-state image sensor is mounted on a thin solid-state image sensor required for mounting on an information mobile device or the like. (8) Further, in the glass cover for a solid-state image sensor of the present invention, the composition of the thin plate glass of the niobium oxide glass is: 56 to 70% of Si〇2, 〇· 5~18% of Al2〇3, 5~2〇% of B2O3, 0.1~20% of R〇(R〇=Mg〇+CaO+ZnO+SrO+BaO), 〇~9% of Zn0, and Bu brain ^^ (M2〇=Li2〇+Na2〇+K2〇), which can increase the transmittance performance in the visible light range, chemical durability such as water resistance and acid resistance, and can form a sufficiently low density as a target for weight reduction. The glass material, in turn, can be made of a material having a corresponding hardness, and therefore, can constitute a glass cover having a lightweight and stable strength property. (9) The method for producing a glass cover for a solid-state image sensor of the present invention comprises the steps of: melting a glass raw material mixture in a heat-resistant container; forming the obtained molten glass into a glass plate; and two of the glass plates a film forming step of forming a coating film on at least one side of the light transmissive surface; and irradiating the glass plate with the coated film on at least one side of the two light transmitting surfaces from the laser beam 128130.doc -28- 200842116 And the step of dividing the glass plate after the injection step into small pieces of glass, so that the coating film is formed into a small piece of glass plate without being constructed to cut the glass plate into small pieces. In the case of complex steps, the manufacture of glass sheets can be effectively achieved. (10) Further, in the method for producing a glass cover for a solid-state image sensor of the present invention, the step of forming the molten glass into a glass plate is to melt the glass; after cooling and solidifying into a glass plate, it is appropriately managed as a mother. The surface material f such as the undulation of the glass plate of the material can realize the precision molding of the molten glass which can satisfy the dimensional accuracy of the customer at a high speed, and can realize the quality and price required by the market by achieving high manufacturing efficiency. (11) Further, in the method of manufacturing a glass cover for a solid-state image sensor of the present invention, if the step of dividing into a small piece of glass is a breaking step, the step of dividing into a small piece of glass does not become a complicated step, and thus can be easily managed. It is also easy to detect the presence of a defect, which can be used as a step of higher yield. [Embodiment] Hereinafter, a glass cover for a solid-state image sensor of the present invention and a method for producing the same will be described in detail based on examples. Embodiment 1 Fig. 2(A) is a perspective view showing a glass cover for a solid-state image sensor of the present invention, and Fig. 2(B) is a partially enlarged cross-sectional view thereof. In Fig. 2, reference numeral 10 denotes a glass cover for a solid-state image sensor, and u denotes a first light-transmitting surface among two light-transmissive surfaces opposite to the thickness direction of the glass sheet G, and a 128130.doc -29-200842116 indicates The smooth surface is the second light-transmissive surface opposite to the eye, u is the first processed surface on the side of the glass plate, 14 is the second processed surface on the side of the glass plate, and C1 is the film covering the first-light-transmissive surface, (10) The film covering the second light transmissive surface is shown.

該固態攝像it件用玻璃蓋1G係使用由無驗㈣酸玻璃而組成之薄玻璃板者，該無鹼瑚矽酸玻璃若以氧化物換算之 f4%表示來表示其玻璃組成，則具有如下組成·· 60%之 Si〇2 ’ 14·7% 之 Al2〇3，11% 之 b2〇3，3%2R〇(R〇=Mg〇+ =〇) ’ u.3%之轉〇=Ca0+Sr0)，以及 565 ppm之〇歸 I，或者該固態攝像元件用玻璃蓋1〇係鋁硼矽酸鹽玻璃，該鋁硼矽酸鹽玻璃具有如下基本組成：58〜69%之Si〇2，〇·5〜15%之Al2〇3 ，5〜2〇%之b2〇3 ，工〜鄕之 M20(M2〇=Li2〇+Na2〇+K2〇)，(M〜20% 之 R〇(R〇=Mg〇+In the solid-state imaging device, a glass cover 1G is used as a thin glass plate composed of non-tested (tetra) acid glass, and if the alkali-free sulphuric acid glass is expressed by f4% in terms of oxide, the glass composition is as follows. Composition·· 60% of Si〇2 '14·7% of Al2〇3,11% of b2〇3,3%2R〇(R〇=Mg〇+=〇) ' u.3% conversion = Ca0 +Sr0), and 565 ppm of bismuth I, or the solid-state image sensor using a glass cover 1 bismuth aluminoborosilicate glass, the aluminoborosilicate glass having the following basic composition: 58 to 69% of Si 〇 2 , 〇·5~15% of Al2〇3, 5~2〇% of b2〇3, work~鄕M20 (M2〇=Li2〇+Na2〇+K2〇), (M~20% of R〇( R〇=Mg〇+

CaO+Zn〇+Sr〇+Ba0)，以及〇〜9%之211〇;固態攝像元件用玻璃蓋10係用作收納有光半導體元件、即CMOS元件之封裝之窗玻璃板者，該CM0S元件之用途係用於搭載在行動電后等之上。該固態攝像元件用玻璃蓋之外形尺寸非常小，為5 mmx5 mmx〇.3 mm，如上所述，藉由採用真空蒸鍍法，使厚度尺寸為1〇 μπι之抗反射膜（亦稱作八化膜）〇1以句專之厚度且無針孔等之缺陷等的狀態，而形成於玻璃板 G之相對向之兩個透光面中的第一透光面〗〗之表面上。又’於與第一透光面U相對向之第二透光面12之表面上，亦與第一透光面11同樣，藉由真空蒸鍍法而形成有厚度為10 μπι之抗反射膜C2。 128130.doc -30- 200842116 覆蓋於兩個透光面上之抗反射膜C1、C2，均係形成於對該破璃板G進行切斷加工以使其成為5 mmx5 mm之透光面之前，因此，被覆膜不會迴繞形成於玻璃板之侧面之一部分。該被覆膜之組成係由4層而組成，該4層由Si〇x-Ti〇x系列構成。進而，上述玻璃板側周之第一加工面13與玻璃板側周之CaO+Zn〇+Sr〇+Ba0) and 〇~9% of 211〇; the glass cover 10 for solid-state image sensor is used as a window glass plate in which an optical semiconductor element, that is, a package of a CMOS element is housed, the CMOS element The purpose is to be used after being mounted on a mobile power. The solid-state image sensor has a very small outer shape of a glass cover of 5 mm x 5 mm x 〇. 3 mm, and as described above, an anti-reflection film having a thickness of 1 μm is used by vacuum evaporation (also referred to as eight). The film 1 is formed on the surface of the first light-transmissive surface of the glass plate G opposite to the two light-transmissive surfaces in a state of a thickness of a sentence and a defect such as a pinhole. Further, on the surface of the second light transmissive surface 12 opposite to the first light transmissive surface U, as in the first light transmissive surface 11, an antireflection film having a thickness of 10 μm is formed by vacuum evaporation. C2. 128130.doc -30- 200842116 The anti-reflection films C1 and C2 covering the two light-transmissive surfaces are formed before the glass plate G is cut to make it a light-transmissive surface of 5 mm×5 mm. Therefore, the coating film does not wrap around a portion of the side surface of the glass sheet. The composition of the coating film is composed of four layers composed of a Si〇x-Ti〇x series. Further, the first processed surface 13 on the side of the glass sheet and the side of the glass sheet are

第一加工面14，係以下述方式藉由雷射照射與其後之按壓之所謂2個階段的雷射切斷加工而形成者，加工面之表面無較大之凹凸，從而，於接著於固態攝像元件用封裝之情形時’可縮小固態攝像元件用封裝與玻璃蓋之接著面積，口此可鈿小封裝整體之外形尺寸。又，即使係具有較大面積之固態攝像元件，亦可增大用以收納固態攝像元件之封裝之模穴部面積’因此，無須增大封裝外形尺寸，即可收納大型固態攝像元件。進而，目雷射切斷面上未形成有較大之凹凸，故可抑制由玻璃板側周之灰塵之產生量，從而可獲得潔淨之玻璃板。其-人，就上述固態攝像元件用玻璃蓋之製造方法加以說明。首先以成為特疋之玻璃組成之方式，對預先選定之高純度玻璃原料進杆避旦& i 一丁輪里後，使用混合器等粉末混合裝置 (省略圖示)加以混合’“形成以均質狀態混合而成的混合玻璃原枓。該混合破璃原料藉由進料機連續地投入至保持為100(TC以上之高㈤沾#也门/皿的耐熱性容器（省略圖示）内，亦即由白金等貴金屬或者 j免寻耐火物所構成之玻璃熔融爐 128130.doc • 31 - 200842116 内。已投入至玻璃熔融爐内之混合玻璃原料，於玻璃熔融爐内以高溫加熱後引起玻璃化反應，成為粗熔融狀態之熔融玻璃。該粗熔融狀態之熔融玻璃，藉由作或發泡等特定物理性之均質化機構，而成為== 熔融玻璃。由此方式而獲得之均質熔融玻璃，流入至配接於耐熱性容器之成形裝置（省略圖示）中。此處，成形裝置有2種形式，、其中-種為可延伸成形者，另一種為藉由鑄漿成形而作成塊狀之母材玻璃後自該母材玻璃切出玻璃板者。首先就$者之延伸成形加以說明。所使用之玻璃板成 I衣置力頂口p具有上部開口之流槽形狀之溶融玻璃供給槽，且具有如下成形體，即，以使該玻璃供給槽之兩側壁、P乍為/皿出之堰’且使兩側壁之外表面部之剖面形狀為大致楔形之方式，使兩側壁之外表面朝向下方而彼此接近’而於下端終結。於熔融爐内經均質化之熔融玻璃，自、l j ί、、u槽之端連續地供給而自兩側壁頂部脊線溢出， :者成形體之兩側壁外表面流下，於大致楔形下端處合、形成為1片玻璃板狀態。藉由適當調整熔融玻璃溫度或l伸速度等諸條件，並藉由安裝於下部之抽取式耐熱性耗特疋速度抽出’而使炼融玻璃以同一速度向下方延伸並冷卻固化’藉此可使玻璃板之成形厚度尺寸適當、為取仏狀怨。以特定長度切割切斷以此方式而成形之帶狀薄坡璃板，Μ Α π丄、^ 猎此形成溥玻璃板母材。對於後者之以鑄漿成形而獲得之母材之塊而言，藉 128l30.doc • 32 200842116 由使用利用㈣研磨粒之線切斷褒切斷為薄玻璃板狀。 U斷衣置將塊璃m供人對於所獲得之已切斷之母材玻使用為成皮革之旋轉研磨機(省略圖示)，一面自動供給使氧化鈽等游離磨工念所磨粒刀放於水等中而成之漿料， ::貝施研磨加工，對玻璃板兩面進行研磨加工直至其成 =面㈣度仏值為之鏡面為止，並加以洗淨、乾秌’攸而形成為鏡面狀態之薄玻璃板母材。The first processing surface 14 is formed by a so-called two-stage laser cutting process by laser irradiation and subsequent pressing in the following manner, and the surface of the processed surface has no large unevenness, and thus is followed by solid state In the case of a package for an image sensor, the area of the package for the solid-state image sensor and the glass cover can be reduced, and the size of the package can be reduced. Further, even in the case of a solid-state image sensor having a large area, the area of the cavity portion for housing the solid-state image sensor can be increased. Therefore, it is possible to accommodate a large-sized solid-state image sensor without increasing the package size. Further, since the large unevenness is not formed on the laser cut surface, the amount of dust generated on the side of the glass plate can be suppressed, and a clean glass plate can be obtained. The method for producing the above-described glass cover for a solid-state image sensor will be described. First, in order to form a special glass composition, a pre-selected high-purity glass material is fed into a rod and a small wheel, and then mixed by a powder mixing device (not shown) such as a mixer. a mixed glass raw material which is mixed in a homogeneous state. The mixed glass raw material is continuously fed into a heat-resistant container (not shown) which is kept at a height of 100 (TC or higher). That is, the glass melting furnace consisting of precious metals such as platinum or j-free refractory material 128130.doc • 31 - 200842116. The mixed glass raw material that has been put into the glass melting furnace is heated at a high temperature in the glass melting furnace to cause the glass. The molten glass in a coarse molten state is obtained by a specific physical homogenization mechanism such as foaming or the like, and becomes a molten glass. The homogeneous molten glass obtained in this manner is obtained. It flows into a molding device (not shown) that is attached to a heat-resistant container. Here, the molding device has two types, one of which is an extendable molder, and the other is a borrower. The base material is formed into a block-shaped base material glass, and the glass plate is cut out from the base material glass. First, the extension molding of the product is described. The glass plate used has an upper opening p. a molten glass supply groove having a flow groove shape, and having a molded body such that both side walls of the glass supply groove and P 乍 are taken out and the cross-sectional shape of the outer surface portions of the two side walls is substantially wedge-shaped In such a manner, the outer surfaces of the two side walls are oriented close to each other and terminate at the lower end. The molten glass which is homogenized in the melting furnace is continuously supplied from the ends of the grooves, and the top ridges of the two side walls are successively supplied. The line overflows, the outer surface of the two side walls of the molded body flows down, and is formed at a substantially wedge-shaped lower end to be formed into a state of one glass plate. By appropriately adjusting conditions such as the temperature of the molten glass or the speed of stretching, and by being attached to the lower portion The extraction heat resistance is specially extracted at a speed, and the smelting glass is extended downward and cooled and solidified at the same speed, thereby making the shape and thickness of the glass sheet suitable for the smashing. Cutting the strip-shaped thin slabs formed in this way, Μ 丄 π 丄, ^ hunting to form the base glass of the enamel glass sheet. For the latter, the block of the base material obtained by casting the slurry, borrow 128l30 .doc • 32 200842116 Cut and cut into thin glass plates by using the line of (4) abrasive grains. U-breaking will be used to make the piece of glass for the obtained base material. In a rotary grinder (not shown), a slurry obtained by placing a free-grinding knife such as cerium oxide in water or the like is automatically supplied to the slurry, and: Bescher grinding is performed to polish both surfaces of the glass plate until The thin glass plate base material is formed into a mirror-like state by the surface of the mirror surface.

可精由以上2種方法而製造之薄玻璃板母材之尺寸，可於縱· 50〜600 mm、谱· αλλ 狄知、.50〜600 _、板厚：0·1〜50 mm之範圍内形成，且可根據需要進行變更。 /如以上之方式而獲得之薄玻璃板母材，經過成膜步驟後可獲付已於在板厚方向上相對向之兩個透光面上覆蓋有被覆膜之已形成被膜之玻璃板母材，上述成膜步驟中，藉由使用A空蒸《置錢由SK)XH㈣構成之4層抗反射膜Cl、C2形成;^上述薄玻璃板母材之在板厚方向上相對向之透光面之兩個表面丨丨、丨2上。為了使已形成被膜之玻璃板母材、亦即藉由於兩個透光面上形成被覆膜之成膜步驟而於2個面上形成有被覆膜之玻璃板，形成為小片玻璃板，應按照如下順序進行。首先，使用利用二氧化碳氣體雷射之熱加工雷射切斷裝置’於成膜為厚度達到已形成被膜之玻璃板母材之板厚方向之20%為止之面上，於作為分割預備線之雷射束移動速度為180土5 mm/sec、或者220土5 mm/sec，且雷射功率為 120±5 W、或者160土5 W的條件下，進行棋盤狀之第一加 128I30.doc -33 - 200842116 工。如此，藉由實施第-加工而形成之面，成為切斷後圖 2(A)中之第一加工面13。The size of the thin glass plate base material which can be manufactured by the above two methods can be in the range of 50 to 600 mm, spectrum, αλλ Dizhi, .50 to 600 _, and plate thickness: 0·1 to 50 mm. It is formed inside and can be changed as needed. / The thin glass substrate obtained by the above method can obtain a glass plate which has been coated with the coating film on the two transparent surfaces which are opposite to each other in the thickness direction after the film forming step In the above-mentioned film forming step, the four-layer anti-reflection films C1 and C2 composed of A-air-steaming "salt by SK" XH (four) are formed; and the thin glass plate base material is opposed to the plate thickness direction. The two surfaces of the light-transmissive surface are 丨丨2 and 丨2. A glass plate on which a coating film is formed on two surfaces by a film forming step of forming a coating film on two light-transmissive surfaces, so as to form a small glass plate, It should be done in the following order. First, a hot-cut laser cutting device using a carbon dioxide gas laser is used to form a film having a thickness of up to 20% of the thickness direction of the glass plate base material on which the film has been formed. The beam movement speed is 180 soil 5 mm / sec, or 220 soil 5 mm / sec, and the laser power is 120 ± 5 W, or 160 soil 5 W, the first addition of 128I30.doc - 33 - 200842116 Workers. As described above, the surface formed by the first processing is the first processed surface 13 in Fig. 2(A) after the cutting.

其次’如圖3中概念性所示，相對於薄玻璃板20之呈有第-加工面13之透光面η，於其相反側之已成膜之透光面 12上’使金屬製之線狀加工頭3〇向作動方向μ移動，同時利用夾具（省略圖示）按壓薄玻璃板2〇之第一加工面丨3側之已成膜之透光面12,藉此對薄玻璃板2〇之第一加工面^施加適當之應力’且以1Χ10·3 m/sec之壓速度為進行壓碎。如此，藉自進行第二加工之割斷操#，可獲得⑨著作為藉由第一加工而形成之破斷之起源的預備線分割而成的長^ 狀玻璃板。藉由該第二加工而形成者，係圖2(A)中之第二加工面14。分別利用真空小攝子（省略圖示），將經上述方式壓碎加工而成之長條狀之玻璃板搬運至下一步驟中。繼而，再次對長條狀之玻璃板進行壓碎加工，藉此獲得最終之固態攝像元件用玻璃蓋。如此而獲得之固態攝像元件用玻璃蓋，藉由形成第一加工面13時所進行之雷射照射，於透光面u之被覆膜ci之外周端，藉由使用有雷射之加熱而成為使被覆膜〇1牢固地與玻璃表面11固著之狀態，因此透光面上之被覆膜難以容易地剝離。其次’表1總結表示對於藉由上述製造方法而獲得之本發明之固態攝像元件用玻璃蓋因其端面所產生之碎片等所引起的凹部缺陷之尺寸進行調查後的結果。關於該玻璃蓋之測量，預先檢查10萬片玻璃蓋，並將於該檢查中確認為 128130.doc • 34 - 200842116 在端面部具有凹部之玻璃蓋集中，進而，為了確認該凹部之尺寸，而利用有電子顯微鏡進行測量。表1中，自樣品Νο·1至樣品No. 17為止，係於包含第一透光面與第一加工面之分界即脊線在内之部分產生有碎片等凹部缺陷者，自樣品No. 18至樣品Νο·26為止，係於包含第二透光面與第二加工面之分界即脊線在内之部分產生有碎片等凹部缺陷者。 [表1]Secondly, as shown conceptually in Fig. 3, the light-transmissive surface η having the first processed surface 13 of the thin glass sheet 20 is made of metal on the oppositely formed light-transmissive surface 12 of the film. The linear processing head 3 is moved in the moving direction μ, and the film-transparent light-transmissive surface 12 on the side of the first processed surface 3 of the thin glass sheet 2 is pressed by a jig (not shown), thereby thin glass plate The first processed surface of the crucible is applied with appropriate stress ' and crushed at a pressure of 1 Χ 10·3 m/sec. As described above, by the cutting operation # for the second processing, a long glass plate in which the preparatory line which is the origin of the breaking formed by the first processing is divided can be obtained. The second processing surface 14 of Fig. 2(A) is formed by the second processing. The long glass sheets which were crushed by the above method were transported to the next step by a vacuum small camera (not shown). Then, the long glass plate was crushed again, whereby the final glass cover for the solid-state image sensor was obtained. The glass cover for a solid-state image sensor obtained in this manner is irradiated by laser light when the first processed surface 13 is formed, and is irradiated with laser light at the outer peripheral end of the coating film ci of the light transmitting surface u. Since the coating film 1 is firmly fixed to the glass surface 11, the coating film on the light-transmissive surface is difficult to be easily peeled off. Next, Table 1 summarizes the results of investigations on the dimensions of the recess defects caused by the fragments of the glass cover of the solid-state image sensor of the present invention obtained by the above-described manufacturing method. Regarding the measurement of the glass cover, 100,000 glass covers were inspected in advance, and it was confirmed that it was 128130.doc in this inspection. 34 - 200842116 The glass cover having the concave portion on the end surface was concentrated, and further, in order to confirm the size of the concave portion, Measurements were made using an electron microscope. In Table 1, from the sample Νο·1 to the sample No. 17, a defect such as a chip is generated in a portion including the boundary between the first light-transmissive surface and the first processed surface, that is, the ridge line, from the sample No. From the 18th to the sample Νο·26, a defect of a concave portion such as a chip is generated in a portion including the boundary between the second light-transmissive surface and the second processed surface, that is, the ridge line. [Table 1]

\ 包含玻璃蓋之第一透光面與第一加工面之分界之脊線在内的凹部缺陷包含玻璃蓋之第二透光面與第二加工面之分界之脊線在内的凹部缺陷樣品NO. 凹部之脊線方向長度(W) 凹部之深度尺寸(L) 凹部之脊線方向長度(W) 凹部之深度尺寸(L) 1 18 3 - - 2 10 2 - - 3 15 5 - - 4 29 4 - - 5 46 9 - - 6 25 3 - - 7 46 6 - - 8 14 5 - - 9 13 4 - - 10 65 5 - - 11 29 2 - - 12 88 4 - - 13 24 5 - - 14 35 3 - - 15 18 3 - - 16 22 4 - - 17 52 3 - - 18 - - 108 17 19 - - 79 10 20 - - 17 7 21 - - 72 10 22 - - 93 13 23 - - 280 6 24 - • 171 10 25 - - 43 9 26 - - 68 12 128130.doc -35- 200842116 根據該表1可知，凹部之脊線方向長度1係處於1〇 ^瓜至 280 μχη為止之範圍内之尺寸值，且均為5〇〇 μηι#下之尺寸。又，凹部之玻璃板透光面方向之深度方向尺寸均大於玻璃板厚度方向之深度尺寸Η，係2 0瓜至17 μηι之範圍内之尺寸值，且均為30 μπι以下。如此，本發明之固態攝像元件用玻璃蓋係具有不存在如較大尺寸之碎片般之凹部缺陷的完整形狀尺寸、且具有較高之尺寸穩定性之優良的玻璃蓋，且不易引起由凹部所導致之強度之降低或膜剝離。【圖式簡單說明】圖1係關於本發明之固態攝像元件用玻璃蓋之端面之說明圖。圖2係本發明之固態攝像元件用玻璃蓋之說明圖，圖 2(A)係立體圖，圖2(Β)係局部剖面圖。口圖3係對第一加工後之附膜之薄板狀玻璃進行第二加工時之加工方法之說明圖。【主要元件符號說明】卜 10 固態攝像元件用玻璃蓋 2 玻璃板之端面 3、 11 玻璃板之第一透光面 4、 12 玻璃板之第二透光面 5、 13 第一加工面 6、 14 第二加工面 20 薄玻璃板 128I30.doc -36- 200842116The concave defect including the ridge line of the boundary between the first transparent surface of the glass cover and the first processed surface includes a concave defect sample including the ridge line of the boundary between the second transparent surface of the glass cover and the second processed surface NO. Length of the ridge line direction of the recess (W) Depth size of the recess (L) Length of the ridge line of the recess (W) Depth of the recess (L) 1 18 3 - - 2 10 2 - - 3 15 5 - - 4 29 4 - - 5 46 9 - - 6 25 3 - - 7 46 6 - - 8 14 5 - - 9 13 4 - - 10 65 5 - - 11 29 2 - - 12 88 4 - - 13 24 5 - - 14 35 3 - - 15 18 3 - - 16 22 4 - - 17 52 3 - - 18 - - 108 17 19 - - 79 10 20 - - 17 7 21 - - 72 10 22 - - 93 13 23 - - 280 6 24 - • 171 10 25 - - 43 9 26 - - 68 12 128130.doc -35- 200842116 According to Table 1, the length of the ridge in the ridge is 1 in the range from 1 〇 to 280 μχ. And are all under 5〇〇μηι#. Further, the depth direction of the direction of the light-transmissive surface of the glass plate of the concave portion is larger than the depth dimension of the thickness direction of the glass plate, and is a size within a range of 20 to 17 μm, and is 30 μm or less. As described above, the glass cover for a solid-state image sensor of the present invention has an excellent glass cover which does not have a complete shape size such as a large-sized piece of concave defect, and has high dimensional stability, and is not easily caused by the concave portion. The resulting decrease in strength or film peeling. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing an end face of a cover glass for a solid-state image sensor of the present invention. Fig. 2 is an explanatory view of a glass cover for a solid-state image sensor of the present invention, Fig. 2(A) is a perspective view, and Fig. 2(Β) is a partial cross-sectional view. Fig. 3 is an explanatory view showing a processing method for performing the second processing on the thin plate glass of the first processed film. [Description of main component symbols] Bu 10 Glass cover for solid-state image sensor 2 End face of glass plate 3, 11 First light-transmissive surface of glass plate 4, 12 Second light-transmissive surface of glass plate 5, 13 First processed surface 6, 14 Second working surface 20 Thin glass plate 128I30.doc -36- 200842116

30 Cl C2 G M W 線狀加工頭形成於玻璃板之第形成於玻璃板之第玻璃板作動方向 —透光面之被膜二透光面之被膜玻璃板端面之凹部之脊線方向長度尺寸30 Cl C2 G M W Linear processing head Formed on the glass plate The third glass plate formed in the glass plate Actuation direction - the film of the light transmissive surface The film of the two translucent surfaces The length of the ridge line of the concave end of the glass plate

HH

L 玻璃板端面之凹部之玻璃板厚度方向之深度尺寸玻璃板端面之凹部之玻璃板透光面方向之深度尺寸L The thickness of the glass plate in the concave end of the end face of the glass plate is the depth dimension of the glass plate.

128130.doc -37 -128130.doc -37 -

Claims

200842116 十、申請專利範圍： 1. 一種固態攝像元件用玻璃蓋，其特徵在於：其係無機氧化物玻璃製之薄板狀之固態攝像元件用玻璃蓋，且於在板厚方向上相對向之兩個透光面之至少一面上具有被覆膜’玻璃盍之外周端面由藉由雷射切斷之面構成’被覆膜係於雷射切斷之前成膜。 2· —種固態攝像元件用玻璃蓋，其特徵在於：其係無機氧化物玻璃製之薄板狀之固態攝像元件用玻璃蓋，且於在板厚方向上相對向之兩個透光面之至少一面上具有被覆膜，被覆膜之外周端固著於透光面。 3·如請求項1或2之固態攝像元件用玻璃蓋，其中被覆膜係抗反射膜。 4·如請求項丨至;^中任一項之固態攝像元件用玻璃蓋，其中被覆膜之外周端係藉由利用雷射切斷之加熱而固著於透光面。 5 ·如明求項1至4中任一項之固態攝像元件用玻璃蓋，其中被覆膜係光學薄膜，且膜厚在〇〇1 )^111至1〇〇 pm之範圍内。 6·如請求項1至5中任一項之固態攝像元件用玻璃蓋，其中玻璃蓋之外周端面之凹部深度為3〇 μιη以下，且凹部長度為500 μηι以下。 7·如請求項〗至6中任一項之固態攝像元件用玻璃蓋，其中固態攝像元件係CCD或CMOS。 8·如請求項1至7中任一項之固態攝像元件用玻璃蓋，其中 128130.doc 200842116 以氧化物換算之質量百分比表示，無機氧化物玻璃製之薄板狀玻璃之組成含有56〜70%之Si02、0.5〜18%之 Abo、、5〜20% 之 Bach、0.1 〜20% 之 R〇(R〇=MgO+CaO+ ZnO+SrO+BaO)、〇〜9%之 ZnO、以及 1〜18%之 Μ20(Μ20= Li20+Na20+K20)。 9· 一種固態攝像元件用玻璃蓋之製造方法，其特徵在於包 ·、含：，於耐熱性容器内熔融玻璃原料混合物之步驟；使所獲得之熔融玻璃成形為玻璃板之步驟；於該玻璃板之兩個透光面之至少一面上囬上形成被覆膜之成膜步驟；將雷射射出至在兩個透光面之至少一的附被覆膜之玻璃板之射出步驟；以及、將射出步驟後之玻璃板分割為小片玻璃之步驟 1〇·如請求項9之固態攝像元件用玻璃蓋之製造^法°， • *熔融玻璃成形為玻璃板之步驟係使熔融破璃’其中伸成形後冷卻固化為玻璃板。下方延 .η·如請求項9之固態攝像元件用玻璃蓋之製造方、、 * 分割為小片玻璃之步驟係折斷步驟。决’其中 128130.doc200842116 X. Patent application scope: 1. A glass cover for a solid-state image sensor, which is characterized in that it is a glass cover for a thin-plate solid-state image sensor made of inorganic oxide glass, and is opposite to each other in the thickness direction. At least one of the light transmissive surfaces has a coating film. The outer peripheral end surface of the glass crucible is formed by a surface cut by a laser. The coating film is formed before the laser cutting. A glass cover for a solid-state image sensor, characterized in that it is a glass cover for a solid-state image sensor having a thin plate shape made of inorganic oxide glass, and at least two light-transmissive surfaces facing each other in a thickness direction A coating film is provided on one surface, and the outer peripheral end of the coating film is fixed to the light transmitting surface. 3. The glass cover for a solid-state image sensor of claim 1 or 2, wherein the coating film is an antireflection film. A glass cover for a solid-state image sensor according to any one of the preceding claims, wherein the outer peripheral end of the coating film is fixed to the light transmitting surface by heating by laser cutting. The glass cover for a solid-state image sensor according to any one of claims 1 to 4, wherein the coating film is an optical film, and the film thickness is in the range of 〇〇1)^111 to 1 pm. The glass cover for a solid-state image sensor according to any one of claims 1 to 5, wherein the outer peripheral end surface of the glass cover has a recess depth of 3 μm or less and a concave length of 500 μm or less. The glass cover for a solid-state image sensor according to any one of claims 1 to 6, wherein the solid-state image pickup device is a CCD or a CMOS. The glass cover for a solid-state image sensor according to any one of claims 1 to 7, wherein 128130.doc 200842116 is expressed by mass percentage of oxide, and the composition of the thin plate glass made of inorganic oxide glass is 56 to 70%. SiO2, 0.5 to 18% Abo, 5 to 20% Bach, 0.1 to 20% R〇 (R〇=MgO+CaO+ZnO+SrO+BaO), 〇~9% ZnO, and 1~18 % between 20 (Μ20= Li20+Na20+K20). A method for producing a glass cover for a solid-state image sensor, characterized by comprising: a step of melting a glass raw material mixture in a heat-resistant container; a step of forming the obtained molten glass into a glass plate; a film forming step of forming a coating film on at least one of the two light transmissive surfaces of the board; and an emitting step of ejecting the laser beam to the glass sheet with at least one of the two light transmitting surfaces; Step 1 of dividing the glass plate after the injection step into small pieces of glass. The manufacturing method of the glass cover for the solid-state image sensor of claim 9 is a method of forming a molten glass into a glass plate. After forming, it is cooled and solidified into a glass plate. The following is a step of breaking the glass cover of the solid-state image sensor of claim 9 and dividing it into a small piece of glass.决' where 128130.doc