201009091 九、發明說明： 【發明所屬之技術領域】 本創作屬於環境保護及廢棄物資源再生技術領域。 【先前技術】 我國為全世界晶圓生產主要國家，故會產生大量的廢石夕晶圓，而 Φ 晶圓中含有大量有價資源(如Si、Cu等），因此極具資源回收之價值。 目前含銅廢矽晶圓中矽回收處理技術大致上可以區分為高溫加熱法、 化學機械研磨、酸液浸潰表面法等方式。然而上述等方式無法完全去 除滲入晶圓内部之銅金屬’且皆須經過表面研磨及拋光等程序以去除 表面之氧化矽層及銅金屬鍍層，而於研磨過程中會造成晶圓表層矽材 料之損耗，將浪費有價矽資源。 經查國内相關廢矽晶圓資源回收之專利，如中華民國專利編號 Φ 1244130「回收矽晶圓的方法」，其内容主要係將廢石夕晶圓先以化學處理 液進行去膜程序，再以加熱法使滲入晶圓内部之銅金屬擴散至晶圓表 面，再利用研磨法去除銅金屬，僅留下矽晶片；中華民國專利編號 00448245「半導體晶圓回收再生之方法」，其内容主要係將矽晶圓片利 用化學機械研磨法(CMP)去除表面鑛層金屬後，再以聚乙稀醋酸(pvA) 刷洗經研磨後之碎晶圓片以恢復半導體晶圓之品質；中華民國專利編 號1235407「晶圓及其製造與回收之方法」，其内容關於回收部份為將 一片矽晶圓先以氫氟酸溶液去除上層之氧化矽層後，再以磷酸溶液去 201009091 除中層之氮化矽層，僅留下矽晶片。 综合上述結果得知，並未發現國内有任何相關專利與技術可利用 含銅廢矽晶圓為原料來進行銅金屬及矽材料資源回收，以獲得硫緩銅 晶體、置換銅與高純度矽材質，故本發明可提供國内相關業者作為資 源回收含銅廢矽晶圓之依據。 【發明内容】 半導體為電子產業之重要基礎元件，自1958年開始發展至今已逾 5〇年’隨著時代的變遷，讀對電子產品之應用與依絲度越來越深， 也使得半導體產f日漸絲。我_半導體產胁_上4目當活耀， 尤其以晶®代工最為發達，因此，我國亦會產生大量之廢棄晶圓，由 於含銅射BaBgJ含有有價之銅及秒魏，如無法回收再個，將會造 成整體資狀浪費，甚為可惜’有齡此，本發明乃麟含銅廢石夕晶 圓進行資源回收之工作。 本發明魄主要是先將所收集之含銅财晶_研磨方式將其研 磨過篩至50mesh(0.297mm)以下，再將含銅廢矽晶圓粉末置於1N硫酸 浸潰液中’在過氧化氫/銅莫耳數比& 2〇〇/1，含銅廢石夕晶圓粉末(公 克)/1Ν硫酸(毫升)比為μ，浸潰溫度為贼下予以浸潰4小時可 得98.6%之銅金屬财时率，_雜之含峨舰先以賊加熱 2小時後’再於室溫進行12小時之靜置晶析步驟後可將浸潰液中之 銅金屬完全晶析為硫酸銅晶^另經過舰所得之固體粉末，因仍殘 201009091 留銅金屬，因此乃針對此固體進行二次銅浸潰溶姓，經二次浸潰過濾 後所得之固體即為高純度矽材質;另浸潰過濾後之液體中尚含有有價銅 離子’經兩次鐵粉置換後即可將其100%置換成銅金屬。 含銅廢梦晶圓經本發明之資源再生方法處理後，可獲得硫酸銅晶 體、置換銅及高純度矽材質可提供相關產業利用，達成含銅廢矽晶圓 資源回收再利用之目的。 β 【實施方式】 本發明之較佳方法示於第一圖，首先將收集之含銅廢石夕晶圓1 (其 外觀如附件-所示），進行研磨筛分2步驟，將含銅廢妙晶圓i研磨過 篩至小於50 mesh (0.297mm)後，進行初次銅浸潰溶韻3步驟，此浸潰 溶蝕之操作條件為：含銅廢矽晶圓粉末(公克)/1N硫酸(毫升)=2/5，過氧 化氫/鋼莫耳數比=200/1，浸潰溫度=7〇。(：，浸潰時間=4小時。經初次 銅浸潰溶蝕3步驟之後，可將含銅廢石夕晶圓丨中98 6%之鋼浸潰溶钱於201009091 IX. Description of invention: [Technical field to which the invention belongs] This creation belongs to the field of environmental protection and waste resource recycling technology. [Prior Art] China is the main country for wafer production in the world, so it will produce a large amount of waste stone wafers, and Φ wafers contain a lot of valuable resources (such as Si, Cu, etc.), so it has great value for resource recovery. At present, the recovery technology of germanium in copper-containing waste crucible wafers can be roughly classified into high-temperature heating method, chemical mechanical polishing, and acid-immersion surface method. However, the above methods cannot completely remove the copper metal that penetrates into the interior of the wafer and must be subjected to surface grinding and polishing procedures to remove the ruthenium oxide layer and the copper metal plating layer on the surface, which may cause the surface layer of the wafer during the grinding process. Loss will waste valuable resources. The patent for the recovery of related waste wafer resources in China, such as the Republic of China Patent No. Φ 1244130 "Method for Recycling Wafer Wafers", the main content of which is to remove the waste stone wafers with a chemical treatment solution. Then, the copper metal infiltrated into the wafer is diffused to the surface of the wafer by heating, and the copper metal is removed by grinding, leaving only the germanium wafer; the Republic of China Patent No. 00448245 "Method for Recycling and Recycling of Semiconductor Wafers", mainly The surface of the crucible wafer is removed by chemical mechanical polishing (CMP), and then the ground wafer is washed with polyethylene acetate (pvA) to restore the quality of the semiconductor wafer; No. 1235407, "Method for Wafer and Its Manufacturing and Recycling", the content of which is to remove a layer of tantalum oxide from a layer of tantalum wafer with a hydrofluoric acid solution, and then remove the nitrogen in the middle layer with a phosphoric acid solution to 201009091. The enamel layer is left with only the ruthenium wafer. Based on the above results, it has not been found that there are any related patents and technologies in China that can use copper-containing waste crucible wafers as raw materials to recover copper metal and tantalum materials to obtain sulfur slow copper crystals, copper replacement and high purity germanium. The material can be used as a basis for the domestic related industry to recover the copper-containing waste wafer as a resource. [Invention] Semiconductor is an important basic component of the electronics industry. It has been in development since 1958. Over the past five years, with the changes of the times, the application and the dependence of electronic products have become deeper and deeper. f is getting more and more. I _ semiconductor production threat _ on the 4th eye to be alive, especially in the crystal ® OEM is the most developed, therefore, China will also produce a large number of discarded wafers, because the copper-containing BaBgJ contains valuable copper and seconds Wei, such as can not be recycled In addition, it will cause a waste of the overall assets, and it is a pity that 'the age of this, this invention is the work of recycling the resources of the copper-containing waste stone wafers. The invention is mainly characterized in that the collected copper-containing crystal crystal_grinding method is ground and sieved to below 50mesh (0.297mm), and then the copper-containing waste crucible wafer powder is placed in 1N sulfuric acid dipping solution. Hydrogen peroxide / copper Molar ratio & 2 〇〇 / 1, copper-containing waste stone wafer powder (g) / 1 Ν sulfuric acid (ml) ratio of μ, impregnation temperature for thieves to be dipped for 4 hours 98.6% of the copper metal time rate, _ miscellaneous 峨 峨 先 以 以 以 以 加热 加热 加热 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼 贼Copper sulphate crystals and solid powder obtained by the ship, because it still remains 201009091 copper metal, so the second copper immersion solution for this solid, the solid obtained after secondary impregnation filtration is high purity bismuth material The other impregnated filtered liquid still contains valuable copper ions, which can be replaced by copper metal after being replaced by two iron powders. After the copper-containing waste dream wafer is processed by the resource regeneration method of the present invention, copper sulfate crystal, replacement copper and high-purity germanium material can be obtained to provide relevant industries, and the purpose of recycling and recycling copper-containing waste wafer resources is achieved. β [Embodiment] The preferred method of the present invention is shown in the first figure. First, the collected copper-containing waste stone wafer 1 (the appearance is as shown in the attachment) is subjected to grinding and screening, and the copper-containing waste is used. After the fine wafer i is ground and sieved to less than 50 mesh (0.297mm), the first copper impregnation process is performed. The operating conditions of the impregnation and erosion are: copper-containing waste crucible wafer powder (g)/1N sulfuric acid ( ML) = 2/5, hydrogen peroxide / steel molar ratio = 200/1, impregnation temperature = 7 〇. (:, impregnation time = 4 hours. After the initial copper impregnation and erosion 3 steps, 98.6% of the steel in the copper-containing waste stone 丨 wafer can be immersed in the money.
籲 ⑦潰液中’再經初次過渡4步驟予以過滤後，可得初次含銅浸潰液W 及初次浸潰濾渣42。 為回收純化此初次含鋼浸潰液41中之銅金屬，乃針對此初次含銅 浸潰液41進行晶析5步驟，其晶析操作條件為：溫度=7此，加熱時 間=2小時’冷卻靜置時間=12小時。經晶析5步驟完成後即可獲得 硫酸銅晶體51 (其外觀如附件二所示）。 另經初次過渡4步驟所得之初次浸潰濾潰42，因其中仍有〇〇ι% 201009091 含量之銅金屬，因此乃將其進行二次銅浸潰溶餘6步驟，其操作條件 為：初次浸潰濾渣(公克V1N硫酸(毫升)=2/5，過氧化氫/鋼莫耳數比 =200/1 ’浸潰温度=70°C，浸漬時間=4小時。經二次銅浸潰溶姓6步驟 後，可將初次浸潰濾渣42中之銅1〇0%浸漬溶兹於溶液中再經二次 過濾7步驟予以過濾後，可收集到二次含銅浸潰液71及二次浸潰濾涪 72，此二次浸潰濾、渣72，即為高純度梦材質73 (其外觀如附件三所示， 另高純度矽材質73之矽純度經能量分散光譜儀(^□幻檢測分析結果如 附件四所示）。 另為回收二次含銅浸潰液71中之銅金屬，可針對二次含銅浸漬液 71進行初次置換8步驟，其置換操作條件為：置換劑=鐵粉，置換時 間=4小時，鐵/銅莫耳數比=1〇/卜經初次置換8步驟後可得初次置換 鋼81 (其外觀如附件五所示）。由於經初攻:置換8步驟後所得之初次置 換殘留液82中尚含有少量銅金屬，為求完全回收銅金屬資源，因此再 針對初次置換殘留液82進行二次置換9步驟，其置換操作條件為··置 換劑==鐵粉，置換時間=4小時’鐵/銅莫耳數比=13〇/卜經二次置換 9步驟後可將初次置換殘留液82中之銅完全置換成二次置換銅91;另經 欠置換9步驟後所付之一次置換殘留液92，即可送交合格處理業者 進行最終廢液處置10。 為使本發明更加顯現出其進步性與實用性’茲將本發明之優點列 舉如下： 1.本發明可回收含銅廢矽晶圓中之有價銅金屬及矽材料，減少鋼 11 201009091 資源及矽材料之浪費 2·本發明之技術成果可獲得具市場銷售價值之「硫酸銅晶體」產 品、「置換銅」產品及「商純度妙材質」產品，達到含銅廢碎 晶圓中銅金屬及矽材料百分之百完全資源化之目標。 3·本發明可避免含銅廢矽晶圓污染環境及危害人體健康。 4. 本發明可提升國内含銅廢矽晶圓資源再生之效益。 5. 本發明具安全性與進步性。 6. 本發明具工商界與產業界之利用價值。 综合上所述，本發明誠已符合發明專利之申請要件，並依法提出 申請，祈請鈞局審查委員明鑑，並賜予本發明專利權，實感德便。 【圖式簡單說明】 第圖係本發明「含銅廢石夕晶圓資源再生之方法」之實施流程圖。 【主要元件符號說明】 無 12After the first step of the filtration step 4 is filtered, the initial copper-containing impregnation liquid W and the first impregnation filter residue 42 are obtained. In order to recover and purify the copper metal in the primary steel-containing impregnation solution 41, the crystallization is carried out for the first copper-containing impregnation solution 41, and the crystallization operation conditions are as follows: temperature=7, heating time=2 hours' Cooling rest time = 12 hours. After completion of the crystallization 5 step, copper sulfate crystal 51 can be obtained (the appearance of which is shown in Annex 2). The first impregnation filter 42 obtained by the first transition 4 step, because there is still copper metal of 〇〇ι% 201009091 content, so it is subjected to secondary copper impregnation and dissolution 6 steps, and the operating conditions are: first time Leaching filter residue (gram V1N sulfuric acid (ml) = 2/5, hydrogen peroxide / steel molar ratio = 200/1 'Immersion temperature = 70 ° C, immersion time = 4 hours. Secondary copper impregnation After the last 6 steps, the copper in the first dipping filter residue 42 can be immersed in the solution and then filtered through the secondary filtration step 7 to collect the secondary copper-containing impregnation solution 71 and the second time. Immersion filter 72, this secondary impregnation filter, slag 72, is a high-purity dream material 73 (its appearance is shown in Annex III, another high purity 矽 material 73 矽 purity by energy dispersion spectrometer (^ □ illusion detection The analysis results are shown in Annex IV. In addition, in order to recover the copper metal in the secondary copper-containing impregnation solution 71, the primary replacement 8 step can be performed on the secondary copper-containing impregnation liquid 71, and the replacement operation conditions are: replacement agent=iron Powder, replacement time = 4 hours, iron / copper molar ratio = 1 〇 / after the initial replacement 8 steps can be obtained the first replacement steel 81 (its appearance As shown in Annex V. Since the initial replacement residue liquid 82 obtained after the replacement of 8 steps still contains a small amount of copper metal, in order to completely recover the copper metal resources, the secondary replacement liquid 82 is subjected to secondary replacement. Step, the replacement operating conditions are: · Displacement agent = = iron powder, replacement time = 4 hours 'iron / copper molar ratio = 13 〇 / after secondary replacement 9 steps can be used in the initial replacement of residual liquid 82 The copper is completely replaced by the secondary replacement copper 91; and the replacement residual liquid 92 which is paid after the 9 steps of the under-replacement is sent to the qualified processor for the final waste disposal 10. In order to make the invention more progressive And the utility's advantages are as follows: 1. The present invention can recover the valuable copper metal and tantalum materials in the copper-containing waste crucible wafer, and reduce the waste of the steel 11 201009091 resource and the crucible material. 2. The technology of the present invention The result is a "copper sulfate crystal" product, a "displacement copper" product and a "commercial purity material" product with market value, which is the goal of 100% complete recycling of copper metal and tantalum materials in copper-containing waste chips. 3. The invention can avoid the environment of copper-containing waste crucibles from polluting the environment and endangering human health. 4. The invention can improve the benefit of domestic copper-containing waste crucible wafer resource regeneration. 5. The invention is safe and progressive. The invention has the utilization value of the industrial and commercial circles and the industrial circle. In summary, the invention has met the application requirements of the invention patent, and filed an application according to law, praying for the examination of the member of the bureau, and granting the patent right of the invention, the real sense BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1 is a flow chart showing the implementation of the method for regenerating copper-containing waste stone wafer resources in the present invention. [Explanation of main component symbols] No 12