五 '發明説明（1 本發明係關於矽半導體與_ 牿仝‘、 興一氧化矽表面之涪、法a , 舌又，本發明提供—清洗货 田 洗溶液，更 半導體與二氧化矽表^ '夜，仵於單—步驟完成碎 ' 矽表面包括有機物、扉私盥入府 <移除的清洗工作。 上’、金屬等污染物 背景 近年來’為符合對料半導體元件與微 非性的要求，業界莫不致力 又效能及可 夭d双刀於其製程的改 靠的加工技術。於半導體元件之製造守求更可 圓與破璃晶圓，再對其—: 要而進行各式加工步驟。於半導體元件製程之改良 均針對該清洗處理。咸信，晶圓表 囲衣面& /了染情形消除或降 低，可大幅増進元件之安定性與可靠性。 /對料導體與二氧㈣表面之$染物清洗，RCA(美國 無線電公司，Rad1〇 Corp〇ratlon of )於197〇年研究發表 經濟部中央樣準局員工消费合作社印裝 一套極有效之清洗系統，該系統包括二清洗步騾其中第 一清洗步驟係採用之混合溶液，以去除有 機污染物。由#第一清洗步驟《清洗溶液會使清洗表面被 該清洗液所含如Fe、Zn及A1之微量金屬物所污染，故必須 使用含HC1混合液之第二清洗步驟’以移除該等金屬冷染 物。根據RCA研究，可有效進行前述清洗效益之操作為： 於第一步驟採用體積比為5 : 1 : 1至7 ; 2 : 1之H20 / 30% HP2 / 27。/。NH4OH混合液，處理10至20分鐘；於第二步驟採 用體積比為 6 : 1 : 1 至 8 : 2 : 1 之 H20 / 30% H202 / 37% HC1 混 本紙張尺度適用中國國家標隼（CNS ) A4現格（210X297公釐） 經濟部中央標準局員工消费合作社印製 A7 B7 五、發明説明（2 ) 合液’處理10至20分鐘。即，RCA清洗系統必定涉及強酸 化學品如HC1之使用，且需採用二分離步驟，而總處理時 間至少20分鐘。 由於RCA清洗系統必須使用含HC1之酸性清洗溶液’雖可 有效移除欲清洗表面之重金屬污染物，但會導致該酸性清 洗液所含微粒黏附於晶圓表面。此外，RCA清洗必須採二 分離步驟，故操作上較為不便。是以，於半導體元件及矽 晶圓工業中，業界莫不致力於尋找代替RCA清洗溶液之新 顆配方，以提供更簡易、有效且-具經濟效益之清洗系統》 於已知改良RCA清洗系統之技藝，大多係關於該第二清 洗步驟。其中，日本特許公開案昭58 _ 3〇135號揭示使用含 HF、HJO4與H2〇2之酸性水溶液；日本特許公開案平2 -100320號揭示合併使用含NH4〇h與h2〇2水溶液、與含HC1及 H2〇2之水溶液；日本特許公開案平3 _ 273629號揭示使用含 HC1與H2〇2之水溶液；日本特許公開案平4 _ 234118號揭示使 用強酸與極少量含氟化合物之溶液；"Tryborozist "第37 冊第3本第218至224頁（1992年）揭示於室溫採含0 5〇/〇册與 〇_1至1% H2〇2之溶液；美國專利第5,56〇,857號則揭示使用含 0.005至0.05% HF與0.3至20.0%氏〇2且pH為1至5之酸性溶液。 即’大部份關於RCA清洗系統之改良，均針對該酸清洗步 驟之替代溶液的研發，以得到具較少微粒污染之結果。 然而’如前所述，除微粒污染之缺點外，Rca清洗溶液 另具有操作不便（即必須採二分離步驟且需時至少2〇分鐘） 與使用強酸化學品等問題。前述改良技藝均無法避免此等 4 c 2 6 Γι. DOC 一 5 — 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ---- (請先閲讀背面之注意事項再f本頁) 訂 經濟部中央標隼局員工消费合作社印製 A7 B7 五、發明説明（3 ) 問題。故而，仍需要一可簡化RCA清洗系統且毋需採用強 酸化學品之有效清洗系統，以滿足業界簡易、有效且具經 濟效益之需求。 發明概述 本發明之一目的，係提供清洗矽半導體與二氧化矽表面 之新穎高效能清洗溶液，其可大幅縮短清洗時間，且簡化 操作流程，另可避免使用強酸化學品。特定言之，本發明 提供一包含NH4OH、H2O2及至少一種選自含氟化合物與異 於NH4OH之銨鹼成分之溶液，弇可取代RCA清洗系統之第 一與第二清洗溶液，而於單一步驟即可達RCA二清洗步驟 之效益。 本發明之另一目的，係提供具良好電性表現之積體電路 元件，其崩潰電場與崩潰電荷均較以RCA清洗溶液所得元 件為佳。 圖式簡單說明 圖1顯示習用製備積體電路電容元件之流程圖，其中 10代表晶片， 20代表氧化層； 30代表光阻層； 40代表閘極氧化層； 50代表複晶矽層； 60代表銘層； 70代表光阻層；且 80代表銘層。 46260.DOC 一 6 — 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X 297公釐） --；----------Γ--1T-------^ (請先閲讀背面之注意事項^-¾本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（4 ) 圖2顯示於本發明清洗溶液採不同NH4OH / TMAH比例所得 電容之崩潰電場分佈圖，其中Δ代表NH4OH / TMAH = 100 / 1 ，㊀代表 NH4OH / TMAH = 300 / 1，且曰代表 NH4OH / TMAH = 500 / 1。 圖3顯示於本發明清洗溶液採不同NH4OH / TMAH比例所得 電容之崩潰電荷分佈圖，其中A代表NH4OH / TMAH = 100 / 1 ，㊀代表 NH4OH / TMAH = 300 / 1，且曰代表 NH4OH / TMAH = 500/1。 圖4顯示分別以傳統RCA二步驟清洗溶液與二種依據本發 明之單步驟清洗溶液清洗所得電容之電流密度與電場強度 ，其中A為以RCA清洗溶液清洗所得對照组試片，㊀代表 本發明清洗溶液中NH4〇H / TMAH = 100 / 1所得試片，且日代 表本發明清洗溶液中NH4OH / NH4F = 30 / 1所得試片。 圖5顯示分別以傳統RCA二步驟清洗溶液與二種依據本發 明之單步驟清洗溶液清洗所得電容之崩潰電場分佈圖，其 中A為以RCA清洗溶液清洗所得對照組試片，㊀代表本發 明清洗溶液中NH4OH / TMAH = 100 / 1所得試片，且日代表本 發明清洗溶液中NH4OH / NH4F = 30 / 1所得試片。 圖6顯示分別以傳統RCA二步驟清洗溶液與二種依據本發 明之單步驟清洗溶液清洗所得電容之崩潰電荷分佈圖，其 中A為以RCA清洗溶液清洗所得對照組試片，㊀代表本發 明清洗溶液中NH4OH / TMAH = 100 / 1所得試片，且曰代表本 發明清洗溶液中NH4OH / NH4F = 30 / 1所得試片。 . DOC 一 Ί - 本紙張尺度適用中國國家標準（CNS > A4規格（210X 297公釐） ：--------裝--------訂------線 (請先閲讀背面之注意事項再^^本頁) 經濟部中央標準局員工消费合作社印製 A7 B7 五、發明説明（5 ) 發明詳細說明 本發明提供一可於單一步驟完成相當於RCA二步驟清洗 溶液效益之清洗溶液，其可用於清洗矽半導體與二氧化矽 表面。特定言之，本發明提供可清除矽半導體與二氧化矽 表面之如有機物、塵粒與金屬等污染物之清洗溶液，其係 含H202、NH4OH與至少一種選自異於NH4OH之銨鹼與含氟 化合物之成分A。 本發明之清洗溶液係含特定量H202、NH4OH及至少一種 選自異於NHUOH之銨鹼與含氟化-合物之成分A。其中，溶 液中之H2〇2含量為使H2〇2與H20之重量比為1 : 5至1 : 50， 較佳為1 : 10至1 : 30，且更佳為1 : 15至1 : 25 ; NH4OH之 濃度為使NH4OH與H20之重量比為1 : 5至1 : 50，較佳為1 :10至1 : 30，且更佳為1 : 15至1 : 25 ;成分A之用量則 為使其與NHtOH之莫耳數比為1 : 10至1 : 5000，較佳1 : 10 至 1 : 1000，更佳 1 : 50 至 1 : 500，尤指 1 : 100 至 1 : 500 〇 適用於本發明清洗溶液成分A之含氟化合物可為任何可 於水溶液中提供氟離子之鹽類。較佳地，該含氟化合物係 選自由氟化銨與非金屬氟化物所組成之族群。適用於本發 明清洗溶液之銨鹼則可為任何可於水溶液中提供異於NRT 之銨陽離子之鹽類。較佳地，該銨鹼係具如下通式I之氫 氧化録驗· 46260.ECC - 8 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） --：-------装！-------,訂------# (請先閱讀背面之注意事項再本頁) 五、發明説明（6 R]—N一R3 I r2 OH' 經濟部中央標準局員工消費合作社印製 。其:广^與〜係分別為叫⑻ Μ烷基’更佳為甲基，其條件為比夂中至少—者、佳為 本發明清洗溶液可取代RCA二步驟清洗容液， :中、以較短時間完成隐二步驟清洗系統所達之效：步 效清洗砂半導體與二氧化，夕表面切染物，如有機：’ 與金屬等。於-具體實施態樣中，本發明清洗溶液使用於在矽半導體與二氧化矽表令 除哕答^、 囬彤成閘極乳化物前，滑 =寺表面^染物，包括有機物、塵粒與金屬等。本發 明：洗溶液，非但不需使用強酸化學品如HC1或Η伽4等： 且得於單-步驟中以較RCA二步驟清洗系統為短的時間， 芫成有效清洗，故可符合業界簡易、經濟之需求。 圖〗為製備積體電路電容元件之流程圖。先以清洗溶 清洗晶片10，再以濕氧化法（wet 〇xidati〇n)於晶片1〇上方 成氧化層20 ,接著覆上光阻且使用光罩以曝出所欲區域 仔光阻層30，以蝕刻劑移除無光阻覆蓋之氧化層且移除 阻層30。以清洗溶液清洗覆有氧化層2〇之晶片1〇，以乾 化法（dry oxidation)形成閘極氧化層4〇，於晶片1〇上形成 晶矽層5 0且可於此時使用摻雜劑以使複晶矽層5 〇摻雜成 k型式。於複晶碎層50上方鍵上銘層6〇，於銘層6〇上覆 光阻且使用光罩以曝出所欲區域，得光阻層7〇，以蝕刻別 移除無光阻覆蓋之鋁層與複晶矽層且移除任何可能於晶片丨〇背 可 清 液 光 氧 所 上 劑 --r-------择—l· (請先閲讀背面之注意事項再•本頁) 訂 線V. Description of the invention (1 The present invention relates to silicon semiconductors and silicon oxides), the surface of silicon monoxide, method a, tongue, and the present invention provides-cleaning solution for cargo field, more semiconductor and silicon dioxide watch ^ 'Night, stubbornly in one step-complete the crushing process' Silicon surface includes organic matter, cleansing and cleaning work. [Top], metal and other pollutants background in recent years' In the industry, we are committed to the processing technology that is efficient and capable of improving the manufacturing process of the double-knife. In the manufacture of semiconductor components, we can meet the requirements of more round and broken glass wafers. Processing steps. Improvements in the manufacturing process of semiconductor components are directed to this cleaning treatment. It is believed that the wafer surface coating surface can be eliminated or reduced, which can greatly improve the stability and reliability of the components. The cleaning of dyes on the surface of dioxin was researched and published by RCA (American Radio Corporation, Rad10 Corporatlon of) in 1970. The Central Consumer Bureau of the Ministry of Economic Affairs printed a set of extremely effective cleaning system for consumer cooperatives. The system package The second cleaning step includes the mixed solution used in the first cleaning step to remove organic pollutants. The #first cleaning step "the cleaning solution will make the cleaning surface be traced by trace metals such as Fe, Zn and A1 contained in the cleaning solution Contamination of the material, it is necessary to use the second cleaning step of HC1 mixed liquid to remove these metal cold dyes. According to RCA research, the operations that can effectively perform the aforementioned cleaning benefits are: In the first step, the volume ratio is 5: 1: 1 to 7; 2: 1 H20 / 30% HP 2 / 27. /. NH4OH mixed solution, treatment for 10 to 20 minutes; in the second step, a volume ratio of 6: 1: 1 to 8: 2: 1 H20 / 30% H202 / 37% HC1 Mixed paper sizes are applicable to Chinese National Standard (CNS) A4 now (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2) 'Processing for 10 to 20 minutes. That is, the RCA cleaning system must involve the use of strong acid chemicals such as HC1 and requires a two-separation step, with a total processing time of at least 20 minutes. Because the RCA cleaning system must use an acidic cleaning solution containing HC1' Although it can effectively remove desire Heavy metal contaminants on the surface, but will cause particles contained in the acidic cleaning solution to adhere to the wafer surface. In addition, RCA cleaning must take two separate steps, which is relatively inconvenient in operation. Therefore, it is used in the semiconductor component and silicon wafer industries. In the industry, the industry is committed to finding a new formula to replace the RCA cleaning solution to provide a simpler, more effective and economical cleaning system. Most of the known techniques for improving the RCA cleaning system are related to the second cleaning step. Among them, Japanese Patent Laid-Open Publication No. Sho 58_3013 discloses the use of an acidic aqueous solution containing HF, HJO4, and H2O2; Japanese Patent Laid-open No. Heisei 2-100320 discloses the combined use of an aqueous solution containing NH4Oh and H2O2, and Aqueous solution containing HC1 and H2O2; Japanese Patent Laid-open No. 3_273629 discloses the use of an aqueous solution containing HC1 and H2O2; Japanese Patent Laid-open No. 4_234118 discloses the use of a solution of a strong acid with a very small amount of a fluorine-containing compound; " Tryborozist " Book 37, Book 3, pages 218 to 224 (1992) reveals that a solution containing 0 50 / 〇 and 0_1 to 1% H2O2 was collected at room temperature; US Patent No. 5, 56〇, 857 It discloses the use of the pH and the acid solution is 〇2 1 to 5 containing 0.005 to 0.05% HF and 0.3 to 20.0% s. That is, most of the improvements on the RCA cleaning system are aimed at the research and development of alternative solutions for the acid cleaning step in order to obtain results with less particulate pollution. However, as mentioned above, in addition to the disadvantages of particulate contamination, Rca cleaning solution also has problems such as inconvenience in operation (that is, the two separation steps must be taken and takes at least 20 minutes) and the use of strong acid chemicals. The aforementioned improvement techniques cannot avoid these 4 c 2 6 Γι. DOC-5 — This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ---- (Please read the precautions on the back before f Page) Order A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs V. Invention Description (3) Question. Therefore, there is still a need for an effective cleaning system that can simplify the RCA cleaning system and does not require the use of strong acid chemicals to meet the industry's simple, effective and economical needs. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel and high-performance cleaning solution for cleaning silicon semiconductor and silicon dioxide surfaces, which can greatly shorten the cleaning time, simplify the operation process, and avoid the use of strong acid chemicals. In particular, the present invention provides a solution containing NH4OH, H2O2 and at least one component selected from a fluorine-containing compound and an ammonium base component different from NH4OH, which can replace the first and second cleaning solutions of the RCA cleaning system in a single step. The benefits of the second RCA cleaning step are achieved. Another object of the present invention is to provide integrated circuit components with good electrical performance. The breakdown electric field and breakdown charge are better than those obtained by using RCA cleaning solution. Brief Description of the Drawings Figure 1 shows a conventional flow chart for the preparation of integrated circuit capacitor elements, where 10 represents a wafer, 20 represents an oxide layer; 30 represents a photoresist layer; 40 represents a gate oxide layer; 50 represents a polycrystalline silicon layer; 60 represents Inscription layer; 70 represents a photoresist layer; and 80 represents an inscription layer. 46260.DOC # 6 — This paper size is applicable to China National Standard (CNS) A4 (21〇X 297 mm)-; ---------- Γ--1T ------- ^ (Please read the precautions on the back ^ -¾ this page) A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) Figure 2 shows the capacitance obtained from the cleaning solution of the present invention using different NH4OH / TMAH ratios. The breakdown electric field distribution diagram, where Δ represents NH4OH / TMAH = 100/1, ㊀ represents NH4OH / TMAH = 300/1, and NH4OH / TMAH = 500/1. FIG. 3 shows the breakdown charge distribution of the capacitor obtained by using different NH4OH / TMAH ratios in the cleaning solution of the present invention, where A represents NH4OH / TMAH = 100/1, ㊀ represents NH4OH / TMAH = 300/1, and NH4OH / TMAH = 500/1. FIG. 4 shows the current density and electric field strength of a capacitor obtained by cleaning with a conventional RCA two-step cleaning solution and two single-step cleaning solutions according to the present invention, where A is a control sample obtained by cleaning with the RCA cleaning solution, and ㊀ represents the present invention. The test piece obtained with NH4OH / TMAH = 100/1 in the cleaning solution, and Japan represents the test piece obtained with NH4OH / NH4F = 30/1 in the cleaning solution of the present invention. FIG. 5 shows the breakdown electric field distribution of the capacitors obtained by cleaning with a conventional RCA two-step cleaning solution and two single-step cleaning solutions according to the present invention, where A is a control strip obtained by cleaning with the RCA cleaning solution, and ㊀ represents the cleaning of the present invention. The test strip obtained with NH4OH / TMAH = 100/1 in the solution, and Japan represents the test strip obtained with NH4OH / NH4F = 30/1 in the cleaning solution of the present invention. Figure 6 shows the breakdown charge distribution of capacitors obtained by cleaning with a conventional two-step cleaning solution of RCA and two single-step cleaning solutions according to the present invention, where A is a control sample obtained by cleaning with RCA cleaning solution, and ㊀ represents the cleaning of the present invention. The test piece obtained with NH4OH / TMAH = 100/1 in the solution, and said that the test piece obtained with NH4OH / NH4F = 30/1 in the cleaning solution of the present invention. DOC 1Ί-This paper size applies to Chinese national standard (CNS > A4 size (210X 297mm)): -------- install -------- order ------ line (Please read the notes on the back before ^^ this page) A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) Detailed description of the invention The present invention provides a method that can be completed in a single step and equivalent to two steps in RCA Cleaning solution benefit cleaning solution, which can be used to clean the surface of silicon semiconductor and silicon dioxide. In particular, the invention provides a cleaning solution that can remove pollutants such as organics, dust particles and metals on the surface of silicon semiconductors and silicon dioxide. It contains H202, NH4OH and at least one ammonium base different from NH4OH and fluorine-containing compound A. The cleaning solution of the present invention contains a specific amount of H202, NH4OH and at least one ammonium base different from NHUOH and contains Component A of the fluorinated compound. The content of H2O2 in the solution is such that the weight ratio of H2O2 to H20 is 1: 5 to 1:50, preferably 1:10 to 1:30, and more It is preferably 1: 15 to 1: 25; the concentration of NH4OH is such that the weight ratio of NH4OH to H20 is 1: 5 to 1: 50, It is preferably 1:10 to 1:30, and more preferably 1:15 to 1:25; the amount of component A is such that the molar ratio of NHtOH to NHtOH is 1:10 to 1: 5000, preferably 1: 10 to 1: 1000, more preferably 1: 50 to 1: 500, especially 1: 100 to 1: 500. The fluorine-containing compound suitable for the component A of the cleaning solution of the present invention may be any salt capable of providing fluoride ion in an aqueous solution. Preferably, the fluorine-containing compound is selected from the group consisting of ammonium fluoride and non-metal fluorides. The ammonium base suitable for the cleaning solution of the present invention can be any ammonium cation that can provide an aqueous solution different from NRT. The salt is preferably the ammonium hydroxide with the following general formula I: 46260.ECC-8-This paper size is applicable to China National Standard (CNS) A4 (210 × 297 mm)-:- ------ install! -------, order ------ # (Please read the notes on the back before this page) 5. Description of the invention (6 R) —N-R3 I r2 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. It is: ^^ and ~ are respectively called Μ Μalkyl ', which is better to be methyl, provided that it is at least one of 、, which is the cleaning solution of the present invention. It can replace the RCA two-step cleaning solution, which can achieve the effect of the hidden two-step cleaning system in a short time: the step effect cleans the semiconductor and the oxide, and the surface cuts and dyes, such as organic: 'and metal, etc. -In a specific embodiment, the cleaning solution of the present invention is used before the silicon semiconductor and the silicon dioxide watch are removed, and the gate emulsion is slipped. The surface of the temple is dyed, including organic matter, dust particles and metals. Wait. The invention: a washing solution, instead of using a strong acid chemical such as HC1 or Η4, etc .: It can be obtained in a single step in a shorter time than the RCA two-step cleaning system, resulting in effective cleaning, which can meet the simple requirements of the industry. And economic needs. Figure 〖is a flowchart of preparing integrated circuit capacitors. First, the wafer 10 is cleaned with a cleaning solution, and then an oxide layer 20 is formed on the wafer 10 by a wet oxidation method (wet oxidation), and then a photoresist is applied and a photomask is used to expose a desired area of the photoresist layer 30. The photoresist-free oxide layer is removed with an etchant and the resist layer 30 is removed. The wafer 10 covered with the oxide layer 20 is washed with a cleaning solution, and the gate oxide layer 40 is formed by dry oxidation. A crystalline silicon layer 50 is formed on the wafer 10, and doping can be used at this time. Agent to dope the polycrystalline silicon layer 50 into a k-type. Put a photoresist layer 60 on the top of the multi-crystal broken layer 50, cover the photoresist layer 60 and use a photomask to expose the desired area to obtain a photoresist layer 70. Do not remove the photoresist-free cover by etching. Aluminum layer and polycrystalline silicon layer and remove any agents that may be on the back of the substrate. 〇〇 Clear liquid photo-oxygen agent--r ------- select-l · (Please read the precautions on the back before • this Page)
-I I I I- I 本紙張尺度適财關家料（CNS ) A4規格（21GX297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（7 ) 侧形成之氧化物。於晶片10背侧鍍上鋁層80且去除表面光 阻層70，將晶片10置於退火爐退火，得所欲積體電路元件 〇 以下實例係用以例示說明本發明，應明瞭者，於不偏離 本發明概念與精神下、舉凡熟悉此項技藝之人士得經由本 發明說明書内容推得之態樣，均在本發明合理保護範圍 内。 實例1 依據圖1所示流程，令晶片先經傳統RCA清洗，然後送入 高溫爐内而於1050°C以濕氧化法歷時1小時以於晶片上形成 厚約5500A之二氧化矽氧化層。於氧化層上方覆上光阻且使 用光罩而曝出所欲區域，以可購自中華民國台灣伊默克化 學科技股份有限公司之B.O.E.蝕刻劑（NH4F與HF以6 : 1混 合而得之缓衝氧化物蚀刻劑混合溶液）蝕刻移除無光阻覆 蓋之氧化層之後，使用98重量％H2S02 : 31重量％H202之體積比為 3 : 1之混合液於120°C煮10分鐘而去除剩餘光阻。使用依據本 發明之含NH4OH、TMAH與H2〇2清洗溶液約1加侖、於75t 清洗晶片歷10分鐘。其中，該混合清洗溶液係以31重量。/〇 H202水溶液、29重量％ NH4OH水溶液、25重量％ TMAH水溶 液與去離子水混合而得（29% NH4OH + 25°/。TMAH ) : 31% H202 :H20體積比為1 : 1 : 5且NH4OH與TMAH莫耳數比為100 : 1。將經清洗之晶片送入高溫爐管，於900°C以乾氧化法歷 時10分鐘而形成厚約7〇A之二氧化矽閘極氧化層，接著將晶 片送入620°C之低壓化學氣相沈積系統以形成厚約3000A之複 46260.DOC — 10 - 本紙張尺度適用中國國家標準（CNS〉Α4規格（210Χ297公釐） — - I n n n ϋ I n Ί· —J ϋ ϋ ^ ϋ n n ϋ n ^ (請先閲讀背面之注意事項再本頁) Α7 Β7 經濟部中央梂準局員工消费合作社印製 五、發明説明（8 晶矽層。使用POCI3於950。(：摻雜複晶矽層歷25分鐘，將 複晶矽層摻雜成η型。以ΒΌ.Ε·蝕刻劑去除晶片表面殘餘之 氧化層，接著於低壓儀器中，以習知方法將鋁經電阻絲加 熱蒸發以於複晶碎上方鍍上厚約500〇Α之鋁層。於銘層上方 覆上光阻且使用光罩而曝出所欲區域，於、以 CH3COOH : ηνο3 : Η3Ρ〇4 : η2〇 = 5 : 5 : 85 : 5之混合溶液 蝕刻鋁層與複晶矽層，且以ΒΌ·Ε·蝕刻劑去除晶片背側可 月匕存在之氧化物，另於晶片背側鑛上厚約5〇〇〇入之紹層作為 量測背面接.觸，之後去除表面殘Γ餘光阻。最後將晶片送入 400 C退火爐歷30分知以使銘與$夕有較好接觸，得電容試片 组I。 實例2 重後《例1步驟’但清洗溶液中之ΝΗ4〇η與ΤΜΑΗ之莫耳 比調整為300 : 1與5〇〇 : i，分別得電容試片組π與m。 實例3 重覆《例1步驟，但清洗溶液中之以取代且 ΝΗβΗ與Nl·^之莫耳比調整為30 : i，得電容試片組w。 比較實例 重覆實例1步驟，但於閘極氧化物形成前，採用傳統RCA 清洗溶液進行清洗。其中，第一清洗步驟與第二清洗步驟 均勺别使用總量為約1加侖之清洗溶液、於75。匸進行且分 別歷時10分鐘，且於第一步驟清洗溶液中之29% NH4〇H : 31% H2〇2 : H20(體積比）=丨：丨：5，第二步驟清洗溶液中 之37%HC1 : 31%咏〇2 : 體積比）=1 : 1 : 6，得對照電 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公羞） (請先閲讀背面之注意事項再本頁) *·*β Γ 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（9 ) 容試片組V。 清洗效益分析 分別量測試片組I - V之電性，所採試片之面積為1.86 X 10"4平方公分，結果分別示於圖2至圖6。圖2與圖3顯示試 片组I - III之崩潰電場與崩潰電荷統計分佈圖；圖4至圖6則 比較試片組I、IV與V之電流密度對電場分佈圖、崩潰電場 統計分佈圖、及崩潰電荷統計分佈圖。其中，崩潰電場與 崩潰電荷係於50毫安培/平方公分之電流密度下量測"由 圖4與圖2及圖3結果可知，當異於NH4OH之銨鹼及/或含 氟化合物之莫耳數含量為NH4OH莫耳數之4或更低時，本 發明清洗溶液可提供較RCA清洗溶液為佳電性表現之試片 ，即，可提供較佳清洗效益。即使於銨鹼及/或含氟化合 物之莫耳數含量達NH4OH莫耳數之^，經本發明清洗溶液 清洗所得試片雖會於較小電場有較大漏電流，仍可提供較 由RCA清洗溶液所得試片為佳之電性表現。換言之，本發 明清洗溶液無RCA清洗溶液使用強酸化學品之缺點，且可 以較少清洗液、於較短時間達與RCA清洗溶液相當或較之 為佳之清佳效益，確可滿足業界之簡易、經濟要求。 46260.DOC ~ 12 — 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐） --Γ-------裝-----：--^--訂------線 (請先閱讀背面之注意事項再本頁)-I I I I- I This paper size is suitable for financial and household materials (CNS) A4 (21GX297 mm) Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Oxide formed on the side of the invention description (7). An aluminum layer 80 is plated on the back side of the wafer 10 and the surface photoresist layer 70 is removed. The wafer 10 is annealed in an annealing furnace to obtain the desired integrated circuit components. The following examples are used to illustrate the present invention. Anyone who deviates from the concept and spirit of the present invention and who is familiar with this technology can derive from the content of the description of the present invention is within the reasonable protection scope of the present invention. Example 1 According to the process shown in FIG. 1, a wafer was first cleaned by a conventional RCA, and then sent to a high-temperature furnace to wet-oxidize at 1050 ° C for 1 hour to form a silicon dioxide oxide layer having a thickness of about 5500A on the wafer. Cover the photoresist layer over the oxide layer and use a photomask to expose the desired area. The BOE etchant (NH4F and HF mixed with 6: 1 can be purchased from Taiwan's Taiwan Immerk Chemical Technology Co., Ltd. Red oxide etchant mixed solution) after etching to remove the oxide layer without photoresist, use 98% by weight H2S02: 31% by weight H202 with a volume ratio of 3: 1 to cook at 120 ° C for 10 minutes to remove the remaining Photoresist. Using a cleaning solution containing NH4OH, TMAH, and H2O2 according to the present invention at about 1 gallon, the wafer was cleaned at 75t for 10 minutes. Wherein, the mixed cleaning solution is 31 weight. / 〇H202 aqueous solution, 29% by weight NH4OH aqueous solution, 25% by weight TMAH aqueous solution mixed with deionized water (29% NH4OH + 25 ° / .TMAH): 31% H202: H20 volume ratio is 1: 1: 5 and NH4OH The molar ratio with TMAH is 100: 1. The cleaned wafer was sent to a high-temperature furnace tube, and a dry oxidation method was used at 900 ° C for 10 minutes to form a silicon oxide gate oxide layer having a thickness of about 70A. Then, the wafer was sent to a low-pressure chemical gas at 620 ° C. Phase deposition system to form a compound with a thickness of about 3000A 46260.DOC — 10-This paper size applies to Chinese national standards (CNS> A4 specification (210 × 297 mm) —-I nnn ϋ I n Ί · — J ϋ ^ ϋ nn nn ϋ ϋ n ^ (Please read the notes on the back before this page) Α7 Β7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (8 crystalline silicon layer. Use POCI3 at 950. (: doped polycrystalline silicon layer) After 25 minutes, the polycrystalline silicon layer was doped into an η-type. The residual oxide layer on the wafer surface was removed with a BΌ.E · etchant, and then the aluminum was heated and evaporated by a resistance wire in a conventional method in a low-voltage instrument to recover the complex. An aluminum layer with a thickness of about 500 Å is plated on the top of the crystal chip. A photoresist is coated on the top layer and a desired area is exposed by using a photomask. CH3COOH: ηνο3: Η3Ρ〇4: η2〇 = 5: 5: 85: 5 mixed solution etched the aluminum layer and the polycrystalline silicon layer, and removed the crystal with BΌ · Ε · etchant The oxide on the back side of the wafer can be present, and a layer of about 5,000 mm thick on the back side of the wafer is used to measure the back contact. After that, the residual photoresist on the surface is removed. Finally, the wafer is fed into The 400 C annealing furnace lasted for 30 minutes so that Ming had better contact with Xixi to obtain the capacitor test piece group I. Example 2 After the "Example 1 step", the molar ratio of ΝΗ4η and TIMA in the cleaning solution was adjusted. It is 300: 1 and 500: i, respectively, to obtain the capacitor test piece groups π and m. Example 3 Repeat the procedure of Example 1, but replace it in the cleaning solution and adjust the molar ratio of NΗβΗ and Nl · ^ to 30. : i, get the capacitor test piece group w. Comparative example Repeats the procedure of example 1, but before the gate oxide is formed, it is cleaned by the traditional RCA cleaning solution. Among them, the first cleaning step and the second cleaning step are used separately. The total amount of the cleaning solution was about 1 gallon at 75 ° C. and each lasted for 10 minutes, and in the first step of the cleaning solution, 29% NH4OH: 31% H2O2: H20 (volume ratio) = 丨:丨: 5, 37% HC1 in the cleaning solution in the second step: 31% yong2 (volume ratio) = 1: 1: 6 to obtain the control paper Applicable to China National Standard (CNS) A4 specification (210X297). (Please read the precautions on the back before this page) * · * β Γ Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (9 ) Test piece group V. Washing benefit analysis The electrical properties of test piece groups I-V were measured separately. The area of the test piece taken was 1.86 X 10 " 4 cm2, and the results are shown in Figures 2 to 6 respectively. Figures 2 and 3 show the statistical distribution diagrams of the breakdown electric field and the breakdown charge of the test strip groups I-III; Figures 4 to 6 compare the current density versus electric field distribution maps of the test strip groups I, IV, and V, and the statistical distribution diagrams of the breakdown electric field , And crash charge statistical distribution chart. Among them, the breakdown electric field and the breakdown charge are measured at a current density of 50 milliamperes per square centimeter. From the results shown in Figures 4 and 2 and 3, it can be seen that when the ammonium base and / or the fluorine compound are different from NH4OH When the ear number content is 4 or less than the NH4OH mole number, the cleaning solution of the present invention can provide a test piece with better electrical performance than the RCA cleaning solution, that is, it can provide better cleaning efficiency. Even if the molar number of the ammonium base and / or fluorine-containing compound reaches NH4OH molar number ^, although the test piece obtained by cleaning with the cleaning solution of the present invention will have a large leakage current in a small electric field, it can still provide more cleaning than RCA cleaning. The test piece obtained from the solution showed good electrical performance. In other words, the cleaning solution of the present invention does not have the disadvantages of using strong acid chemicals in the RCA cleaning solution, and can use less cleaning liquid and achieve a good benefit equivalent to or better than the RCA cleaning solution in a short time, which can indeed satisfy the industry ’s simplicity, Economic requirements. 46260.DOC ~ 12 — This paper size applies to Chinese National Standards (CNS > A4 size (210X297 mm) --Γ ------- Packing -----:-^-Order --- --- Line (Please read the precautions on the back before this page)