1263329 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於 SIMOX ( Sepai. atio n by Implanted Oxygen )晶圓之製造方法，對矽晶圓內部注入氧離子後， 利用熱處理在距離晶圓表面之特定深度之區域形成塡埋氧 ‘化膜，其後，在該晶圓表面形成 SOI ( Silicon on Insulator )層。 【先前技術】 傳統之 SIMOX晶圓之製造處理時，氧離子注入時附 著之粒子在其後之退火處理會成爲缺陷之形成核種係大家 所熟知之事實’故必須在退火處理前除去上述粒子。除去 • 該粒子之方法包括一般之利用氨水及過氧化氫及純水之混 合液（以下稱爲SC-1洗淨液）之洗淨方法、利用硫酸及 過氧化氫及純水之混合液之洗淨方法、利用臭氧水及濃度 φ 0.2〜2重量％之氟酸水溶液之洗淨方法、以及組合上述洗 淨方法之洗淨方法等。然而，即使以上述洗淨方法進行晶 圓之洗淨，晶圓表面之粒子除去率最大爲80%程度，若在 殘留粒子之情形下進入晶圓之退火步驟，則減少晶圓之缺 陷有其限界。此外，上述粒子除去率要求以SurfScan642 0 (美國KLA-Tencor公司製之表面檢查裝置）分別計測洗 淨前後之粒徑〇 . 2 0 // m以上之粒子數。 另一方面，亦有在對矽晶圓注入氧離子之步驟之途中 ，實施噴射施加超音波之水流之噴射洗淨、利用SC_1洗 -4- (2) 1263329 合液之洗 。該半導 在矽晶圓 含有利用 之注入步 氧離子注 ，而可降 晶圓形成 圓之氧離 氧化膜， 同時被除 之製造方 之蝕刻率 注入時， 粒子，即 。在該狀 圓之電性 i 度 2 3 °C 後所觀察 淨液之洗淨、或利用鹽酸及過氧化氫及純水之混 淨之半導體製造方法（例如，參照專利文獻1 ) 體之製造方法之構成上，係在注入氧離子前預先 形成表面氧化膜，並在氧離子之注入步驟之途中 稀氟酸水溶液來除去表面氧化膜之步驟。 此種構成之半導體製造方法時，係在氧離子 驟之途中進行晶圓洗淨來除去粒子，故在其後之 • 入時可減少因爲晶圓因爲粒子所造成之遮蔽面積 低塡埋氧化膜之電流路徑缺陷。此外，在預先在 表面氧化膜之狀態下對晶圓注入氧離子，而在晶 子之注入步驟途中，利用稀氟酸水溶液除去表面 ' 故附著於表面氧化膜之表面之粒子與表面氧化膜 ' 去，而有效減少晶圓表面之粒子。 然而，上述傳統之專利文獻1所示之半導體 法時’稀氟酸水溶液之濃度較低，且表面氧化膜 # 較低。因此，雖然可除去表面氧化膜，在氧離子 難以除去全部經由矽及氧而獲得強固化學結合之 使利用該方法，仍然有最多除去 8 0 %程度之問題 態下製造SIMOX晶圓的話，有存在眾多對該晶 特性會產生不良影響之貫穿SOI層之深缺陷（雄 下，浸漬於濃度5 0重量％之氟酸水溶液3 0分鐘 之缺陷）之問題。 〔專利文獻1〕 日本特開平8 -7 8 64 7號公報（申請 專利範圍第1〜5、段落（0019)、段落（0024)、第5圖 (3) 1263329 【發明內容】 本發明之目的在提供一種SIMOX晶圓之製造方法及 利用該方法製造之S I Μ Ο X晶圓，可有效除去氧離子注入 時所附著之粒子，且可減少貫穿SIMOX構造之上述SOI 層之深缺陷。 φ 本發明之SIMOX晶圓之製造方法之一實施形態，係 含有對矽晶圓注入氧離子之步驟、對已注入氧離子之矽晶 圓進行洗淨之步驟、以及對該已洗淨之矽晶圓進行熱處理 而在矽晶圓之內部形成塡埋氧化膜之步驟之SIMOX晶圓 ' 之製造方法之改良。 ' 具有上述特徵之構成，在對矽晶圓注入氧離子後且對 矽晶圓進行洗淨前，尙含有將矽晶圓浸漬於氟酸水溶液而 對形成矽晶圓表面之 Si 02膜進行鈾刻處理之步驟，該蝕 φ 刻處理時，氟酸水溶液對Si〇2膜之蝕刻率爲150〜3 000A/ 分。 依據本發明之SIMOX晶圓之製造方法之一實施形態 ，因爲將矽晶圓浸漬於對晶圓表面之Si02膜之鈾刻率爲 ' 150〜3 0 00A/分之氟酸水溶液，故可對矽晶圓之表面進行 高速蝕刻。此時，因爲對二氧化矽之蝕刻率較高，故可切 斷大量含有砂及氧之結合之粒子之強固結合。結果，幾乎 可以將矽晶圓表面之粒子完全除去。 本發明之SIMOX晶圓製造方法之一實施形態亦可爲 (4) 1263329 如下所示’亦即，將對矽晶圓之氧離子注入分成複數次， 在該氧離子注入步驟之其中任一次之注入步驟後或2次以 上之各注入步驟後，立即將矽晶圓浸漬於氟酸水溶液。 此時，在氧離子注入步驟之其中任一次之注入步驟後 ’例如’在最初之氧離子注入後，將晶圓浸漬於氟酸水溶 液來進行表面處理，下一次氧離子注入前，可減少殘留於 晶圓表面之粒子。結果，因爲可減少粒子所導致之氧離子 Φ 注入之遮蔽效果，故可減少經過S IΜ Ο X熱處理步驟之晶 圓表面之貫穿S ΟI層之深缺陷（溫度2 3 °C下，浸漬於濃 度50重量％之氟酸水溶液30分鐘後所觀察之缺陷）之數 〇 此外，本發明之S IΜ Ο X晶圓製造方法之一實施形態 、 ，係氟酸水溶液之溫度爲超過該氟酸水溶液1 2之凝固點 且爲4 0 °C以下，且矽晶圓浸漬於氟酸水溶液之時間爲1 〇 〜6 0 0秒。 # 此外，本發明之SIMOX晶圓製造方法之一實施形態 ，係氟酸水溶液12對Si02膜之蝕刻率爲R ( A/分）、矽 晶圓1 1浸潰於氟酸水溶液12時間爲Η (秒），以Η-( 1 5 00/R)(秒）之方式設定上述浸漬時間。 本發明之SIMOX晶圓製造方法之一實施形態，係氟 酸水溶液添加著界面活性劑。 此時，將矽晶圓從添加著界面活性劑之氟酸水溶液撈 起時，界面活性劑可產生晶圓表面保護膜之作用，可防止 粒子再附著於晶圓表面。此外，利用純水清洗晶圓時，亦 (5) 1263329 可獲得良好脫水。 本發明之SIMOX晶圓之一實施形態，係利用本發明 之SIMOX晶圓製造方法進行製造，且貫穿SOI層之深缺 陷（溫度2 3 °C下，浸漬於濃度5 0重量％之氟酸水溶液3 0 分鐘後所觀察之缺陷）之數爲〇.〇5個/cm2以下。 依據該本發明之SIMOX晶圓之一實施形態，因爲利 用本發明之SIMOX晶圓製造方法進行製造，故氧離子注 入前，可減少殘留於晶圓表面之粒子。因此，可減少粒子 所導致之氧離子注入之遮蔽效果，故可極度減少貫穿SOI 層之深缺陷（溫度23t下，浸漬於濃度50重量％之氟酸 水溶液3 0分鐘後所觀察之缺陷）之數。 依據本發明，在對矽晶圓注入氧離子後且對矽晶圓進 行洗淨前，將矽晶圓浸漬於氟酸水溶液對形成於矽晶圓表 面之Si02膜進行蝕刻處理，該蝕刻處理時，因爲氟酸水 溶液對Si02膜之蝕刻率爲150〜3 000A/分，故可對矽晶圓 表面實施高速蝕刻。此時，因爲對二氧化矽之蝕刻率較高 ’故可切斷大量含有矽及氧之結合之粒子之強固結合。結 果，幾乎可以將矽晶圓表面之粒子完全除去。 此外，將對矽晶圓之氧注入分成複數次，在該氧離子 注入步驟之其中任一次之注入步驟後或2次以上之各注入 步驟後，立即將矽晶圓浸漬於氟酸水溶液，則在下一次氧 離子注入前，可減少殘留於晶圓表面之粒子。因此，可降 低粒子所導致之氧離子注入之遮蔽效果。結果，可減少經 過SIMOX處理步驟之晶圓之貫穿SOI層之深缺陷（溫度 (6) 1263329 2 3 °C下，浸漬於濃度5 0重量。/。之氟酸水溶液3 0分鐘後所 觀察之缺陷）之數。 此外，對氟酸水溶液添加界面活性劑，將矽晶圓從添 加著界面活性劑之氟酸水溶液撈起時，界面活性劑可產生 晶圓表面保護膜之作用。結果，可防止粒子再附著於晶圓 表面，此外，利用純水清洗晶圓時，亦可獲得良好脫水。 此外，利用上述方法製造之 SIMOX晶圓，貫穿 SOI 層之深缺陷（溫度23 t下，浸漬於濃度50重量％之氟酸 水溶液30分鐘後所觀察之缺陷）之數爲極少之0.05個 /cm2以下。 【實施方式】 其次，參照圖面，針對以實施本發明爲目的之最佳實 施形態進行說明。 如第1圖及第2圖所示，SIMOX晶圓製造方法包含對 矽晶圓1 1注入氧離子之步驟、對已注入氧離子之晶圓1 1 進行洗淨之步驟、以及對該已洗淨之晶圓1 1進行熱處理 而在晶圓1 1之內部形成塡埋氧化膜之步驟。 此實施形態係分成3階段實施氧離子之注入。 此外，晶圓1 1之洗淨方法可以爲利用S C-1洗淨液之 洗淨方法、利用硫酸及過氧化氫及純水之混合液之洗淨方 法、利用鹽酸及過氧化氫及純水之混合液之洗淨方法、利 用臭氧水及濃度〇 . 2〜2重量％之氟酸水溶液之洗淨方法、 組合著前述洗淨方法之洗淨方法、或組合著前述洗淨方法 -9- (7) 1263329 及m e g a s ο n i c洗淨之洗淨方法等。此處，m e g a s ο n i c洗淨 係在液中對被洗淨物照射0.8〜10MHz之極超音波之洗淨 〇 將利用丘克拉斯基法撈起之矽晶錠進行切片並實施表 面硏磨後，進行第1洗淨步驟之洗淨（第2圖）。對該已 經過洗淨之晶圓1 1進行第1次之氧離子注入（第1氧離 子注入步驟）。該氧離子之注入係在將晶圓1 1加熱至3 0 0 〜500 °C、氧離子之劑量爲5xl0]6〜2xl017atoms/cm2之狀 態下進行。 其次，對晶圓1 1進行洗淨前，將晶圓1 1浸漬於氟酸 水溶液1 2對形成於晶圓1 1表面之S i 02膜進行蝕刻處理 (第1圖及第2圖）。 該蝕刻處理時，氟酸水溶液12對Si 02膜之蝕刻率爲 150〜3 000A/分，5 00〜1 000A/分更佳，5 00〜600A/分最好 。此外，以達成1 50〜3 000A/分之蝕刻率爲目的之氟酸水 溶液之濃度在 23 °C時爲 2.5〜50重量％，以達成 500〜 1 00 0 A/分之蝕刻率爲目的之氟酸水溶液之濃度在23 °C時爲 10〜20重量％，以達成500〜600 A/分之蝕刻率爲目的之氟 酸水溶液之濃度在2 3 °C時爲1 〇〜1 2重量％。 利用上述蝕刻處理可對晶圓Π表面進行高速蝕刻， 除了晶圓1 1表面之自然氧化膜以外，含有大量矽及氧之 結合之粒子之強固結合亦會被切斷，亦即，氧離子注入時 ，利用矽及氧強固結合之粒子之化學結合亦會被切斷。 具體而言，氧及粒子之化學結合，對於1個粒子並非 -10- 12633291263329 (1) IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to a method for fabricating a SIMOX (Spiai atio n by Implanted Oxygen) wafer by injecting oxygen ions into the interior of the germanium wafer and using heat treatment in the distance crystal A region of a certain depth of the circular surface forms a buried oxide film, and thereafter, an SOI (Silicon on Insulator) layer is formed on the surface of the wafer. [Prior Art] In the conventional SIMOX wafer manufacturing process, the subsequent annealing of the particles attached by oxygen ion implantation becomes a well-known fact that the formation of defects is a nuclear species. Therefore, it is necessary to remove the particles before the annealing treatment. The method of removing the particles includes a general method of washing a mixture of ammonia water and hydrogen peroxide and pure water (hereinafter referred to as SC-1 washing liquid), and a mixture of sulfuric acid and hydrogen peroxide and pure water. A washing method, a washing method using ozone water and a hydrofluoric acid aqueous solution having a concentration of 0.2 to 2% by weight, and a washing method in combination with the above washing method. However, even if the wafer is cleaned by the above-described cleaning method, the particle removal rate on the wafer surface is at most 80%. If the wafer is subjected to the annealing step in the case of residual particles, the defects of the wafer are reduced. Limit. Further, the particle removal rate is required to be measured by SurfScan642 0 (surface inspection apparatus manufactured by KLA-Tencor Co., Ltd.) for particle diameters before and after washing, respectively. On the other hand, in the process of injecting oxygen ions into the wafer, the jetting of the jet of ultrasonic waves is performed, and the washing with SC_1 washing -4-(2) 1263329 is performed. The semiconductor is contained in the germanium wafer using an implanted oxygen ion implant, which reduces the wafer to form a circular oxygen oxide film, while being removed by the manufacturer's etch rate, the particles, ie, . In the case of the semiconductor manufacturing method in which the cleaning of the liquid is observed at a temperature of 2 ° C, or the use of a mixture of hydrochloric acid and hydrogen peroxide and pure water (for example, refer to Patent Document 1) In the constitution of the method, a surface oxide film is formed in advance before the oxygen ions are implanted, and a step of removing the surface oxide film by diluting the aqueous solution of the hydrofluoric acid in the middle of the oxygen ion implantation step. In the semiconductor manufacturing method of such a configuration, the wafer is washed in the middle of the oxygen ion to remove the particles, so that the wafer can be reduced due to the low shielding area of the wafer due to the particles. Current path defect. Further, oxygen ions are implanted into the wafer in a state in which the surface oxide film is previously formed, and in the middle of the implantation step of the crystal, the surface of the surface oxide film is removed by a dilute aqueous solution of the hydrofluoric acid, so that the surface is bonded to the surface oxide film. , effectively reducing the particles on the surface of the wafer. However, in the semiconductor method shown in the above-mentioned conventional Patent Document 1, the concentration of the aqueous solution of the dilute hydrofluoric acid is low, and the surface oxide film # is low. Therefore, although the surface oxide film can be removed, it is difficult to remove the entire strong oxygen-cure bond by the oxygen ion, and there is still a case where the SIMOX wafer is manufactured under the problem of removing the most 80%. There are a number of problems in the deep defects of the SOI layer which are adversely affected by the crystal characteristics (male, immersed in a 50% by weight aqueous solution of hydrofluoric acid for 30 minutes). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 8-7-8 64 No. 7 (Patent Application Nos. 1 to 5, Paragraph (0019), Paragraph (0024), and 5 (3) 1263329 [Description of the Invention] Providing a method for manufacturing a SIMOX wafer and a SI Μ 晶圆 X wafer manufactured by the method can effectively remove particles adhered during oxygen ion implantation, and can reduce deep defects of the SOI layer penetrating through the SIMOX structure. An embodiment of the method for fabricating a SIMOX wafer of the invention includes the steps of: implanting oxygen ions into the germanium wafer, washing the germanium wafer into which the oxygen ions have been implanted, and cleaning the wafer Improvement of the manufacturing method of the SIMOX wafer' in which the heat treatment is performed to form the buried oxide film inside the germanium wafer. ' With the above characteristics, after the oxygen ions are implanted into the germanium wafer and the germanium wafer is washed Before the net, the crucible contains a step of immersing the germanium wafer in a hydrofluoric acid aqueous solution to perform uranium engraving on the Si 02 film forming the surface of the crucible wafer, and the etching rate of the hydrofluoric acid aqueous solution to the Si〇2 film during the etching treatment For 150~3 000A/min According to an embodiment of the method for fabricating a SIMOX wafer of the present invention, since the ruthenium wafer is immersed in an aqueous solution of fluoric acid having a uranium engraving rate of 150 to 300 Å/min on the SiO 2 film on the surface of the wafer, The surface of the germanium wafer is subjected to high-speed etching. At this time, since the etching rate of the germanium dioxide is high, a strong bond of a large amount of particles containing a combination of sand and oxygen can be cut off. As a result, the surface of the germanium wafer can be almost The particle is completely removed. One embodiment of the SIMOX wafer manufacturing method of the present invention may also be (4) 1263329 as shown below. That is, the oxygen ion implantation of the germanium wafer is divided into a plurality of times, in the oxygen ion implantation step. Immediately after each of the implantation steps or after each injection step of 2 or more, the germanium wafer is immersed in the aqueous solution of hydrofluoric acid. At this time, after any one of the oxygen ion implantation steps, 'for example, 'in the first place After the oxygen ion implantation, the wafer is immersed in a hydrofluoric acid aqueous solution for surface treatment, and the particles remaining on the surface of the wafer can be reduced before the next oxygen ion implantation. As a result, the particles can be reduced. The shielding effect of the ion Φ implantation can reduce the deep defects of the S ΟI layer on the surface of the wafer subjected to the heat treatment step of S I Μ Ο X (after immersion in a 50% by weight aqueous solution of hydrofluoric acid for 30 minutes at a temperature of 2 3 ° C The number of defects observed 〇 In addition, in one embodiment of the method for producing a wafer of the present invention, the temperature of the aqueous solution of hydrofluoric acid is higher than the freezing point of the aqueous solution of the hydrofluoric acid 12 and is 40 ° C or less. And the time during which the germanium wafer is immersed in the aqueous solution of the hydrofluoric acid is 1 〇 to 600 sec. # Furthermore, one embodiment of the SIMOX wafer manufacturing method of the present invention is an etching rate of the fluorinated acid aqueous solution 12 to the SiO 2 film. (A/min), the crucible wafer 1 was immersed in the aqueous solution of hydrofluoric acid for 12 hours (seconds), and the immersion time was set in the manner of Η-(1 5 00/R) (sec). In one embodiment of the SIMOX wafer manufacturing method of the present invention, a surfactant is added to the aqueous fluoric acid solution. At this time, when the germanium wafer is picked up from the aqueous solution of the hydrofluoric acid to which the surfactant is added, the surfactant can act as a protective film on the surface of the wafer to prevent the particles from adhering to the surface of the wafer. In addition, when the wafer is cleaned with pure water, good dehydration is also obtained (5) 1263329. One embodiment of the SIMOX wafer of the present invention is manufactured by the SIMOX wafer manufacturing method of the present invention and penetrates deep defects of the SOI layer (immersion in a concentration of 50% by weight of a hydrofluoric acid solution at a temperature of 2 3 ° C) The number of defects observed after 30 minutes is 〇.〇5/cm2 or less. According to one embodiment of the SIMOX wafer of the present invention, since the SIMOX wafer manufacturing method of the present invention is used for fabrication, particles remaining on the surface of the wafer can be reduced before oxygen ion implantation. Therefore, the shielding effect of the oxygen ion implantation caused by the particles can be reduced, so that the deep defects penetrating through the SOI layer (the defects observed after immersing in a 50% by weight aqueous solution of hydrofluoric acid for 30 minutes at a temperature of 23 t) can be extremely reduced. number. According to the present invention, after the oxygen ions are implanted into the germanium wafer and the germanium wafer is cleaned, the germanium wafer is immersed in a hydrofluoric acid aqueous solution to etch the SiO 2 film formed on the surface of the germanium wafer, and the etching process is performed. Since the etching rate of the aqueous solution of fluoric acid to the SiO 2 film is 150 to 3 000 A/min, high-speed etching can be performed on the surface of the ruthenium wafer. At this time, since the etching rate of cerium oxide is high, a strong bond of a large amount of particles containing a combination of cerium and oxygen can be cut. As a result, particles on the surface of the crucible wafer can be completely removed. In addition, the oxygen implantation of the germanium wafer is divided into a plurality of times, and after the implantation step of the oxygen ion implantation step or after each of the injection steps of 2 or more, the germanium wafer is immediately immersed in the aqueous solution of the hydrofluoric acid. The particles remaining on the surface of the wafer can be reduced before the next oxygen ion implantation. Therefore, the shielding effect of the oxygen ion implantation caused by the particles can be reduced. As a result, it is possible to reduce the deep defects of the through-SOI layer of the wafer subjected to the SIMOX processing step (temperature (6) 1263329 2 3 ° C, immersed in a concentration of 50% by weight of the aqueous solution of hydrofluoric acid for 30 minutes. The number of defects). Further, when a surfactant is added to the aqueous solution of the hydrofluoric acid to remove the ruthenium wafer from the aqueous solution of the hydrofluoric acid to which the surfactant is added, the surfactant can function as a protective film on the surface of the wafer. As a result, the particles can be prevented from reattaching to the surface of the wafer, and when the wafer is cleaned with pure water, good dehydration can be obtained. Further, the SIMOX wafer manufactured by the above method has a deep defect (the defect observed after immersing in a 50% by weight aqueous solution of hydrofluoric acid for 30 minutes at a temperature of 23 t at a temperature of 23 t) is extremely small at 0.05/cm 2 . the following. [Embodiment] Next, a best mode for carrying out the invention will be described with reference to the drawings. As shown in FIGS. 1 and 2, the SIMOX wafer manufacturing method includes a step of implanting oxygen ions into the wafer 1 1 , a step of cleaning the wafer 1 1 into which oxygen ions have been implanted, and a step of washing the wafer. The cleaned wafer 1 1 is subjected to a heat treatment to form a buried oxide film inside the wafer 11. This embodiment is divided into three stages of performing oxygen ion implantation. In addition, the cleaning method of the wafer 1 1 may be a washing method using the S C-1 washing liquid, a washing method using a mixed solution of sulfuric acid and hydrogen peroxide and pure water, using hydrochloric acid, hydrogen peroxide, and pure A method for washing a mixed liquid of water, a method for washing a hydrofluoric acid aqueous solution using ozone water and a concentration of 2 to 2% by weight, a washing method in combination with the above washing method, or a combination of the above washing methods-9 - (7) 1263329 and megas ο nic cleaning method, etc. Here, the megas ο nic washing system is used to wash the washed object with a super-sonic wave of 0.8 to 10 MHz in the liquid, and the sliced ingot is picked up by the Czochralski method and subjected to surface honing. Washing in the first washing step (Fig. 2). The first oxygen ion implantation (first oxygen ion implantation step) is performed on the cleaned wafer 1 1 . The injection of oxygen ions is carried out by heating the wafer 11 to 300 to 500 ° C and the dose of oxygen ions to 5 x 10] 6 to 2 x 1017 atoms/cm 2 . Next, before the wafer 11 is cleaned, the wafer 11 is immersed in a hydrofluoric acid aqueous solution 12 to etch the Si02 film formed on the surface of the wafer 1 (Fig. 1 and Fig. 2). In the etching treatment, the etching rate of the aqueous solution of the hydrofluoric acid 12 to the Si 02 film is 150 to 3 000 A/min, more preferably 500 to 1,000 A/min, and most preferably 500 to 600 A/min. Further, the concentration of the aqueous solution of the hydrofluoric acid for the purpose of achieving an etching rate of 1 50 to 3 000 A/min is 2.5 to 50% by weight at 23 ° C to achieve an etching rate of 500 to 100 A/min. The concentration of the aqueous solution of the hydrofluoric acid is 10 to 20% by weight at 23 ° C, and the concentration of the aqueous solution of the hydrofluoric acid for the purpose of achieving an etching rate of 500 to 600 A/min is 1 〇 to 12% by weight at 23 ° C. . The surface of the wafer crucible can be etched at a high speed by the above etching treatment. In addition to the natural oxide film on the surface of the wafer 11, the strong bonding of particles containing a large amount of cerium and oxygen is also cut off, that is, oxygen ion implantation. At the same time, the chemical combination of particles that are strongly bound by hydrazine and oxygen will also be cut off. Specifically, the chemical combination of oxygen and particles is not for one particle -10- 1263329
只有1個結合，而係存在著多數之結合。爲了切斷該結合 ，必須使H F或H F 2 _遇到S i - 0，且其相遇之機率應爲限速 〇 爲了切斷存在於狹窄物理間隙之多數結合，對Si 02 膜之蝕刻率爲150A/分以下之氟酸水溶液，在HF或HF；r 到達深處部份之前，即會與Si-Ο相遇而被消耗，故難以 間隙之深處。 然而，若爲對Si02膜之蝕刻率爲150〜3 000A/分之氟 酸水溶液時，則HF或HF2_到達間隙之深處時仍殘存著HF 或HF2_，故應可完全切斷存在於狹窄間隙之多數結合。結 果，大致可將晶圓1 1表面之粒子完全除去。 不採用對旋轉之晶圓表面噴射氟酸水溶液之方法，而 限定採用將晶圓浸漬於氟酸水溶液之方法，其理由如下所 示。對旋轉之晶圓表面噴射氟酸水溶液之方法時，在晶圓 表面之自然氧化膜溶解後，晶圓表面會成爲溝流面，氟酸 水溶液無法浸入晶圓表面。因此，液滴轉動並乾燥固化所 造成的痕跡會殘留於晶圓表面，其會被檢測成粒子或晶圓 表面處於不均勻之粗糙狀態，而使晶圓表面之品質處於不 良狀態。因此，本實施形態採用將晶圓浸漬於氟酸水溶液 之方法。 此外，以執行利用SC-1洗淨液之處理取代上述浸漬 於對Si〇2膜之蝕刻率爲150〜3 000A/分之氟酸水溶液之晶 圓表面處理時，SC-1洗淨液對矽及二氧化矽（Si02 )之蝕 刻率以20A/分程度爲限界。即使延長處理時間來增加蝕刻 -11 - (9) 1263329 量’仍會殘留多數無法除去之不動點粒子，而爲爲晶圓之 缺陷原因。 此處’不動點粒子係指第2洗淨步驟前後殘存於同一 位置之粒子。 上述氟酸水溶液1 2之溫度應超過該氟酸水溶液之凝 固點且爲4 0 C以下，2 0〜2 5 °C爲佳。晶圓1 1浸漬於氟 酸水丨谷液1 2之時間應爲1 〇〜6 0 0秒，3 0〜1 0 0秒爲佳。 此處’氟酸水溶液1 2對S i 0 2膜之蝕刻率若爲1 5 〇 A / 分以下’對晶圓1 1表面之蝕刻率會較慢，無法切斷含有 大量矽及氧之結合之粒子之強固結合，亦即，無法切斷氧 離子注入時經由矽及氧而獲得強固結合之粒子之化學結合 。此外，超過3 000A/分的話，晶圓11之表面會變得十分 粗糙。因此，氟酸水溶液12對Si 02膜之蝕刻率應在於 150〜3000A/分之範圍。 此外’氟酸水溶液1 2之溫度在氟酸水溶液之凝固點 以下時，無法執行蝕刻處理。超過4 0 °C時，氟酸水溶液會 產生霧氣而難以處理，而且表面亦會變得粗糙。因此，氟 酸水溶液1 2之溫度應在於超過該氟酸水溶液之凝固點且 爲4(TC以下之範圍。 此外，晶圓1〗浸漬於氟酸水溶液1 2之時間爲1 〇秒 以下時，浸漬時間太短，而無法切斷含有大量矽及氧之結 合之粒子之強固結合’亦即，無法切斷氧離子注入時經由 矽及氧而獲得強固結合之粒子之化學結合。超過600秒時 ’表面會變得糙粗。因此，晶圓1 1浸漬於氟酸水溶液1 2 -12- (10) 1263329 之時間在於1 0〜6 0 0秒之範圍。 此外’浸漬於對形成於晶圓11表面之Si02膜之蝕刻 率爲R ( A/分）之氟酸水溶液1 2時，若晶圓1 1浸漬於氟 酸水溶液1 2之時間爲Η (秒），則應以Η - ( 1 5 00/R )( 秒）來設定浸漬時間。藉此，可快速求取以氟酸水溶液1 2 之蝕刻率爲基礎之最佳晶圓1 1浸漬時間。 此外’上述氟酸水溶液1 2應添加界面活性劑。因爲 對氟酸水溶液1 2添加界面活性劑，可利用界面活性劑產 生晶圓1 1表面保護膜之作用，故可防止粒子再附著於晶 圓1 1表面。此外，利用純水清洗該晶圓1 1時，可獲得良 好脫水。 上述界面活性劑可以採用離子性界面活性劑、及非離 子性界面活性劑等。界面活性劑之添加量爲〇. 1〜1 〇重量 %，0.3〜1重量°/〇爲佳。 界面活性劑之添加量爲〇. 1重量％以下時，無法發揮 晶圓1 1表面保護膜之機能，超過1 〇重量％時，會發生鹽 析而妨礙蝕刻。因此，界面活性劑之添加量在於0 ·1〜10 重量％之範圍。 其次，將上述晶圓11浸漬於貯存純水1 4之清洗槽13 來進行清洗後，將其榜起並使其乾燥（第】圖）。該清洗 槽1 3具有用以貯存純水1 4之槽主體1 3 a、及配設於該槽 主體1 3 a之上部外緣之用以承接從槽主體1 3 a溢流之純水 14之溢流槽13b。此外，槽主體13a之下部連結著用以將 純水1 4供應給槽主體1 3 a之供應管1 3 c，溢流槽1 3 b之下 -13- (11) 1263329 面則連結著用以排出積存於溢流槽1 3 b之純水1 4之排出 管 1 3d。 此外，在經過第2氧離子注入步驟、第3洗淨步驟、 第3氧離子注入步驟、以及第4洗淨步驟後，對上述晶圓 1 1實施SIMOX熱處理（第2圖）。 第2氧離子注入步驟之氧離子之注入係使晶圓保持在 3 0 0 〜5 00 t、氧離子之劑量爲 5xl016 〜2xl017atoms/cm2 之狀態下執行。第3氧離子注入步驟之氧離子之注入係在 晶圓保持於室溫、氧離子之劑量爲 lxlO15〜lx 1 0 1 7 a t 〇 m s / c m2之狀態執行。 此外，此實施形態係將對矽晶圓之氧離子注入分成3 次來實施，然而，矽晶圓之氧離子注入可以爲1次，或者 ，也可爲2次或4次以上。 此外，此實施形態係在最初之氧離子注入後立即將矽 晶圓浸漬於氟酸水溶液，然而，在第2次或第3次之氧離 子注入後、第1〜3次之其中任2次之各氧離子注入後、 或3次之各氧離子注入後，立即將矽晶圓浸漬於氟酸水溶 液亦可。 此種方式製造之SIMOX晶圓，因爲氧離子注入前殘 存於晶圓表面之粒子較少，粒子所導致之氧離子注入之遮 蔽效果較少，故貫穿SOI層之深缺陷（溫度23 °C下，浸 漬於濃度5 0重量％之氟酸水溶液1 2 3 0分鐘後所觀察之缺 陷）之數爲極少之〇.〇5個/cm2以下。 -14- (12) 1263329 〔實施例〕 g次，針對本發明之實施例及比較例進行詳 (實施例1〜3 ) $口第 2圖所示，將利用丘克拉斯基法撈 200mm之矽晶錠進行切片並實施表面之硏磨及名 洗淨步驟）後’分成3次實施氧離子注入° 如第1圖及第2圖所示，第1氧離子注入衫 該晶圓11浸漬於對晶圓11表面之si〇2膜之 600A/分（氟酸水溶液之濃度：10重量％ )、溫 之氟酸水溶液12，浸漬時間爲60秒，進行蝕亥 次，將該晶圓11浸漬於可溢流純水1 4之清洗槽 3分鐘後進行乾燥。 其次，以逐片旋轉方式對該晶圓11進行沒 而言，逐片使晶圓1 1進行旋轉，對其表面 15 ppm之臭氧水進行20秒之洗淨後，再對其噴ί 重量％之氟酸水溶液進行1 0秒之洗淨。重複3攻 (第2洗淨步驟），實施晶圓之乾燥。 此外，經過第2氧離子注入步驟、第3洗ί 3氧離子注入步驟、以及第4洗淨步驟後，對該 施SIMOX熱處理。將該晶圓視爲實施例1〜3。 (實施例4〜6 ) 第1氧離子注入後，立即將該晶圓浸漬於添 細說明。There is only one combination, and there is a combination of the majority. In order to cut the bond, it is necessary to make HF or HF 2 _ encounter S i - 0, and the probability of encountering it should be a speed limit. In order to cut off most of the bonds existing in the narrow physical gap, the etching rate of the Si 02 film is The aqueous solution of hydrofluoric acid of 150 A/min or less, before HF or HF; r reaches the deep part, will be consumed by the Si-Ο, so it is difficult to deepen the gap. However, if the etch rate of the SiO 2 film is 150 to 3 000 A/min, the HF or HF 2 _ remains at the depth of the gap, and HF or HF 2 _ remains, so it should be completely cut off in the stenosis. The majority of the gap is combined. As a result, the particles on the surface of the wafer 11 can be completely removed. The method of spraying the aqueous solution of the hydrofluoric acid on the surface of the rotating wafer is not employed, and the method of immersing the wafer in the aqueous solution of hydrofluoric acid is limited, and the reason is as follows. When a method of spraying an aqueous solution of hydrofluoric acid on the surface of a rotating wafer is performed, after the natural oxide film on the surface of the wafer is dissolved, the surface of the wafer becomes a channel surface, and the aqueous solution of the hydrofluoric acid cannot be immersed in the surface of the wafer. Therefore, the traces caused by the rotation and drying of the droplets remain on the surface of the wafer, which is detected as a non-uniform roughness of the surface of the particles or the wafer, and the quality of the surface of the wafer is deteriorated. Therefore, in this embodiment, a method of immersing a wafer in a hydrofluoric acid aqueous solution is employed. Further, when the surface treatment of the wafer immersed in the aqueous solution of the hydrofluoric acid having an etching rate of 150 to 3,000 A/min on the Si〇2 film is performed by the treatment using the SC-1 cleaning solution, the SC-1 cleaning solution is applied. The etching rate of cerium and cerium oxide (SiO 2 ) is limited to 20 A/min. Even if the processing time is extended to increase the amount of etching -11 - (9) 1263329', most of the fixed-point particles that cannot be removed remain, which is the cause of defects in the wafer. Here, the "fixed point particle" means a particle remaining at the same position before and after the second washing step. The temperature of the aqueous solution of the hydrofluoric acid 1 2 should exceed the condensation point of the aqueous solution of the hydrofluoric acid and be 40 ° C or less, preferably 20 to 25 ° C. The time during which the wafer 1 1 is immersed in the sulphuric acid sorghum solution 1 2 should be 1 〇 to 600 sec, preferably 3 0 to 1 0 0 sec. Here, the etching rate of the aqueous solution of the hydrofluoric acid 1 2 to the S i 0 2 film is 15 〇A / min or less. The etching rate on the surface of the wafer 1 1 is slow, and the combination containing a large amount of hydrazine and oxygen cannot be cut. The strong bonding of the particles, that is, the chemical bonding of the particles which are strongly bonded via the helium and oxygen at the time of oxygen ion implantation cannot be cut off. In addition, if it exceeds 3 000 A/min, the surface of the wafer 11 becomes very rough. Therefore, the etching rate of the aqueous solution of hydrofluoric acid 12 to the Si 02 film should be in the range of 150 to 3000 A/min. Further, when the temperature of the aqueous solution of the hydrofluoric acid 1 is not more than the freezing point of the aqueous solution of the hydrofluoric acid, the etching treatment cannot be performed. When it exceeds 40 °C, the aqueous solution of hydrofluoric acid will be foggy and difficult to handle, and the surface will become rough. Therefore, the temperature of the aqueous solution of the hydrofluoric acid 1 should be more than the freezing point of the aqueous solution of the hydrofluoric acid and be 4 (the range of TC or less. Further, when the wafer 1 is immersed in the aqueous solution of the hydrofluoric acid at a time of 1 sec or less, the immersion is performed. The time is too short to cut off the strong bond of particles containing a large amount of a combination of helium and oxygen', that is, the chemical bond of the particles which are strongly bonded via the helium and oxygen at the time of oxygen ion implantation cannot be cut off. The surface becomes rough. Therefore, the time during which the wafer 11 is immersed in the aqueous solution of the hydrofluoric acid 1 2 -12-(10) 1263329 lies in the range of 10 to 600 seconds. Further, the immersion is formed on the wafer 11 When the etching rate of the SiO 2 film on the surface is 1 (2/min) of the aqueous solution of the hydrofluoric acid, if the time during which the wafer 11 is immersed in the aqueous solution of the hydrofluoric acid 1 2 is Η (sec), then Η - ( 1 5 00/R) (seconds) to set the immersion time. Thereby, the optimum immersion time of the wafer 1 1 based on the etching rate of the aqueous solution of hydrofluoric acid can be quickly obtained. Further, the above aqueous solution of hydrofluoric acid 1 2 should be added. Surfactant. Because surfactant is added to the aqueous solution of hydrofluoric acid 12, the interface can be used. The agent generates the surface protective film of the wafer 1 1 and thus prevents the particles from reattaching to the surface of the wafer 11. Further, when the wafer 11 is cleaned with pure water, good dehydration can be obtained. An ionic surfactant, a nonionic surfactant, etc. The amount of the surfactant added is 1. 1~1 〇% by weight, 0.3~1 by weight/〇 is preferred. The amount of surfactant added is 〇. When the amount is 1% by weight or less, the function of the surface protective film of the wafer 1 1 cannot be exhibited, and when it exceeds 1% by weight, salting out occurs and the etching is inhibited. Therefore, the amount of the surfactant added is 0.1 to 10% by weight. Next, the wafer 11 is immersed in a cleaning tank 13 for storing pure water 14 to be cleaned, and then listed and dried (Fig.). The cleaning tank 13 has a function for storing pure water. The trough main body 1 3 a and the overflow groove 13b disposed on the outer edge of the upper portion of the trough main body 1 3 a for receiving the pure water 14 overflowing from the trough main body 13 a. Further, the trough main body 13a a supply pipe 1 3 c for supplying pure water 14 to the tank main body 1 3 a is connected to the lower portion, The discharge tube 1 3d for discharging the pure water 14 accumulated in the overflow tank 13 b is connected to the surface of the flow channel 1 3 b - 13 - (11) 1263329. Further, after the second oxygen ion implantation step After the third cleaning step, the third oxygen ion implantation step, and the fourth cleaning step, the wafer 11 is subjected to SIMOX heat treatment (Fig. 2). The oxygen ion implantation step of the second oxygen ion implantation step is performed. The wafer is held at a state of 300 to 500 00 t and an oxygen ion dose of 5 x 1016 to 2 x 1017 atoms/cm 2 . The injection of oxygen ions in the third oxygen ion implantation step is performed while the wafer is kept at room temperature and the dose of oxygen ions is lxlO15~lx 1 0 1 7 a t 〇 m s / c m2 . Further, in this embodiment, the oxygen ion implantation of the germanium wafer is carried out three times. However, the oxygen ion implantation of the germanium wafer may be performed once or twice or four times or more. Further, in this embodiment, the tantalum wafer is immersed in the aqueous solution of hydrofluoric acid immediately after the first oxygen ion implantation, but after the second or third oxygen ion implantation, any one of the first to third times Immediately after each oxygen ion implantation or after three times of oxygen ion implantation, the ruthenium wafer may be immersed in a hydrofluoric acid aqueous solution. The SIMOX wafer manufactured in this way has fewer particles remaining on the surface of the wafer before the oxygen ion implantation, and the shielding effect of the oxygen ion implantation caused by the particles is less, so the deep defect penetrates the SOI layer (at a temperature of 23 ° C) The number of defects observed after immersion in a 50% by weight aqueous solution of hydrofluoric acid for 1 2 3 0 minutes was extremely small. 〇 5 / cm 2 or less. -14- (12) 1263329 [Examples] g times, the examples and comparative examples of the present invention are detailed (Examples 1 to 3). As shown in Fig. 2, the Chuklaski method is used to fish 200 mm. After the bismuth ingot is sliced and subjected to surface honing and name washing step), the oxygen ion implantation is performed in three steps. As shown in FIGS. 1 and 2, the wafer 11 is immersed in the first oxygen ion implantation shirt. 600 A/min of the Si〇2 film on the surface of the wafer 11 (concentration of the aqueous solution of the hydrofluoric acid: 10% by weight) and the aqueous solution of the hydrofluoric acid 12 in the temperature were immersed for 60 seconds, and the wafer 11 was immersed. Drying was carried out for 3 minutes in a washing tank capable of overflowing pure water. Next, the wafer 11 is rotated one by one, and the wafer 11 is rotated one by one, and the surface water of 15 ppm is washed for 20 seconds, and then the weight is sprayed. The aqueous solution of hydrofluoric acid was washed for 10 seconds. Repeat 3 attacks (second cleaning step) to dry the wafer. Further, after the second oxygen ion implantation step, the third cleaning ion implantation step, and the fourth cleaning step, the SIMOX is heat-treated. This wafer was regarded as Examples 1 to 3. (Examples 4 to 6) Immediately after the first oxygen ion implantation, the wafer was immersed in a fine description.
起之直徑 U爭（第1 t，立即將 :鈾刻率爲 度爲2 3 t： [I處理。其 13，浸漬 i淨。具體 噴射濃度 I寸濃度0.5 :該洗淨後 〖步驟、第 晶圓Π實 加著1重 -15- (13) 1263329 量％非離子系界面活性劑之對晶圓表面之Si〇2膜之蝕刻率 爲7 00A/分（氟酸水溶液之濃度：50重量％ )、溫度爲5 °C之氟酸水溶液，浸漬時間爲3 0秒，進行蝕刻處理。其 次，將該晶圓浸漬於可溢流純水之清洗槽，浸漬5分鐘。 除了以上之條件以外，其餘與實施例〗〜3相同，製作3 _ 片SIMOX晶圓。將該晶圓視爲實施例4〜6。 _ (實施例7〜9 ) 第1氧離子注入後，立即將該晶圓浸漬於對晶圓表面 之 S i Ο 2膜之蝕刻率爲4 0 0 A /分（氟酸水溶液之濃度：2 5 重量％ )、溫度爲1 5 t之氟酸水溶液，浸漬時間爲3 00秒 ^ ，進行蝕刻處理。其次，將該晶圓浸漬於可溢流純水之清 ' 洗槽，浸漬1分鐘。除了以上之條件以外，其餘與實施例 1〜3相同，製作3片SIMOX晶圓。將該晶圓視爲實施例 ^7 9 ° (實施例1 0〜1 2 ) 第1氧離子注入後，立即將該晶圓浸漬於添加著3重 量°/。離子系界面活性劑之對晶圓表面之Si02膜之蝕刻率爲 350A/分（氟酸水溶液之濃度：2重量％ )、溫度爲35°C之 氟酸水溶液，浸漬時間5 00秒，進行蝕刻處理。將該晶圓 浸漬於可溢流純水之清洗槽，浸漬時間1分鐘間浸漬後進 行乾燥。並將該晶圓浸漬於80°C之SC-1洗淨液（NH4OH ：H202 ： H2〇- 0.5 ： 1 ： 10)，浸漬時間5分鐘，進行洗 -16- (14) 1263329 淨。除了以上之條件以外，其餘與實施例1〜3相同，製 作3片SIMOX晶圓。將該晶圓視爲實施例10〜12。 (比較例1〜1 3 ) 將利用丘克拉斯基法撈起之直徑2 00mm之矽晶錠進 行切片並實施表面之硏磨及洗淨（第1洗淨步驟）後’分 成3次實施氧離子注入。 • 第1氧離子注入後，立即將該晶圓浸漬於80°c之SC-1 洗淨液（NH4OH: H202: Η2Ο=0·5: 1: 10)，浸瀆時 間爲1 〇分鐘，進行洗淨後（第2洗淨步驟）實施乾燥° 其次，經過第2氧離子注入步驟、第3洗淨步驟、第 * 3氧離子注入步驟、以及第4洗淨步驟後，對該晶圓實施 • SIMOX熱處理。將該晶圓視爲比較例1〜13。 (比較例1 4〜2 6 ) # 將利用丘克拉斯基法撈起之直徑200mm之矽晶錠進 行切片並實施表面之硏磨及洗淨（第1洗淨步驟）後’分 成3次實施氧離子注入。 第1氧離子注入後，立即逐片旋轉方式對該晶圓進行 洗淨。具體而言，逐片使晶圓進行旋轉，對其表面噴射濃 度15PPm之臭氧水進行20秒之洗淨後，再對其噴射濃度 〇. 5重量％之氟酸水溶液進行1 〇秒之洗淨。重複3次該洗 淨後（第2洗淨步驟），實施晶圓之乾燥。 其次，經過第2氧離子注入步驟、第3洗淨步驟、第 -17- (15) 1263329 3氧離子注入步驟、以及第4洗淨步驟後，對該晶圓實施 S I Μ Ο X熱處理。將該晶圓視爲比較例1 4〜2 6。 (比較例2 7〜3 9 ) 第1氧離子注入後，立即將該晶圓浸漬於對晶圓表面 之Si02膜之蝕刻率爲30Α/分（氟酸水溶液之濃度·· 0.5重 量％ )、溫度爲2 3 °C之氟酸水溶液，浸漬時間爲3 0秒， 進行蝕刻處理。除了該條件以外，其餘與實施例1相同， 製作S IΜ Ο X晶圓。將該晶圓視爲比較例2 7〜3 9。 (比較例40〜52 ) 第1氧離子注入後，立即將該晶圓浸漬於對晶圓表面 之Si 02膜之蝕刻率爲120 Α/分（氟酸水溶液之濃度：2.0 重量％ )、溫度爲2 3 °C之氟酸水溶液，浸潰時間爲3 0秒 ，進行蝕刻處理。除了該條件以外，其餘與實施例1相同 ，製作SIMOX晶圓。將該晶圓視爲比較例40〜52。 (比較試驗1及評估） 計測實施例1〜1 2及比較例1〜5 2之矽晶圓之第2洗 淨步驟前後之不動點粒子之除去率。 該不動點粒子之除去率係利用以下之方法計算。首先 ，利用 SurfScan6420 (美國KLA-Tencor公司製之表面檢 查裝置）計測第2洗淨步驟前後之粒徑0.20 v m以上之粒 子數。其次，以百分率表示將第2洗淨步驟後之粒徑〇.20 -18- (16) 1263329 // m以上之粒子數除以第2洗淨步驟前之粒徑0.20 e m以 上之粒子數之比例，並將其視爲不動點粒子之除去率。結 果如第3圖A〜第3圖C、第4圖A、以及第4圖B所示 〇 由第3圖A〜第3圖C、第4圖A、以及第4圖B可 知，比較例〗〜5 2之不動點粒子之除去率爲較低之4 5〜 8 5 %，相對於此’實施例1〜1 2之不動點粒子之除去率爲 φ 極高之8 8〜1 0 0 %。其理由爲，分3次注入氧離子，並在 第2次氧離子注入前減少粒子，可使實施例之不動點粒子 之除去率變成極高。亦即，因爲第3次氧離子注入爲低溫 ，即使存在某程度之導入粒子，亦無法成爲缺陷種。此外 ，注入時間方面，滯留於晶圓表面之時間較長之粒子會成 ’ 爲缺陷種，第1次及第2次氧離子注入時存在之粒子容易 成爲缺陷種，然而，第2次及第3次氧離子注入時存在之 粒子卻難以成爲缺陷種。 (比較試驗2及評估）From the diameter U contend (1 t, immediately: uranium engraving rate is 2 3 t: [I treatment. Its 13, immersion i net. Specific injection concentration I inch concentration 0.5: after washing, step, first Wafer tamping with 1 -15-(13) 1263329% non-ionic surfactant to the wafer surface of the Si〇2 film etching rate of 700 A / min (fluoric acid aqueous solution concentration: 50 weight %), a hydrofluoric acid aqueous solution having a temperature of 5 ° C, an immersion time of 30 seconds, and an etching treatment. Next, the wafer was immersed in a cleaning tank capable of overflowing pure water, and immersed for 5 minutes. The other three sheets of SIMOX wafer were produced in the same manner as in the examples 〜3. The wafer was regarded as Examples 4 to 6. _ (Examples 7 to 9) Immediately after the first oxygen ion implantation, the wafer was immediately The etching rate of the S i Ο 2 film immersed on the surface of the wafer is 400 A / min (concentration of aqueous solution of hydrofluoric acid: 25 wt%), aqueous solution of hydrofluoric acid having a temperature of 15 t, and the immersion time is 300 Second, the etching process is performed. Next, the wafer is immersed in a clear water washing tank of the overflowing pure water, and immersed for 1 minute. In addition to the above conditions, Three SIMOX wafers were produced in the same manner as in Examples 1 to 3. This wafer was regarded as an example of ^7 9 ° (Examples 10 to 12). Immediately after the first oxygen ion implantation, the wafer was immersed. An aqueous solution of fluoric acid having an etching rate of 350 Å/min (concentration of aqueous solution of hydrofluoric acid: 2% by weight) and a temperature of 35 ° C on the surface of the wafer to which 3 parts by weight of the ion-based surfactant is added is added. The immersion time was 5,000 seconds, and etching was performed. The wafer was immersed in a cleaning bath capable of overflowing pure water, immersed for 1 minute, and then dried, and the wafer was immersed in an SC-1 wash at 80 °C. The clean solution (NH4OH: H202: H2〇-0.5 : 1 : 10), the immersion time was 5 minutes, and the washing was carried out - 16 - (14) 1263329. The same procedure as in the above Examples 1 to 3 was carried out except that the above conditions were carried out, and 3 was produced. A sheet of SIMOX wafer. The wafer was regarded as Examples 10 to 12. (Comparative Examples 1 to 1 3) A twin crystal ingot having a diameter of 200 mm picked up by the Czochralski method was sliced and subjected to surface honing. After washing (the first washing step), the oxygen ion implantation is performed in three steps. • Immediately after the first oxygen ion implantation, the wafer is immersed. The SC-1 washing solution (NH4OH: H202: Η2Ο = 0.55: 1: 10) stained at 80 ° C, the dipping time is 1 〇 minutes, and after washing (the second washing step), drying is performed. Next, after the second oxygen ion implantation step, the third cleaning step, the third oxygen ion implantation step, and the fourth cleaning step, the wafer is subjected to a SIMOX heat treatment. The wafer is regarded as Comparative Example 1 ~13. (Comparative Example 1 4 to 2 6 ) #Slice the ingot of 200 mm in diameter which was picked up by the Czochralski method, and perform surface honing and washing (first washing step), and then divide it into 3 times. Oxygen ion implantation. Immediately after the first oxygen ion implantation, the wafer is cleaned one by one. Specifically, the wafer is rotated one by one, and the surface water is sprayed with a concentration of 15 ppm of ozone water for 20 seconds, and then sprayed with a concentration of 5% by weight of a hydrofluoric acid aqueous solution for 1 sec. . After the washing was repeated three times (the second washing step), the wafer was dried. Next, after the second oxygen ion implantation step, the third cleaning step, the -17-(15) 1263329 3 oxygen ion implantation step, and the fourth cleaning step, the wafer is subjected to a heat treatment of S I Μ Ο X. This wafer was regarded as Comparative Example 14 to 26. (Comparative Example 2 7 to 3 9 ) Immediately after the first oxygen ion implantation, the wafer was immersed in an etch rate of SiO 2 film on the surface of the wafer of 30 Å/min (concentration of aqueous solution of hydrofluoric acid · 0.5% by weight), The aqueous solution of hydrofluoric acid at a temperature of 23 ° C was immersed for 30 seconds and etched. Except for this condition, in the same manner as in Example 1, an S I Μ Ο X wafer was produced. This wafer was regarded as Comparative Example 2 7 to 3 9 . (Comparative Examples 40 to 52) Immediately after the first oxygen ion implantation, the wafer was immersed in a Si 02 film on the surface of the wafer at an etching rate of 120 Å/min (concentration of a hydrofluoric acid aqueous solution: 2.0% by weight), and a temperature. It was an aqueous solution of hydrofluoric acid at 23 ° C, and the etching time was 30 seconds, and etching treatment was performed. Except for this condition, the SIMOX wafer was produced in the same manner as in Example 1. This wafer was regarded as Comparative Examples 40 to 52. (Comparative Test 1 and Evaluation) The removal rates of the fixed point particles before and after the second cleaning step of the tantalum wafers of Examples 1 to 1 2 and Comparative Examples 1 to 5 were measured. The removal rate of the fixed point particles was calculated by the following method. First, the number of particles having a particle diameter of 0.20 v m or more before and after the second washing step was measured by SurfScan 6420 (surface inspection device manufactured by KLA-Tencor Co., Ltd., USA). Next, the number of particles having a particle diameter of 20.20 -18-(16) 1263329 // m or more after the second washing step is divided by the percentage of the particles having a particle diameter of 0.20 em or more before the second washing step. The ratio is considered as the removal rate of the particles at the fixed point. The results are as shown in FIGS. 3A to 3C, 4A, and 4B. As is apparent from FIGS. 3A to 3C, 4A, and 4B, the comparative example The removal rate of the particles of the fixed point of ~5 2 is 4 5~ 8 5 %, and the removal rate of the fixed point particles of the 'Examples 1 to 1 2' is extremely high 8 8 to 1 0 0 %. The reason for this is that the oxygen ions are injected three times, and the particles are reduced before the second oxygen ion implantation, so that the removal rate of the fixed point particles in the embodiment can be extremely high. That is, since the third oxygen ion implantation is low in temperature, even if there is a certain amount of introduced particles, it cannot be a defective species. In addition, in terms of injection time, particles that remain on the surface of the wafer for a long period of time become 'defective species', and the particles present at the first and second oxygen ion implantations are likely to be defective species. However, the second and the second The particles present at the third oxygen ion implantation are difficult to be defective. (Comparative Test 2 and Evaluation)
計測實施例1、4、7、1 0、比較例3〜6、以及比較例 16〜19之貫穿經過第1〜第3氧離子注入步驟及SIMOX 熱處理步驟之矽晶圓之SOI層之深缺陷之數。 該缺陷之數係將上述晶圓浸漬於2 3 t、濃度5 0重量 %之氟酸水溶液，浸漬時間30分鐘，使SOI層之缺損明 顯化後，利用光學顯微鏡觀察所得之明顯化缺損數。其結 果如第5圖所示。 -19- (17) 1263329 由第5圖可知，比較例3〜6及比較例1 6 S 〇 I層之深缺陷之數多達1 7〜2 6個，相對於此 、4、7、以及10之貫穿SOI層之深缺陷之數| 亦即，直徑200mm之SIMOX晶圓時，爲極少 /cm2以下。 依據本發明之 SIMOX晶圓製造方法，亦 大量砂及氧之結合之粒子之強固結合，故可有 表面完全除去粒子。因此，可製造缺陷極少之 圓。 【圖式簡單說明】 第1圖係本實施形態之利用蝕刻率150〜 氟酸水溶液之蝕刻處理步驟及利用純水之清洗 圖。 弟2圖係本貫施形態之含有砂晶圓之氧離 及洗淨步驟在內之方塊圖。 第3圖A係實施例1〜1 2之粒子除去率圖 第3圖B係比較例1〜1 3之粒子除去率圖 第3圖C係比較例1 4〜2 6之粒子除去率圖 第4圖A係比較例2 7〜3 9之粒子除去率圖 第4圖B係比較例4 0〜5 2之粒子除去率圖 第5圖係實施例及比較例之貫穿SOI層之: 度23 °C下，浸漬於濃度50重量％之氟酸水溶液 所觀察之缺陷）之個數圖。 〜19之貫穿 ，實施例1 i 0〜5個， 之0.0 1 6個 可切斷含有 效從矽晶圓 SIMOX 晶 3000A/分之 步驟之步驟 子注入步驟 :缺陷（溫 3 〇分鐘後 -20- (18) (18)1263329The deep defects of the SOI layer of the tantalum wafer which passed through the first to third oxygen ion implantation steps and the SIMOX heat treatment step were measured in Examples 1, 4, 7, and 10, Comparative Examples 3 to 6, and Comparative Examples 16 to 19. The number. The number of defects was obtained by immersing the above-mentioned wafer in a 25 wt% aqueous solution of hydrofluoric acid having a concentration of 50% by weight, and immersing for 30 minutes to visualize the defects of the SOI layer, and then observing the number of apparent defects by an optical microscope. The result is shown in Figure 5. -19- (17) 1263329 As can be seen from Fig. 5, the number of deep defects in the layers of Comparative Examples 3 to 6 and Comparative Example 1 6 S 〇I is as many as 17 to 26, and in contrast to this, 4, 7, and The number of deep defects throughout the SOI layer of 10 | that is, the SIMOX wafer having a diameter of 200 mm is extremely small/cm 2 or less. According to the SIMOX wafer manufacturing method of the present invention, a large amount of particles of a combination of sand and oxygen are combined, so that the surface can be completely removed. Therefore, it is possible to manufacture a circle with few defects. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an etching treatment step using an etching rate of 150 to a hydrofluoric acid aqueous solution and a cleaning diagram using pure water in the present embodiment. The second figure is a block diagram of the oxygen-containing and cleaning steps of the sand wafer in the present embodiment. Fig. 3A is a particle removal rate diagram of Examples 1 to 1 2, Fig. 3B is a particle removal rate diagram of Comparative Examples 1 to 1 3, and Fig. 3 is a comparison of the particle removal ratio of the comparative example 1 4 to 2 6 4A is a particle removal rate of Comparative Example 2 7 to 3 9Fig. 4B is a comparative example 4 particle removal rate diagram of 0 to 5 2 Fig. 5 is a through-SOI layer of the embodiment and the comparative example: Degree 23 A graph showing the number of defects observed by immersing in a 50% by weight aqueous solution of hydrofluoric acid at °C. Throughout the 19th, the embodiment 1 i 0~5, the 0.016 can cut off the step of the step of injecting effective from the OX wafer SIMOX crystal 3000A / minute sub-injection step: defect (temperature 3 〇 minutes after -20 - (18) (18) 1263329
【主要元件符號說明】 1 1 :砂晶圓 1 2 :氟酸水溶液 -21[Main component symbol description] 1 1 : Sand wafer 1 2 : Hydrofluoric acid aqueous solution -21