TW399230B - Process and apparatus for cleaning the interior of semiconductor substrate - Google Patents
Process and apparatus for cleaning the interior of semiconductor substrate Download PDFInfo
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- TW399230B TW399230B TW087102964A TW87102964A TW399230B TW 399230 B TW399230 B TW 399230B TW 087102964 A TW087102964 A TW 087102964A TW 87102964 A TW87102964 A TW 87102964A TW 399230 B TW399230 B TW 399230B
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- 239000000758 substrate Substances 0.000 title claims abstract description 219
- 239000004065 semiconductor Substances 0.000 title claims abstract description 107
- 238000004140 cleaning Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000012535 impurity Substances 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 239000007787 solid Substances 0.000 claims abstract description 48
- 239000011343 solid material Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 104
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 104
- 238000010438 heat treatment Methods 0.000 claims description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 51
- 229910052710 silicon Inorganic materials 0.000 claims description 51
- 239000010703 silicon Substances 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- 230000007246 mechanism Effects 0.000 claims description 29
- 238000011049 filling Methods 0.000 claims description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 16
- 238000007872 degassing Methods 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 13
- 239000013042 solid detergent Substances 0.000 claims description 12
- 230000002079 cooperative effect Effects 0.000 claims description 10
- 239000011538 cleaning material Substances 0.000 claims description 9
- 235000015170 shellfish Nutrition 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims 2
- 238000010926 purge Methods 0.000 claims 2
- 238000004806 packaging method and process Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 39
- 239000001301 oxygen Substances 0.000 description 39
- 229910052760 oxygen Inorganic materials 0.000 description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 35
- 229910052802 copper Inorganic materials 0.000 description 35
- 239000010949 copper Substances 0.000 description 35
- 235000012431 wafers Nutrition 0.000 description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 238000010943 off-gassing Methods 0.000 description 18
- 239000010408 film Substances 0.000 description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 238000009792 diffusion process Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000011109 contamination Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000272168 Laridae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229940098465 tincture Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
經濟部中央搮準局員工消費合作社印装 A7 ______ B7 五、發明説明（I ) 發明背景 1. 發明的範圍 本發明是有關於一種淸潔半導體基板內部的方法和裝 置。特定而言，它是有關於一種從半導體基板內部移除快 速擴散的金屬雜質的淸潔方法和淸潔裝置。 2. 先前技術的敘述 在例如爲矽的半導體基板表面上，在組裝金屬氧化物 半導體(MOS)元件或雙極結構元件時，帶有重金屬雜質之 半導體基板汙染，通常會造成嚴重的問題，例如：氧化薄 膜的崩潰強度降低和經由pn接合點的漏電流增加β特別是 銅和鎳’在矽中快速地擴散，以致會對元件造成很大的影 響。再者’來自於這些金屬的汙染，是很容易在操作製造 裝置時產生’或是在操作之前和之後產生。 據此’將這些金屬雜質從半導體基板的元件作用區域 隔離的技術’在此領域中，已知的方法有被稱爲本質性除 氣（intrinsic gettering, IG)和非本質性除氣（extrinsic gettedng，EG) »這些方法是在元件作用區域的以外的區域 中’提供了一個可迅速吸收晶體缺陷或是金屬雜質的薄膜 層，使得金屬雜質在加熱步驟中，從元件作用區域被移向 的這些層，而在此被捕獲。 因爲上述的除氣作用，對元件作用區域有很強的純化 效果’任何來自每一個製造步驟的製程裝置之汙染性金屬 元素，隨著製程的進行，被除氣處捕獲愈來愈多。特別是 在離子植入和乾式蝕刻步驟中，汙染物可能產生太多，以 —_ _____ 4_____ ^紙张尺度適用中國國家標準（CNS ) Λ4規格（210X 297公势> (請先閱讀背面之注意事項再填寫本頁) -·訂 嗖 經濟部中央標準局員工消费合作社印製 A7 B7 五、發明説明（>) 致除氣的功能可能達到飽和或趨近於飽和，導致隨著製程 的進行，除氣作用較差。 此外’已被除氣到的金鷗雜質，有可能會被釋放出來 ，再次地進入到元件作用區域。舉例來說，一些元素，例 如甚至在300°C或是以下時仍擴散相當快速的銅，在製程 中的某些加熱條件下，會從飽和的或趨近於飽和的除氣層 中釋放出來。 在IG中，在除氣層中之氧濃度低的部份，具有相對低 程度的缺陷，因此與銅的結合相當弱，以致金屬雜質甚至 在300°C或是以下，仍相當容易地釋放出.來(再次釋放h具Printed by the Consumers' Cooperative of the Central Economic and Technical Bureau of the Ministry of Economic Affairs A7 ______ B7 V. Description of the Invention (I) Background of the Invention 1. Scope of the Invention The present invention relates to a method and a device for cleaning the inside of a semiconductor substrate. In particular, it relates to a cleaning method and cleaning device for removing fast-diffusing metal impurities from the inside of a semiconductor substrate. 2. The description of the prior art on the surface of a semiconductor substrate such as silicon. When assembling a metal oxide semiconductor (MOS) element or a bipolar structure element, contamination of the semiconductor substrate with heavy metal impurities usually causes serious problems, such as : The breakdown strength of the oxidized film is reduced and the leakage current through the pn junction is increased β, especially copper and nickel 'diffuse rapidly in silicon, so that the device is greatly affected. Furthermore, 'contamination from these metals is easily generated during operation of the manufacturing apparatus' or before and after operation. Based on this, the technique of isolating these metal impurities from the device active region of the semiconductor substrate is known in this field as intrinsic gettering (IG) and intrinsic gettedng. EG) »These methods' provide a thin film layer that can rapidly absorb crystal defects or metal impurities in areas other than the element active area, so that metal impurities are moved from the element active area to these during the heating step. Layer while being captured here. Because of the above-mentioned degassing effect, there is a strong purification effect on the action area of the component ′ Any contaminating metal element from the process equipment of each manufacturing step, as the process progresses, more and more is captured by the degassing place. Especially in the ion implantation and dry etching steps, the pollutants may be generated too much. —_ _____ 4_____ ^ Paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 public momentum) (Please read the back Please fill out this page again)-· Order printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (>) The function of degassing may reach saturation or approach saturation, resulting in In addition, the degassing effect is poor. In addition, the gold gull impurities that have been degassed may be released and enter the element action area again. For example, some elements, such as even at 300 ° C or below Copper, which still diffuses very quickly, is released from the saturated or near-saturated degassing layer under certain heating conditions in the process. In IG, the oxygen concentration in the degassing layer is low. It has a relatively low degree of defects, so the bond with copper is quite weak, so that metal impurities can be released relatively easily even at 300 ° C or below.
有高氧濃度的微缺陷捕獲銅的力量強，因此在低於300°C 時，此種再次釋放並不顯著，但是在約500°C時就容易了 〇 在EG中，當捕獲金屬雜質層是背面製作的缺陷層時 ’金屬雜質的再次釋放傾向於發生在相對低溫。當捕獲金 屬雜質層是背面多晶矽層時，再次釋放發生在高溫的加熱 中。 因此’即使當提供了除氣的機制，在除氣區域內所捕 獲的雜質’最好儘可能愈少量愈好。 發明槪沭 據此’车發明的目標是提供一種淸潔的方法和淸潔裝 置，可以從半導體基板移除雜質到λ面，以純化基板一 •产一 —_ ................ w ----------------------............—·.— -— I t//、 的內部。 (請先閱讀背面之注意事項再填寫本頁)Micro-defects with high oxygen concentration have a strong ability to capture copper, so this re-release is not significant at less than 300 ° C, but it is easy at about 500 ° C. In EG, when the metal impurity layer is captured When a defect layer is produced on the back side, the re-release of metallic impurities tends to occur at relatively low temperatures. When the trapped metal impurity layer is a back-side polycrystalline silicon layer, the release again occurs in high-temperature heating. Therefore, even when a degassing mechanism is provided, the amount of impurities captured in the degassing area is preferably as small as possible. According to the invention, the objective of the invention is to provide a cleaning method and cleaning device that can remove impurities from the semiconductor substrate to the λ plane to purify the substrate. ........ w ----------------------............— · .— -— I t //, inside. (Please read the notes on the back before filling this page)
、1T 線、 本紙張尺度適用中國國家標隼（CNS > Λ4規格（21.0X 297公釐） 經濟部中央樣準扃貝工消费合作社印装 A7 _ B7 五、發明説明（1) 爲了達到此目標，本發明提出一種淸潔方法，包含步 驟有： . 將含有一種固體材料的固體淸潔物，與在其內部含有 金屬雜質的半導體基板表面接觸；該金屬雜質相對於該固 體淸潔物之溶解度，大於該金屬雜質相對於該半導體的溶 解度；而且 在接觸的狀態中，將半導體基板和固態淸潔物，於半 導體基板不會與固體淸潔物反應的高溫範圍之中加熱，藉 此可從半導體基板的內部移除金屬雜質。 傳雜_層於對半導體有不良影響之重金屬汙染的半導體 基板淸潔方法，只對半導體基板的表面淸潔有效果，然而 本發明使得有可能去淸潔半導體基板的內部。 此外，即使在半導體基板中有一強的除氣機制，在其 除氣區域中，有害的金靥如銅和鎳可以被沖走。 本發明可應用在製造元件的步驟中，藉此可事先保住 基板的除氣能力，以免達到它的飽和狀態，而且可以防止 被除氣處捕獲的重金屬，.在後續的相對低溫步驟中再次釋 放出來，及防止汙染元件作用區域的表面區域。結果，基 板的除氣能力可以總是顯示在其最大値。 與傳統的基板淸潔方法不同的是’本發明的方法可完 美地免於產生有害氣體和廢液等等，且與環境污染問題毫 無關係。本發明的方法使得例如使用超純水和排出氣體的 處理’完全不必要’而這些對於傳統的淸潔處理是不可缺 少的，而且甚至是在一般大氣環境中實行，亦可有效地淸 __6__ 本紙伕尺度適用中國國家標準（CNS ) Λ4現格（2丨〇><297公釐） . <--------.訂------1 (請先閱讀背面之注意事項再填寫本頁) A7 A7 經濟部中央橾隼局貝工消費合作社印裝 五、發明説明（ 潔基板。因此，此方法可以 在本發明的方法ψ 1個簡單的裝置來實行。 物的材料，例如高純度的;=材料只有用做固體淸潔 I故帶來約酿的_7點片’同時誠溫度大約爲500 胤式簡沭 圖-是槪略地以圖說明，—個用來實行本發明方法的 淸潔裝置的實例。 圖二是-個用在圖一淸潔裝置中之真空夾盤的剖面圖 ’其可分離地抓住半導體基板。 圖二是槪略地以圖說明，在兩鋁片中夾住矽基板，以 從兩面淸潔其內部的實例。 較佳實施例敘沭 在本發明的淸潔方法中’ 一個含有特定固體材料的固 體淸潔物’帶去和內部有金屬雜質的半導體基板的表面接 觸’且在接觸的狀態下，半導體基板與固體淸潔物加熱到 特定的高溫，藉此從半導體基板的內部移除金屬雜質0 與固體淸潔物捽觸中加熱 要淸潔的基板，可以是生產基板製程中的任一站，或 是製造元件的製程中任一站中的基板，而沒有任何特別的 限制5本發明可應用在任何一個內部被金屬雜質汙染的半 導體基板上。更特定而言，它可以應用在元件製造於基板 --------^--<-------訂------气 1 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公浼） 經濟部中央橾隼局員工消費合作社印犁 A7 B7 五、發明説明（$ ) 的元件作用區域之前、在製造的過程中、和製造之後的任 何可得到的基板上。在半導體基板裡，除氣機制，例如IG 或EG，可能尙未形成或是可能已經形成。 可以矽基板爲半導體基板來舉例。在基板的厚度上也 沒有特別的限制。本發明當然可應用在經常使用的基板， 厚度在500到8〇Ομιη。 可經由本發明方法而移除的金屬雜質，在加熱溫度的 條件下，其在半導體基板上擴散的擴散係數至少爲10·7平 方公分/秒。典型的金屬雜質包括了銅、鎳和鐵。這些金屬 雜質在矽基板上，顯示出上述之擴散係數時的溫度，也就 是較佳的加熱溫度，可以在30(TC或以上，在400°C或以上 更好；而對於銅更好的溫度在450°C或以上；對於鎳的溫 度在50(TC或以上，550°C或以上更好；對於鐵的溫度在 5.50°C或以上，600°C或以上更好。舉例來說，因爲一個典 型的半導體基板是約600μηι厚，擴散係數至少在10·7率方 公分/秒的金屬雜質，在加熱處理中從基板擴散出來要數十 分鐘3 用作固體淸潔物之固體材料，需要在加熱溫度中爲固 體’在此溫度下不會與半導體基板產生反應，而且要符合 被移除的金屬雜質之相對於該固體淸潔物的溶解度要夠大 的要求，最好是明顯地大很多，特定而言，比該金屬雜質 之相對於該半導體的溶解度大1〇3倍或更多。因爲在圊體 溶解度上的差異，金屬雜質迅速地從半導體基板內部移動 進入固體淸潔物中’只要在固體淸潔物上的任何自然氧化 ______8 ___^-- 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210'乂 297公兹） (請先閱讀背面之注意事項再填寫本頁), 1T line, This paper size is applicable to Chinese national standard (CNS > Λ4 specification (21.0X 297 mm)) Central sample of the Ministry of Economic Affairs Printed by Shellfisher Consumer Cooperative A7 _ B7 V. Description of the invention (1) In order to achieve this Objective, the present invention provides a cleaning method, comprising the steps of: contacting a solid cleaning material containing a solid material with a surface of a semiconductor substrate containing a metal impurity inside the metal cleaning material; The solubility is greater than the solubility of the metal impurity with respect to the semiconductor; and in the contact state, the semiconductor substrate and the solid substrate are heated in a high temperature range where the semiconductor substrate does not react with the solid substrate, thereby enabling The metal impurities are removed from the inside of the semiconductor substrate. The impurity transfer layer is a method for cleaning a semiconductor substrate that is contaminated by heavy metals that has an adverse effect on the semiconductor, and is only effective for cleaning the surface of the semiconductor substrate. However, the invention makes it possible to remove The inside of the semiconductor substrate. In addition, even in a semiconductor substrate, there is a strong outgassing mechanism. Gold tincture such as copper and nickel can be washed away. The present invention can be applied in the step of manufacturing components, whereby the outgassing ability of the substrate can be maintained in advance, so as not to reach its saturation state, and it can prevent the Heavy metals are released again in the subsequent relatively low temperature steps, and prevent the surface area of the area where the element is affected. As a result, the outgassing capacity of the substrate can always be displayed at its maximum. Unlike traditional substrate cleaning methods, the difference is 'The method of the present invention is perfectly free from the generation of harmful gases, waste liquids, etc., and has nothing to do with environmental pollution issues. The method of the present invention makes treatment such as the use of ultrapure water and exhaust gases' completely unnecessary' and these The traditional cleaning treatment is indispensable, and even implemented in the general atmospheric environment, it can also effectively __6__ This paper's scale is applicable to the Chinese National Standard (CNS) Λ4 grid (2 丨 〇 > < 297 Mm). ≪ --------. Order ------ 1 (Please read the notes on the back before filling out this page) A7 A7 Printed by the Shellfish Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs2. Description of the invention (Clean the substrate. Therefore, this method can be implemented in the method ψ 1 simple device of the present invention. Material of the material, such as high purity; _7-point film 'At the same time, the temperature is about 500. The simplified diagram-is schematically illustrated, an example of a cleaning device used to implement the method of the present invention. Figure 2 is-used in Figure 1 A cross-sectional view of a vacuum chuck in a cleaning device, which detachably grasps a semiconductor substrate. Figure 2 is a diagrammatic illustration of a silicon substrate sandwiched between two aluminum sheets to clean the inside from both sides. In a preferred embodiment, in the cleaning method of the present invention, 'a solid cleaning material containing a specific solid material is brought out of contact with the surface of a semiconductor substrate having metallic impurities inside', and in a state where the semiconductor substrate is in contact with The solid substrate is heated to a specific high temperature to remove metal impurities from the inside of the semiconductor substrate. The substrate to be cleaned is heated in contact with the solid substrate. It can be any station in the substrate production process, or Manufacturing element The substrate in any station in the manufacturing process without any particular limitation 5 The present invention can be applied to any semiconductor substrate contaminated with metal impurities inside. More specifically, it can be applied to components manufactured on substrates -------- ^-< --------- Order ------ Gas 1 (Please read the precautions on the back first (Please fill in this page again) This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 gong) The Central Government Bureau of the Ministry of Economic Affairs Employees' Cooperatives Cooperative A7 B7 V. The component area of the invention description ($), before manufacturing Process, and any available substrate after manufacturing. In semiconductor substrates, degassing mechanisms, such as IG or EG, may not be formed or may have been formed. For example, a silicon substrate can be used as a semiconductor substrate. There is no particular limitation on the thickness of the substrate. The present invention can of course be applied to a substrate that is frequently used, and has a thickness of 500 to 800 μm. The metal impurities that can be removed by the method of the present invention have a diffusion coefficient of at least 10 · 7 cm 2 / s under the condition of heating temperature. Typical metal impurities include copper, nickel, and iron. The temperature at which these metal impurities show the above-mentioned diffusion coefficient on the silicon substrate, that is, the preferred heating temperature, may be 30 ° C or more, and preferably 400 ° C or more; and a better temperature for copper At 450 ° C or above; for nickel at 50 ° C or above, 550 ° C or above is better; for iron at 5.50 ° C or above, 600 ° C or above is better. For example, because A typical semiconductor substrate is a metal impurity with a thickness of about 600 μηι and a diffusion coefficient of at least 10 · 7 cm³ / sec. It will diffuse out of the substrate during heat treatment for several tens of minutes. 3 A solid material used as a solid detergent requires Solid in heating temperature 'At this temperature, it will not react with the semiconductor substrate, and it must meet the requirements for the solubility of the removed metal impurities with respect to the solid detergent to be sufficiently large, preferably significantly larger. Many, in particular, 103 times or more greater than the solubility of the metal impurity with respect to the semiconductor. Because of the difference in the solubility of the carcass, the metal impurity quickly moves from the inside of the semiconductor substrate into the solid In the cleansing, as long as any natural oxidation on the solid cleansing is ______8 ___ ^-This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210 '公 297mm) (Please read the precautions on the back before (Fill in this page)
1T 趣濟部中央棣隼局貝工消費合作社印製 Λ7 --------------1________ 友、發明説明（l ) 物薄膜沒有長厚即可。 像這樣的固體淸潔物的材料，包括有鋁、銀和鉻，例 如，在500°C時，銅在矽中的固態溶解度大約爲1〇15個原 子/立方公分（亦即50 ppb)，然而它在鋁中的固態溶解度 約爲5%，在銀中的固態溶解度約爲5%，在路中的固態溶 解度約500 ppm，這些是無法比較的大。相似地，在500X： 時，鎳和鐵在矽中的固態溶解度是非常小，然而它們在鋁 中的固態溶解度約有20〇 ppm，在銀和絡中的固態溶解度 也比在矽中的固態溶解度大得無法比較。 半導體基板和固體淸潔物在接觸時，加熱(或是熱處理 )的溫度和時間’可以根據固體淸潔物的種類、金屬雜質的 種類、半導體基板的種類、和加熱的環境氣氛來作適當地 選擇。特定而言，溫度的選擇是依照固體淸潔物不會與半 導體起反應、金屬雜質在半導體中以如前述夠高的速率擴 散、而且同時金屬雜質在固體淸潔物中有夠高的固體溶解 度。 當固體淸潔物爲鋁時，雖然可以使用純鋁，但最好使 用已加入〇.5到1.5%重量比之矽的鋁。 在使用純鋁的例子中，加熱的溫度範圍最好在300到 55〇°C。鋁和矽形成的共晶點在577°C,。鋁相對於矽的固態 溶解度，甚至是在共晶點之下，仍大約有。因此，假如 加熱溫度高於550°C，當加熱至一段長時間時’則有可能 鋁的固髒淸潔物會黏著在矽基板上，而且經過加熱之後， 從矽基板分離下來有困難。 C锖先閱讀背面之注意事項存填寫本頁) )11 本紙张尺度適用中國國家標準（CNS ) A4規格（2IOX297公龙）Printed by 1T Shellfish Consumer Cooperative of the Central Government Bureau of the Ministry of Interest, Λ7 -------------- 1________ Friends, Invention Description (l) The material film does not have to be thick. Materials for such solid detergents include aluminum, silver, and chromium. For example, at 500 ° C, the solid solubility of copper in silicon is approximately 1015 atoms / cm3 (that is, 50 ppb). However, its solid solubility in aluminum is about 5%, its solid solubility in silver is about 5%, and its solid solubility in road is about 500 ppm. These are incomparable. Similarly, at 500X: the solid solubility of nickel and iron in silicon is very small, but their solid solubility in aluminum is about 20 ppm, and the solid solubility in silver and iron is also higher than that in silicon. Solubility is too large to compare. The temperature and time of heating (or heat treatment) when the semiconductor substrate and the solid substrate are in contact can be appropriately determined according to the type of the solid substrate, the type of metal impurities, the type of the semiconductor substrate, and the heating ambient atmosphere. select. In particular, the temperature is selected in accordance with the fact that the solid detergent does not react with the semiconductor, the metal impurities diffuse in the semiconductor at a sufficiently high rate as described above, and at the same time the metal impurities have a sufficiently high solid solubility in the solid detergent . When the solid detergent is aluminum, although pure aluminum can be used, it is preferable to use aluminum to which silicon has been added in an amount of 0.5 to 1.5% by weight. In the case of using pure aluminum, the heating temperature range is preferably 300 to 55 ° C. The eutectic point of aluminum and silicon is 577 ° C. The solid solubility of aluminum relative to silicon is still approximately even below the eutectic point. Therefore, if the heating temperature is higher than 550 ° C, when it is heated for a long time, it is possible that aluminum solids and dirt will adhere to the silicon substrate, and after heating, it is difficult to separate from the silicon substrate. C 锖 Please read the notes on the back and fill in this page)) 11 This paper size is applicable to China National Standard (CNS) A4 specification (2IOX297 male dragon)
五、發明説明（7) 經濟部中央橾準局員工消費合作社印裝 使用上述添加矽的鋁，能夠在約600°C的高溫下處理 。因此，加熱的溫度範圍從300到600Ϊ.。處理溫度愈高 ，本發明所針對的純化作用愈有效。所以，使用此種添加 矽的鋁使得生產力更高，而且是有利的。 在選用銀爲固體淸潔物的例子中，加熱可達約6〇0到 800°C的溫度。甚至在約7〇〇3C的高溫下，銀不會和矽起反 應。溫度愈高，金屬雜質的擴散係數就愈大’而且在短時 間內的淸潔也就愈有效。雖然銀在約800°C時不會和矽起 反應，但加熱時間應控制在幾分鐘內(例如約5分鐘），因 爲某些不方便的現象有可能會發生，例如硼在某些微小元 件中擴散。 鉻的固體淸潔物適合用在當基板具有強的EG效果的 淸潔時。雖然鉻在矽中有相對校較高的擴散速率，但鉻在 利用EG作用的基板中擴散，會被它捕獲，而不能進入到 元件作用區域。在此，加熱最好是在一短時間內，大約從 600到800°C的溫度。 可以根據所使用的固體淸潔物種類和加熱溫度，適當 地擇定加熱的時間。通常約爲3到60分鐘。 組成固體淸潔物的材料’對於除了矽以外的雜質，儘 可能以高純度爲適合。商業可得的高純度產品，其含有不 同的金屬雜質，含量約爲1 PPm或以下，即相當符合這項 需求。即使銅、鎳等等含量超過1 PPm，也可期待一個合 理的淸潔效果。 只要能與半導體基板的表面做緊密的接觸，固體淸潔 10 ---------—-----ir------^ I (請先閲请.背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Λ4说格（2丨0x 297公势) 經濟部中央橾隼局貝工消费合作社印裝 Μ _Β7^________ 五、發明説明(:,、:名 物的形狀在理論上並沒有限制。以實用的觀點，它可以是 具有柔軟性的薄板、片材或是薄膜的形狀，特別是類似帶 狀的片材。類似片狀或是薄膜的固體淸潔物，其厚度可以 從約15到300μηι。特別是約ΙΟΟμιη的厚度，通常較容易 處理。 在半導體基板和固體淸潔物接觸加熱時的環境，並沒 有特別的限制。特定而言，加熱可在大氣中進行，或是如 氬或氮氣的鈍性氣體的氣氛中，也可以在真空中。在真空 中或鈍性氣體的氣氛中進行加熱，可以抑制自然氧化物薄 膜的成長，而且有縮短加熱時間的優點。在大氣中進行加 熱的優點是操作很簡單，而且裝置也不需要變得複雜。 當本發明的淸潔方法在大氣中進行，而且固體淸潔物 由鋁或鉻組成的情況下，原本存在它表面上的自然氧化物 薄膜會變得較厚，金屬雜質應該要通過這自然氧化物薄膜 才可被引出。據此，這樣的狀態中，應該在更高的溫度來 進行加熱。例如’當矽的半導體基板被鋁的固體淸潔物淸 潔過’無論是在大氣中或是在真空中，亦或是鈍性氣體的 氣氛中，加熱通常進行到4〇〇°C'或以上，因爲這層自然氧 化物薄膜經常已經在鋁的表面形成。在當半導體基板使用 由鉻組成的固體淸潔物做相似的淸潔情況下，加熱進行到 6〇〇°c或以上。在此溫度下’把金屬雜質從基板內部，經週 在接觸表面所產生的氧化物薄膜而引出的作用，對於本發 明而言太弱了而達不到好的效果。 甚至當由鋁或鉻組成的固體淸潔物，和半導體基板在 ____11 5张尺度適用中國國家標準（CNS ) Λ4規格（210X 297公筇_) " ----------V ——.——：——：1T------f'r (請先閱讀背面之注意事項再填寫本頁) 經濟部中央樣準局貝工消費合作社印裝 A7 B7 五、發明説明（1) 互相接觸加熱時，出現在固體淸潔物上的氧化物薄膜一般 可視爲妨礙金屬雜質的移動。然而，本發明者已發現一個 未預期的事實：雖然原因並不淸楚，金屬雜質可以迅速地 穿透如上所述的自然氧化物薄膜，而在鋁或鉻中被吸收， 而且它們移動的力量強到足夠引起釋放除氣處捕獲的銅。 所以，它們已達成了本發明。 半導體基板和固體淸潔物如前所述地互相接觸後加熱 ，使得在基板內部所捕獲的金屬雜質的量，有可能顯著地 降低，其不只是在有高氧含量’例如1·5 X 1013個原子/立 方公分的IG晶圓的基板’也包括進一步在背面形成多晶 矽薄膜的IG晶圓的基板。 俥用硫酵淸潔 在半導體基板和固體淸潔物於接觸中加熱的步驟之後 ，半導體基板最好進一步與高溫的硫酸接觸。在此使用硫 酸的淸潔中，在加熱中己經從除氣處中釋放出但尙未完全 遷移到固體淸潔物的金屬雜質，會遷移到硫酸中，使得內 部淸潔進一步進行。在此，即使某些銅已經從固體淸潔物 中擴散到矽，由除氣處所施加捕獲銅的力量是如此弱’以 致大部分的銅會遷移到硫酸中° 至於此硫酸，最好使用具有高純度的濃縮硫酸。濃縮 的硫酸相對於除了水以外的雜質而言，以具有99%或者 更高的純度爲適當。特別是金屬雜質的濃度以不超過1 ppm爲適當，不超過1 ppb更好： 12_____ 本紙張尺度適用中國國家標準（CNS ) Λ4規格< 2丨〇>< 297公势） (請先閲讀背面之注意事項再填寫本頁)V. Description of the invention (7) Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs of the People's Republic of China The silicon-added aluminum can be processed at a high temperature of about 600 ° C. Therefore, the heating temperature ranges from 300 to 600Ϊ. The higher the processing temperature, the more effective the purification effect targeted by the present invention. Therefore, the use of such silicon-added aluminum results in higher productivity and is advantageous. In the case of using silver as a solid detergent, heating can reach a temperature of about 600 to 800 ° C. Even at a high temperature of about 7000C, silver does not react with silicon. The higher the temperature, the greater the diffusion coefficient of metallic impurities' and the more effective the cleaning in a short time. Although silver does not react with silicon at about 800 ° C, the heating time should be controlled within a few minutes (for example, about 5 minutes), because some inconvenient phenomena may occur, such as boron in some small components Medium diffusion. The chromium solid detergent is suitable for use when the substrate has a strong EG effect. Although chromium has a relatively high diffusion rate in silicon, chromium diffuses in substrates that use EG and will be captured by it, and cannot enter the device's active area. Here, the heating is preferably performed at a temperature of about 600 to 800 ° C in a short period of time. The heating time can be appropriately selected according to the type of solid concrete used and the heating temperature. Usually about 3 to 60 minutes. The material constituting the solid detergent is suitable for impurities other than silicon as high purity as possible. Commercially available high-purity products that contain different metal impurities at levels of about 1 PPm or less are quite suitable for this need. Even if the content of copper, nickel, etc. exceeds 1 PPm, a reasonable cleaning effect can be expected. As long as it can make intimate contact with the surface of the semiconductor substrate, solid cleanliness 10 ---------------- ir ------ ^ I (Please read first. Please note on the back (Fill in this page again) This paper size applies the Chinese National Standard (CNS) Λ4 grid (2 丨 0x 297 public momentum) Printed by the Central Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives _Β7 ^ ________ V. Description of the invention (: ,,, : The shape of the famous thing is not theoretically limited. From a practical point of view, it can be a flexible sheet, sheet or film, especially a sheet-like sheet. A sheet-like or film-like solid The thickness of the cleaning material can be from about 15 to 300 μηι. Especially the thickness of about 100 μιη is usually easier to handle. There is no particular limitation on the environment when the semiconductor substrate and the solid cleaning material are in contact with the heating. In particular, heating It can be performed in the atmosphere, or in an inert gas atmosphere such as argon or nitrogen, or in a vacuum. Heating in a vacuum or an inert gas atmosphere can suppress the growth of natural oxide films, and The advantage of shortening the heating time. The advantage of heating in air is that the operation is simple, and the device does not need to be complicated. When the cleaning method of the present invention is performed in the atmosphere, and the solid cleaning material is composed of aluminum or chromium, it originally exists on its surface The natural oxide film on it will become thicker, and metal impurities should be drawn out through this natural oxide film. Accordingly, in such a state, heating should be performed at a higher temperature. For example, 'When silicon's The semiconductor substrate is cleaned with a solid aluminum substrate. 'Whether it is in the atmosphere, in a vacuum, or in an inert gas atmosphere, the heating is usually performed to 400 ° C or higher because this layer Natural oxide films are often already formed on the surface of aluminum. In the case where a semiconductor substrate is made of a similar cleaning material using chromium, the heating is performed to 600 ° C or more. At this temperature, the The effect of metal impurities drawn from the inside of the substrate and contacting the oxide film produced on the surface is too weak for the present invention to achieve a good effect. Even when composed of aluminum or chromium For solid concrete and semiconductor substrates, the Chinese National Standard (CNS) Λ4 specification (210X 297 public 筇 _) is applied to __11 5 sheets of scales. &Quot; ---------- V ——.———————— —: 1T ------ f'r (Please read the notes on the back before filling this page) Printed by the Central Samples Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed A7 B7 V. Description of the invention (1) When heating in contact with each other The oxide film appearing on solid concrete is generally regarded as hindering the movement of metal impurities. However, the inventors have discovered an unexpected fact: although the reason is not good, metal impurities can quickly penetrate as described above The natural oxide film described above is absorbed in aluminum or chromium, and the force of their movement is strong enough to cause release of the copper captured at the outgassing place. Therefore, they have reached the present invention. The semiconductor substrate and the solid substrate are heated after being in contact with each other as described above, so that the amount of metal impurities trapped inside the substrate may be significantly reduced, and it is not only in the presence of high oxygen content, such as 1 · 5 X 1013 The substrate of the IG wafer of one atom / cm3 also includes a substrate of an IG wafer in which a polycrystalline silicon thin film is further formed on the back surface.淸 Cleaning with Sulfur Fermentation After the step of heating the semiconductor substrate and the solid substrate in contact, the semiconductor substrate is preferably further contacted with high-temperature sulfuric acid. In the cleaning using sulfuric acid, metal impurities which have been released from the outgassing place during heating but have not completely migrated to the solid cleaning material will migrate to sulfuric acid, making the internal cleaning further. Here, even if some copper has diffused from the solid detergent to silicon, the force to capture the copper exerted by the outgassing space is so weak 'that most of the copper will migrate to sulfuric acid. As for this sulfuric acid, it is best to use High purity concentrated sulfuric acid. The concentrated sulfuric acid has a purity of 99% or more with respect to impurities other than water. In particular, the concentration of metal impurities is appropriate not to exceed 1 ppm, and it is better not to exceed 1 ppb: 12_____ This paper size applies Chinese National Standards (CNS) Λ4 specifications < 2 丨 〇 > < 297 public power) (please first (Read the notes on the back and fill out this page)
*1T 經濟部中央標隼局員工消費合作社印裝 A7 B7 五、發明説明（丨4 對於如何讓半導體基板與硫酸作接觸，並沒有特殊的 限制。在一般狀態下，半導體基板可事先用氫氟酸處理， 以移除自然氧化物薄膜，然後再浸入硫酸中。硫酸的溫度 可在200 C或以上而低於硫酸的沸點，最好是從250到300 °C β通常半導體基板在此溫度下，與硫酸接觸的時間爲3 到20分鐘。 淸潔裝置 至於有效率地實行上述淸潔方法的裝置，本發明提出 一種從半導體基板內部移除金屬雜質的半導體基板內部淸 潔裝置，其包含有： (Α) —個將固體材料組成的像帶狀的片材水平地延長和 展開的機構，該金屬雜質相對於該固體材料的溶解度，大 於該金屬雜質相對於該半導體的溶解度； (Β)—個在像帶狀的片材縱向上，可卸式地排放數個半 導體基板在像帶狀的片材上，而且與像帶狀的片材接觸的 俄稱， (C) —個將排放在像帶狀的片材上的半導體基板，壓向 像帶狀的片材的機構，以使得半導體基板的表面與像帶狀 的片材的表面做緊密的接觸：和 (D) —個將第一個和第二個像帶狀的片材與半導體基板 加熱的機構，而此時二者藉機構(C)保持互相緊密的接觸。 本發明亦提出一個，從半導體基板的內部移除金屬雜 質的半導體基板內部淸潔裝置，其包含有 13 (請先閲讀背面之注意事項再填寫本頁)* 1T Printed by A7 B7, Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs. 5. Description of the Invention (丨 4 There are no special restrictions on how to make semiconductor substrates in contact with sulfuric acid. In general, semiconductor substrates can be pretreated with hydrogen fluoride. Acid treatment to remove the natural oxide film, and then immersed in sulfuric acid. The temperature of sulfuric acid can be 200 C or above and lower than the boiling point of sulfuric acid, preferably from 250 to 300 ° C β. Generally semiconductor substrates at this temperature The contact time with sulfuric acid is 3 to 20 minutes. Cleaning device As for the device for efficiently performing the cleaning method described above, the present invention proposes a semiconductor substrate internal cleaning device for removing metal impurities from the inside of a semiconductor substrate. (A) a mechanism for horizontally extending and unrolling a strip-like sheet composed of a solid material, the solubility of the metal impurity relative to the solid material is greater than the solubility of the metal impurity relative to the semiconductor; (B) —Removably discharge several semiconductor substrates on the sheet-like sheet in the longitudinal direction of the sheet-like sheet, and connect them with the sheet-like sheet. (C) — a mechanism that presses a semiconductor substrate that is discharged onto a sheet-like sheet material against the sheet-like sheet material so that the surface of the semiconductor substrate and the surface of the sheet-like sheet material do Close contact: and (D)-a mechanism for heating the first and second strip-like sheets and the semiconductor substrate, and at this time the two are kept in close contact with each other by the mechanism (C). The present invention also Propose a semiconductor substrate internal cleaning device that removes metal impurities from the inside of the semiconductor substrate, which contains 13 (Please read the precautions on the back before filling this page)
,1T 本紙張尺度遍用中國國家標準（CNS ) Λ4規格（210X297公t ) Λ7 B7 五、發明説明（[1 -) (A) —個將固體材料組成的像帶狀的片材水平地延長和 展開的機構，該金屬雜質相對於該固體材料的溶解度’大 於該金屬雜質相對於該半導體的溶解度； • ' (B)—個在像帶狀的片材縱向上，可卸式地排放數個半 導體基板在第一個像帶狀的片材上，而且與第一個像帶狀 的片材接觸的機構； (E) —個將固體材料組成的第二個像帶狀的片材，在 數個半導體基板上水平地延長和展開的機構，該金屬雜質 相對於本步驟所用之該固體材料的溶解度，大於該金屬雜 質相對於該半導體的溶解度： (C) 一個加壓介於第一與第二個像帶狀的片材之間的 半導體基板之機構’使得半導體基板的表面與第一和第二 個像帶狀的片材的表面做緊密的接觸；和 (D) —個將第一個和第二個像帶狀的片材與半導體基 板加熱的機構，而此時基板與片材都藉著機構(C)保持互相 緊密的接觸。 本發明的裝置將參考圖一作特定地描述。 經濟部中央標準局員工消費合作社印裝 (請先閱讀背面之注意事項再填窍本頁) 纏繞在滾輪1上的第一個鋁片2，由滾輪1捲出，通 過導向滾輪3和4而纏繞在滾輪5上。它在導向滾輪3、4 的上方被水平地延展開來^在這個鋁片的水平部份上，經 由顯示在圖二的真空夾盤之機構，多個半導體基板以規律 的間隔排放在鋁片的縱向上。每個夾盤都是由石英所製成 ，它的外圍13 —面是彎的，而另一面的中心提供一管子 14，整體是一個凸緣的形狀。管子14與一個真空機構(未 本紙張尺度適用中國國家標隼（CNS ) Λ4規格（2丨OX 297公疫） 經濟部中央標隼局員工消费合作社印製 A7 B7 五、發明説明（丨y 顯示出來)相接，在夾盤與半導體基板6之間形成的空間15 帶成真空’所以基板6被固定住。當內部導入一低真空時 ，基板6就被放下。此真空夾盤是被例如機械手臂16所握 住，可以很自由地移動到想要的地方。 同時，纏繞在滾輪8上的第二個鋁片7，由滾輪8捲 _出，經過導向滾輪9和1〇而纏繞在滾輪11上。第二個鋁 片7同樣在導向滾輪9、1〇間保持水平。第二個鋁片7如 此被水平地延展開，使得該片材7和每一個半導體基板的 頂端接觸，或是到達在片材7和每一個半導體基板頂端之 間留下的細小空隙的位置。半導體基板被排放在第一個鋁 片上之後，第二個鋁片可以被移到這一位置上。或者是說 ，第一個鋁片和第二個鋁片在一個給定的距離中水平地配 置之後，半導體基板經由真空夾盤機構在它們之間可卸式 地排放在第一個鋁片上。在此，半導體基板僅由於重力而 與第一個鋁片接觸到，而不會和第二個鋁片接觸到，或者 頂多是輕微地碰觸到。或者是說，在二個鋁片之間的距離 設定成可調整的，所以當半導體基材被排放時，保持夠寬 的距離，使半導體基板容易排放，而且在半導體基板被排 放後，此一寬度則變窄，使得二個鋁片幾乎互相接觸在一 起。 接下來，第一個鋁片、半導體基板和~第二個鋁片像三 明治一樣，由在上、下方的施壓機構12加壓而夾在一起， 因此個別接觸的表面變成緊密的接觸。 在此緊密的接觸狀態下，第一和第二個鋁片、以及半 ___15_ 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨OX297公釐） ： (請先閲讀背面之注意事項再填寫本f), 1T This paper uses the Chinese National Standard (CNS) Λ4 specification (210X297g t) Λ7 B7 V. Description of the invention ([1-) (A) — a strip-shaped sheet made of solid material is horizontally extended And the unfolded mechanism, the solubility of the metal impurity with respect to the solid material is greater than the solubility of the metal impurity with respect to the semiconductor; • (B) —a number of detachable discharges in the longitudinal direction of the sheet-like sheet A semiconductor substrate on the first sheet-like sheet material, and a mechanism which is in contact with the first sheet-like sheet material; (E) a second sheet-like sheet material composed of a solid material, In the mechanism of horizontally extending and unfolding on several semiconductor substrates, the solubility of the metal impurity with respect to the solid material used in this step is greater than the solubility of the metal impurity with respect to the semiconductor: (C) a pressurized intermediate The mechanism of the semiconductor substrate with the second sheet-like sheet material 'makes the surface of the semiconductor substrate in close contact with the surfaces of the first and second sheet-like sheet materials; and (D) — a The first and second ones are band-like Means heating the material and the semiconductor substrate, but this time both the sheet substrate by means (C) held in close contact with each other. The device of the present invention will be specifically described with reference to FIG. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The first aluminum sheet 2 wound on the roller 1 is rolled out by the roller 1, and is guided by the rollers 3 and 4. It is wound on the roller 5. It is extended horizontally above the guide rollers 3, 4 ^ On the horizontal part of this aluminum sheet, through the mechanism of the vacuum chuck shown in Fig. 2, a plurality of semiconductor substrates are discharged at regular intervals on the aluminum sheet Vertical. Each chuck is made of quartz. Its outer surface 13 is curved, and the center of the other surface provides a tube 14, which is a flange in its entirety. Tube 14 and a vacuum mechanism (not applicable to the Chinese paper standard (CNS) Λ4 specification (2 丨 OX 297 public epidemic)) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (丨 y show (Out)), the space 15 formed between the chuck and the semiconductor substrate 6 is brought into a vacuum, so the substrate 6 is fixed. When a low vacuum is introduced inside, the substrate 6 is put down. This vacuum chuck is, for example, The robot arm 16 holds it and can move freely to the desired place. At the same time, the second aluminum sheet 7 wound on the roller 8 is rolled out by the roller 8 and wound around the guide rollers 9 and 10. On the roller 11. The second aluminum sheet 7 is also kept horizontal between the guide rollers 9 and 10. The second aluminum sheet 7 is extended horizontally so that the sheet 7 is in contact with the top of each semiconductor substrate, or Is to reach the position of the small gap left between the sheet 7 and the top of each semiconductor substrate. After the semiconductor substrate is discharged on the first aluminum sheet, the second aluminum sheet can be moved to this position. Or Said the first aluminum sheet and After the two aluminum wafers are arranged horizontally in a given distance, the semiconductor substrate is detachably discharged on the first aluminum wafer between them via a vacuum chuck mechanism. Here, the semiconductor substrate is connected with the first aluminum wafer only by gravity. One aluminum sheet is in contact with the second aluminum sheet, or at least slightly touched. Or that is, the distance between the two aluminum sheets is set to be adjustable, so when When the semiconductor substrate is discharged, keep a wide enough distance to make the semiconductor substrate easy to discharge, and after the semiconductor substrate is discharged, this width becomes narrower, so that the two aluminum sheets almost touch each other. Next, the first This aluminum sheet, the semiconductor substrate and the second aluminum sheet are sandwiched together and pressed together by the pressure mechanism 12 above and below, so that the individual contacting surfaces become in close contact. Here in a close contact state Next, the first and second aluminum sheets, and half ___15_ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 OX297 mm): (Please read the precautions on the back before filling in this f)
*1T A7 B7 , 五、發明説明（[>) 導體基板，經由一個加熱機構（未顯示出來）來加熱。關於 此加熱機構，在其上邊和下邊使用了例如電阻加熱的組件 〇 適合於此裝置的鋁片，每個的厚度約從20到Ι50μιη 〇 經過指定的加熱時間，在上、下方的施壓機構6分別 向上、向下打開，且第二個鋁片7從半導體基板上分開。 加熱淸潔因此完成之後，半導體基板則由真空夾盤從第一 個鋁片上舉起而移到外面。然後，運出的滾輪1和8及纏 繞的滾輪5和11運轉，則第一和第二個鋁片上用過的部份 在滾輪5、11中捲起，鋁片新的部份就移動到二個個別的 導向滾輪之間的範圍內》隨後，重複相似的淸潔處理。用 此方法，本發明的淸潔方法可以連續地重複進行。 雖然在上述的裝置中，第一和第二個鋁片是放置爲水 平的，但設置的方法並沒有限制。其他的排列方式也是可 以的，只要半導體基板可以在二個鋁片中固定即可。 經濟部中央標隼局負工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 只在背面處理時，第二個鋁片是不必要的。在此狀態 下，半導體基板的不處理面，最好保持溫暖，例如，用一 個塞以石英棉的石英製實驗皿蓋住，做爲絕熱之用。 當使用一相對爲厚的片材，如厚度約爲200.um的固 體淸潔物，可以是在直徑上與基板實質一>案大小的圓形片 材，此一圓形的片材可用真空夾盤放在加熱平板上。然後 矽基扳放在圓形片材上。相似地，另一個相同大小的_形 鋁片夾放在另一個加熱平板上，然後再放到矽基板的另一 A. ___ 16 張尺度適用中國國家標準（CNS ) Λ4規格（2丨0X297公f ) ： ~ 經濟部中央標準局貝工消费合作社印聚 A7 ____B7___ 五、發明説明（/+) 面上。所以，矽基板可以固定在這二片圓形的鋁片間而被 處理。此裝置的運作，使得圓形鋁片的移動，和被夾在前 述鋁片中的基板加熱，重複地操作。 應用件 本發明可應用在任何有由於金屬雜質汙染可能性的階 段，例如在準備晶圓要製成半導體基板的步驟中、在製作 IG或EG除氣處的步驟中、在製造元件的步驟中、以及元 件製造之後。當應用在製作除氣處的步驟中，和在熱氧化 、熱擴散、離子植入、乾式蝕刻及其他等等這些經常發生 汙染的步驟時，基板在元件製造的步驟中展現相當好的除 氣能力。 節例 本發明將經由舉例在下面更仔細地插述，但本發明並 沒有受限於那些範例。 在接下來的敘述中，關於矽基板的氧濃度，”低氧濃度 ”是指氧濃度約在1·2χ1018個原子/立方公分，”高氧濃度” 是指氧濃度約在l.klO18個原子/立方公分。 樣本某板 ' 作爲實例中和參考實例中要淸潔的基板樣本，準備了 下列幾種矽晶圓，其中每一個都具有除氣襃。 (1)高氧濃度HI晶圓和低氧濃度HI晶圓：p型（1〇〇)和 ______17__ 本紙張尺度適中國國家樣举（CNsTm规格（2丨OX2Q7公釐Ί ' " (請先閱讀背面之注意事項再填寫本頁)* 1T A7 B7, V. Description of the invention ([>) The conductor substrate is heated by a heating mechanism (not shown). Regarding this heating mechanism, components such as resistance heating are used on the upper and lower sides. Aluminum sheets suitable for this device, each having a thickness of about 20 to 150 μm. After a specified heating time, the upper and lower pressure mechanisms 6 is opened upward and downward respectively, and the second aluminum sheet 7 is separated from the semiconductor substrate. After the heating process is completed, the semiconductor substrate is lifted from the first aluminum wafer by a vacuum chuck and moved to the outside. Then, the rolled out rollers 1 and 8 and the wound rollers 5 and 11 are operated, and the used parts of the first and second aluminum sheets are rolled up in the rollers 5 and 11, and the new parts of the aluminum sheet are moved to Within the range between the two individual guide rollers> Then, a similar cleaning process is repeated. With this method, the cleaning method of the present invention can be continuously repeated. Although in the above-mentioned device, the first and second aluminum pieces are placed horizontally, the method of setting is not limited. Other arrangements are also possible, as long as the semiconductor substrate can be fixed in two aluminum sheets. Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives (please read the precautions on the back before filling out this page). The second aluminum sheet is unnecessary when processing on the back only. In this state, it is best to keep the untreated surface of the semiconductor substrate warm. For example, cover it with a quartz tester stuffed with quartz wool for thermal insulation. When using a relatively thick sheet, such as a solid concrete with a thickness of about 200.um, it can be a circular sheet with a size substantially equal to that of the substrate in diameter. This circular sheet can be used. The vacuum chuck is placed on a heated plate. The silicon substrate is then placed on a circular sheet. Similarly, another _-shaped aluminum sheet of the same size is placed on another heating plate, and then placed on another A of the silicon substrate. ___ 16 scales are applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 0X297) f): ~ A7 ____B7___, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs. 5. Description of Invention (/ +). Therefore, the silicon substrate can be fixed between these two circular aluminum pieces and processed. The operation of this device causes the movement of the circular aluminum sheet and the heating of the substrate sandwiched in the aforementioned aluminum sheet to repeat the operation. Applicability The present invention can be applied to any stage where there is a possibility of contamination due to metal impurities, for example, in a step of preparing a wafer to be made into a semiconductor substrate, in a step of producing IG or EG degassing place, in a step of manufacturing a component And after component manufacturing. When applied in the steps of making outgassing, and in the steps of frequent contamination such as thermal oxidation, thermal diffusion, ion implantation, dry etching and other, etc., the substrate exhibits quite good outgassing in the step of component manufacturing ability. Sections The present invention will be more carefully inserted below by way of examples, but the present invention is not limited to those examples. In the following description, regarding the oxygen concentration of the silicon substrate, “low oxygen concentration” means that the oxygen concentration is about 1.2 × 1018 atoms / cm 3, and “high oxygen concentration” means that the oxygen concentration is about 1.klO18 atoms. / Cubic centimeter. Sample board 'As a sample of the substrate to be cleaned in the example and the reference example, the following silicon wafers were prepared, each of which has a degassing device. (1) High Oxygen Concentration HI Wafer and Low Oxygen Concentration HI Wafer: p-type (100) and ______17__ This paper is suitable for China's national example (CNsTm specification (2 丨 OX2Q7 mmΊ '" (Please (Read the notes on the back before filling out this page)
經濟部中央標準局員工消費合作社印製 A7 __B7 五、發明説明（if ) 約10 Ω cm的矽晶圓，具有IG結構和具有約650.um的厚 度，在1200°C氫氣氣氛中加熱形成。 (2) 高氧濃度BSP晶圓：ρ型（100)和約10 Ω cm的矽晶 圓，厚度約650μπι的，在背面具有一多晶矽薄膜作用如同 EG機制。多晶矽薄膜是經由化學氣相沉積法從單體矽烷所 形成的。 (3) 高氧濃度HI+BSP晶圓：高氧濃度HI晶圓經由在背 面的多晶矽薄膜具有提高的除氣能力。 爲何使用P型矽作爲矽晶圓的理由是：在傳統的表面 淸潔過程中，已知作爲汙染物的銅在P型表面上要移除， 比銅在η型矽表面上要困難。 接下來，每一個具有除氣作用的晶圓，浸入一個添加 了 64Cii的氫氟酸緩衝溶液中(NHUF+HF)做吸附處理，使得 基板表面64Cu的平均濃度有lxlO13個原子/平方公分。如 此處理過的每一個晶圓，然後在氬氣的氣氛中，以900°C 加熱30分鐘，以使64Cu擴散進入基板。因此，可得到下 面實例一到四以及參考實例中的基板樣本晶圓。 放射能的量測可顯示出存在這些基板樣本內部中， 64Cu接下來的數童和其分佈狀態。 已進入內部而標示64Cu的銅，每平方公分的平均量 ，在所有的基板中決定大約爲2xl013個原¥/平方公分。因 爲晶圓大約650μπι厚，在基板中標示爲64Cu的銅的平均濃 度約爲3xl014個原子/立方公分。 沿著基板的深度來量測64Cu濃度的分佈，發現了下述 _ 18______ 本紙張尺度適州中國國家標準（CNS ) Λ4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局負工消費合作社印製 A7 _B7_ 五 '發明説明（//") -在高氧濃度的HI基板中，向內擴散的64Cu的總量 約有90%在IG區域中被捕獲，而靠近表面的元件作用區域 只含有微少分量的64〇ιι。 -在高氧濃度的BSP基板中’從它的背面算起3μηι 的深度之中，向內擴散的64Cu的總量約有50%被捕獲，而 且表面作用區域的64Cu濃度沒有減少很多，顯示在表面上 的除氣效果爲弱。 -在HI+BSP基板中，向內擴散的64Cu的總量約有 90%在IG區域被捕獲，所剩下的主要是在背面附近被捕獲 ，而在靠近表面的作用層中’ 64Cu很少偵測到，顯示除氣 作用很有效。 淸潔能力的評量 對銅的淸潔能力是用下面的方法來評量。首先，標示 爲64Cu的銅（半衰期：12.8小時）(在此之後簡單標記爲 ”64Cu”），在900°C、30分鐘內，擴散進入基板樣本內。已 經進入基板內部的64Cu ’每1平方公分的平均量(A)，是由 其放射能的量測來決定。其次，因此被64Cu污染的基板， 每個接受接觸加熱和/或高溫硫酸處理的固體淸潔，然後殘 留在基板中的MCu，每1平方公分的平均k(B)，由其放射 能的量測來決定。計算淸潔處理前64Cu數量的百分比，意 即銅的存留率B/A (¼)，以指出對內部汙染金屬的淸潔能力 〇 _19 本‘張尺度適用國家&準（CNS ) A4規^( 210X 297公鏟] ' (請先閲讀背面之注意事項再填寫本頁)A7 __B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (if) A silicon wafer of about 10 Ω cm has an IG structure and a thickness of about 650.um. It is formed by heating in a hydrogen atmosphere at 1200 ° C. (2) BSP wafer with high oxygen concentration: ρ-type (100) and silicon wafer of about 10 Ω cm, with a thickness of about 650 μm. It has a polycrystalline silicon film on the back, which acts like the EG mechanism. Polycrystalline silicon films are formed from monomeric silanes by chemical vapor deposition. (3) High oxygen concentration HI + BSP wafer: The high oxygen concentration HI wafer has an improved outgassing ability through a polycrystalline silicon film on the backside. The reason why P-type silicon is used as a silicon wafer is that in the traditional surface cleaning process, copper, which is known as a contaminant, is more difficult to remove on the P-type surface than copper on the n-type silicon surface. Next, each wafer with degassing effect was immersed in a hydrofluoric acid buffer solution (NHUF + HF) added with 64Cii for adsorption treatment, so that the average concentration of 64Cu on the surface of the substrate was 1 × 10 13 atoms / cm 2. Each wafer thus processed was then heated at 900 ° C for 30 minutes in an argon atmosphere to diffuse 64Cu into the substrate. Therefore, the substrate sample wafers in the following examples 1 to 4 and the reference example can be obtained. Radiometric measurements can show the next few children of 64Cu and their distribution in these substrate samples. The average amount of copper per square centimeter that has entered the interior and is marked with 64Cu is determined to be about 2xl013 original ¥ / cm2 in all substrates. Because the wafer is approximately 650 μm thick, the average concentration of copper labeled 64Cu in the substrate is approximately 3x1014 atoms / cm3. Measured the distribution of 64Cu concentration along the depth of the substrate, and found the following _ 18______ This paper size is suitable for China National Standard (CNS) Λ4 specification (210X297 mm) (Please read the precautions on the back before filling this page) The A7 _B7_ five 'invention description printed by the Central Laboratories of the Ministry of Economic Affairs and Consumer Cooperatives (// ")-In a high oxygen concentration HI substrate, about 90% of the total 64Cu diffused in the IG area It is captured, while the area of the component near the surface contains only a small amount of 64 ιι. -In a BSP substrate with a high oxygen concentration, within a depth of 3 μm from its backside, about 50% of the total 64Cu diffused inward was captured, and the 64Cu concentration in the surface-active region did not decrease much, as shown in The outgassing effect on the surface is weak. -In the HI + BSP substrate, about 90% of the total inwardly diffused 64Cu is captured in the IG region, and the rest is mainly captured near the back surface, while in the active layer near the surface, '64Cu is rarely Detected to show that outgassing is effective. Evaluation of cleaning ability The cleaning ability of copper is evaluated using the following method. First, copper labeled with 64Cu (half-life: 12.8 hours) (hereafter simply labeled as "64Cu") diffused into the substrate sample at 900 ° C for 30 minutes. The average amount (A) of 64Cu 'per square centimeter that has entered the substrate is determined by the measurement of its radiation energy. Secondly, each of the substrates contaminated with 64Cu is subjected to contact heating and / or high-temperature sulfuric acid treatment, and the MCu remaining in the substrate is an average k (B) per square centimeter. To determine. Calculate the percentage of the amount of 64Cu before the cleaning process, which means the copper retention rate B / A (¼), to indicate the cleaning ability for internal contaminated metals. _19 This standard is applicable to the national & standard (CNS) A4 regulations. ^ (210X 297 male shovel) '(Please read the precautions on the back before filling this page)
.1T 經濟部中央標準局貝工消费合作社印聚 A7 B7 五、發明説明（/) 對鎳的淸潔能力，如銅的例子，用相同的方法來評量 ，除了以57Ni (半衰期：36小時)來代替64Cu。標示爲57Ni 的鎳，在此之後簡單稱爲”57Ni”》 實例一 (銅的移除；固體淸潔物：加了 0.5%矽的鋁片） 關於要淸潔的基板，高氧濃度HI晶圓和高氧濃度 HI+BSP晶圓，其中64Cu如上所述的做熱擴散，被選擇作 爲具有最強除氣作用的樣本。 關於固體淸潔物，特別準備200μηι厚的高純度鋁，其 含有0.5%的矽而低於O.lppm的銅，且從片材上切下比晶 圓直徑梢大一點的圓盤。圓盤的表面用稀釋的鹽酸淸潔過 ，然後用超純水洗滌，接著乾燥。由此所穫得的鋁盤，貯 存在氮氣的氣氛中，直到要用作樣本爲止。 如圖三所示，在加熱器21上提供一個具有接合處22 供溫度控制的高純度碳化矽圓盤23，並加熱到530°C。在 此圓盤上，放上前面所準備的鋁盤24 »要淸潔的基板25 的鏡面朝上地叠上去，而且在這基板上面疊上第二個鋁盤 26。進一步叠上一個厚5mm的高純度碳化矽圓盤27，做 爲一個重量，以使鋁盤24和26分別與矽基板的底面和上 表面緊密的接觸。此碳化矽圓盤用石英棉(覆蓋住，以防熱 散失。 在此安置好的狀態中，基板和鋁盤在530°C加熱40分 鐘。加熱之後，在基板25中殘留64Cu的數量、在上方鋁 20 本紙涞尺度適用中國國家標孪（CNS ) Α4规格（2丨0X297公釐） (請先閲讀背面之注意事項再填寫本ί ).1T Printed Poly A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of Invention (/) The cleaning ability of nickel, such as the example of copper, is evaluated in the same way, except that it is 57Ni (half-life: 36 hours) ) Instead of 64Cu. Nickel marked 57Ni, hereafter referred to simply as "57Ni" "Example 1 (removal of copper; solid cleaning: aluminum sheet with 0.5% silicon) About the substrate to be cleaned, high oxygen concentration HI crystals Round and high oxygen concentration HI + BSP wafers, of which 64Cu was thermally diffused as described above, were selected as the sample with the strongest outgassing effect. Regarding the solid concrete, a 200 µm thick high-purity aluminum was prepared, which contained 0.5% silicon and less than 0.1 ppm copper, and a disc larger than the diameter of the crystal circle was cut from the sheet. The surface of the disc was rinsed with diluted hydrochloric acid, then washed with ultrapure water, and then dried. The aluminum pan thus obtained was stored in a nitrogen atmosphere until it was used as a sample. As shown in FIG. 3, a high-purity silicon carbide disk 23 having a joint 22 for temperature control is provided on the heater 21 and heated to 530 ° C. On this disk, put the aluminum plate 24 prepared previously »The substrate 25 to be cleaned is stacked with the mirror surface facing up, and a second aluminum plate 26 is stacked on the substrate. A 5 mm high-purity silicon carbide disk 27 was further stacked as a weight so that the aluminum disks 24 and 26 were in close contact with the bottom surface and the top surface of the silicon substrate, respectively. This silicon carbide disc is covered with quartz wool (to prevent heat loss. In this installed state, the substrate and the aluminum disc are heated at 530 ° C for 40 minutes. After heating, the amount of 64Cu remaining in the substrate 25 is above. Aluminium 20 paper size is applicable to China National Standard (CNS) Α4 specification (2 丨 0X297 mm) (Please read the precautions on the back before filling this one)
A7 B7 五、發明説明（/j) 盤26中的64Cu數量、和在下方鋁盤24中的64Cu數量， 由量測放射能來決定，以計算基板中64Cu殘留量’和被每 個鋁盤吸收的銅對於總量的百分比(％)(意即64(：11被引出的 分量）。 在各個成員中64Cu分佈(％)，所穫得的結果顯示於表 --〇 (請先閲讀背面之注意事項再填寫本頁) 表一 要淸潔的基 板 經過接觸加熱淸潔後，64Cu分 佈(％) 高氧濃度 HI晶圓 上方鋁盤 35.5 砍基板 26.3 下方鋁盤 38.2 高氧濃度 HI+BSP晶圓 上方鋁盤 20.5 矽基板 28.5 下方鋁盤 51.0 訂 經濟部中央標準局貝工消費合作社印裝 謇例二 (銅的移除；固體淸潔物：鋁片） 參考圖三來描述，在碳化矽圓盤23上，放置與碳化矽 圓盤23具有實質相同形狀和大小的1〇〇μ^厚的鋁片24 » 鋁片是由商業可得的高純度鋁所製’而且容許的銅濃度在 lppm以下。鋁片24的表面溫度控制在500°C，而低氧濃 度HI基板鏡面朝上地放在上面，作爲要淸潔的基板。在 _21_ 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐）' ' 經濟部中央標隼局員工消費合作社印笨 ΑΊ ______Β7____ 五、發明説明（./》） HI基板上不放置鋁片26。取而代之的是一個石英玻璃環， 放在HI基板的圓周，梢微進到其外圍，然後在環上再放上 如實例一中所用的碳化矽圓盤27以增加重量。因此，矽基 板的底表面和鋁片24的上表面做緊密的接觸。在此安排下 ’它們在500°C加熱4〇分鐘。 加熱之後，在基板和鋁片中64Cu的數量，可如實例一 中用相同的方法來量測，以計算基板中64Cu的殘留量和在 鋁片中64Cu被引出的分量；發現分別爲35%和65%。從這 些結果可看出，在IG區域補獲的64Cu將近有1/2被引出來 〇 窗例三 (銅的移除；固體淸潔物：鉻片） 加熱進行的方法和在實例二中用的完全相同，除了用 來做淸潔的樣本由低氧濃度的HI基板，換成高氧濃度的 BSP基板，鋁片換成了 lmm厚的鉻板，此BSP基板放置 在它們之間，其鏡面朝上，而這些在750°C下加熱1〇分鐘 〇 加熱之後，在基板和鉻板中銅的數量，用如同實例一 中的相同方法來量測，以計算54Cu在基板中的殘留量和 64Cu在鉻板中所引出的分量；發現這些金分別爲1P/。和 89%。從這些結果可以看出，幾乎所有被具有強除氣能力. 的多晶矽層所捕獲的64Cu，在一短時間內被引出而進入到 鉻板中。 _____22 _ ^紙张尺度適用中國國'家標準（CNS ) Λ4規格（2丨0X297公楚) ' (請先聞讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局貝工消费合作社印裝 A7 _ B7 五、發明説明0) 爲了知道基板的作用區域是否被鉻污染，由SIMS分 析來檢査此基板從作用區域那一邊表面算起l.um的深度， 結果，確認了基板的作用區域沒有被鉻污染。 啻例四 (銅的移除；固體淸潔物：銀板） 加熱進行的方法和在實例二中用的完全相同，除了用 來做淸潔的樣本由低氧濃度的HI基板，換成高氧濃度的 BSP基板，鋁片用0.4mm厚的銀板代替，此BSP基板的鏡 面朝上，放在那上面：銀板的表面溫度控制在800°C，把 它們加熱5分鐘。 加熱之後，在基板和在銀板中銅的數量，用如同實例 一中的相同方法來量測，以計算64Cu在基板中的殘留量和 64Cu在銀板中被引出的分量；發現這些値分別爲7%和 93%。從這些結果可以看出，幾乎所有被具有強除氣能力 的多晶矽層所捕獲的64Cu，在一短時間內被引出而進入到 銀板中。 因爲銀在矽中的擴散速率低，在80〇°C時’擴散係數 大約爲6χ10·11平方公分/秒，像此一溫度、短時間處理下 ，任何銀的污染是處於可忽略的地位。 實例π 在實例一和實例二中，在經過鋁接觸淸潔之後’砂晶 圓的三種型態，再進一步地經過高溫硫酸來淸潔° __23____ 张尺度適用I7國國家標準(CNS )A4規格（2丨0X 297公釐） (請先閲讀背面之注意事項再填寫本頁)A7 B7 V. Description of the Invention (/ j) The amount of 64Cu in the disc 26 and the amount of 64Cu in the aluminum disc 24 below are determined by measuring the radioactivity to calculate the residual amount of 64Cu in the substrate 'and each aluminum disc Percentage (%) of total copper absorbed (meaning 64 (: 11)). The distribution (%) of 64Cu in each member. The results obtained are shown in Table-0 (please read the Note: Please fill in this page again.) Table 1. After the substrate to be cleaned is cleaned by contact heating, 64Cu distribution (%) High oxygen concentration HI aluminum plate above wafer 35.5 Cut substrate 26.3 Aluminum plate below bottom 38.2 High oxygen concentration HI + BSP crystal Aluminium disc above the circle 20.5 Silicon substrate 28.5 Aluminium disc below 51.0 Order printed by the Central Standards Bureau of the Ministry of Economic Affairs Shellfish Consumer Cooperative Co., Ltd. Example 2 (removal of copper; solid concrete: aluminum sheet) Refer to Figure 3 for description of silicon carbide On the disc 23, a 100 μm thick aluminum sheet 24 having substantially the same shape and size as the silicon carbide disc 23 is placed. »The aluminum sheet is made of commercially available high-purity aluminum. lppm or less. The surface temperature of the aluminum sheet 24 is controlled at 500 ° C, and The low-oxygen-concentration HI substrate is placed on top of the mirror surface as the substrate to be cleaned. At _21_ this paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm). Consumption Cooperative Printing Ben AΊ ______ Β7 ____ 5. Description of the Invention (./ >>) No aluminum sheet 26 is placed on the HI substrate. Instead, it is a quartz glass ring, placed on the circumference of the HI substrate, the tip is slightly advanced to its periphery, and then on the ring Then put the silicon carbide disc 27 as used in Example 1 to increase the weight. Therefore, the bottom surface of the silicon substrate and the upper surface of the aluminum sheet 24 are in close contact. Under this arrangement, they are heated at 500 ° C. for 4 days. After heating, the amount of 64Cu in the substrate and aluminum sheet can be measured in the same way as in Example 1, to calculate the residual amount of 64Cu in the substrate and the amount of 64Cu extracted in the aluminum sheet; it was found that 35% and 65%. From these results, it can be seen that nearly 1/2 of the 64Cu replenished in the IG area is drawn out. Window example 3 (removal of copper; solid detergent: chromium plate) Method of heating Exactly the same as used in example two In addition to the samples used for cleaning, the low-oxygen-concentration HI substrate was replaced with a high-oxygen-concentration BSP substrate, and the aluminum sheet was replaced with a lmm-thick chrome plate. This BSP substrate was placed between them with the mirror surface facing up After heating at 750 ° C for 10 minutes, the amount of copper in the substrate and the chrome plate was measured by the same method as in Example 1 to calculate the residual amount of 54Cu in the substrate and 64Cu in The amount drawn from the chrome plate; these golds were found to be 1P / respectively. And 89%. From these results, it can be seen that almost all of the 64Cu captured by the polycrystalline silicon layer with strong outgassing ability was drawn out into the chromium plate in a short time. _____22 _ ^ The paper size is applicable to China's National Standard (CNS) Λ4 specification (2 丨 0X297). (Please read the notes on the back before filling out this page.) Printed by the Central Standards Bureau of the Ministry of Economic Affairs. Installation A7 _ B7 V. Description of the invention 0) In order to know whether the active area of the substrate is contaminated by chromium, SIMS analysis was used to check the depth of the substrate from the surface of the active area to a depth of 1 um. As a result, the active area of the substrate was confirmed Not contaminated by chromium. Example 4 (removal of copper; solid concrete: silver plate) The method of heating is exactly the same as that used in Example 2, except that the sample used for cleaning is replaced by a low-oxygen-concentrated HI substrate. For the oxygen-concentrated BSP substrate, the aluminum sheet was replaced with a 0.4 mm thick silver plate. The BSP substrate had the mirror surface facing up and placed on top of it: the surface temperature of the silver plate was controlled at 800 ° C, and they were heated for 5 minutes. After heating, the amount of copper in the substrate and in the silver plate was measured in the same way as in Example 1 to calculate the residual amount of 64Cu in the substrate and the component extracted from the 64Cu in the silver plate; these 値 were found separately It is 7% and 93%. From these results, it can be seen that almost all the 64Cu captured by the polycrystalline silicon layer with strong outgassing ability was drawn out into the silver plate in a short time. Because silver has a low diffusion rate in silicon, its diffusion coefficient is about 6x10 · 11 cm2 / s at 80 ° C. Under such a temperature and short-term treatment, any silver pollution is negligible. Example π In Example 1 and Example 2, after the aluminum contact cleaning, the three types of sand wafers were further cleaned by high temperature sulfuric acid ° __23____ Zhang scale is applicable to I7 national standard (CNS) A4 specifications ( 2 丨 0X 297 mm) (Please read the notes on the back before filling this page)
B7 經滴部中央標隼局員工消费合作社印裝 五、發明説明fV〇 也就是說，每一個矽晶圓浸入稀釋的氫氟酸中，以除 去自然氧化物薄膜，然後浸入300°C±i〇°C.、用石英玻璃容 器裝的硫酸中1〇分鐘。 在每個經過此硫酸淸潔的晶圓之64CU殘留量，顯示在 表二中。爲了做比較，經過鋁片接觸淸潔的64Cu殘留量， 也在一起顯示。 要淸潔的基板 經過淸潔後 在基板中的MCu殘留量 鋁片接觸之 後 再加上浸泡在高溫硫酸中 之後 高氧濃度HI (二面)26.3 6.3 高氧濃度HI+BSP (二面)28,5 10.5 低氧濃度HI (二面）35 8.9 實例六 在一厚度ΙΟΟμπι、高純度鋁片製的盤子的一面上，經 由分析，它的銅含量在O.lppm以下，64Cu是從含有64Cu 的醋酸溶液中所沈積上去的。經過此處理的鋁盤裁成 15x15mm2的細片，然後其在50(TC.加熱20分鐘，使64Cu 擴散到它們的內部中。經過此處理的鋁細片，用稀釋的氫 氟酸淸潔，用純水洗滌，接著乾燥。然後，這些細片經過 (請先閱讀背面之注意事項再填寫本頁) ,11 本紙張尺度適用中國國家標卑（CNS ) Λ4规格（2!0Χ2<Π公釐） 經濟部中央標準局貝工消费合作社印家 A7 _B7_ 五、發明説明（_/!/') 放射能量測，來決定向內擴散的銅的數量，然後貯存在氮 氣的氣氛中。因爲發現擴散在細片內的64Cu大約有lxlO13 個原子/平方公分，在它們中選出銅含量靠近ΙχΙΟ13個原子 /平方公分的，以用在下面的實驗中。假設銅在鋁中是均勻 地擴散，給定其平均濃度値爲O.lppm。 此時，從每一個高氧濃度HI基板和高氧濃度的BSP 基板上，各切下二個20mm見方的細片，在90(TC氬氣的 氣氛中加熱30分鐘，而沒有64Cu的擴散。這樣做是爲了 提供與64Cu擴散的樣品一樣，具有同樣熱歷程的測試基板 。一個鋁細片放在二個HI基板細片其中之一的下方，另一 個鋁細片放在剩下的另一個基板細片中心上，二個基板細 片的鏡面都朝上；這些都排放在如實例一中所用的加熱板 上。在此，鋁細片這樣排放，使得有64Cu沈積的表面與矽 的表面接觸。這二個BSP基板細片也做相似的排放。這二 個組裝物如圖三所顯示的方法安裝，然後在500°C加熱40 分鐘，以試驗在鋁中有多少64Cu遷移到矽的樣本中。64Cu 的數量由放射能童測來計算。 獲得的結果顯示在表三之中。 (請先閲讀背面之注意事項再填寫本頁)B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Distillation 5. Description of invention fV〇 That is, each silicon wafer is immersed in diluted hydrofluoric acid to remove the natural oxide film, and then immersed in 300 ° C ± i 0 ° C. In sulfuric acid in a quartz glass container for 10 minutes. The 64CU residues on each wafer cleaned by this sulfate are shown in Table 2. For comparison, the amount of 64Cu remaining after contact with aluminum flakes is also shown together. The substrate to be cleaned is cleaned. After the cleaning, the MCu residue in the substrate is contacted with aluminum flakes, and then immersed in high-temperature sulfuric acid. High oxygen concentration HI (two sides) 26.3 6.3 High oxygen concentration HI + BSP (two sides) 28 , 5 10.5 Low oxygen concentration HI (two sides) 35 8.9 Example 6 On one side of a plate made of 100 μm thick, high-purity aluminum flakes, after analysis, its copper content was below 0.1 ppm, and 64Cu was obtained from Deposited in acetic acid solution. The aluminum discs after this treatment were cut into 15x15mm2 pieces, and then heated at 50 ° C for 20 minutes to diffuse 64Cu into their interior. The aluminum flakes after this treatment were cleaned with diluted hydrofluoric acid. Wash with pure water, and then dry. Then, these pieces pass through (please read the precautions on the back before filling out this page), 11 This paper size applies to China National Standards (CNS) Λ4 specification (2! 0 × 2 < Π mm) ) Yinjia A7, _B7_, Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (_ /! / ') Radiation energy measurement to determine the amount of copper that diffuses inward, and then store it in a nitrogen atmosphere. The 64Cu diffused in the flakes has about lxlO13 atoms / cm2. Among them, the copper content is selected to be close to 1 × 1013 atoms / cm2 for use in the following experiments. Assuming copper is uniformly diffused in aluminum, give The average concentration 値 was set to 0.1 ppm. At this time, from each of the high oxygen concentration HI substrate and the high oxygen concentration BSP substrate, two 20 mm square pieces were cut out, and in a 90 (TC argon atmosphere) Heating for 30 minutes without diffusion of 64Cu This was done to provide a test substrate with the same thermal history as the 64Cu diffusion sample. One aluminum chip was placed under one of the two HI substrate chips, and the other aluminum chip was placed on the remaining other. On the center of one substrate chip, the mirror surfaces of the two substrate chips are facing upwards; these are discharged on the heating plate used in Example 1. Here, the aluminum chips are discharged in such a way that a 64Cu-deposited surface and silicon Surface contact. The two BSP substrate slivers were similarly discharged. The two assemblies were installed as shown in Figure 3 and then heated at 500 ° C for 40 minutes to test how much 64Cu migrated to silicon in aluminum. In the sample, the amount of 64Cu is calculated by the radioactivity test. The obtained results are shown in Table 3. (Please read the precautions on the back before filling this page)
、1T 表三 上層：鋁細片 下層：矽基板 64Cu濃度(原子數/平方公分） 高氧濃度HI 基板 高氧濃度BSP 基板 在鋁片中 9.7xl〇12 9.8χ1012 在基板中 1_9χ1010 8.0χ1Ό10 _25 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐1 Λ7 五、發明説明（·7>) 上層：矽基板 下層：鋁細片 64Cu濃度（原子數/平方公分） 高氧濃度HI 基板 高氧濃度BSP 基板 在鋁片中 ι.οδχίο13 9.1x10。 在基板中 2.0χ1010 5.0xl〇u， 經濟部中央標準局員工消費合作社印裝 從上面的表格中可以推論，在實例一中’從矽基板的 二面都放置的鋁片中，進入到基板之內的64Cu，和在實例 二中，從只在矽基板下面放置的鋁片中，進入到基板之內 的64Cu，爲2X1011個原子/平方公分或以下。在本實例中， 在64Cu擴散的晶圓中，64Cu的數量全都約爲2χ1013個原子 /平方公分，而在實例一與實例二這兩者中，它們的3/4到 2/3，經由銘接觸淸潔而被移除。據此，在這淸潔程序中， 任何包含在鋁片中微量銅的不利效果是可忽略的。 已從鋁片進入到矽基板的64Cu ’在大約500°C接觸淸 潔的結果，被認爲不會被基板中的除氣處所強力捕獲3經 由一個相似的隨後實驗確認：已如此進入的64Cu的90%或 更多，可以經由在300°C、1〇分鐘的硫酸中，由溶解而移 除。 因此己發現，甚至是使用一個不純的、含有Ippm銅 的鋁片，只要在鋁接觸淸潔之後，做高溫硫酸淸潔，大致 上是沒有問題的。 啻例七 (鎳的移除；固體淸潔物：鋁片） (讀先閱讀背面之注意事項再填寫本頁) 訂 本紙張尺度逍用中國國家標準（CNS ) Λ4規格（210X29?公泠） Μ 經濟部中央標準局員工消費合作社印製 五、發明説明（Υ、） 用迴旋粒子加速器造成5<5Fe (3He.2t!) 57Ni反應而製備 57犯，且用在本實例中。在矽基板內的IG區域中所捕獲的 57Ni之淸潔效果，是由下列的方法加以檢驗。 從高氧濃度HI基板上切下一個20mm見方的細片，浸 入添加 57Ni 的 SC-1 (NH4OH : H202 : H20=1 : 1 : 10 體積 比）中，以使57Ni吸附在基板的表面上^然後，基板細片在 9〇(TC加熱30分鐘，以得到一個57Ni在IG區域內被捕獲的 樣本。在基板細片中的57Ni濃度，經量測爲2χ1012個原子/ 平方公分。一個ΙΟΟμηι厚的高純度鋁片，切成20 mm見方 的細片。基板細片置入二個鋁細片之中，這些用如實例一 中的相同方法，在450°C加熱30分鐘。加熱之後，量測在 基板細片（矽細片）中鎳的濃度，並顯示57Ni的殘留量爲 68%。 接下來，將此矽細片浸入硫酸中，且在300°C加熱10 分鐘。然後，再次量測它的放射能，顯示出57犯的殘留量 爲 450/〇。 參考實例一 64Cu，用先前所描述的方法，擴散到沒有除氣作用的 高氧濃度的晶圓、低氧濃度HI晶圓、高氧濃度的HI晶圓 、以及高氧濃度的BSP晶圓之中，且這些用高溫硫酸淸潔 來處理。也就是說，每個矽晶圓浸入稀釋的氫氟酸中，以 移除在擴散處理中所形成的自然氧ί匕物薄膜，然後浸入用 石英玻璃容器裝的300°C.±10t的硫酸中10分鐘來淸溪， W I_ 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)1T Table 3 Upper layer: Aluminum flakes Lower layer: Silicon substrate 64Cu concentration (atomic number / cm 2) High oxygen concentration HI substrate High oxygen concentration BSP substrate in aluminum sheet 9.7x1012 9.8 × 1012 in substrate 1_9 × 1010 8.0χ1Ό10 _25 copies Paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm1 Λ7 V. Description of invention (· 7 >) Upper layer: Silicon substrate Lower layer: Aluminum flakes 64Cu concentration (atoms / cm²) High oxygen concentration HI substrate high The oxygen concentration BSP substrate is ι.οδχί13 9.1x10 in the aluminum sheet. 2.0χ1010 5.0xl0u in the substrate, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs can be inferred from the above table. In Example 1, 'from the silicon substrate In the aluminum sheet placed on both sides, 64Cu entered into the substrate, and in Example 2, from the aluminum sheet placed only under the silicon substrate, 64Cu entered into the substrate was 2 × 1011 atoms / square. Cm or less. In this example, in a 64Cu diffusion wafer, the amount of 64Cu is all about 2 × 1013 atoms / cm 2, and in both Example 1 and Example 2, their 3 / From 4 to 2/3, it was removed by contact with the cleaning agent. According to this, any adverse effect of trace copper contained in the aluminum sheet during this cleaning process is negligible. It has entered the silicon substrate from the aluminum sheet. As a result of contacting Pujie at approximately 500 ° C, it is believed that it will not be strongly captured by the outgassing space in the substrate. 3 A similar subsequent experiment confirmed that 90% or more of the 64Cu that has been so entered, can It is removed by dissolution in sulfuric acid at 300 ° C for 10 minutes. Therefore, it has been found that even an impure aluminum flake containing 1 ppm copper is used, as long as the aluminum is contacted and cleaned, the high-temperature sulfuric acid is cleaned. Generally speaking, there is no problem. 啻 Example 7 (removal of nickel; solid concrete: aluminum sheet) (read the precautions on the back before filling this page) The paper size of the book is free to use Chinese National Standards (CNS) Specification Λ4 (210X29? Gong Ling) Μ Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (Υ,) Using a cyclotron accelerator to cause 5 < 5Fe (3He.2t!) 57Ni reaction to prepare 57 offenses, and use In this example, the IG in the silicon substrate The cleaning effect of 57Ni captured in the domain was examined by the following method: A 20mm square thin piece was cut from a high oxygen concentration HI substrate and immersed in SC-1 (NH4OH: H202: H20 = 1) with 57Ni added. : 1:10 (volume ratio), so that 57Ni is adsorbed on the surface of the substrate ^ Then, the thin substrate piece is heated at 90 ° C for 30 minutes to obtain a sample of 57Ni captured in the IG region. The 57Ni concentration in the substrate fines was measured to be 2 × 10 12 atoms / cm 2. A 100 μm thick high-purity aluminum sheet was cut into 20 mm square pieces. The substrate fine pieces were placed in two aluminum fine pieces, and these were heated at 450 ° C for 30 minutes in the same manner as in Example 1. After heating, the nickel concentration in the substrate fines (silicon fines) was measured, and it was shown that the residual amount of 57Ni was 68%. Next, the silicon flakes were immersed in sulfuric acid and heated at 300 ° C for 10 minutes. Then, the radioactivity was measured again, and the residual amount of 57 offenders was 450/0. Referring to Example 1, 64Cu, using the method described previously, diffused to high oxygen concentration wafers, low oxygen concentration HI wafers, high oxygen concentration HI wafers, and high oxygen concentration BSP wafers without degassing. Medium, and these are treated with high temperature sulfuric acid cleaning. That is, each silicon wafer is immersed in diluted hydrofluoric acid to remove the natural oxygen film formed in the diffusion process, and then immersed in 300 ° C. ± 10t sulfuric acid in a quartz glass container. Come to Minxi in 10 minutes, W I_ This paper size applies to the Chinese National Standard (CNS) Λ4 size (210X 297 mm) (Please read the precautions on the back before filling this page)
-1T A7 B7 五、發明説明（>& ) 在經此處理的每個晶圓中，64Cu的殘留量顯示在表四 中。 表四 淸潔的基板· 淸潔之後的64Cu殘留量 (%) 高氧濃度鏡面晶圓 6.8 低氧濃度HI晶圓 65 高氧濃度HI晶圓 96 高氧濃度BSP晶圓 85 表四中的結果顯示：從一般的商業可得的沒有任何除 氣作用的鏡面晶圓，已進入其內部的64Cu，經由高溫硫酸 淸潔，可以效果良好地被引出；但是從基板上提供了強的 除氣作用時，就很難移除被捕獲在其內的64Cu。特別的是 ，結果顯示：在除氣作用歸因於高氧濃度的案例中，移除 它幾乎是不可能的。 ---------- --------1T------^ I #lts\ ♦ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 28 本紙張尺度適用中'國國家標準（CNS ) Λ4規格（210X 297公埯）-1T A7 B7 V. Explanation of the invention (>) In each wafer processed by this process, the residual amount of 64Cu is shown in Table IV. Table 4 Clean substrates · Residual amount of 64Cu after cleaning (%) High oxygen concentration mirror wafer 6.8 Low oxygen concentration HI wafer 65 High oxygen concentration HI wafer 96 High oxygen concentration BSP wafer 85 Table 4 Results Shows: From commercially available mirror wafers without any outgassing, the 64Cu that has entered it can be extracted well through high temperature sulfuric acid cleaning; but it provides strong outgassing from the substrate At this time, it is difficult to remove the 64Cu trapped therein. In particular, the results show that in cases where outgassing is attributable to high oxygen concentrations, it is almost impossible to remove it. ---------- -------- 1T ------ ^ I #lts \ ♦ (Please read the notes on the back before filling out this page) Staff of the Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumer Cooperatives 28 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 cm)
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| JP06189597A JP3809503B2 (en) | 1997-02-28 | 1997-02-28 | Method and apparatus for cleaning the inside of a semiconductor substrate |
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| TW399230B true TW399230B (en) | 2000-07-21 |
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| TW087102964A TW399230B (en) | 1997-02-28 | 1998-03-02 | Process and apparatus for cleaning the interior of semiconductor substrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI481450B (en) * | 2003-04-14 | 2015-04-21 | Nitto Denko Corp | Carrying member with a cleaning function and method of cleaning substrate processing equipment |
| CN107369607A (en) * | 2016-05-11 | 2017-11-21 | 万润科技股份有限公司 | Wiping mechanism and wafer residual glue cleaning device using same |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000349025A (en) * | 1999-03-26 | 2000-12-15 | Semiconductor Energy Lab Co Ltd | Manufacture of semiconductor device |
| JP3728406B2 (en) * | 2000-06-15 | 2005-12-21 | シャープ株式会社 | Substrate cleaning device |
| JP2003007709A (en) * | 2001-06-26 | 2003-01-10 | Shin Etsu Handotai Co Ltd | Silicon single crystal wafer having gettering capability and its manufacturing method |
| JP5440126B2 (en) * | 2009-11-26 | 2014-03-12 | 信越半導体株式会社 | Substrate heat treatment method |
| US9815091B2 (en) * | 2014-06-19 | 2017-11-14 | Applied Materials, Inc. | Roll to roll wafer backside particle and contamination removal |
-
1997
- 1997-02-28 JP JP06189597A patent/JP3809503B2/en not_active Expired - Fee Related
-
1998
- 1998-02-28 KR KR1019980006568A patent/KR19980071847A/en not_active Application Discontinuation
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI481450B (en) * | 2003-04-14 | 2015-04-21 | Nitto Denko Corp | Carrying member with a cleaning function and method of cleaning substrate processing equipment |
| CN107369607A (en) * | 2016-05-11 | 2017-11-21 | 万润科技股份有限公司 | Wiping mechanism and wafer residual glue cleaning device using same |
| CN107369607B (en) * | 2016-05-11 | 2019-10-08 | 万润科技股份有限公司 | Wiping mechanism and wafer residual glue cleaning device using same |
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| KR19980071847A (en) | 1998-10-26 |
| JPH10242099A (en) | 1998-09-11 |
| JP3809503B2 (en) | 2006-08-16 |
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