TWI267911B - Method of cleaning a semiconductor - Google Patents
Method of cleaning a semiconductor Download PDFInfo
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- TWI267911B TWI267911B TW92129871A TW92129871A TWI267911B TW I267911 B TWI267911 B TW I267911B TW 92129871 A TW92129871 A TW 92129871A TW 92129871 A TW92129871 A TW 92129871A TW I267911 B TWI267911 B TW I267911B
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- cleaning
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- hydrogen peroxide
- semiconductor
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- 238000004140 cleaning Methods 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 84
- 239000004065 semiconductor Substances 0.000 title claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910001868 water Inorganic materials 0.000 claims abstract description 45
- 238000007667 floating Methods 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 62
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000000356 contaminant Substances 0.000 claims description 10
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 9
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 9
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 9
- 229920002120 photoresistant polymer Polymers 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 5
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 4
- 239000001301 oxygen Substances 0.000 claims 4
- 229910052760 oxygen Inorganic materials 0.000 claims 4
- 239000013078 crystal Substances 0.000 claims 2
- 229910052732 germanium Inorganic materials 0.000 claims 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 2
- HXXNMYYNRKYGMH-UHFFFAOYSA-N [Ru]=O.N#[N+][O-] Chemical compound [Ru]=O.N#[N+][O-] HXXNMYYNRKYGMH-UHFFFAOYSA-N 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 52
- 235000012431 wafers Nutrition 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- 229910000449 hafnium oxide Inorganic materials 0.000 description 11
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 11
- 239000000758 substrate Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- ISQINHMJILFLAQ-UHFFFAOYSA-N argon hydrofluoride Chemical compound F.[Ar] ISQINHMJILFLAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- ORQBXQOJMQIAOY-UHFFFAOYSA-N nobelium Chemical compound [No] ORQBXQOJMQIAOY-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
1267911 五、發明說明（1) 【發明所屬之技術領域】 本發明是有關於一種矽晶圓的清洗方法，且特別是有 關於一種使用含有臭氧之去離子水來清洗晶圓的方法。 【先前技術】 在半導體製程中，高分子、光阻或是不可溶之有機物 等污染物可能會存在並且堆積於半導體晶圓上，如此將不 利於半導體元件的操作。第1圖是繪示一個半導體元件之 剖面示意圖，且在製程過程中此半導體元件上係堆積有污 染物。 請參照第1圖，半導體元件1 0 0包括半導體基底1 0 2以 及一個快閃記憶胞（未繪示）之閘極結構（未標號），此閘極 結構包括穿隧氧化層1 0 4、浮置閘極1 0 6與介電層1 0 8。其 中，浮置閘極1 0 6的材質包括多晶矽或是氮化矽，介電層 1 0 8的材質包括氧化矽或是習知由氧化矽/氮化矽/氧化矽 所構成之多層結構。 在進行半導體元件100的製程中，一些污染物110可能 會殘留於快閃記憶胞之閘極結構的側壁上，這些污染物例 如是有機殘留物或是金屬離子。其中，有機殘留物可能在 光阻進行蝕刻、塗佈（C 〇 a t i n g )以及顯影的過程中產生， 而金屬離子可能在蝕刻或是離子植入的過程中產生。 因此，為了獲得具有較好之效能表現 (High-Performance)以及高可靠度（High-Reliability)之 快閃記體，所以必須將污染物去除，亦即必須對元件1 0 0 進行清洗。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of cleaning a tantalum wafer, and more particularly to a method of cleaning a wafer using ozone-containing deionized water. [Prior Art] In a semiconductor process, contaminants such as a polymer, a photoresist, or an insoluble organic substance may exist and accumulate on a semiconductor wafer, which is disadvantageous for the operation of the semiconductor element. Fig. 1 is a schematic cross-sectional view showing a semiconductor device in which a semiconductor material is deposited with a contaminant during the process. Referring to FIG. 1, the semiconductor device 100 includes a semiconductor substrate 102 and a gate structure (not labeled) of a flash memory cell (not shown). The gate structure includes a tunnel oxide layer 104. Floating gate 1 0 6 and dielectric layer 1 0 8 . The material of the floating gate 106 includes polysilicon or tantalum nitride, and the material of the dielectric layer 108 includes yttrium oxide or a multilayer structure which is conventionally composed of yttrium oxide/tantalum nitride/yttria. During the fabrication of the semiconductor device 100, some of the contaminants 110 may remain on the sidewalls of the gate structure of the flash memory cells, such as organic residues or metal ions. Among them, organic residues may be generated during etching, coating (C 〇 a t i n g ) and development of photoresist, and metal ions may be generated during etching or ion implantation. Therefore, in order to obtain a flash with good performance and high-reliability, it is necessary to remove the contaminants, that is, the component 100 must be cleaned.
11064twf.ptd 第8頁 1267911 五、發明說明（2) 一種由R C A實驗室所開發，且用於矽晶圓清洗之清洗 製程已成為業界之標準清洗製程，此清洗製程稱為RCA清 洗製程。一個R C A清洗製程包括依序進行下面三個主要的 清洗步驟· 1 .使用水（H20) /過氧化氫（H2 02 ) /氨水（NH4OH)之混合液 (標準清洗液s C 1 )來移除不可溶的有機污染物，其中水、 過氧化氫與氨水的混合比例係為5 : 1 : 1 ; 2. 使用水（H20) /氫氟酸（HF)之混合液來移除薄的氧化 矽層，其中在步驟1所產生之金屬污染物會對堆積於此氧 化石夕層上。此外，混合液中的水與氫氣酸其稀釋比例係為 50 : 1 ;以及 3. 使用水（H20) /過氧化氫（H202 )/鹽酸（HC1 )之混合液 (標準清洗液SC2)來移除重金屬原子以及重金屬離子污染 物，其中水、過氧化氫與鹽酸的混合比例係為6 : 1 : 1。 雖然R C A清洗製程已廣泛地使用於半導體製程中，但 是隨著半導體製程技術之不斷改良，以及各種新材料的出 現，此清洗製程不再能夠滿足各種半導體製程的需求。舉 例來說，對於在現今的半導體元件（例如：快閃記憶體） 中，所使用之金屬材料或是低介電常數（Low-K)材料來 說，使用RCA清洗製程中的清洗液就可能會造成腐蝕問 題。 【發明内容】 因此，本發明的目的就是在提供一種新穎的晶圓清洗 方法，以解決在現今半導體元件的製程中，使用習知清洗11064twf.ptd Page 8 1267911 V. INSTRUCTIONS (2) A cleaning process developed by R C A Laboratories for cleaning wafers has become the industry's standard cleaning process. This cleaning process is called the RCA cleaning process. An RCA cleaning process consists of the following three main cleaning steps: 1. Use a mixture of water (H20) / hydrogen peroxide (H2 02 ) / ammonia (NH4OH) (standard cleaning solution s C 1 ) to remove Insoluble organic pollutants, wherein the mixing ratio of water, hydrogen peroxide and ammonia is 5:1:1; 2. Use a mixture of water (H20) / hydrofluoric acid (HF) to remove thin cerium oxide A layer in which the metal contaminants produced in step 1 are deposited on the oxidized stone layer. In addition, the dilution ratio of water to hydrogen acid in the mixture is 50:1; and 3. using a mixture of water (H20) / hydrogen peroxide (H202) / hydrochloric acid (HC1) (standard cleaning solution SC2) In addition to heavy metal atoms and heavy metal ion contaminants, the mixing ratio of water, hydrogen peroxide and hydrochloric acid is 6:1:1. Although the R C A cleaning process has been widely used in semiconductor processes, with the continuous improvement of semiconductor process technology and the emergence of various new materials, this cleaning process can no longer meet the needs of various semiconductor processes. For example, in today's semiconductor components (eg, flash memory), the metal material used or the low dielectric constant (Low-K) material, it is possible to use the cleaning solution in the RCA cleaning process. It can cause corrosion problems. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a novel wafer cleaning method for solving conventional semiconductor device manufacturing processes using conventional cleaning.
11064twf.ptd 第9頁 1267911 五、發明說明（3) 方法所遭遇到問題。 本發明提出一種半導體的清洗方法，此清洗方法係適 用於快閃記憶體之閘間介電層形成之後，此方法包括先提 供一半導體晶圓。然後，於半導體晶圓上形成第一氧化矽 層。接著，於第一氧化矽層上形成浮置閘極層。之後，於 浮置閘極層上形成第二氧化矽層。繼之，蝕刻第一氧化矽 層、浮置閘極層與第二氧化矽層，以形成閘極結構，其中 第二氧化矽層係作為閘間介電層之用。然後，使用含臭氧 (Ozonated)之去離子水（De-Ionized，DI)清洗包含有閘極 結構之半導體晶圓。接著’更包括使用第一清洗液清洗已 經過含有臭氧之去離子水清洗之晶圓。之後，使用第二清 洗液清洗已經過第一清洗液清洗之晶圓。 本發明提出另一種半導體清洗的方法，此清洗方法係 適用於快閃記憶體之閘間介電層形成之後，此方法包括先 提供一半導體晶圓。然後，於半導體晶圓上形成第一氧化 矽層。接著，於第一氧化矽層上形成浮置閘極層。之後， 於浮置閘極層上形成第二氧化石夕層。繼之，於第二氧化石夕 層上形成氮化矽層。然後，於氮化矽層上形成第三氧化矽 層。接著，蝕刻第一氧化矽層、浮置閘極層、第二氧化矽 層、氮化矽層與第三氧化矽層，以形成閘極結構，其中第 二氧化矽層、氮化矽層與第三氧化矽層係作為閘間介電層 之用。之後，使用含臭氧之去離子水清洗半導體晶圓。繼 之，使用一清洗液清洗半導體晶圓。然後，使用含臭氧之 去離子水清洗半導體晶圓。11064twf.ptd Page 9 1267911 V. INSTRUCTIONS (3) Problems encountered in the method. The present invention provides a method of cleaning a semiconductor, which is suitable for forming a dielectric layer between the gates of a flash memory, the method comprising first providing a semiconductor wafer. A first ruthenium oxide layer is then formed on the semiconductor wafer. Next, a floating gate layer is formed on the first hafnium oxide layer. Thereafter, a second hafnium oxide layer is formed on the floating gate layer. Then, the first hafnium oxide layer, the floating gate layer and the second hafnium oxide layer are etched to form a gate structure, wherein the second hafnium oxide layer is used as a inter-gate dielectric layer. Then, the semiconductor wafer containing the gate structure was cleaned using Ozonated deionized water (De-Ionized, DI). Then' more includes cleaning the wafer that has been washed with ozone-containing deionized water using the first cleaning solution. Thereafter, the wafer that has been washed by the first cleaning liquid is cleaned using the second cleaning liquid. The present invention provides another method of semiconductor cleaning which is applied to the formation of a dielectric layer between the gates of a flash memory, the method comprising first providing a semiconductor wafer. A first ruthenium oxide layer is then formed over the semiconductor wafer. Next, a floating gate layer is formed on the first hafnium oxide layer. Thereafter, a second layer of oxidized stone is formed on the floating gate layer. Subsequently, a tantalum nitride layer is formed on the second layer of the oxidized oxide. Then, a third ruthenium oxide layer is formed on the tantalum nitride layer. Next, etching the first hafnium oxide layer, the floating gate layer, the second hafnium oxide layer, the tantalum nitride layer and the third hafnium oxide layer to form a gate structure, wherein the second hafnium oxide layer and the tantalum nitride layer The third hafnium oxide layer serves as a dielectric layer between the gates. Thereafter, the semiconductor wafer is cleaned using ozone-containing deionized water. The semiconductor wafer is then cleaned using a cleaning solution. The semiconductor wafer is then cleaned using ozone-containing deionized water.
11064twf.ptd 第10頁 1267911 五、發明說明（4) 值得一提的是，上述之第一清洗液或清洗液例如是使 用水（h2o) /過氧化氫（h2o2)/氨水（nh4oh)之混合液、水（h2 0) /過氧化氫（H2 02 ) /鹽酸（HC1)之混合液或氫氟酸（HF) /鹽 酸（H C 1 )之混合液，或是依序使用水/過氧化氫/氨水之混 合液，以及水/過氧化氫/鹽酸之混合液。 本發明的其他目的與優點將於以下的描述中被提出， 而且亦可藉由以下之實施例或是依照本發明之内容加以施 行而使本發明之優點與目的更淺顯易見。除此之外，本發 明之目的與優點可以藉由後附之申請專利範圍來加以實施 並達到其目的。 在上述的描述與以下之實施例中係用以解釋本發明之 精神與内容而使其更淺顯易懂，但本發明並不限定於此， 本發明之保護範圍當視後附之申請專利範圍所界定者為 準。 為讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉一較佳實施例，並配合所附圖式，作詳 細說明如下： 【實施方式】 以下舉出來較佳實施例來說明本發明，在實施例之圖 示與文字的敘述中，相同或相似的參考標號係指相同的或 相似之部分。 本發明提供一種新穎的晶圓清洗方法，此清洗方法係 適用於快閃記憶體之閘間介電層形成之後。第2圖是繪示 經過本發明之清洗方法清洗所得之半導體元件2 0 0的剖面11064twf.ptd Page 10 1267911 V. INSTRUCTIONS (4) It is worth mentioning that the first cleaning solution or cleaning solution is, for example, a mixture of water (h2o) / hydrogen peroxide (h2o2) / ammonia (nh4oh). a mixture of liquid, water (h2 0) / hydrogen peroxide (H2 02 ) / hydrochloric acid (HC1) or hydrofluoric acid (HF) / hydrochloric acid (HC 1 ), or water/hydrogen peroxide in sequence / Ammonia mixture, and a mixture of water / hydrogen peroxide / hydrochloric acid. The other objects and advantages of the present invention will be made apparent from the description of the appended claims. In addition, the objects and advantages of the present invention can be implemented and achieved by the scope of the appended claims. The above description and the following examples are intended to explain the spirit and content of the present invention to make it easier to understand, but the invention is not limited thereto, and the scope of protection of the present invention is attached to the scope of the patent application. The definition is final. The above and other objects, features, and advantages of the present invention will become more apparent and understood. In the description of the embodiments, the same or similar reference numerals are used to refer to the same or similar parts. The present invention provides a novel wafer cleaning method that is suitable for use after formation of a dielectric layer between gates of a flash memory. Figure 2 is a cross-sectional view showing the semiconductor device 200 obtained by the cleaning method of the present invention.
11064twf.ptd 第11頁 1267911 五、發明說明（5) 示意圖。請參照第2圖，半導體元件2 0 0包括半導體基底 2 0 2，且此半導體基底2 0 2上係形成有多數個元件（未繪 示）。然後，於半導體基底2 0 2上形成穿隧氧化層2 0 4。接 著，於穿隧氧化層2 0 4上形成浮置閘極2 0 6。之後，於浮置 閘極2 0 6上形成介電層2 0 8。繼之，蝕刻介電層2 0 8、浮置 閘極2 0 6與穿隧氧化層2 0 4，以形成數個閘極結構2 1 0，其 中介電層2 0 8係作為閘間介電層之用。 其中，半導體基底2 0 2的材質例如是任何習知技術所 使用之基底材料，其例如是矽、鍺或是矽鍺化合物。此 外，浮置閘極2 0 6的材質例如是多晶矽或是氮化矽。另 外，介電層2 0 8的材質例如是氧化矽或是由氧化矽/氮化矽 /氧化石夕所構成之多層結構。 另一方面，當於基底上形成光阻時，可以藉由進行微 影蝕刻製程，而於基底上形成一些圖案。在第2圖中亦繪 示出這樣的一層光阻層212，其中此光阻層212係形成於介 電層2 0 8上。接著，進行本發明之清洗方法，以去除光阻 殘留物： 1.使用含有臭氧（Ozonated)之去離子水 (De-Ionized，DI)進行第一次的清洗； 2 .使用清洗液進行清洗步驟；以及 3 ·使用含有臭氧之去離子水進行第二次的清洗， 其中，含有臭氧之去離子水的製備係藉由將臭氧導入 去離水中而完成的，且臭氧濃度例如是介於10至80 ppm， 而較佳之使用濃度例如是4 0 p p m。11064twf.ptd Page 11 1267911 V. Description of the invention (5) Schematic. Referring to Fig. 2, the semiconductor device 200 includes a semiconductor substrate 220, and a plurality of components (not shown) are formed on the semiconductor substrate 220. Then, a tunneling oxide layer 220 is formed on the semiconductor substrate 220. Next, a floating gate 206 is formed on the tunnel oxide layer 204. Thereafter, a dielectric layer 208 is formed on the floating gate 206. Then, the dielectric layer 208, the floating gate 060 and the tunneling oxide layer 220 are etched to form a plurality of gate structures 2 1 0, wherein the dielectric layer 208 is used as the gate inter-layer. For the electric layer. The material of the semiconductor substrate 220 is, for example, a substrate material used in any of the prior art, and is, for example, a ruthenium, osmium or iridium compound. Further, the material of the floating gate 206 is, for example, polysilicon or tantalum nitride. Further, the material of the dielectric layer 208 is, for example, yttrium oxide or a multilayer structure composed of yttrium oxide/tantalum nitride/oxide oxide. On the other hand, when a photoresist is formed on the substrate, some pattern can be formed on the substrate by performing a photolithography process. Also shown in Fig. 2 is a layer of photoresist layer 212 formed on dielectric layer 208. Next, the cleaning method of the present invention is performed to remove the photoresist residue: 1. The first cleaning is performed using deionized water (De-Ionized, DI) containing ozone; 2. The cleaning step is performed using the cleaning solution. And 3: using a deionized water containing ozone for the second cleaning, wherein the preparation of ozone-containing deionized water is performed by introducing ozone into the water, and the ozone concentration is, for example, 10 to 80 ppm, and the preferred use concentration is, for example, 40 ppm.
11064twf.ptd 第12頁 1267911 五、發明說明（6) 在本發明之第一個實施例中，清洗液是sc 1，其例如 是水（h2o)/過氧化氫（h2o2)/氨水（nh4oh)之混合液，且水、 過氧化氫與氨水的混合比例係為4〜8 0 : 1〜5 : 1 ，而較佳之 混合比例例如是8 0 : 3 · 1 : 2 . 2。在本發明之第二個實施例 中，清洗液是SC2，其例如是水（H20)/過氧化氫（H2〇2)/鹽酸 (H C 1 )之混合液，且水、過氧化氫與鹽酸的混合比例係為 4〜8 0 : 1〜5 : 1 ，而較佳之混合比例例如是8 0 : 2 · 2 : 1 · 3。 在本發明之第三個實施例中，清洗液是依序使用水/過氧 化氫/氨水之混合液（SCI )，以及水/過氧化氫/鹽酸之混合 液（S C 2 )。其中，水、過氧化氫與氨水的混合比例係為 4〜8 0 : 1〜5 : 1 ，且水、過氧化氫與鹽酸的混合比例係為 4〜8 0 : 1〜5 : 1 ，而且較佳之混合比例S C 1例如是8 0 : 3 · 1 : 2· 2，且SC2例如是80 : 2. 2 : 1 . 3。在本發明之第四個實施 例中，清洗液是氩氟酸（HF) /鹽酸（HC1 )之混合液，其中氫 氟酸、鹽酸與水之混合比例例如是1 : 1〜5 ·· 5 0〜5 0 0，而較 佳之混合比例例如是1 : 1 . 3 : 4 0 0。 雖然在上述的說明中係以光阻為例來說明本發明，但 是本發明之方法亦可使用在晶圓上殘留有其他如高分子、 金屬離子或是其他微粒等污染物的清洗上。 為了量測本發明之清洗效果，以下係進行數個試驗’ 其結果如第3圖與第4圖所示。第3圖是繪示記憶胞結構之 朋潰電荷（B r e a k d 〇 w n C h a r g e ) ( QBD)值的量測結果，且其係 為在進行記憶胞結構的製程時使用本發明之清洗方法以及 標準清洗方法SCI與SC2所得之量測結果。其中，橫軸係表11064twf.ptd Page 12 1267911 V. INSTRUCTION DESCRIPTION (6) In the first embodiment of the present invention, the cleaning liquid is sc 1, which is, for example, water (h2o) / hydrogen peroxide (h2o2) / ammonia (nh4oh) The mixed solution, and the mixing ratio of water, hydrogen peroxide and ammonia water is 4 to 80: 1 to 5:1, and the preferable mixing ratio is, for example, 80:3 ·1:2.2. In a second embodiment of the present invention, the cleaning liquid is SC2, which is, for example, a mixture of water (H20) / hydrogen peroxide (H 2 〇 2) / hydrochloric acid (HC 1 ), and water, hydrogen peroxide and hydrochloric acid. The mixing ratio is 4 to 80: 1 to 5: 1, and the preferred mixing ratio is, for example, 8 0 : 2 · 2 : 1 · 3. In the third embodiment of the present invention, the cleaning liquid is a mixture of water/hydrogen peroxide/aqueous ammonia (SCI) and a mixture of water/hydrogen peroxide/hydrochloric acid (S C 2 ). Wherein, the mixing ratio of water, hydrogen peroxide and ammonia water is 4 to 80: 1 to 5:1, and the mixing ratio of water, hydrogen peroxide and hydrochloric acid is 4 to 80: 1 to 5:1, and A preferred mixing ratio SC 1 is, for example, 8 0 : 3 · 1 : 2 · 2, and SC 2 is, for example, 80 : 2. 2 : 1.3. In a fourth embodiment of the present invention, the cleaning solution is a mixture of argon fluoride (HF) / hydrochloric acid (HC1), wherein the mixing ratio of hydrofluoric acid, hydrochloric acid and water is, for example, 1: 1 to 5 · · 5 0 to 5 0 0, and a preferred mixing ratio is, for example, 1: 1 . 3 : 4 0 0. Although the invention has been described by taking a photoresist as an example in the above description, the method of the present invention can also be used for cleaning on the wafer with other contaminants such as polymers, metal ions or other particles. In order to measure the cleaning effect of the present invention, several tests were carried out hereinafter. The results are shown in Figs. 3 and 4. Figure 3 is a graph showing the measurement results of the B reakd 〇 wn C harge (QBD) value of the memory cell structure, and is a method of using the cleaning method and the standard of the present invention in the process of performing the memory cell structure. Cleaning method The measurement results obtained by SCI and SC2. Among them, the horizontal axis table
H〇64twf.Ptci 第13頁 1267911___ 五、發明説明 系四種不同的清洗過程，縱軸係表示經過這些清洗過程 後，所量測到之個別對應之閘氧化層的崩潰電荷qbd值。這 四個清洗過程包括本發明之第一個實施例與第二個實施 例，以及習知之使用SCI與SC2之標準清洗方法，其中在本 發明之第一個實施例中係使用標準清洗液S C 1 ，而在本發 明之第二個實施例中係使用標準清洗液SC2。此外，崩潰 電猗Qbd值的單位係為庫侖（Coul0 mb)/平方公分（cm2)。由第 3圖中玎清楚地知道’使用本發明的方法其閘氧化層的崩 清電荷Qbd值相較於習知之標準清洗方法具有較佳的表現。 第4圖是繪示記憶體元件之閘極耦合率（g a t e C o u p 1 i n S R a t丨0 s，G C R )的量測結果，且其係為在進行記 憶體元件的製程時使用本發明之清洗方法以及標準清洗方 法S C 1與S C 2所付之里測結果。由第4圖可知，本發明相較 於習知之標準清洗方法係提供一較佳的閘極耦合率。 此外，亦對使用本發明之清洗方法與習知使用標準清 洗液S C 1之清洗方法所得之記憶體胞元件，進行良率 (Y i e 1 d )量測，並進行比較。在一個晶圓上總共可製作出 8 7 0晶粒（D i e )，而使用本發明的方法可使得一晶圓上會有 7 5 4個晶粒通過規格測試，而使用習知的清洗方法一晶圓 上卻僅有6 8 2個晶粒通過規格測試。此外，使用本發明之 方法來進行閘極結構之製程，在閘極結構的側壁上會具有 較少之缺陷數目，其每一單位（Arbitrary Unit)約有65個 缺陷數目，而使用習知之清洗方法，每一單位（A r b i t r a r y ϋ n i t )的缺陷數目約有6 8 2個。H〇64twf.Ptci Page 13 1267911___ V. INSTRUCTIONS INSTRUCTIONS There are four different cleaning processes. The vertical axis represents the value of the crash charge qbd of the individual gate oxides measured after these cleaning processes. The four cleaning processes include the first embodiment and the second embodiment of the present invention, as well as the conventional standard cleaning method using SCI and SC2, wherein in the first embodiment of the present invention, the standard cleaning solution SC is used. 1 , and in the second embodiment of the invention, the standard cleaning solution SC2 is used. In addition, the unit of the Qbd value of the crash is Coulomb (cm) and square centimeters (cm2). It is apparent from Fig. 3 that the use of the method of the present invention has a better performance of the gate oxide layer Qbd of the gate oxide layer than the conventional standard cleaning method. Figure 4 is a graph showing the measurement results of the gate coupling ratio (gate C oup 1 in SR at 丨 0 s, GCR ) of the memory device, and is the cleaning using the present invention in the process of performing the memory device. The method and the results of the standard cleaning methods SC 1 and SC 2 were measured. As can be seen from Figure 4, the present invention provides a preferred gate coupling ratio as compared to conventional standard cleaning methods. Further, the memory cell elements obtained by the cleaning method of the present invention and the conventional cleaning method using the standard cleaning solution S C 1 were also subjected to yield measurement (Y i e 1 d ) and compared. A total of 870 dies (D ie ) can be fabricated on a single wafer, and the method of the present invention allows 754 dies on a wafer to pass specification testing using conventional cleaning methods. On the wafer, only 682 die were tested by specification. In addition, using the method of the present invention to perform the gate structure process, there will be fewer defects on the sidewalls of the gate structure, and each unit (Arbitrary Unit) has about 65 defect numbers, and the conventional cleaning is used. In this way, the number of defects per unit (A rbitrary ϋ nit ) is about 682.
H〇64twf .ptd 第14頁 1267911 五、發明說明（8) 由上述關於本發明之實施例的說明可知，本發明之清 洗方法並不需要製備習知清洗方法中所使用的所有清洗 液，例如於RCA清洗中所使用之稀釋比例為50 : 1 iH20/HF 混合液。因此本發明對於製程來說可以降低持有成本 (Cost of Ownership，C〇0)，並且改善良率及降低缺陷數 目。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。H〇64twf.ptd Page 14 1267911 V. INSTRUCTION DESCRIPTION (8) From the above description of the embodiments of the present invention, it is understood that the cleaning method of the present invention does not require preparation of all cleaning liquids used in conventional cleaning methods, for example The dilution ratio used in RCA cleaning is 50: 1 iH20/HF mixture. Therefore, the present invention can reduce the cost of ownership (C〇0) for the process, and improve the yield and the number of defects. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.
11064twf.ptd 第15頁 1267911 圖式簡單說明 第1圖是一個半導體元件之剖面示意圖，且在製程過 程中此半導體元件上係堆積有污染物。 第2圖是經過本發明之清洗方法清洗所得之半導體元 件的剖面示意圖。 第3圖是M0S結構之崩潰電荷（QBD)值的量測結果，且其 係為在進行Μ 0 S結構的製程時使用本發明之清洗方法以及 標準清洗方法SCI與SC2之比較結果。 第4圖是記憶體元件之閘極耦合率（G a t e C 〇 u p 1 i n g Rat i os，GCR)的量測結果，且其係為在進行記憶體元件的 製程時使用本發明之清洗方法以及標準清洗方法SCI與SC 2 之比較結果。 【圖式標記說明】 1 0 0、2 0 0 ··半導體元件 102、202 :半導體基底 104、204 :穿隧氧化層 1 0 6、2 0 6 :浮置閘極 1 08、2 0 8 :介電層 1 1 0 :污染物 2 1 0 :閘極結構 2 1 2 :光阻層11064twf.ptd Page 15 1267911 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view of a semiconductor device in which contaminants are deposited on the semiconductor device during the process. Fig. 2 is a schematic cross-sectional view showing a semiconductor device obtained by the cleaning method of the present invention. Fig. 3 is a measurement result of the breakdown charge (QBD) value of the MOS structure, and is a result of comparison between the cleaning method of the present invention and the standard cleaning methods SCI and SC2 in the process of performing the Μ 0 S structure. Figure 4 is a measurement result of the gate coupling ratio (Gate C 〇 up 1 ing Rat i os, GCR) of the memory device, and is a cleaning method using the present invention in the process of performing the memory device and Comparison of standard cleaning methods SCI and SC 2 . [Description of Schematic Mark] 1 0 0, 2 0 0 ··Semiconductor element 102, 202: Semiconductor substrate 104, 204: Tunneling oxide layer 1 0 6 , 2 0 6 : Floating gate 1 08, 2 0 8 : Dielectric layer 1 1 0 : contaminant 2 1 0 : gate structure 2 1 2 : photoresist layer
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