TWI304439B - Solution for removal residue of post dry etch - Google Patents

Solution for removal residue of post dry etch Download PDF

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Publication number
TWI304439B
TWI304439B TW092102154A TW92102154A TWI304439B TW I304439 B TWI304439 B TW I304439B TW 092102154 A TW092102154 A TW 092102154A TW 92102154 A TW92102154 A TW 92102154A TW I304439 B TWI304439 B TW I304439B
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Taiwan
Prior art keywords
cleaning solution
residue
cleaning
wafer
dry etching
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TW092102154A
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Chinese (zh)
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TW200413501A (en
Inventor
Tu Sheng-Hung
Wen Shoei Sheen
Kwo Hung Shen
Jack Ting
Ying Hao Li
Chih Peng Lu
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Merck Kanto Advanced Chemical
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Priority to TW092102154A priority Critical patent/TWI304439B/en
Priority to PCT/IB2003/001720 priority patent/WO2004067692A1/en
Priority to AU2003223027A priority patent/AU2003223027A1/en
Publication of TW200413501A publication Critical patent/TW200413501A/en
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Publication of TWI304439B publication Critical patent/TWI304439B/en

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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
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (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)

Description

1304439 案號 92102154 Λ_L· 曰 修正 五、發明說明（1) [發明所屬之技術領域] 本發明是有關於一種半導體清洗製程，且特別是有關 於去除乾#刻後（P 〇 s t d r y e t c h )殘留物之清洗溶液。 [先前技術] 蝕刻製程可說是整個半導體製程中，最重要的步驟之 一。一般而言，光罩上面的元件圖案是先藉著微影製程而 轉移到光阻上。然後再利用蝕刻製程，來完成整個圖案轉 移到薄膜上的最終目的。這層經過微影與蝕刻的薄膜，將 成半導體元件的一部分。以金氧半導體元件或互補式金氧 半導體元件的製程為例，這層薄膜可能是二氧化矽（S i 〇2 )，氮化矽（Si3N4)，複晶矽（poly-Si)，鋁合金（A1 alloy) 或是磷石夕玻璃（？1103口1103丨1丨0316，？36)等。也就是說，幾 乎構成半導體元件的主要材料，都必須經過薄膜沈積、微 影、以及蝕刻的這個流程，以便一層一層地進行元件的製 作。 舉例來說，在一般形成導體圖案的製程中，通常會先 於基底上依序形成一層氧化矽層與一層導體層（複晶矽或 其他金屬材料如鋁等）後，再於此導體層上形成一圖案化 光阻層。接著，利用光阻層作為蝕刻罩幕，利用乾蝕刻法 對曝露之導體層進行蝕刻，以形成導體圖案。之後再去除 光阻層。 然而，在上述形成導體圖案的製程中，由於蝕刻導體 層之氣體含有碳、氣或氧等氣體，而上述氣體會與光阻層 以及導體層產生化學反應而在光阻層與導體層的側壁形成1304439 Doc. No. 92102154 Λ_L· 曰Revision 5. Invention Description (1) [Technical Field of the Invention] The present invention relates to a semiconductor cleaning process, and in particular to the removal of dry (P 〇stdryetch) residues. Wash the solution. [Prior Art] The etching process can be said to be one of the most important steps in the entire semiconductor process. In general, the component pattern on the reticle is transferred to the photoresist by a lithography process. The etching process is then used to accomplish the final purpose of transferring the entire pattern onto the film. This layer of lithography and etching will form part of the semiconductor component. Taking the process of a MOS device or a complementary MOS device as an example, the film may be ruthenium dioxide (S i 〇 2 ), tantalum nitride (Si 3 N 4 ), poly-Si, aluminum alloy. (A1 alloy) or Phosphorus glass (?1103 port 1103丨1丨0316, ?36) and so on. That is to say, almost all of the main materials constituting the semiconductor element must pass through the processes of thin film deposition, lithography, and etching to fabricate the layers one by one. For example, in a process for generally forming a conductor pattern, a layer of yttrium oxide and a layer of a conductor layer (a polycrystalline silicon or other metal material such as aluminum) are sequentially formed on the substrate, and then on the conductor layer. A patterned photoresist layer is formed. Next, the exposed conductor layer is etched by dry etching using a photoresist layer as an etching mask to form a conductor pattern. Then remove the photoresist layer. However, in the above process of forming a conductor pattern, since the gas for etching the conductor layer contains a gas such as carbon, gas or oxygen, the gas reacts with the photoresist layer and the conductor layer to form a side wall of the photoresist layer and the conductor layer. form

8858twf1.ptc 第9頁 13044398858twf1.ptc Page 9 1304439

2分子殘留物，此高分子殘留物除了會影響後續製程之 L還會造成導體層之性能變差，因此在移除圖案化光阻 二^，通常會進行一洗淨製程以移除乾蝕刻後附著於 圖案表面之高分子殘留物。 极2 molecular residues, this polymer residue will not only affect the subsequent process L, but also cause the performance of the conductor layer to deteriorate. Therefore, after removing the patterned photoresist, a cleaning process is usually performed to remove the dry etching. The polymer residue attached to the surface of the pattern. pole

!知移除上述之高分子殘留物的方法是以灰化 ^ s h 1 n g )光阻層後’再浸入熱硫酸溶液中。然而，以臭 $，及熱硫酸法並無法完全去除附著於側壁上之高分子殘 。因此，經臭氧灰化與熱硫酸處理之晶片仍須要浸入 釋的氫氟酸液體中，而且浸入氫氟酸溶液之時間不能太 纽以?免晶片上之氧化物層受到蝕刻。雖然，高分子殘 ^3可藉由特殊剝離劑以移除之，但不是很便利。因此， 无乾姓刻後之清洗溶液仍是未來發展的重點。 L發明内容] 留物之清 案側壁高 本發 洗溶液至 劑所構成 含量為1 銨、氟化 含量為0. 10000pm 子型界面 於此，本發明之一目的為提供一種去乾蝕刻後殘 洗溶液，可以有效的移除乾蝕刻後殘留於導體 分子殘留物。 明提供一種去乾姓刻後殘留物之清洗溶液，此清 >'疋由硫酸、含氟化合物、過氧化氫與界面活性 ’其中硫酸含量為lwt%至30wt% ;含氟化合物之 ppm至lOOOOppm，含氟化合物可為氫氟酸°、氟化 二氫銨、六氟矽酸、氟硼酸（HBFj ;過氧化氫之 1 w t %至1 5 w t % ;界面活性劑之含量為} 冚至 ，而界面活性劑可為陽離子型界面活性p^m陰離 活性劑或非離子型界面活性劑。It is known that the above method of removing the polymer residue is carried out by ashing the s h 1 n g ) photoresist layer and then immersing it in the hot sulfuric acid solution. However, it is impossible to completely remove the polymer residue adhering to the side wall by the odor$ and the hot sulfuric acid method. Therefore, the wafer subjected to ozone ashing and hot sulfuric acid treatment still needs to be immersed in the hydrofluoric acid liquid, and the time of immersion in the hydrofluoric acid solution cannot be too high to avoid etching of the oxide layer on the wafer. Although the polymer residue ^3 can be removed by a special stripper, it is not very convenient. Therefore, the cleaning solution without the name of the surname is still the focus of future development. The content of the invention is as follows: the content of the residue of the residue is 1 ammonium, and the fluorination content is 0. 10000 pm sub-interface, one of the objects of the present invention is to provide a residual cleaning solution after dry etching. It can effectively remove residual molecules remaining in the conductor after dry etching. The invention provides a cleaning solution for removing the residue after the engraving, which is composed of sulfuric acid, a fluorine-containing compound, hydrogen peroxide and an interfacial activity, wherein the sulfuric acid content is from 1% by weight to 30% by weight; the ppm of the fluorine-containing compound is up to lOOOOppm, the fluorine-containing compound may be hydrofluoric acid °, ammonium dihydrogen fluoride, hexafluoroantimonic acid, fluoroboric acid (HBFj; 1 wt% to 15 wt% of hydrogen peroxide; the content of surfactant is 冚 to The surfactant may be a cationic interfacial active p^m anion active agent or a nonionic surfactant.

1304439 五、發明說明 曰 修正^ 此方法包 ，且此導 I發明另 ^ 括提供一晶m 提供一種乾蝕刻後之清洗方法， 體層表面上夏女ΐ日日圓上具有一餘刻後之導體層 含氟化合物Γ有向分f殘留物。然後，以至少包括硫f、 圓，以去咚一過氧化氫與界面活性劑之清洗溶液清洗晶 使ΐ ί 7分子殘留物。 圖案線表面1Γ之清洗溶液不但可以徹底移除殘留在導體 因此可以接古兩分子殘留物，又可以避免毀害導體圖案’ 率、節省、々，氣程裕度（Process Window)、提高清洗政 為讓太=托相’而能夠降低成本並增加產能。 顯易丨i， $明之上述和其他目的、特徵、和優點能更明 說明如下下文特舉較佳實施例，並配合所附圖式，作詳細 [實施方式] 产砵t發日月係提供一種去乾#刻後殘留物之清洗溶液’此 n卞/谷液至少疋由硫酸、含氟化合物、過氧化氫與界面活 人劑所構成’其中硫酸含量範圍為lwt%至3〇以％ ;含氟化 二物之含量範圍為1 ppm至lOOOOppm，含氟化合物可為氫 ^酸、氟化銨、氟化二氫銨、氟矽酸、氟硼酸（HBf4);過 氧化氫之含量範圍為〇· 1 wt%至1 5wt% ;界面活性劑之含量 為1 ppm 至lOOOOppm 〇 界面活性劑例如是脂肪酸酯類、脂肪酸甘油脂類、脂 肪酸山梨醇酯類、琥珀酸酯類、脂肪酸醯胺類、磷酸酯 類、硫酸酯類、磺酸鹽類與醋酸鹽類或上述化合物之氟化 衍生物。1304439 V. INSTRUCTION DESCRIPTION 曰 MODIFICATION ^ This method package, and the invention of the invention provides a crystal m to provide a cleaning method after dry etching, which has a conductor layer on the surface of the body layer on the Japanese yen The fluorine-containing compound has a residue of the fraction f. Then, the crystal residue is washed with a cleaning solution containing at least sulfur f, a circle, and dehydrogen peroxide and a surfactant. The cleaning solution on the surface of the pattern line can not only completely remove the residual resin, so it can pick up the two molecules of the residue, and can avoid the destruction of the conductor pattern' rate, saving, smashing, process margin, and improving the cleaning policy. Too = support phase can reduce costs and increase production capacity. The above and other objects, features, and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments and the accompanying drawings. A cleaning solution for removing the residue after the engraving. The n卞/gluten solution is composed of at least sulfuric acid, a fluorine-containing compound, hydrogen peroxide and an interface active agent. The sulfuric acid content ranges from 1% by weight to 3% by weight. The content of the fluorine-containing compound is in the range of 1 ppm to 1000 ppm, and the fluorine-containing compound may be hydrogen acid, ammonium fluoride, ammonium dihydrogen fluoride, fluoroantimonic acid, fluoroboric acid (HBf4); 〇·1 wt% to 15 wt%; surfactant content of 1 ppm to 1000 ppm 〇 surfactants such as fatty acid esters, fatty acid glycerides, fatty acid sorbitol esters, succinates, fatty acid guanamine Classes, phosphates, sulfates, sulfonates and acetates or fluorinated derivatives of the above compounds.

8858twfl.ptc 第11頁 1304439 銮號 92102154_± 五、發明說明（4) 修正8858twfl.ptc Page 11 1304439 Nickname 92102154_± V. Description of invention (4) Amendment

使用本發明之清洗溶液可以有效的除去乾蝕刻後附— 於導體圖案側壁之高分子殘留物，而且不會增加製程困^ 度。 為更詳細的說明本發明，特配製以包括硫酸、含氣化 合物、過氧化氫與界面活性劑之清洗溶液之樣品。 樣品甲為硫酸含量為1 2 w t %、過氧化氫2 · 5 w t %、氣化 銨5 Op pm、界面活性劑A 5 Op pm。其中，界面活性劑a為全 氟化辛烷基磺酸胺。 $ 樣品乙為硫酸含ϊ為7.5 wt %、過氧化氮2·5 wt%、 氟化二氫銨50ppm、界面活性劑B 300ppm。其中，界面活 性劑B 為烧基奈橫酸（Alkylnaphthalene sulphonic acid BASF Nekal SBC) 〇By using the cleaning solution of the present invention, the polymer residue attached to the sidewall of the conductor pattern after dry etching can be effectively removed without increasing the process difficulty. For a more detailed description of the invention, a sample comprising a cleaning solution comprising sulfuric acid, a gas-containing compound, hydrogen peroxide and a surfactant is specifically formulated. Sample A was a sulfuric acid content of 1 2 w t %, hydrogen peroxide 2 · 5 w t %, vaporized ammonium 5 Op pm, and surfactant A 5 Op pm. Among them, the surfactant a is a perfluorooctyl sulfonate amine. $ Sample B is 7.5 wt% of bismuth sulfate, 2.5% by weight of nitrogen peroxide, 50 ppm of ammonium dihydrogen fluoride, and 300 ppm of surfactant B. Among them, the surfactant B is Alkylnaphthalene sulphonic acid BASF Nekal SBC.

樣品丙為硫酸含量為3 wt %、過氧化氫2· 5 wt%、界 面活性劑B 3 0 0 ppm。界面活性劑B為烷基萘磺酸(Alkylnaphthalene sulphonic acid BASF Nekal SBC)。 樣品丁為硫酸含量為7· 5 wt %、過氧化氫2· 5 wt%、 氟石夕酸250ppm。 樣品戊為硫酸含量為7. 5 wt % 氟石夕酸5 0??111界面活性劑(：15〇1)1)111 t氧乙稀5^硫酸胺。 一 ^巧例為硫酸含量為7.5 wt %、過氧化氫2.5 wt % 風乳酸1 0 〇 p p m。 浐Μ ί 分別以上述六種溶液以浸泡，喷灑（Spray)或 疋 < Spinetch)之方式移除經乾餘刻後附著於導靡 過氧化氫2 界面活性劑C為壬酚^Sample C had a sulfuric acid content of 3 wt%, hydrogen peroxide of 2.5 wt%, and an surfactant B 3 0 0 ppm. Surfactant B is an alkylnaphthalenesulfonic acid (Alkylnaphthalene sulphonic acid BASF Nekal SBC). The sample diced was sulfuric acid content of 7.5 wt%, hydrogen peroxide of 2.5 wt%, and fluorhexidine acid of 250 ppm. The sample pentane is sulfuric acid content of 7. 5 wt % fluorite oxime acid 5 0?? 111 surfactant (: 15 〇 1) 1) 111 t oxyethylene 5 sulphate. A good example is sulfuric acid content of 7.5 wt%, hydrogen peroxide of 2.5 wt%, wind lactic acid 10 〇 p p m.浐Μ ί Use the above six solutions to remove the dry residue after the dry solution, spray (Spray) or 疋 (Spinetch), and attach it to the hydrogen peroxide. 2 Surfactant C is phenol.

第12頁 1304439 案號 92102154 Λ_L· 曰 修正 五、發明說明（5) 圖案表面之高分子殘留物。其中，對晶圓進行清洗之溫度 為0°C〜90 °C左右。以喷灑（spray)或喷灑旋轉（spin etch) 之方式對晶圓進行清洗時之喷洗壓力為0.5大氣壓力〜2.0 大氣壓力之間。喷灑旋轉之方式對晶圓進行清洗時旋轉之 速度為0 rpm〜5000 rpm. 首先，於基底上形成一層複晶石夕層與一層圖案化光阻 層後，以圖案化光阻層為罩幕，利用乾蝕刻法移除圖案化 光阻層所暴露之複晶矽層，之後移除圖案化光阻層，而製 備出複數個具有經乾蝕刻後導體圖案之基底。然後，將具 有經乾蝕刻後導體圖案之基底分別以浸泡方式浸入樣品 曱、樣品乙、樣品戊與比較例之清洗溶液中。 另外，分別以喷灑之方式將樣品丙與樣品丁喷灑於具 有經乾蝕後導體圖案之基底表面。 接者’說明樣品甲、樣品乙、樣品丙、樣品丁、樣品 戊與比較例之差異。 請參照第1圖所繪示之未經過清潔溶液處理前之導體 圖案的掃瞄式電子顯微鏡照相圖。在此圖中，導體圖案之 表面附著有高分子殘留物。 接著，請參照第2圖、第3圖、第4圖、第5圖、第6 圖、第7圖所繪示之分別以樣品甲、樣品乙、樣品丙、樣 品丁、樣品戊與比較例之清洗溶液處理後之導體圖案的掃 瞄式電子顯微鏡照相圖。在第2圖中，於導體圖案上方表 面之高分子聚合物已被完全清除，但仍然可以很明顯的看 出有部分高分子殘留物附著於導體圖案側邊表面。Page 12 1304439 Case No. 92102154 Λ_L· 曰 Correction V. Invention Description (5) Polymer residue on the surface of the pattern. Among them, the temperature for cleaning the wafer is about 0 °C to 90 °C. The spray pressure when cleaning the wafer by spraying or spin etch is between 0.5 at atmospheric pressure and 2.0 at atmospheric pressure. Spraying the wafer to clean the wafer at a speed of 0 rpm to 5000 rpm. First, a layer of a polycrystalline stone layer and a patterned photoresist layer are formed on the substrate, and the patterned photoresist layer is used as a mask. In the screen, the polysilicon layer exposed by the patterned photoresist layer is removed by dry etching, and then the patterned photoresist layer is removed to prepare a plurality of substrates having a dry-etched conductor pattern. Then, the substrate having the dry-etched conductor pattern was immersed in the sample solution, the sample B, the sample pent, and the cleaning solution of the comparative example, respectively. Further, the sample C and the sample were sprayed on the surface of the substrate having the dried conductor pattern, respectively, by spraying. The receiver' indicates the difference between Sample A, Sample B, Sample C, Sample D, and Sample E and Comparative Example. Please refer to the scanning electron microscope photograph of the conductor pattern before the treatment with the cleaning solution as shown in Fig. 1. In this figure, a polymer residue adheres to the surface of the conductor pattern. Next, please refer to Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, and Fig. 7 for sample A, sample B, sample C, sample D, sample pent, and comparative example, respectively. A scanning electron microscope photograph of the conductor pattern after the cleaning solution treatment. In Fig. 2, the polymer on the surface above the conductor pattern has been completely removed, but it is still apparent that some of the polymer residue adheres to the side surface of the conductor pattern.

8858twf1.ptc 第13頁 1304439 案號 92102154 Λ_Ά 曰 修正 五、發明說明（6) 接著，請參照第3圖所繪示之樣品乙之清洗溶液處理 後之導體圖案的掃瞄式電子顯微鏡照相圖。在第3圖中， 導體圖案表面高分子殘留物附著物已被清除，可知增加界 面活性之含量對於導體側邊高分子殘留附著物之清除有顯 著之效果。 接著，請參照第4圖所繪示之樣品丙之清洗溶液處理 後之導體圖案的掃瞄式電子顯微鏡照相圖。在第4圖中， 可明顯看出導體圖案側邊高分子殘留附著物完全無法去 除，故可知不含氟離子化合物之溶液無法去除高分子殘留 附著物。 接者’請參照第5圖所繪不之樣品丁之清洗溶液處理 後之導體圖案的掃瞄式電子顯微鏡照相圖。在第5圖中， 大部分之高分子殘留物附著物已被清除。 接著，請參照第6圖所繪示之樣品戊之清洗溶液處理 後之導體圖案的掃瞄式電子顯微鏡照相圖。在第6圖中， 導體圖案上高分子殘留物附著物已被完全清除。 接著，請參照第7圖所繪示之比較例之清洗溶液處理 後之導體圖案的掃瞄式電子顯微鏡照相圖。在第7圖中， 雖然導體圖案表面高分子殘留物附著物已被清除，但是卻 造成導體圖案之腐蝕。 本發明係利用至少包括硫酸、含氟化合物、過氧化 氫、緩衝溶液與界面活性劑所構成之清洗溶液移除乾蝕刻 後之高分子殘留物。硫酸含量為2wt%至30wt% ;含氟化合 物之含量為lppm至lOOOOppm，含氟化合物可為氫氟酸、氟8858twf1.ptc Page 13 1304439 Case No. 92102154 Λ_Ά 修正 Correction V. Description of the invention (6) Next, please refer to the scanning electron microscope photograph of the conductor pattern after the cleaning solution of sample B shown in Fig. 3. In Fig. 3, the deposit of the polymer residue on the surface of the conductor pattern was removed, and it was found that increasing the content of the interface activity has a remarkable effect on the removal of the polymer residual deposit on the side of the conductor. Next, please refer to the scanning electron micrograph of the conductor pattern after the cleaning solution of the sample C shown in Fig. 4. In Fig. 4, it is apparent that the polymer residual deposit on the side of the conductor pattern cannot be removed at all, and it is understood that the solution containing no fluorine ion compound cannot remove the polymer residue. Pick-up Please refer to the scanning electron micrograph of the conductor pattern after the cleaning solution of the sample D. In Figure 5, most of the polymer residue deposits have been removed. Next, please refer to the scanning electron micrograph of the conductor pattern after the sample cleaning solution of the sample shown in Fig. 6. In Fig. 6, the polymer residue deposit on the conductor pattern has been completely removed. Next, please refer to the scanning electron microscope photograph of the conductor pattern after the cleaning solution of the comparative example shown in Fig. 7. In Fig. 7, although the polymer residue deposit on the surface of the conductor pattern has been removed, it causes corrosion of the conductor pattern. In the present invention, the dry residue polymer residue is removed by using a cleaning solution comprising at least sulfuric acid, a fluorine-containing compound, hydrogen peroxide, a buffer solution and a surfactant. The sulfuric acid content is 2% by weight to 30% by weight; the content of the fluorine-containing compound is 1 ppm to 1000 ppm, and the fluorine-containing compound may be hydrofluoric acid or fluorine.

8858twf1.ptc 第14頁 1304439 _案號 92102154_年月日__ 五、發明說明（7) 化銨、氟化二氫銨、氟矽酸、氟硼酸（HBF4);過氧化氫之 含量為0.1至15wt% ;界面活性劑之含量為1 ppm至 1 0 0 0 0 pm。由於含氟化合物之濃度較低，因此使用本發明 之清洗溶液不但可以徹底移除殘留在導體圖案線表面之高 分子殘留物，又可以避免毀害導體圖案，因此可以提高製 程裕度（P r 〇 c e s s w i n d 〇 w )、提高清洗效率、節省溶劑耗 損，而且能夠降低成本並增加產能。 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，當可作各種之更動與潤飾，因此本發明之保護8858twf1.ptc Page 14 1304439 _ Case No. 92102154_年月日日__ V. Description of invention (7) Ammonium, ammonium dihydrogen fluoride, fluoroantimonic acid, fluoroboric acid (HBF4); hydrogen peroxide content is 0.1 Up to 15% by weight; the surfactant content is from 1 ppm to 1 000 pm. Since the concentration of the fluorine-containing compound is low, the use of the cleaning solution of the present invention can not only completely remove the polymer residue remaining on the surface of the conductor pattern line, but also avoid the destruction of the conductor pattern, thereby improving the process margin (P r 〇cesswind 〇w ), improve cleaning efficiency, save solvent consumption, and reduce costs and increase production capacity. While the present invention has been described above by way of a preferred embodiment, it 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. Protection

8858twfl.ptc 第15頁 1304439 案號 92102154 年 月 曰 修正 圖式簡單說明 - 第1圖所繪示之未經過清潔溶液處理前之導體圖案的 掃猫式電子顯微鏡（scanning electron microsocope ， SEM)照相圖。 第2圖所繪示為以實驗例1之清洗溶液處理後之導體圖 案的掃瞄式電子顯微鏡照相圖。 第3圖所繪示為以實驗例2之清洗溶液處理後之導體圖 案的掃瞄式電子顯微鏡照相圖。 第4圖所繪示為以實驗例3之清洗溶液處理後之導體圖 案的掃瞄式電子顯微鏡照相圖。 第5圖所繪示為以實驗例4之清洗溶液處理後之導體圖 案的掃瞄式電子顯微鏡照相圖。 第6圖所繪示為以實驗例5之清洗溶液處理後之導體圖 案的掃瞄式電子顯微鏡照相圖。 第7圖所繪示為以比較例之清洗溶液處理後之導體圖 案的掃瞄式電子顯微鏡照相圖。8858twfl.ptc Page 15 1304439 Case No. 92102154 Yearly Correction Diagram Simple Description - Figure 1 Scanning electron microsocope (SEM) photograph of the conductor pattern before treatment with the cleaning solution . Fig. 2 is a scanning electron micrograph of the conductor pattern after the cleaning solution of Experimental Example 1. Fig. 3 is a scanning electron micrograph of the conductor pattern after the cleaning solution of Experimental Example 2. Fig. 4 is a scanning electron micrograph of a conductor pattern after treatment with the cleaning solution of Experimental Example 3. Fig. 5 is a scanning electron micrograph of a conductor pattern after treatment with the cleaning solution of Experimental Example 4. Fig. 6 is a scanning electron micrograph of the conductor pattern after the cleaning solution of Experimental Example 5. Fig. 7 is a scanning electron micrograph showing a conductor pattern after treatment with a cleaning solution of a comparative example.

8858twf1.ptc 第16頁8858twf1.ptc Page 16

Claims (1)

獅4_ 案號 92102154Lion 4_ case number 92102154 六、申請專利範圍Sixth, the scope of application for patents 修正 1 . 一種去除乾餘刻後殘留物之清洗溶液，該清洗溶液 至少包括硫酸、一含氟化合物、過氧化氫與一界面活性 劑，其中該硫酸含量為2wt%至30wt%。 2 .如申請專利範圍第1項所述之去乾蝕刻後殘留物之 清洗溶液，其中該含氟化合物係選自氫氟酸、氟化銨、氟 化二氫銨、氟矽酸、與氟硼酸所組成之族群。 3 .如申請專利範圍第2項所述之去除乾蝕刻後殘留物 之清洗溶液，其中該含氟化合物之含量為lppm至 10000pmoCorrection 1. A cleaning solution for removing a residue after a dry residue, the cleaning solution comprising at least sulfuric acid, a fluorine-containing compound, hydrogen peroxide and an interface agent, wherein the sulfuric acid content is from 2 wt% to 30 wt%. 2. The cleaning solution for the residue after dry etching as described in claim 1, wherein the fluorine-containing compound is selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium dihydrogen fluoride, fluoroantimonic acid, and fluorine. A group of boric acid. 3. A cleaning solution for removing a residue after dry etching as described in claim 2, wherein the content of the fluorine-containing compound is from 1 ppm to 10,000 pmo. 4. 如申請專利範圍第1項所述之去除乾蝕刻後殘留物 之清洗溶液，其中過氧化氫之含量為O.lwt%至15wt%。 5. 如申請專利範圍第1項所述之去乾蝕刻後殘留物之 清洗溶液，其中該界面活性劑係選自脂肪酸酯類、脂肪酸 甘油脂類、脂肪酸山梨醇酯類、琥珀酸酯類、脂肪酸醯胺 類、磷酸酯類、硫酸酯類、磺酸鹽類與醋酸鹽類所組之族 群。 6. 如申請專利範圍第5項所述之去除乾蝕刻後殘留物 之清洗溶液，其中該界面活性劑之含量為1 p P m至 10000pm 〇4. The cleaning solution for removing the post-dry etching residue as described in claim 1, wherein the hydrogen peroxide content is from 0.1% by weight to 15% by weight. 5. The cleaning solution of the residue after dry etching as described in claim 1, wherein the surfactant is selected from the group consisting of fatty acid esters, fatty acid glycerides, fatty acid sorbitol esters, succinates, A group of fatty acid amides, phosphates, sulfates, sulfonates and acetates. 6. The cleaning solution for removing dry etching residue as described in claim 5, wherein the surfactant is in a range of from 1 p Pm to 10000 pm. 7. 如申請專利範圍第1項所述之去乾蝕刻後殘留物之 清洗溶液，其中該界面活性劑係選自脂肪酸酯類、脂肪酸 甘油脂類、脂肪酸山梨醇酯類、琥珀酸酯類、脂肪酸醯胺 類、磷酸酯類、硫酸酯類、磺酸鹽類與醋酸鹽類之氟化衍 生物所組之族群。7. The cleaning solution for removing dry etching residue according to claim 1, wherein the surfactant is selected from the group consisting of fatty acid esters, fatty acid glycerides, fatty acid sorbitol esters, succinates, A group of fatty acid amides, phosphates, sulfates, sulfonates, and fluorinated derivatives of acetates. 8858twfl.ptc 第17頁 1304439 __案號92102154 年月日 修正 六、申請專利範圍 8 ·如申請專利範圍第7項所述之去除乾蝕刻後殘留物 之清洗溶液，其中該界面活性劑之含量為1 p p m至 10000pmo 9 · 一種乾餘刻後之清洗方法，至少包括下列步驟· 提供一晶圓，該晶圓上具有乾蝕刻及灰化處理後之一 導體層，該導體層表面上具有一高分子殘留物；以及 以一清洗溶液清洗該晶圓，以去除該高分子殘留物， 該清洗溶液至少包括硫酸、一含氟化合物、過氧化氫與一 界面活性劑，其中硫酸含量為2 w t %至3 0 w t % ;該含氟化合8858twfl.ptc Page 17 1304439 __ Case No. 92102154 Year Month Amendment VI. Patent Application Range 8 · The cleaning solution for removing residual residue after dry etching as described in item 7 of the patent application scope, wherein the content of the surfactant 1 ppm to 10000 pmo 9 · A dry after-cleaning method comprising at least the following steps: providing a wafer having a dry etching and ashing one of the conductor layers, the conductor layer having a surface a polymer residue; and cleaning the wafer with a cleaning solution to remove the polymer residue, the cleaning solution comprising at least sulfuric acid, a fluorine-containing compound, hydrogen peroxide and a surfactant, wherein the sulfuric acid content is 2 wt % to 30% by weight; the fluorine-containing compound 物之含量為lppm至lOOOOppm ;過氧化氫之含量為O.lwt%至 15wt% ;該界面活性劑之含量為ippm至ι〇〇〇〇ρριη。 1 0 ·如申請專利範圍第9項所述之去除乾蝕刻後殘留物 之清洗方法，其中以該清洗溶液清洗該晶圓之方法包括： 將該清洗溶液置於一清洗槽中，以及將該晶圓浸泡 (d 1 p )入含該清洗溶液之該清洗槽中；或將該清洗溶液喷 灑（s p r a y )於該晶圓上，或將該清洗溶液喷瀵於該晶圓上 並旋轉該晶圓（Spin etch)。 u .如申請專利範圍第1 〇項所述之去除乾蝕刻後之清 洗方法，其中該清洗溶液清洗該晶圓之操作溫度為 9 0 °C之間。 1 2.如中請專利圍第1 Q項所述之去除乾㈣後之清 洗方法，其中將該清洗溶液噴灑（spray)於該晶圓上；或 將該清洗溶液喷灑於^該晶圓上並旋轉該晶圓（Spi n etc/) 之喷洗壓力為0.5大氣塗力〜2. 〇大氣壓力之間。The content of the substance is from 1 ppm to 1000 ppm; the content of hydrogen peroxide is from 0.1% by weight to 15% by weight; and the content of the surfactant is from ippm to ι〇〇〇〇ρρηη. The cleaning method for removing the residue after dry etching as described in claim 9, wherein the cleaning the solution by the cleaning solution comprises: placing the cleaning solution in a cleaning tank, and Wafer immersion (d 1 p) into the cleaning bath containing the cleaning solution; or spraying the cleaning solution onto the wafer, or squirting the cleaning solution onto the wafer and rotating the wafer Spin etch. u. The method of removing the dry etching after the cleaning solution according to the first aspect of the patent application, wherein the cleaning solution cleans the wafer at an operating temperature of 90 °C. 1 2. The cleaning method after removing the dry (four) described in the first paragraph Q of the patent, wherein the cleaning solution is sprayed on the wafer; or the cleaning solution is sprayed on the wafer The spray pressure of the wafer (Spi n etc/) is up and rotated to 0.5 atmosphere application force ~ 2. 〇 between atmospheric pressure. 1304439 _案號92102154_年月曰 修正_；_ 六、申請專利範圍 1 3.如申請專利範圍第1 0項所述之去除乾蝕刻後之清 洗方法，其中將該清洗溶液喷灑於該晶圓上並旋轉該晶圓 (Spin etch)之旋轉之速度為0 rpm〜5000 rpm。1304439 _ Case No. 92102154_Yearly 曰 Revision _; _ Six, the scope of application for patents 1. 3. The method of cleaning after dry etching as described in claim 10, wherein the cleaning solution is sprayed on the crystal The rotation speed of the wafer (Spin etch) is 0 rpm to 5000 rpm. 8858twfl.ptc 第19頁8858twfl.ptc Page 19
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