WO2006125369A1 - Composition pour l’elimination d’une couche de photoresist et procede pour l'utiliser - Google Patents

Composition pour l’elimination d’une couche de photoresist et procede pour l'utiliser Download PDF

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Publication number
WO2006125369A1
WO2006125369A1 PCT/CN2006/000955 CN2006000955W WO2006125369A1 WO 2006125369 A1 WO2006125369 A1 WO 2006125369A1 CN 2006000955 W CN2006000955 W CN 2006000955W WO 2006125369 A1 WO2006125369 A1 WO 2006125369A1
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Prior art keywords
composition
composition according
organic
wafer
polishing pad
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PCT/CN2006/000955
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English (en)
French (fr)
Inventor
Shumin Wang
Chris Chang Yu
Original Assignee
Anji Microelectronics (Shanghai) Co., Ltd.
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Application filed by Anji Microelectronics (Shanghai) Co., Ltd. filed Critical Anji Microelectronics (Shanghai) Co., Ltd.
Priority to US11/920,248 priority Critical patent/US20090095320A1/en
Publication of WO2006125369A1 publication Critical patent/WO2006125369A1/zh

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds

Definitions

  • composition for removing photoresist layer Composition for removing photoresist layer and method of using same
  • the present invention relates to a composition for removing a photoresist layer in a semiconductor manufacturing process and a method of using the same. Do not discuss
  • the application, exposure and imaging of the photoresist layer can be used to fabricate the necessary component patterns during the fabrication of semiconductor components.
  • the remaining photoresist material is removed before proceeding to the next process step.
  • ion bombardment hardens the photoresist layer polymer, so the photoresist layer is more difficult to dissolve and thus difficult to remove.
  • plasma etching and wet etching have been used to remove the photoresist layer.
  • the first step is to remove most of the photoresist layer by plasma etching.
  • the second step is to use the wet etching process.
  • the cleaning process takes a long time to complete and usually requires an elevated temperature to aid the reaction. Because the two-step process requires two different sets of equipment, the cost is higher. In addition, prior art processes sometimes do not clean all of the photoresist layers, leaving residue.
  • It is an object of the present invention to provide a novel photoresist removal-removing composition comprising a polar solvent, characterized by further comprising an oxidizing agent.
  • the photoresist layer typically contains organic matter and/or polymer.
  • the polar solvent softens or dissolves the organic matter and the polymer in the photoresist layer or the photoresist layer, and the oxidizing agent oxidizes the organic substance and the polymer to destroy the original molecular structure, thereby achieving the effect of dissolution and removal.
  • the composition may further comprise a surfactant, an inhibitor and/or a carrier.
  • the inhibitors can reduce or prevent damage, corrosion and pitting corrosion caused by chemical or mechanical methods on the underlying substrate.
  • a typical substrate is a silicon substrate, and sometimes a thin oxide layer is deposited on the silicon substrate.
  • the polishing pad is any plastic sheet having a flat surface or a plastic sheet of different surface treatment/ditch to ensure that there is sufficient 'clean solution' distributed over the polishing substrate.
  • the underlying substrate includes, but is not limited to, silicon, silicon dioxide, ion doped silicon dioxide, a material having a low dielectric constant k, and a substrate such as metal such as aluminum or copper.
  • the carrier is preferably water.
  • the concentration of the polar solvent is 5%-80%, the concentration of the oxidizing agent is 0.01%-8%, the concentration of the surfactant is 0.001%-5%, and the concentration of the inhibitor is 0.005%-10%.
  • the carrier is the balance, and the above percentages all refer to the mass percentage concentration of the entire composition.
  • the oxidizing agent is one or more of organic or inorganic peroxides, preferably hydrogen peroxide, peracetic acid, perboric acid, sodium peroxide, ammonium persulfate, potassium permanganate, nitric acid and/or Nitrate.
  • the polar solvent is preferably an organic amine, an organic alcohol, an organic alcohol amine, an organic ether and/or an organic ketone, and the organic alcohol is preferably an alkanol or a polyhydric alcohol.
  • the inhibitors are mono- or polycarboxylic acids and their salts, water-soluble charged ionic organic materials, water-soluble charged ionic polymer materials and/or water-soluble nitrogen-containing polymeric materials.
  • Preferred nitrogen-containing polymeric materials are polyamines such as polyvinylamine and its salts, amides such as polyamide-imides or polyamides, Polyamines and / or azoles.
  • the azoles are preferably benzotriazole, benzimidazole, triazole and/or derivatives thereof.
  • the composition may also include one or more of a complexing agent, a dispersing agent, a catalyst, and a pH adjusting agent.
  • Another object of the present invention is to provide a method of using the above composition in which the substrate to be cleaned is immersed in the composition of the present invention until the photoresist layer is completely removed.
  • the method of soaking is carried out at room temperature or under an elevated temperature, and the heating temperature does not exceed the boiling point of the composition.
  • Another preferred method of use is to mechanically oscillate the substrate during soaking.
  • Yet another preferred method of use is to treat the composition with ultrasonic energy.
  • a further object of the present invention is to provide another method of using the above composition for immersing a rotating substrate in the composition of the present invention or applying the composition of the present invention to a rotating substrate.
  • the wafer can be taken out from the fixing clip and cleaned.
  • the wafer can be washed only with deionized water, which may also contain additives to better remove residual composition and polished material from the wafer.
  • the wafer is brushed while the wafer is being cleaned. Cleaning a wafer can mean using the same or different polishing pads on the same or different polishing platforms.
  • the positive progress of the present invention is as follows: 1.
  • the composition uses a chemical substance with low toxicity and small flammability and reduces the amount of chemical components, making it more environmentally friendly and reducing the cost of chemical waste treatment;
  • the use method shortens the cleaning process time, thereby increasing the yield; 3. Removing the residue more thoroughly, and finally improving the conductivity; 4.
  • the polishing method of the present invention the cost can also be reduced.
  • FIG. 1 is a flow chart of a coating, exposure and imaging, and plasma etching process of a photoresist layer in the prior art. Summary of the invention
  • composition of the composition 20 g of ammonium persulfate, 500 g of ethylene glycol and 480 g of deionized water.
  • the substrate to be cleaned was placed in a coverable solution tank, the above composition was added, the composition was warmed to 45 C, the substrate was immersed for 5 minutes, taken out, and then rinsed with deionized water.
  • composition of the composition 40 g of hydrogen peroxide, 500 g of N-methyl-ethyl-pyrrolidone and 460 g of deionized water.
  • the substrate to be cleaned was placed in a stopperable solution tank, the above composition was added, the composition was warmed to 45 ° C, the substrate was immersed for 5 minutes, taken out, and then rinsed with deionized water.
  • composition of the composition 20 g of ammonium persulfate, 500 g of ethylene glycol, O.lg nonionic surfactant and 479.9 g deionized water.
  • the substrate to be cleaned was placed in a stopperable solution tank, the above composition was added, the composition was warmed to 45 ° C, the substrate was immersed for 5 minutes, taken out, and then rinsed with deionized water.
  • composition of the composition 40 g of hydrogen peroxide, 500 g of N-methyl-ethyl-pyrrolidone, O.lg nonionic surfactant, lg benzotriazole and 458.9 g of deionized water.
  • the substrate to be cleaned was placed in a stopperable solution tank, the above composition was added, the composition was warmed to 45 ° C, the substrate was immersed for 5 minutes, taken out, and then rinsed with deionized water.
  • composition of the composition O.lg peracetic acid, 800 g of N-methyl-ethyl-pyrrolidone, O.Olg nonionic surfactant, 0.05 g of benzimidazole and 199.84 g of deionized water.
  • the substrate to be cleaned was immersed in the composition, and then the composition was subjected to ultrasonic waves having a frequency of 40 megawatts of HZ. After 5 minutes, the substrate was taken out and rinsed with deionized water.
  • composition of the composition 80 g of potassium permanganate, 50 g of acetone, 5 g of nonionic surfactant, 50 g of triazole and 815 g of deionized water.
  • the substrate to be cleaned was placed on a rotating disk at 375 rpm, the rotating substrate was immersed in the above composition, or the above composition was applied to a rotating substrate until the photoresist layer was completely removed.
  • composition of the composition 80 g of potassium permanganate, 50 g of acetone, 50 g of nonionic surfactant, 100 g of triazole and 720 g of deionized water.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Detergent Compositions (AREA)

Description

一种去除光阻层的组合物及其使用方法 技术领域
本发明涉及一种在半导体制造过程中去除光阻层的组合物及其使用方 法。 议不冃
在半导体元器件制造过程中， 光阻层的涂敷、暴光和成像可用来制造必 要的元器件图案。 在制图工艺结束时（即在光阻层的涂敷、 成像、 离子注入 刻蚀后） （如图 1所示），在进行下一个工艺步骤前，剩下的光阻材料需除去。 在离子注入的惨杂过程中， 离子轰击使得光阻层聚合物变硬了， 因此光阻层 更难溶了， 从而难以除去。至今在半导体制造工业中一直使用等离子刻蚀和 湿刻蚀两步法除去这层光阻层膜，第一步利用等离子刻蚀除去光阻层的大部 分；第二步的湿刻蚀工艺利用含高浓度和通常含有毒性的化学成分的清洁组 合物。清洁工艺需要花费很长的时间来完成， 且通常需要升高温度来辅助该 反应。 又因该两步工艺需要两套不同的设备， 所以成本较高。 除此之外， 现 有技术的工艺方法有时并不能把所有的光阻层都能清洗干净， 会留下残留 物。
现有技术中通常使用浓度相对较高的化学成分， 如有机溶剂、极性溶剂 和含氟化合物， 例如 Small EKC的专利 US6777380, Park Samsung的专利 US6274537, 和 Kanno等人的专利申请号为 US 20040106531的专利。
总之，该工艺的成本高、产量低又涉及到环境和光阻去除不干净等问题， 因此针对上述问题迫切需要提出一种新的清洁光阻层的工艺。 确 认 本 发明概要
本发明的目的正是针对上述问题， 提供一种新的去除光阻层的组合物， 其包括极性溶剂，其特征在于还包括氧化剂。该光阻层通常含有机物和 /或聚 合物。该极性溶剂能软化或溶解光阻层或光阻层中的有机物和聚合物， 该氧 化剂可以氧化有机物和聚合物，破坏原分子结构，从而达到溶解除去的效果。
其中， 该组合物还可以包括表面活性剂、抑制剂和 /或载体。所述的抑制 剂能降低或阻止底层衬底上由化学或机械方法所引起的损减、 腐蚀和点腐 蚀。 在离子注入中， 典型的衬底为硅衬底， 有时候一薄层氧化层沉积在硅衬 底上。 该抛光垫为具有平表面的任何塑料片或不同表面处理 /渠沟的塑料片， 以确保有足够的' 洁溶液分布在抛光衬底上。底层衬底包括但不限于硅、二 氧化硅、 离子掺杂的二氧化硅、低介电常数 k的材料和金属等衬底， 如铝或 铜。 所述的载体较佳地为水。
所述的极性溶剂的浓度为 5%-80%、该氧化剂的浓度为 0.01%-8%、该表 面活性剂的浓度为 0.001%-5%、 该抑制剂的浓度为 0.005%-10%和载体为余 量， 以上百分比均指占整个组合物的质量百分比浓度。
所述的氧化剂为有机或无机过氧化物中的一种或几种，较佳地为过氧化 氢、 过乙酸、 过硼酸、 过氧化钠、 过硫酸铵、 高锰酸钾、 硝酸和 /或硝酸盐。
所述的极性溶剂较佳地为有机胺、有机醇、有机醇胺、有机醚和 /或有机 酮， 所述的有机醇较佳地为链烷醇或多元醇。
所述的抑制剂为一元或多元羧酸以及它们的盐、水溶性带电离子有机材 料、水溶性带电离子聚合物材料和 /或水溶性含氮聚合物材料。较佳的含氮聚 合物材料为聚胺， 如聚乙烯胺及其盐类， 酰胺， 如聚酰胺 -酰亚胺或聚酰胺， 多元胺和 /或唑类。 所述的唑类较佳地为苯并三唑、 苯并咪唑、 三唑和 /或它 们的衍生物。
该组合物还可以包括络合剂、 分散剂、 催化剂和 pH调节剂中的一种或 几种。
本发明的另一目的是提供上述组合物的一种使用方法，其为将待清洁的 衬底浸泡在本发明的组合物中， 直至光阻层彻底除去。
较佳的使用方法为在室温下或在加温的环境下进行浸泡，加热温度不超 过该组合物的沸点。
另一种较佳的使用方法为在浸泡时并机械振荡该衬底。
又一种较佳的使用方法为用超声能量处理所述的组合物。
本发明的又一目的是提供上述组合物的另一种使用方法，该方法为将旋 转的衬底浸入本发明的组合物中， 或将本发明的组合物施加于旋转的衬底 上。
本发明的再一目的是提供上述组合物的又一种使用方法， 包括如下步 骤： 1 )将抛光垫置于抛光平台上， 将晶片置于晶片固定夹内， 在施加合适 的压力下， 使晶片与抛光垫接触； 2)施加本发明的组合物于抛光垫和与其 接触的晶片上，旋转抛光垫和 /或晶片使抛光垫摩擦晶片表面，直至彻底除去 光阻层。
其中， 上述晶片抛光后， 可以从固定夹内取出， 清洗之。 可以仅用去离 子水清洗晶片， 该去离子水也可以含有添加剂， 以更好地除去晶片上残余的 组合物和抛光下来的物质。较佳地为清洗晶片时边刷晶片。清洗晶片可以是 指在同一或不同的抛光平台上使用同一或不同的抛光垫。 本发明的积极进步效果在于： 1、 该组合物使用毒性小、 可燃性小的化 学物质且减少化学成分的用量， 使得其与环境更加友善、减少化学废物处理 的费用； 2、 该组合物的使用方法缩短了清洁工艺时间， 从而提高产量； 3、 将残留物除去得更彻底， 最终提高导电性能； 4、 采用本发明的抛光方法， 成本也可降低。
附图说明
图 1为现有技术中光阻层的涂敷、暴光和成像、等离子刻蚀工艺流程图。 发明内容
下面给出本发明较佳实施例， 以详细说明本发明的技术方案。
实施例 1
组合物的组成： 20g过硫酸铵、 500g乙二醇和 480g去离子水。
将被清洗的衬底放在一可封盖的溶液槽内， 添加上述组合物， 将该组合 物加温至 45 C， 浸泡衬底 5分钟， 取出， 然后用去离子水冲洗。
实施例 2
组合物的组成： 40g过氧化氢、 500g N-甲基 -乙-吡咯垸酮和 460g去离子 水。
将被清洗的衬底放在一可封盖的溶液槽内， 添加上述组合物， 将该组合 物加温至 45°C， 浸泡衬底 5分钟， 取出， 然后用去离子水冲洗。
实施例 3
组合物的组成： 20g过硫酸铵、 500g乙二醇、 O.lg非离子表面活性剂和 479.9g去离子水。
将被清洗的衬底放在一可封盖的溶液槽内， 添加上述组合物， 将该组合 物加温至 45°C， 浸泡衬底 5分钟， 取出， 然后用去离子水冲洗。
实施例 4
组合物的组成： 40g过氧化氢、 500g N-甲基-乙 -吡咯烷酮、 O.lg非离子 表面活性剂、 lg苯并三唑和 458.9g去离子水。
将被清洗的衬底放在一可封盖的溶液槽内， 添加上述组合物， 将该组合 物加温至 45°C， 浸泡衬底 5分钟， 取出， 然后用去离子水冲洗。
实施例 5
组合物的组成： O.lg过乙酸、 800g N-甲基-乙 -吡咯垸酮、 O.Olg非离子 表面活性剂、 0.05g苯并咪唑和 199.84g去离子水。
将待清洗的衬底浸入该组合物中， 然后对该组合物施于超声波， 该波振 荡频率为 40兆 HZ， 5分钟后取出衬底以去离子水清洗。
实施例 6
' 组合物的组成： 80g高锰酸钾、 50g丙酮、 5g非离子表面活性剂、 50g 三唑和 815g去离子水。
将待清洁的衬底置于旋转盘上 375转 /分钟，将旋转的衬底浸入上述组合 物中， 或将上述组合物施加于旋转的衬底上， 直至光阻层彻底除去。
实施例 7
组合物的组成： 80g高锰酸钾、 50g丙酮、 50g非离子表面活性剂、 100g 三唑和 720g去离子水。
将抛光垫置于抛光平台上，将晶片置于晶片固定夹内，在施加 3Psi压力 下， 使晶片与抛光垫接触； 施加上述组合物于抛光垫和与其接触的晶片上， 以每分钟 75转的转速旋转抛光垫和每分钟 55转的转速旋转晶片使抛光垫摩 擦晶片表面， 直至彻底除去光阻层。

Claims

权利要求
1、 一种去除光阻层的组合物， 其包括极性溶剂， 其特征在于还包括氧 化剂。
2、 根据权利要求 1所述的组合物， 其特征在于还包括表面活性剂、 抑 制剂和 /或载体。
3、 根据权利要求 2 所述的组合物， 其特征在于该极性溶剂的浓度为 5%-80%、该氧化剂的浓度为 0.01%-8%、该表面活性剂的浓度为 0.001%-5%、 该抑制剂的浓度为 0.005%-10%和载体为余量， 以上百分比均指占整个组合 物的质量百分比浓度。
4、 根据权利要求 1所述的组合物， 其特征在于该氧化剂为有机或无机 过氧化物中的一种或几种。
5、 根据权利要求 4所述的组合物， 其特征在于该氧化剂为过氧化氢、 过乙酸、 过硼酸、 过氧化钠、 过硫酸铵、 高锰酸钾、 硝酸和 /或硝酸盐。
6、 根据权利要求 1所述的组合物， 其特征在于该极性溶剂为有机胺、 有机醇、 有机醇胺、 有机醚和 /或有机酮。
7、 根据权利要求 6所述的组合物， 其特征在于所述的有机醇为链烷醇 或多元醇。
8、 根据权利要求 2所述的组合物， 其特征在于该抑制剂为一元或多元 羧酸以及它们的盐、水溶性带电离子有机材料、水溶性带电离子聚合物材料 和 /或水溶性含氮聚合物材料。
9、 根据权利要求 8所述的组合物， 其特征在于所述的含氮聚合物材料 为聚胺、 酰胺、 多元胺和 /或唑类。
10、根据权利要求 9所述的组合物，其特征在于所述的唑类为苯并三唑、 苯并咪唑、 三唑和 /或它们的衍生物。
11、 根据权利要求 1至 10任一项所述的组合物， 其特征在于该组合物 还包括络合剂、 分散剂、 催化剂和 pH调节剂中的一种或几种。
12、 一种权利要求 1至 10任一项所述的组合物的使用方法， 其特征在 于将待清洁的衬底浸泡在权利要求 1至 10任一项所述的组合物中， 直至光 阻层彻底除去。
13、 根据权利要求 12所述的使用方法， 其特征在于在室温下或在加温 的环境下进行浸泡， 加热温度不超过该组合物的沸点。
14、 根据权利要求 12所述的使用方法， 其特征在于在浸泡时并机械振 荡该衬底。
15、 根据权利要求 12所述的使用方法， 其特征在于用超声能量处理所 述的组合物。
16、 一种权利要求 1至 10任一项所述的组合物的使用方法， 其特征在 于将旋转的衬底浸入权利要求 1至 10任一项所述的组合物中， 或将权利要 求 1至 10任一项所述的组合物施加于旋转的衬底上。
17、 一种权利要求 1至 10任一项所述的组合物的使用方法， 包括如下 步骤： 1 )将抛光垫置于抛光平台上， 将晶片置于晶片固定夹内， 在施加合 适的压力下， 使晶片与抛光垫接触； 2)施加权利要求 1至 10任一项所述的 组合物于抛光垫和与其接触的晶片上，旋转抛光垫和 /或晶片使抛光垫摩擦晶 片表面， 直至彻底除去光阻层。
PCT/CN2006/000955 2005-05-13 2006-05-12 Composition pour l’elimination d’une couche de photoresist et procede pour l'utiliser WO2006125369A1 (fr)

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CN102626699A (zh) * 2012-04-25 2012-08-08 华灿光电股份有限公司 一种提高芯片亮度的方法
CN102854761A (zh) * 2012-08-08 2013-01-02 华灿光电股份有限公司 一种刻蚀后去胶的溶液和方法
CN113721430B (zh) * 2021-03-30 2022-09-23 腾讯科技（深圳）有限公司 光刻胶去除方法以及光刻胶去除系统
CN115066104A (zh) * 2022-07-09 2022-09-16 南通群安电子材料有限公司 针对厚光阻抗蚀剂的剥除液

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