WO2014089941A1 - Etchant and preparation method and application thereof - Google Patents

Etchant and preparation method and application thereof Download PDF

Info

Publication number
WO2014089941A1
WO2014089941A1 PCT/CN2013/073276 CN2013073276W WO2014089941A1 WO 2014089941 A1 WO2014089941 A1 WO 2014089941A1 CN 2013073276 W CN2013073276 W CN 2013073276W WO 2014089941 A1 WO2014089941 A1 WO 2014089941A1
Authority
WO
WIPO (PCT)
Prior art keywords
etchant
ammonium persulfate
wafer
sulfuric acid
cleaning
Prior art date
Application number
PCT/CN2013/073276
Other languages
French (fr)
Chinese (zh)
Inventor
亨利·萨莉·安
黄金涛
马嘉
吴仪
苏宇佳
Original Assignee
北京七星华创电子股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京七星华创电子股份有限公司 filed Critical 北京七星华创电子股份有限公司
Priority to US14/127,978 priority Critical patent/US20150144160A1/en
Publication of WO2014089941A1 publication Critical patent/WO2014089941A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/82—Auxiliary processes, e.g. cleaning or inspecting
    • 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
    • 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
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • 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
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means

Definitions

  • the invention belongs to the field of cleaning optical components, and in particular to an etchant and a preparation method and application thereof.
  • the organic matter remaining on the wafer includes photoresist, equipment oil, grease from skin produced by humans, fingerprint marks, dander, and particles in the breath.
  • the removal of organics in the semiconductor industry is critical because when attempting to remove the oxide layer using an HF solution, the residual organic material forms a film that prevents the HF solution from contacting the oxide layer, ie, the membrane isolating the HF.
  • the chemical solution is rendered inaccessible to the oxide film, i.e., the organic residue will interfere with the operation of removing the oxide layer, thereby inhibiting deposition of the selected dopant in the wafer or photomask region.
  • H 2 S0 4 sulfuric acid
  • 30% H 2 0 2 hydrogen peroxide
  • This mixture is often referred to as the "Piranha Candle Engraving Agent" (the piranha etchant because of its enormous ability to remove organic matter).
  • the piranha etchant because of its enormous ability to remove organic matter.
  • hydrogen peroxide one of the by-products is water. If the amount of hydrogen peroxide is too large, the solution will be diluted in a very short period of time, reducing the cleaning efficiency.
  • Another drawback of removing organic contaminants from wafers is that organic matter is converted to carbon dioxide.
  • the prior art is to add hydrogen peroxide in time before introducing the wafer to ensure that there is a relatively sufficient oxygen atom to promote the complete removal of carbon in the form of CO 2 ; it also reduces the sulfuric acid caused by the increase of water. Release.
  • the reaction of mixing hydrogen peroxide with sulfuric acid is:
  • the present invention proposes an etchant.
  • Another object of the invention is to propose the use of the etchant in cleaning wafers.
  • An etchant is formed by reacting sulfuric acid and ammonium persulfate, and the ammonium persulfate added during the reaction has a mass concentration of 1-25%.
  • the ammonium persulfate has a mass concentration of 5-10%.
  • sulfuric acid is 97-99% by mass of sulfuric acid.
  • the purity of ammonium persulfate is chemically pure or analytically pure.
  • a method of preparing an etchant according to the present invention is to add ammonium persulfate to sulfuric acid at 100 to 200 ° C and stir to dissolve.
  • ammonium persulfate is added to the hot sulfuric acid to form HO-0-(S0 2 )-(S0 2 )-0-OH (H 2 S 2 0 8 , persulfuric acid).
  • the hot sulfuric acid is placed in a quartz tank at 120 degrees, and the added ammonium persulfate powder is slowly dissolved in sulfuric acid, and after stirring, it is dissolved in a mixture of 5-10% by weight. If the ammonium persulfate ratio exceeds 25%, a quicker agitation is required.
  • the reaction of mixing ammonium persulfate and sulfuric acid is:
  • ammonium persulfate is added to the sulfuric acid at 110-130 ° C, Stir and dissolve.
  • the method of cleaning a wafer or a photomask by using the etchant of the present invention is to immerse the wafer or photomask to be cleaned in the etchant, soak for 5-20 minutes, and take out the wafer or photomask.
  • ammonium persulfate reacts with the organic matter represented by (CHO) x remaining on the wafer to form C0 2 , H 2 0 and H 2 S0 4 , and the reaction can be expressed as:
  • Ammonium persulfate is stable in sulfuric acid, does not decompose to produce a large amount of water, and produces persulfuric acid.
  • the reaction with organic matter also produces sulfuric acid, which enables the liquid to stabilize a certain concentration of the liquid for a long time.
  • hydrogen peroxide is very unstable, and it is easy to decompose and produce water, so that the concentration of water in the solution rises rapidly, resulting in low concentration of the solution and failure.
  • the etchant must be used with care when handling, and operators should wear goggles, face shields, and gloves when working with sulfuric acid, ammonium persulfate, and mixtures thereof, and working near these mixtures.
  • the temperature of the etchant is 100-200 °C. The temperature does not rise after immersion in the wafer because the reaction is not an exothermic reaction.
  • the wafer or photomask to be processed is washed with a cleaning solution and deionized water before being immersed in the etchant
  • the cleaning solution is a cleaning liquid of 58-65 degrees
  • the deionized water It is 68-72 degrees deionized water.
  • the wafer or photomask is washed with a 58-65 degree SC1 solution, then washed with 68-72 degrees of deionized water, and then dried.
  • the etchant proposed by the present invention is prepared by adding ammonium persulfate to sulfuric acid at 100-200 ° C and replacing oxidant hydrogen peroxide with ammonium persulfate.
  • Ammonium persulfate is a powder that makes handling easier;
  • the etchant proposed by the present invention treats wafers because sulfuric acid is a by-product of reaction with organic substances, and water is not a by-product, so that the etchant is not diluted after repeated cleaning, saving production costs.
  • Another advantage of the present invention is that by-product sulfuric acid is produced during cleaning. Since sulfuric acid is a by-product of ammonium persulfate, the addition of excess ammonium persulfate does not reduce the effectiveness of the solution.
  • the concentration of ammonium persulfate in sulfuric acid can range from 1% to 25% can be used to clean the wafer, as well as to clean the photomask. detailed description
  • Example 1 The ammonium persulfate in the examples was purchased from BASF, FMC Chemicals, and the purity was chemically pure.
  • Example 1 The ammonium persulfate in the examples was purchased from BASF, FMC Chemicals, and the purity was chemically pure.
  • the wafer to be processed is first cleaned with a standard cleaning solution (SC1) at a temperature of 60 ° C, then washed with deionized water at 70 ° C and dried.
  • SC1 standard cleaning solution
  • the wafer is taken out. It was then washed with a standard cleaning solution No. 1 at 60 ° C and then with 70 ° C of deionized water. It was then dried using IPA vapor isopropanol steam.
  • the tank will turn red or purple.
  • the life of a liquid medicine is determined according to how many wafers are washed. If it is washed more, the liquid medicine will fail quickly, and the washing will be less. The liquid can be used for a little longer. However, about 4 hours after the ratio of the liquid medicine, it is necessary to replace the new liquid.
  • the medical solution used in this embodiment can reach a use time of 4 hours.
  • the processed wafers are cleaned to SEMI (Industry Standard) cleaning specifications.
  • the wafer to be processed was first cleaned with a SC1 cleaning solution at a temperature of 60 ° C, then washed with 70 ° C of deionized water and dried.
  • the wafer is taken out. It was then washed with a standard cleaning solution No. 1 at 60 ° C and then with 70 ° C of deionized water. It was then dried using IPA vapor isopropanol steam. The wafer cleanliness after processing has reached SEMI (Industry Standard) cleaning specifications.
  • the wafer to be processed was first washed with a SC1 cleaning solution at a temperature of 62 ° C, then washed with deionized water at 72 ° C and dried.
  • the wafer is taken out. It was then washed with a No. 1 standard cleaning solution at 60 ° C and then with 68 ° C of deionized water. It was then dried using IPA vapor isopropanol steam. The wafer cleanliness after processing has reached SEMI (Industry Standard) cleaning specifications.
  • the sulfuric acid filled with 98% concentration is heated to 150 degrees in a quartz bath, and ammonium persulfate powder is slowly added at this temperature, the weight ratio is 25%, and the stirring strength is large, and the ammonium persulfate powder is dissolved. Then, immerse the wafer into the cleaning bath for 5 minutes.
  • the other steps are the same as in the first embodiment.
  • the processed wafers are cleaned to SEMI (Industry Standard) cleaning specifications.
  • SEMI Industry Standard
  • the same method can also clean the photomask, which is another device when lithographic wafers. It is also possible to be contaminated with organic matter, so sometimes it is necessary to clean the photomask as if it were a wafer.
  • the present invention provides an etchant which is obtained by reacting sulfuric acid and ammonium persulfate, and the ammonium persulfate added at the time of the reaction has a mass concentration of 1-25%.
  • the sulfuric acid is 98% by mass of sulfuric acid.
  • the present invention also proposes a method of preparing the etchant by adding ammonium persulfate to sulfuric acid at 100 to 200 °C.
  • the present invention uses ammonium persulfate in place of the oxidant hydrogen peroxide.
  • Ammonium persulfate is a powder that makes the operation simpler; the wafer or photomask is treated with the etchant proposed by the present invention, because sulfuric acid is a by-product of reaction with organic matter, not water, so the etchant is not washed after repeated cleaning. Will be diluted, saving production costs.
  • the proposed etchant produces a by-product sulfuric acid during cleaning. Since sulfuric acid is a by-product of ammonium persulfate, the addition of excess ammonium persulfate does not reduce the effectiveness of the solution.
  • the concentration of ammonium persulfate in sulfuric acid can range from 1% to 25% can be used to clean the wafer, as well as to clean the photomask for better industrial applicability.

Landscapes

  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

Provided is an etchant, which is formed by the reaction of sulphuric acid and ammonium persulfate, the mass concentration of ammonium persulfate being 1-25%. The sulphuric acid is a sulphuric acid with a mass concentration of 98%. Also provided is a method for preparing the etchant, which comprises adding ammonium persulfate into sulphuric acid of 100-200°C. Ammonium persulfate replaces an oxidant of hydrogen peroxide in the present invention. Ammonium persulfate is a powder, so the operation is relatively simple. The etchant provided in the present invention treats wafers or photomasks. Since sulphuric acid, instead of water, is the byproduct of the reaction with organics, the etchant will not be diluted after multiple cleanings, saving the production costs.

Description

一种蚀刻剂及其制备方法和应用 技术领域  Etchant and preparation method and application thereof
本发明属于光学元件的清洗的领域，具体为一种蚀刻剂及其制备 方法和应用。  The invention belongs to the field of cleaning optical components, and in particular to an etchant and a preparation method and application thereof.
背景技术 Background technique
晶片上残留的有机物包括光致抗蚀剂、 设备油、 人类所产生的皮 肤的油脂、 指紋痕迹、 皮屑以及呼吸中的颗粒等。 半导体工业中除去 有机物的步骤是至关重要的， 因为当试图使用 HF溶液去除氧化层时， 残留的有机物会形成一个膜， 所形成的膜妨碍 HF溶液接触到氧化层， 也就是膜隔离了 HF药液使之接触不到氧化膜， 即有机物残留将妨碍 去除氧化层的操作，从而抑制所选择的掺杂剂在晶片或光掩膜区域的 沉积。  The organic matter remaining on the wafer includes photoresist, equipment oil, grease from skin produced by humans, fingerprint marks, dander, and particles in the breath. The removal of organics in the semiconductor industry is critical because when attempting to remove the oxide layer using an HF solution, the residual organic material forms a film that prevents the HF solution from contacting the oxide layer, ie, the membrane isolating the HF. The chemical solution is rendered inaccessible to the oxide film, i.e., the organic residue will interfere with the operation of removing the oxide layer, thereby inhibiting deposition of the selected dopant in the wafer or photomask region.
通常情况下， 98 %的 H2S04 (硫酸） 和 30 % H202 (过氧化氢） 的体积比分别为 2-4:1混合物在 100°C和更高的温度下使用， 以去除残 留的有机物。 该混合物通常被称为 "Piranha烛刻剂 "（食人鱼刻蚀剂， 因为其巨大的去除有机物的能力）。 使用过氧化氢时， 副产物之一是 水， 如果过氧化氢用量过多， 则在一个非常短的时间内溶液会被稀 释， 降低清洗效率。 从晶片上去除有机污染物的另一缺陷在于有机物 会转化为二氧化碳。 因此， 在处理槽中添加过多过氧化氢的后果是十 分严重。 系统中加入过量的过氧化氢会迅速的稀释硫酸， 从而使产品 清洁不够。 过氧化氢分解成氧原子和水； 其中的水会稀释的硫酸， 从 而降低化学清洗效果。 现有技术的操作过程是先倒入硫酸， 然后将其 加热到所需的温度， 在工艺槽中放入过氧化氢， 之后马上放入待清洗 的晶片。 原子氧开始产生并在十分钟左右停止。 因此， 现有技术是在 导入晶片之前及时加入过氧化氢以确保有相对足够的氧原子来促进 以 C02形式存在的碳的完全去除； 它也减少了水的增加引起的硫酸稀 释。 Typically, 98% of H 2 S0 4 (sulfuric acid) and 30% H 2 0 2 (hydrogen peroxide) are used in a volume ratio of 2-4:1 mixture at 100 ° C and higher, respectively. Remove residual organic matter. This mixture is often referred to as the "Piranha Candle Engraving Agent" (the piranha etchant because of its enormous ability to remove organic matter). When hydrogen peroxide is used, one of the by-products is water. If the amount of hydrogen peroxide is too large, the solution will be diluted in a very short period of time, reducing the cleaning efficiency. Another drawback of removing organic contaminants from wafers is that organic matter is converted to carbon dioxide. Therefore, the consequence of adding too much hydrogen peroxide to the treatment tank is very serious. The addition of excess hydrogen peroxide to the system rapidly dilutes the sulfuric acid, making the product less clean. Hydrogen peroxide decomposes into oxygen atoms and water; the water therein dilutes the sulfuric acid, thereby reducing the chemical cleaning effect. The prior art operation involves first pouring sulfuric acid, then heating it to the desired temperature, placing hydrogen peroxide in the process tank, and immediately placing the wafer to be cleaned. Atomic oxygen begins to form and stops in about ten minutes. Therefore, the prior art is to add hydrogen peroxide in time before introducing the wafer to ensure that there is a relatively sufficient oxygen atom to promote the complete removal of carbon in the form of CO 2 ; it also reduces the sulfuric acid caused by the increase of water. Release.
过氧化氢和硫酸混合的反应为：  The reaction of mixing hydrogen peroxide with sulfuric acid is:
H202 + H2S04 H2S05 + H20 ( 1 ) 根据已有的报道， 在单晶片清洗机上使用 Piranha, 只有将室温下 的过氧化氢与 120到 150摄氏度的硫酸混合才有效果。混合反应（ 1 ) 为 一个放热反应， 混合物达到 200摄氏度， 可使抗蚀剂在 60秒到 90秒之 间被剥离。然而清洗机中用这些高温物，使清洗机材料受到很大压力。 此外，在这样的高温下会导致氮化硅沿着硅的晶格结构破裂同时暴露 在栅极周围， 也被刻蚀。 在这个过程中， 硫酸被用来把有机物转换成 碳。 使用之前才被混合的化学药品要被排放掉， 因为清洗的有效时间 短， 水浓度升高， 因而导致化学品损失高。 碳和原子氧反应形成二氧 化碳， 从工艺槽中溢出， 原子氧的产生是因为过氧化氢的分解。 晶片 上残留的液体非常粘稠， 在 60度 SC1溶液 （1号标准清洗液） 漂洗之 前， 用 70度去离子水冲洗晶片表面的粘稠液体是必不可少的。 Piranha 刻蚀剂可高效去除有机残留， 然而， 它不能去除无机污染物， 例如重 金属。 发明内容 H 2 0 2 + H 2 S0 4 H 2 S0 5 + H 2 0 ( 1 ) According to prior reports, using Piranha on a single wafer cleaner, only hydrogen peroxide at room temperature is mixed with sulfuric acid at 120 to 150 degrees Celsius. Only effective. The mixed reaction (1) is an exothermic reaction, and the mixture reaches 200 degrees Celsius, so that the resist can be peeled off between 60 seconds and 90 seconds. However, the use of these high temperature materials in the washing machine places great pressure on the material of the washing machine. In addition, at such high temperatures, silicon nitride is caused to rupture along the crystal lattice structure of the silicon while being exposed around the gate electrode, and is also etched. In this process, sulfuric acid is used to convert organic matter into carbon. Chemicals that are mixed before use are discharged because the effective time of cleaning is short and the water concentration is increased, resulting in high chemical loss. Carbon and atomic oxygen react to form carbon dioxide, which overflows from the process tank. The generation of atomic oxygen is due to the decomposition of hydrogen peroxide. The residual liquid on the wafer is very viscous. It is essential to rinse the viscous liquid on the surface of the wafer with 70-degree deionized water before rinsing with a 60-degree SC1 solution (standard cleaning solution No. 1). Piranha etchants remove organic residues efficiently, however, they do not remove inorganic contaminants such as heavy metals. Summary of the invention
针对现有技术存在的不足之处， 本发明提出一种蚀刻剂。  In view of the deficiencies of the prior art, the present invention proposes an etchant.
本发明的另一目的是提出所述蚀刻剂在清洗晶片中的应用。  Another object of the invention is to propose the use of the etchant in cleaning wafers.
实现本发明上述目的的技术方案为：  The technical solution for achieving the above object of the present invention is:
一种蚀刻剂， 是由硫酸和过硫酸铵反应而成， 反应时加入的过硫 酸铵的质量浓度为 1-25%。  An etchant is formed by reacting sulfuric acid and ammonium persulfate, and the ammonium persulfate added during the reaction has a mass concentration of 1-25%.
优选地， 所述过硫酸铵的质量浓度为 5-10%。  Preferably, the ammonium persulfate has a mass concentration of 5-10%.
其中， 所述硫酸为 97-99%质量浓度的硫酸。 过硫酸铵的纯度为 化学纯或分析纯。  Wherein the sulfuric acid is 97-99% by mass of sulfuric acid. The purity of ammonium persulfate is chemically pure or analytically pure.
制备本发明所述的蚀刻剂的方法， 其是将过硫酸铵加入 100-200 °C的硫酸中， 搅拌溶解。 当过硫酸铵添加到热硫酸中形成 HO-0-(S02)-(S02)-0-OH (H2S208 , 过硫酸)。 热硫酸在 120度的时候放在石英槽里， 加入的过 硫酸铵粉末缓慢的溶解在硫酸中， 经过搅拌， 溶解为 5-10%重量比例 的混合物。 如果过硫酸铵比例超过 25%的时候需要比较急促的搅拌。 A method of preparing an etchant according to the present invention is to add ammonium persulfate to sulfuric acid at 100 to 200 ° C and stir to dissolve. When ammonium persulfate is added to the hot sulfuric acid to form HO-0-(S0 2 )-(S0 2 )-0-OH (H 2 S 2 0 8 , persulfuric acid). The hot sulfuric acid is placed in a quartz tank at 120 degrees, and the added ammonium persulfate powder is slowly dissolved in sulfuric acid, and after stirring, it is dissolved in a mixture of 5-10% by weight. If the ammonium persulfate ratio exceeds 25%, a quicker agitation is required.
过硫酸铵和硫酸混合的反应为：  The reaction of mixing ammonium persulfate and sulfuric acid is:
(NH4)S208 + H2S04—► (NH4)S04 + H2S208 ( 2 ) 优选地， 是将过硫酸铵加入到 110-130°C的硫酸中， 搅拌溶解。 本发明所述的蚀刻剂在清洗晶片或光掩膜中的应用。 (NH 4 )S 2 0 8 + H 2 S0 4 —► (NH 4 )S0 4 + H 2 S 2 0 8 ( 2 ) Preferably, ammonium persulfate is added to the sulfuric acid at 110-130 ° C, Stir and dissolve. The use of the etchant of the present invention in cleaning wafers or photomasks.
釆用本发明所述的蚀刻剂清洗晶片或光掩膜的方法，是将待清洗 的晶片或光掩膜浸入所述蚀刻剂， 浸泡 5-20分钟， 取出晶片或光掩 膜。  The method of cleaning a wafer or a photomask by using the etchant of the present invention is to immerse the wafer or photomask to be cleaned in the etchant, soak for 5-20 minutes, and take out the wafer or photomask.
该蚀刻剂处理晶片时，过硫酸铵与晶片上残留的用 (CHO)x表示的 有机物反应生成 C02, H20和 H2S04, 该反应可表示为： When the etchant treats the wafer, ammonium persulfate reacts with the organic matter represented by (CHO) x remaining on the wafer to form C0 2 , H 2 0 and H 2 S0 4 , and the reaction can be expressed as:
H2S208 + (CHO)x —► xC02 + xH20 + H2S04 ( 3 ) 过硫酸铵混合在硫酸里比较稳定， 不会分解产生大量的水， 并且 生成的过硫酸和有机物反应还会产生硫酸，使药液能够长时间稳定一 定的药液浓度。 相比于过氧化氢， 因过氧化氢很不稳定， 很容易分解 产生水，使溶液中水的浓度迅速升高，导致溶液浓度变低而导致失效。 H 2 S 2 0 8 + (CHO) x —► xC0 2 + xH 2 0 + H 2 S0 4 ( 3 ) Ammonium persulfate is stable in sulfuric acid, does not decompose to produce a large amount of water, and produces persulfuric acid. The reaction with organic matter also produces sulfuric acid, which enables the liquid to stabilize a certain concentration of the liquid for a long time. Compared with hydrogen peroxide, hydrogen peroxide is very unstable, and it is easy to decompose and produce water, so that the concentration of water in the solution rises rapidly, resulting in low concentration of the solution and failure.
在进行操作时，必须小心使用该蚀刻剂，操作人员应在使用硫酸、 过硫酸铵及其混合物和在这些混合物附近工作时佩戴护目镜、面罩和 手套。  The etchant must be used with care when handling, and operators should wear goggles, face shields, and gloves when working with sulfuric acid, ammonium persulfate, and mixtures thereof, and working near these mixtures.
其中， 所述待清洗的晶片或光掩膜浸入蚀刻剂时， 蚀刻剂的温度 为 100-200°C。 浸入晶片后温度不会升高， 因为反应不是一个放热反 应。  Wherein, when the wafer or photomask to be cleaned is immersed in the etchant, the temperature of the etchant is 100-200 °C. The temperature does not rise after immersion in the wafer because the reaction is not an exothermic reaction.
其中，所述待处理的晶片或光掩膜在浸入蚀刻剂之前先使用清洗 液和去离子水清洗， 所述清洗液为 58-65度的清洗液， 所述去离子水 为 68-72度的去离子水。 Wherein the wafer or photomask to be processed is washed with a cleaning solution and deionized water before being immersed in the etchant, the cleaning solution is a cleaning liquid of 58-65 degrees, and the deionized water It is 68-72 degrees deionized water.
其中， 取出晶片或光掩膜后， 还包括将晶片或光掩膜用 58-65度 的 SC1溶液清洗，然后用 68-72度的去离子水冲洗，然后烘干的步骤。  Wherein, after the wafer or photomask is taken out, the wafer or photomask is washed with a 58-65 degree SC1 solution, then washed with 68-72 degrees of deionized water, and then dried.
本发明的有益效果：  The beneficial effects of the invention:
本发明提出的蚀刻剂的制备方法， 是将过硫酸铵加入 100-200°C 的硫酸中， 用过硫酸铵替代氧化剂过氧化氢。 过硫酸铵是一种粉末， 使操作更简单；  The etchant proposed by the present invention is prepared by adding ammonium persulfate to sulfuric acid at 100-200 ° C and replacing oxidant hydrogen peroxide with ammonium persulfate. Ammonium persulfate is a powder that makes handling easier;
本发明提出的蚀刻剂处理晶片， 因为硫酸是与有机物反应的副产 物， 而不是水为副产物， 所以多次清洗后蚀刻剂也不会被稀释， 节约 了生产成本。  The etchant proposed by the present invention treats wafers because sulfuric acid is a by-product of reaction with organic substances, and water is not a by-product, so that the etchant is not diluted after repeated cleaning, saving production costs.
本发明的另一优点是清洗时产生副产物硫酸， 由于硫酸是过硫 酸铵的副产物， 加入过量的过硫酸铵不会降低溶液的效力， 过硫酸铵 在硫酸中浓度就可以从 1% 到 25%,可以用来清洁晶片， 同样还可以 清洁光掩膜。 具体实施方式  Another advantage of the present invention is that by-product sulfuric acid is produced during cleaning. Since sulfuric acid is a by-product of ammonium persulfate, the addition of excess ammonium persulfate does not reduce the effectiveness of the solution. The concentration of ammonium persulfate in sulfuric acid can range from 1% to 25% can be used to clean the wafer, as well as to clean the photomask. detailed description
以下实施例用于说明本发明， 但不用来限制本发明的范围。  The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
实施例中的过硫酸铵购自 BASF, FMC Chemicals,纯度为化学纯。 实施例 1  The ammonium persulfate in the examples was purchased from BASF, FMC Chemicals, and the purity was chemically pure. Example 1
待处理的晶片先用温度为 60°C的 1号标准清洗液 （SC1 ) 清洗， 然后用 70°C的去离子水清洗， 烘干。  The wafer to be processed is first cleaned with a standard cleaning solution (SC1) at a temperature of 60 ° C, then washed with deionized water at 70 ° C and dried.
装满浓度为 98%的硫酸在石英材质的清洗槽中并加热到 120度， 并在此温度下缓慢的加入过硫酸铵粉末， 质量比例为 7%,搅拌溶解。 然后， 浸入晶片到清洗槽中 10分钟。  Fill the 98% sulfuric acid in a quartz bath and heat it to 120 °C. At this temperature, slowly add ammonium persulfate powder at a mass ratio of 7% and stir to dissolve. Then, immerse the wafer into the cleaning bath for 10 minutes.
将晶片取出。 再用 60°C的 1号标准清洗液清洗， 然后用 70°C的去 离子水清洗。 然后用 IPA vapor异丙醇蒸汽烘干。  The wafer is taken out. It was then washed with a standard cleaning solution No. 1 at 60 ° C and then with 70 ° C of deionized water. It was then dried using IPA vapor isopropanol steam.
如果没有足够的氧化剂， 清洗槽内会变成红色或紫色。 一次药液 的寿命是根据洗多少晶片而定， 洗的多， 药液就失效的快， 洗的少， 药液就能多用一些时间。 但是在药液配比完之后的 4个小时左右， 也 需要更换新的药液。 本实施例使用的药液可达到 4小时的使用时间。 If there is not enough oxidant, the tank will turn red or purple. The life of a liquid medicine is determined according to how many wafers are washed. If it is washed more, the liquid medicine will fail quickly, and the washing will be less. The liquid can be used for a little longer. However, about 4 hours after the ratio of the liquid medicine, it is necessary to replace the new liquid. The medical solution used in this embodiment can reach a use time of 4 hours.
处理后的晶片清洁度均达到 SEMI (行业标准） 清洁规格。  The processed wafers are cleaned to SEMI (Industry Standard) cleaning specifications.
实施例 2 Example 2
待处理的晶片先用温度为 60°C的 SC1清洗液清洗， 然后用 70°C的 去离子水清洗， 烘干。  The wafer to be processed was first cleaned with a SC1 cleaning solution at a temperature of 60 ° C, then washed with 70 ° C of deionized water and dried.
装满浓度为 98%的硫酸在石英材质的清洗槽中并加热到 130度， 并在此温度下缓慢的加入过硫酸铵粉末， 重量比率 10%, 搅拌溶解。 然后， 浸入晶片到清洗槽中 8分钟。  Fill the 98% sulfuric acid in a quartz bath and heat it to 130 °C. At this temperature, slowly add ammonium persulfate powder at a weight ratio of 10% and stir to dissolve. Then, immerse the wafer into the cleaning bath for 8 minutes.
将晶片取出。 再用 60°C的 1号标准清洗液清洗， 然后用 70°C的去 离子水清洗。 然后用 IPA vapor异丙醇蒸汽烘干。 处理后的晶片清洁度 均达到 SEMI (行业标准） 清洁规格。  The wafer is taken out. It was then washed with a standard cleaning solution No. 1 at 60 ° C and then with 70 ° C of deionized water. It was then dried using IPA vapor isopropanol steam. The wafer cleanliness after processing has reached SEMI (Industry Standard) cleaning specifications.
实施例 3 Example 3
待处理的晶片先用温度为 62°C的 SC1清洗液清洗， 然后用 72°C的 去离子水清洗， 烘干。  The wafer to be processed was first washed with a SC1 cleaning solution at a temperature of 62 ° C, then washed with deionized water at 72 ° C and dried.
装满浓度为 98%的硫酸在石英材质的清洗槽中并加热到 110度， 并在此温度下缓慢的加入过硫酸铵粉末， 重量比率 5%, 搅拌溶解。 然后， 浸入晶片到清洗槽中 20分钟。  Fill the 98% sulfuric acid in a quartz bath and heat it to 110 °C, and slowly add ammonium persulfate powder at this temperature, 5% by weight, stir and dissolve. Then, the wafer was immersed in the cleaning bath for 20 minutes.
将晶片取出。 再用 60°C的 1号标准清洗液清洗， 然后用 68°C的去 离子水清洗。 然后用 IPA vapor异丙醇蒸汽烘干。 处理后的晶片清洁度 均达到 SEMI (行业标准） 清洁规格。  The wafer is taken out. It was then washed with a No. 1 standard cleaning solution at 60 ° C and then with 68 ° C of deionized water. It was then dried using IPA vapor isopropanol steam. The wafer cleanliness after processing has reached SEMI (Industry Standard) cleaning specifications.
实施例 4 Example 4
装满浓度为 98%的硫酸在石英材质的清洗槽中加热到 150度， 并 在此温度下缓慢的加入过硫酸铵粉末，重量比率 25%,搅拌强度较大， 至过硫酸铵粉末溶解。 然后， 浸入晶片到清洗槽中 5分钟。 其他步骤 同实施例 1。  The sulfuric acid filled with 98% concentration is heated to 150 degrees in a quartz bath, and ammonium persulfate powder is slowly added at this temperature, the weight ratio is 25%, and the stirring strength is large, and the ammonium persulfate powder is dissolved. Then, immerse the wafer into the cleaning bath for 5 minutes. The other steps are the same as in the first embodiment.
处理后的晶片清洁度均达到 SEMI (行业标准） 清洁规格。 实施例 5 The processed wafers are cleaned to SEMI (Industry Standard) cleaning specifications. Example 5
同样的方法也可以清洁光掩膜，光掩膜是在光刻晶片的时候的另 一个器件。 也有可能被有机物污染， 所以有时候也需要像清洗晶片一 样清洗光掩膜。  The same method can also clean the photomask, which is another device when lithographic wafers. It is also possible to be contaminated with organic matter, so sometimes it is necessary to clean the photomask as if it were a wafer.
清洁光掩模的过程同实施例 1。  The process of cleaning the photomask is the same as in Embodiment 1.
虽然， 以上通过实施例对本发明进行了说明， 但本领域技术人员 应了解， 在不偏离本发明精神和实质的前提下， 对本发明所做的改进 和变型， 均应属于本发明的保护范围内。 工业实用性  While the invention has been described by the embodiments of the present invention, it should be understood by those skilled in the art that the modifications and variations of the present invention are within the scope of the present invention without departing from the spirit and scope of the invention. . Industrial applicability
本发明提供一种蚀刻剂， 其是由硫酸和过硫酸铵反应而成， 反应 时加入的过硫酸铵的质量浓度为 1-25%。 硫酸为 98%质量浓度的硫 酸。本发明还提出制备该蚀刻剂的方法，其是将过硫酸铵加入 100-200 °C的硫酸中。 本发明用过硫酸铵替代氧化剂过氧化氢。 过硫酸铵是一 种粉末， 使操作更简单； 用本发明提出的蚀刻剂处理晶片或光掩模， 因为硫酸是与有机物反应的副产物， 而不是水， 所以多次清洗后蚀刻 剂也不会被稀释， 节约了生产成本。 本发明的提出的蚀刻剂清洗时产 生副产物硫酸， 由于硫酸是过硫酸铵的副产物， 加入过量的过硫酸铵 不会降低溶液的效力， 过硫酸铵在硫酸中浓度就可以从 1% 到 25% , 可以用来清洁晶片，同样还可以清洁光掩膜，具有更好的工业实用性。  The present invention provides an etchant which is obtained by reacting sulfuric acid and ammonium persulfate, and the ammonium persulfate added at the time of the reaction has a mass concentration of 1-25%. The sulfuric acid is 98% by mass of sulfuric acid. The present invention also proposes a method of preparing the etchant by adding ammonium persulfate to sulfuric acid at 100 to 200 °C. The present invention uses ammonium persulfate in place of the oxidant hydrogen peroxide. Ammonium persulfate is a powder that makes the operation simpler; the wafer or photomask is treated with the etchant proposed by the present invention, because sulfuric acid is a by-product of reaction with organic matter, not water, so the etchant is not washed after repeated cleaning. Will be diluted, saving production costs. The proposed etchant produces a by-product sulfuric acid during cleaning. Since sulfuric acid is a by-product of ammonium persulfate, the addition of excess ammonium persulfate does not reduce the effectiveness of the solution. The concentration of ammonium persulfate in sulfuric acid can range from 1% to 25% can be used to clean the wafer, as well as to clean the photomask for better industrial applicability.

Claims

权 利 要 求 书 claims
1、 一种蚀刻剂， 其特征在于， 所述蚀刻剂是由硫酸和过硫酸铵 反应而成， 反应时加入的过硫酸铵的质量浓度为 1-25%。 1. An etchant, characterized in that the etchant is formed by reacting sulfuric acid and ammonium persulfate, and the mass concentration of ammonium persulfate added during the reaction is 1-25%.
2、 如权利要求 1所述的蚀刻剂， 其特征在于， 所述过硫酸铵的质 量浓度为 5-10%。 2. The etchant according to claim 1, wherein the mass concentration of the ammonium persulfate is 5-10%.
3、如权利要求 1所述的蚀刻剂，其特征在于，所述硫酸为 97-99% 质量浓度的硫酸。 3. The etchant according to claim 1, wherein the sulfuric acid is sulfuric acid with a mass concentration of 97-99%.
4、 制备权利要求 1-3任一所述的蚀刻剂的方法， 其特征在于， 是将过硫酸铵加入 100-200°C的硫酸中， 搅拌溶解。 4. The method for preparing the etchant according to any one of claims 1 to 3, characterized in that ammonium persulfate is added to sulfuric acid at 100-200°C, and stirred to dissolve.
5、 如权利要求 4所述的方法， 其特征在于， 是将过硫酸铵加入 到 110-130°C的硫酸中， 搅拌溶解。 5. The method of claim 4, characterized in that ammonium persulfate is added to sulfuric acid at 110-130°C, and stirred to dissolve.
6、 权利要求 1-3任一所述的蚀刻剂在清洗晶片或光掩模中的应 用。 6. Application of the etchant according to any one of claims 1 to 3 in cleaning wafers or photomasks.
7、 釆用权利要求 1-3任一所述的蚀刻剂清洗晶片或光掩模的方 法， 其特征在于， 将待清洗的晶片或光掩模浸入所述的蚀刻剂， 浸泡 5-20分钟， 取出晶片或光掩模。 7. A method for cleaning a wafer or photomask using the etchant of any one of claims 1 to 3, characterized in that the wafer or photomask to be cleaned is immersed in the etchant for 5-20 minutes. , take out the wafer or photomask.
8、 如权利要求 7所述的方法， 其特征在于， 所述待处理的晶片 或光掩模在浸入蚀刻剂之前先使用清洗液和去离子水清洗，所述清洗 液为 58-65度的清洗液， 所述去离子水为 68-72度的去离子水。 8. The method of claim 7, wherein the wafer or photomask to be processed is cleaned with a cleaning solution and deionized water before being immersed in the etchant, and the cleaning solution is 58-65 degrees Celsius. Cleaning liquid, the deionized water is 68-72 degree deionized water.
9、 如权利要求 7或 8所述的方法， 其特征在于， 取出晶片或光 掩模后， 还包括将晶片用 58-65度的清洗液清洗， 再用 68-72度的去 离子水冲洗， 然后烘干的步骤。 9. The method according to claim 7 or 8, characterized in that after taking out the wafer or photomask, it also includes cleaning the wafer with a cleaning solution at 58-65 degrees, and then rinsing with deionized water at 68-72 degrees , and then the drying step.
PCT/CN2013/073276 2012-12-13 2013-03-27 Etchant and preparation method and application thereof WO2014089941A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/127,978 US20150144160A1 (en) 2012-12-13 2013-03-27 Etchant, preparation thereof and method of using the same in the cleaning process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210540299.0 2012-12-13
CN201210540299.0A CN103013523B (en) 2012-12-13 2012-12-13 Etching agent as well as preparation method and application thereof

Publications (1)

Publication Number Publication Date
WO2014089941A1 true WO2014089941A1 (en) 2014-06-19

Family

ID=47962646

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/073276 WO2014089941A1 (en) 2012-12-13 2013-03-27 Etchant and preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN103013523B (en)
WO (1) WO2014089941A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104047004A (en) * 2014-06-23 2014-09-17 梧州恒声电子科技有限公司 Reagent for removing oxide scale on surface of copper and preparation method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103013523B (en) * 2012-12-13 2014-05-14 北京七星华创电子股份有限公司 Etching agent as well as preparation method and application thereof
CN107315316A (en) * 2017-07-27 2017-11-03 常州瑞择微电子科技有限公司 A kind of photomask cleaning agent to metal low corrosion

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2000525A (en) * 1977-06-24 1979-01-10 Polychrome Corp Aluminum desmutting agent
KR20090081545A (en) * 2008-01-24 2009-07-29 동우 화인켐 주식회사 Etchant composition and method for fabricating metal pattern
CN103013523A (en) * 2012-12-13 2013-04-03 北京七星华创电子股份有限公司 Etching agent as well as preparation method and application thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855805A (en) * 1996-08-08 1999-01-05 Fmc Corporation Microetching and cleaning of printed wiring boards
JP2006066889A (en) * 2004-07-29 2006-03-09 Mitsui Mining & Smelting Co Ltd Printed circuit board, manufacturing method thereof, and semiconductor device
CN101245462A (en) * 2007-02-13 2008-08-20 峻科技有限公司 Etching liquid composition and etching method
CN101033550B (en) * 2007-03-27 2010-09-29 广东东硕科技有限公司 Micro-corrosion liquid and application thereof in printing wiring board silver aggradation pretreatment
CN101453838A (en) * 2007-11-29 2009-06-10 富葵精密组件(深圳)有限公司 Manufacturing method for circuit board
CN101460011B (en) * 2007-12-12 2012-03-21 富葵精密组件(深圳)有限公司 Circuit board manufacturing method
CN101935838A (en) * 2010-08-01 2011-01-05 梅州博敏电子有限公司 Microetching processing method used before copper deposition of printed circuit board
CN102797000B (en) * 2012-07-11 2014-12-31 常州大学 Choline-chloride-based chemical silvering solution and application method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2000525A (en) * 1977-06-24 1979-01-10 Polychrome Corp Aluminum desmutting agent
KR20090081545A (en) * 2008-01-24 2009-07-29 동우 화인켐 주식회사 Etchant composition and method for fabricating metal pattern
CN103013523A (en) * 2012-12-13 2013-04-03 北京七星华创电子股份有限公司 Etching agent as well as preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104047004A (en) * 2014-06-23 2014-09-17 梧州恒声电子科技有限公司 Reagent for removing oxide scale on surface of copper and preparation method thereof

Also Published As

Publication number Publication date
CN103013523B (en) 2014-05-14
CN103013523A (en) 2013-04-03

Similar Documents

Publication Publication Date Title
TWI376273B (en) Semiconductor substrate process
KR100863159B1 (en) Composition comprising an oxidizing and complexing compoung
TW200423244A (en) Dilute sulfuric peroxide at point-of-use
JP2008535250A (en) Composition for cleaning ion-implanted photoresist in a pre-wiring process
KR20000076362A (en) A process for photoresist removal
JP4744228B2 (en) Semiconductor substrate cleaning liquid and semiconductor substrate cleaning method
CN105914137A (en) Wet silicon wafer cleaning method
WO2014089941A1 (en) Etchant and preparation method and application thereof
US6147042A (en) Detergent for processes for producing semiconductor devices or producing liquid crystal devices
JPS63274149A (en) Semiconductor treatment
JP2012505293A5 (en)
JP2006505132A (en) Semiconductor surface treatment and compounds used in it
JP6327207B2 (en) Method for cleaning Ge or SiGe or germanide
TWI615896B (en) 矽 Wafer manufacturing method
JPWO2019167971A1 (en) Alumina protective liquid, a protective method, and a method for manufacturing a semiconductor substrate having an alumina layer using the same.
KR100823714B1 (en) Cleaning solution for removing polymer and method of removing polymer using the same
US20150144160A1 (en) Etchant, preparation thereof and method of using the same in the cleaning process
JP4506177B2 (en) Etching composition
JPH11340182A (en) Cleaning agent for semiconductor surface, and method for cleaning
KR20090048715A (en) Cleaning solution for removing impurity and method of removing impurity using the same
JP2005074413A (en) Cleaning method for substrate for electronic industry
JP2008153271A (en) Method of cleaning used jig and cleaning solution composition
WO2018104992A1 (en) Ge, sige or germanide washing method
JPH11293288A (en) Cleaning water for electronic material and cleaning liquid for electronic material
JP2008084883A (en) Composition for cleaning semiconductor manufacturing apparatus and cleaning method employing the same

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 14127978

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13862682

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC ( EPO FORM 1205A DATED 20-11.2015 )

122 Ep: pct application non-entry in european phase

Ref document number: 13862682

Country of ref document: EP

Kind code of ref document: A1