WO2010083655A1 - Cleaning method for photomask - Google Patents
Cleaning method for photomask Download PDFInfo
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- WO2010083655A1 WO2010083655A1 PCT/CN2009/070303 CN2009070303W WO2010083655A1 WO 2010083655 A1 WO2010083655 A1 WO 2010083655A1 CN 2009070303 W CN2009070303 W CN 2009070303W WO 2010083655 A1 WO2010083655 A1 WO 2010083655A1
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- WIPO (PCT)
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- photomask
- cleaning
- infrared light
- deionized water
- wavelength
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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
- 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
Definitions
- the present invention relates to the field of cleaning and surface pretreatment of semiconductor chips, and more particularly to a method of cleaning a photomask.
- Photomask is a stencil for batch printing circuit in the manufacture of integrated circuit chips. Through the lithography process, the circuit pattern on the photomask can be printed on the silicon chip in large quantities, and therefore, any defects on the photomask Will have a great impact on the yield of the chip. In the well-documented range of the semiconductor industry, photomask contamination has cost the industry approximately $1 billion annually.
- sulfuric acid S0 4
- S0 4 sulfuric acid
- the sulfate ion combines with a cation such as an ammonium radical in the air to form a crystal such as ammonium sulfate.
- a crystal such as ammonium sulfate.
- the fog-like defect grows larger by photochemical reaction, and eventually the mask must be re-covered by the repel l process, that is, the reticle is from the production line. Remove it, remove the old protective mold, clean the reticle, and then cover the new protective mold.
- the most common and most common haze-like defect was ammonium sulphate, which was derived from photoresist repellent and residual contaminants after the cleaning process, and was subjected to reticle storage. The impact of storage conditions and the working environment.
- the second type of haze defects are various oxalic acids such as carboxylic acid and ammonium oxalate. Such defects are generally only found in a few chip factories, and the reasons are not clear.
- the third category is organic defects, which tend to be small, and are derived from protective organic compounds, encapsulating materials, and volatile organic carbon (VOC) in storage/exposure equipment.
- the haze problem of the photomask appeared on the 90nm photomask. After the photomask technology entered the 65nm node, the problem of haze was particularly prominent. It is widely recognized that the residual sulfuric acid used in the traditional cleaning method is the main cause of haze.
- UV cleaning Ultraviolet Rays is abbreviated to UV
- UV cleaning technology is the use of photosensitive oxidation of organic compounds to achieve adhesion removal
- the organic matter on the surface of the material, the surface of the material after light cleaning can achieve "atomic cleanliness".
- the light cleaning removes the surface of the object by photosensitization and oxidation reaction Carbon and organic compounds, so the surface that is prone to oxidation is not suitable for light cleaning. It is only suitable for surface dirt cleaning, unsuitable for dirt, and inorganic soil cleaning.
- an object of the present invention is to provide an efficient and simple method of cleaning a photomask.
- the invention adopts the method of using the hot water rinsing method, and adopts the means of infrared light irradiation to strengthen the ability to remove sulfate, and can remove more pollutants remaining on the surface layer of the photomask, so that the sulfate mask on the photomask after cleaning
- the residual amount of ions is less than 1ppb.
- the present invention provides a method of cleaning a photomask, comprising: illuminating the photomask with 50-9 CTC of deionized water, wherein the light is irradiated with infrared light having a wavelength of 0.5-100 ⁇ ⁇ during the cleaning process.
- Mask, time is 3-30 minutes.
- the photomask is rotated at a rotation speed of 50 to 300 rpm during the cleaning process.
- the photomask is rotated at a speed of 50 to 150 rpm during the cleaning.
- the infrared light generating means for generating the infrared light has a height of 10-500 mm from the photomask during the cleaning process.
- the infrared light generating means for generating the infrared light has a height of 100 to 200 from the photomask during the cleaning process.
- the infrared light generating means for generating the infrared light has a height of 10-20 mm from the photomask during the cleaning process.
- the wavelength of the infrared light is 1-50 ⁇ ⁇ during the cleaning process.
- the wavelength of the infrared light is 2-20 ⁇ m during the cleaning process.
- the deionized water has a flow rate of 1. 5 - 3 1 / min and a time of 15 - 25 minutes during the cleaning.
- the deionized water has a flow rate of 2-4 1 / min and a time of 3 - 10 minutes during the cleaning.
- the mechanism by which sulfate ions are adsorbed by the photomask is due to the action of hydrogen bonds.
- the substrate of the photomask is quartz glass. On the surface of the quartz glass, sulfate ions are bonded to the silica molecules in the quartz glass by hydrogen bonds in the form of hydrogen bonds. Due to the presence of hydrogen bonds, it is difficult for sulfate ions to escape from the surface of the photomask by molecular diffusion, which is the main reason why it is difficult to clean the sulfate ions by cold water washing.
- the high temperature of hot water increases the kinetic energy of sulfate ions and increases the probability of hydrogen bond rupture. Therefore, the effect of hot water is much greater than that of cold water.
- the invention employs infrared light to illuminate the photomask while rinsing the photomask with hot water. By calculation, when the wavelength of infrared light is 1 ⁇ 5 ⁇ ⁇ , the photon energy is the closest to the hydrogen bond energy of the photomask surface. After the sulfate ion and the silica molecule absorb the photon energy of the wavelength, they The hydrogen bond between the two will break, and the free sulfate ion will be taken away by the hot water in time.
- the infrared light irradiation method is introduced to enhance the ability to remove sulfate, so that the residual amount of sulfate ions on the cleaned photomask is less than 1 ppb, thereby making the photomask There is no fog defect in its life cycle.
- Photomask rotation speed 50 rpm ⁇ 500 rpm
- the infrared light generating device that generates infrared light has a height of 10-20 mm from the photomask, and the photomask rotates at a high speed of 50-300 rpm, which is beneficial to the surface layer of the photomask.
- the strong hydrogen bond absorbs the infrared energy sufficiently, and the hydrogen bond between the sulfate and the water is broken, and the deionized water is removed from the surface of the photomask, thereby effectively removing the sulfuric acid residue.
- high-temperature deionized water i.e., high-purity water
- high-purity water Due to its high electrical resistance, it can be used in the cleaning process in the electronics industry.
- the invention adopts the method of infrared light irradiation to strengthen the ability to remove sulfate by using the hot water rinsing method. Since the cost of the wet cleaning is relatively low, the process technology is relatively mature, and the improvement is performed on the basis of the method. Can remove more contaminants remaining on the surface of the photomask, making the photomask after cleaning
- FIG. 1 shows the residue of sulfate ion on the photomask before cleaning by the cleaning method of the present invention.
- FIG. 2 shows the residue of sulfate ion on the photomask after cleaning by the cleaning method of the present invention.
- the photomask was placed on a special chuck of the washing machine, and the photomask was rinsed with deionized water at a temperature of 50-7 CTC at a flow rate of 0. 5-2 1 / min for 20-30 minutes.
- the photomask rotates at a speed of 50-200 rpm, and the deionized water can be horizontally moved along the axis of the nozzle, and the infrared light wave is generated by the infrared generator to irradiate the photomask.
- the height of the infrared ray generator is 10-100 mm from the photomask, and the power is 100-40 ⁇
- the wavelength is 0. 5-40 ⁇ m.
- the photomask Place the photomask on the special chuck of the washing machine, rinse the photomask with deionized water at 60-80 ° C, flow rate is 2-5 1 / min, time is 10-20 minutes, photomask Rotating at 50-200 rpm, the infrared generator that generates infrared light waves is mounted on the washing machine and horizontally moved relative to the photomask.
- the height of the photomask is 100-300 legs.
- the power of the infrared radiator is 200 W, and the wavelength is 1. -50 ⁇ ⁇
- the photomask Place the photomask on the special chuck of the washing machine, rinse the photomask with deionized water at 70-90, the flow rate is 2-4 1/min, the time is 3-10 minutes, and the photomask is 150_300rpm.
- the speed of rotation, the infrared generator that generates infrared light waves is installed on the washing machine, the distance from the photomask is 200-400mm, the power is 300W, and the wavelength is 2-30 ⁇ .
- the photomask is placed on a special chuck of the cleaning machine, and the photomask is rinsed with a deionized water having a temperature of 80-9 CTC at a flow rate of 1.5-3 lbs.
- a deionized water having a temperature of 80-9 CTC at a flow rate of 1.5-3 lbs.
- an infrared generator that generates infrared light waves is mounted on the washing machine and horizontally moved relative to the photomask.
- the height of the photomask is 300-500mm, its power is 500W, and the wavelength is 2-20 ⁇ m.
- Example 6 The photomask was cleaned as in Example 1, except that the infrared wavelength was 40-60 ⁇ m.
- Example 6
- Example 7 the photomask was cleaned except that the infrared wavelength was 60-100 ⁇ m.
- the photomask was cleaned as in Example 1, except that the height of the infrared light generating means was 10-20 mm from the photomask.
- Example 9
- Example 10 The photomask was cleaned as in Example 3 except that the infrared wavelength was 5-20 ⁇ .
- Example 10
- the photomask was cleaned as in Example 4 except that the infrared wavelength was 2 - 10 ⁇ m.
- the cleaning method of the present invention can reduce the residual amount of sulfate ions on the photomask after cleaning to less than 1 ppb, which can improve the fabrication level of the photomask.
- infrared light is introduced based on the hot water rinsing method
- the means of light irradiation enhances the ability to remove sulfate.
- the cost of wet cleaning is relatively low, and the process technology is relatively mature. Based on this improvement, it can remove more pollutants remaining on the surface of the photomask. , so that the residual amount of sulfate ions on the cleaned photomask is less than 1 ppb.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Preparing Plates And Mask In Photomechanical Process (AREA)
Abstract
A wet cleaning process for photomask is provided,which comprises:rinsing the photomask with deionized water at 50-90℃ and irradiating the surface of the photomask with infrared light,to break the hydrogen bond between the sulfate ion and the photomask,so as to remove dissociating sulfate ions from the surface of the photomask.
Description
一种光掩模的清洗方法 技术领域 Method for cleaning photomasks
本发明涉及半导体芯片的清洗和表面预处理技术领域， 具体地说， 本发明涉 及一种光掩模的清洗方法。 The present invention relates to the field of cleaning and surface pretreatment of semiconductor chips, and more particularly to a method of cleaning a photomask.
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背景技术 Background technique
在标准的 IC制造工艺中， 涉及芯片（晶圆）清洗和表面预处理的工艺步骤有 100多步， 在整个 IC制造的发展过程中， 湿法书清洗一直在芯片清洗中占据主导地 位， 其中浸泡式 （批处理） 和喷雾式 （单芯片） 目前被广泛应用于半导体制造。 In the standard IC manufacturing process, there are more than 100 steps involved in chip (wafer) cleaning and surface pretreatment. In the development of IC manufacturing, wet book cleaning has always dominated chip cleaning. Immersion (batch) and spray (single chip) are now widely used in semiconductor manufacturing.
"光掩模"是集成电路芯片制造中用于批量印刷电路的模版，通过光刻工艺， 光掩模上的电路图案可被大批量印刷到硅芯片上， 因此， 光掩模上的任何缺陷都 会对芯片的成品率造成很大的影响。 在半导体行业有据可査的范围中， 光掩模的 污染使得业界每年耗费约 10亿美元。 "Photomask" is a stencil for batch printing circuit in the manufacture of integrated circuit chips. Through the lithography process, the circuit pattern on the photomask can be printed on the silicon chip in large quantities, and therefore, any defects on the photomask Will have a great impact on the yield of the chip. In the well-documented range of the semiconductor industry, photomask contamination has cost the industry approximately $1 billion annually.
近年来，人们对一些新型的芯片清洗方法展开了研究，在 90nm和更低节点的 工艺中， 已经开发了不同的芯片清洗的化学物质和超临界清洗， 包括湿法清洗、 干法清洗和超临界流体清洗在内的各种清洗方法都获得了重要的发展。 In recent years, some new methods of chip cleaning have been studied. In the process of 90nm and lower nodes, different chip cleaning chemicals and supercritical cleaning have been developed, including wet cleaning, dry cleaning and super cleaning. Significant developments have been made in various cleaning methods, including critical fluid cleaning.
在光掩模的制造和处理过程中， 除胶 （剥离光刻胶） 和传统的湿法清洗都需 要用到硫酸（ S04)， 因此， 光掩模表层会残留有硫酸根离子。 该硫酸根离子与空 气中的铵根等阳离子结合， 形成硫酸铵等晶体。 随着晶体的缓慢长大， 当其尺寸 与光掩模上电路线宽尺寸相当时， 就形成我们所说的雾状缺陷 （haze ) , 雾状缺陷 (haze) 是可见或可印刷的晶体结构， 从污染生长而来， 己是困扰半导体业界长达十年 以上的大问题，半导体制造商们至今还未能提出良好的解决方案。当使用波长为 193nm 的光来对掩模版进行曝光吋， 雾状缺陷会通过光化学反应而生长变大， 并最终导 致必须对掩模版进行再覆盖保护模 （repel l ) 工艺， 即将掩模版从生产线上取下 来、 去除旧的保护模、 清洗掩模版、 然后覆盖新的保护模。 In the manufacture and processing of photomasks, sulfuric acid (S0 4 ) is required for both the de-bonding (stripping photoresist) and the conventional wet cleaning, and therefore, sulfate ions remain in the surface layer of the photomask. The sulfate ion combines with a cation such as an ammonium radical in the air to form a crystal such as ammonium sulfate. As the crystal grows slowly, when it is sized to correspond to the line width dimension of the photomask, it forms what we call haze, which is a visible or printable crystal structure. Growing up from pollution has been a big problem that has plagued the semiconductor industry for more than a decade. Semiconductor manufacturers have yet to come up with good solutions. When the reticle is exposed using light with a wavelength of 193 nm, the fog-like defect grows larger by photochemical reaction, and eventually the mask must be re-covered by the repel l process, that is, the reticle is from the production line. Remove it, remove the old protective mold, clean the reticle, and then cover the new protective mold.
最经常出现的雾状缺陷共有三类。 但最早被发现且最常见的雾状缺陷是硫酸 铵， 它的来源是光刻胶剥离和清洗工艺之后残留的污染物， 而且受到掩模版的储
藏条件和工作环境的影响。 第二类雾状缺陷是羧酸和草酸铵等各种草酸。 这类缺 陷一般只出现在少数几个芯片厂内， 原因尚不清楚。 第三类是有机物缺陷， 它们 往往很小， 来源是保护模、封装材料和储藏 /曝光设备内的挥发性有机碳（V0C) 。 光掩模的 haze问题早在 90nm光掩模上出现，光掩模技术进入 65nm节点后， haze 的问题尤为突出， 业界普遍的认识是传统清洗方式中使用的硫酸残留是造成 haze 的主要原因。 There are three types of fog defects that occur most often. But the most common and most common haze-like defect was ammonium sulphate, which was derived from photoresist repellent and residual contaminants after the cleaning process, and was subjected to reticle storage. The impact of storage conditions and the working environment. The second type of haze defects are various oxalic acids such as carboxylic acid and ammonium oxalate. Such defects are generally only found in a few chip factories, and the reasons are not clear. The third category is organic defects, which tend to be small, and are derived from protective organic compounds, encapsulating materials, and volatile organic carbon (VOC) in storage/exposure equipment. The haze problem of the photomask appeared on the 90nm photomask. After the photomask technology entered the 65nm node, the problem of haze was particularly prominent. It is widely recognized that the residual sulfuric acid used in the traditional cleaning method is the main cause of haze.
在光掩模的生产过程中， 除胶 （剥离光刻胶） 和清洗工艺都需要用到硫酸。 如何最大限度减少光掩模表层残留的硫酸根离子是解决雾状缺陷核心问题。 目前 行业内对此有以下几种处理手段： In the production of photomasks, sulfuric acid is required for both the glue removal (stripping photoresist) and the cleaning process. How to minimize the residual sulfate ion in the photomask surface is the core problem to solve the fog defect. At present, there are several ways to deal with this in the industry:
1、使用热水冲洗光掩模。高温会提高硫酸根离子的活性， 增加其脱离光掩模 表层的几率， 因此， 热水去除硫酸根的效果远远大于冷水的效果。 但是， 这并不 能彻底去除光掩模表面的硫酸根离子。 有数据表明， 在不使用热水的情况下， 清 洗后光掩模表面残留的硫酸根离子浓度在几十 ppb以上， 使用热水后， 浓度降到 2〜5ppb。虽然用热水冲洗光掩模延长了其上生成雾状缺陷的周期，但在光掩模生 命周期内， 雾状缺陷的问题依然存在。 1. Rinse the photomask with hot water. High temperatures increase the activity of sulfate ions and increase their chances of leaving the photomask surface. Therefore, the effect of hot water removal of sulfate is much greater than that of cold water. However, this does not completely remove the sulfate ions from the surface of the photomask. There is data showing that the concentration of sulfate ions remaining on the surface of the photomask after cleaning is above several tens of ppb without using hot water, and the concentration is lowered to 2 to 5 ppb after using hot water. Although rinsing the photomask with hot water prolongs the period of fogging defects formed thereon, the problem of haze defects remains in the photomask life cycle.
2、 使用热板加热光掩模。 在 300〜500Ό的高温环境下， 光掩模表层的硫酸 根离子会脱离光掩模， 以气态的形式挥发掉。 这种方法能够比较彻底地去除光掩 模表层的硫酸根离子， 但过高的温度会使光掩模上的污染物固化而无法清洗， 甚 至造成电路图案破损， 从而导致光掩模报废。 同时， 光掩模在热板加热的过程中， 由于没有水流的冲洗， 被二次污染的风险很大。 2. Use a hot plate to heat the photomask. In a high temperature environment of 300 to 500 Torr, the sulfate ions in the surface layer of the photomask are released from the photomask and volatilized in a gaseous state. This method can completely remove the sulfate ions in the surface of the photomask, but the excessive temperature will cure the contaminants on the photomask and will not be cleaned, and even the circuit pattern will be damaged, resulting in the photomask being scrapped. At the same time, during the heating of the hot plate, there is no risk of secondary contamination due to the absence of flushing of the water stream.
3、 采用无硫工艺， 以臭氧水替代硫酸清洗光掩模。然而， 无硫清洗工艺中存 在清洗效率和光掩模损伤的矛盾， 较低剂量的臭氧对污染比较严重的光掩模难以 清洗干净， 而较高剂量的臭氧则会造成对光掩模图形的腐蚀破坏。 因此， 现有的 无硫清洗工艺只能处理污染程度较轻的光掩模。 目前在除胶工艺中， 尚无成熟的 无硫工艺来取代硫酸以有效去除在除胶环节残留的硫酸根离子。 3. Use a sulfur-free process to clean the photomask with ozone water instead of sulfuric acid. However, there is a contradiction between cleaning efficiency and photomask damage in the sulfur-free cleaning process. Lower doses of ozone are difficult to clean the photomasks with more serious pollution, while higher doses of ozone cause corrosion of the photomask pattern. damage. Therefore, the existing sulfur-free cleaning process can only handle photomasks that are less polluted. At present, in the degreasing process, there is no mature sulfur-free process to replace sulfuric acid to effectively remove sulfate ions remaining in the degumming step.
此外， 使用兆声清洗、 单片清洗工艺及气相清洗方法等的缺点是设备造价昂 贵， 整体清洗效果不佳。 使用臭氧去离子水（DI03 )也会对掩模版表面造成损伤。 In addition, the disadvantages of using megasonic cleaning, single-chip cleaning processes, and gas phase cleaning methods are that the equipment is expensive and the overall cleaning effect is poor. The use of ozone deionized water (DI03) can also cause damage to the surface of the reticle.
还有一种新方法是紫外光清洗（Ultraviolet Rays缩写成 UV)是可见紫色光 以外的一段电磁辐射，波长在 l(T400rai的范围。 紫外光清洗技术是利用有机化合 物的光敏氧化作用达到去除黏附在材料表面上的有机物质， 经过光清洗后的材料 表面可以达到 "原子清洁度"。 但由于光清洗是通过光敏、 氧化反应去除物体表面
的碳和有机化合物， 所以容易发生氧化的表面不宜用光清洗方法， 只适对表面污 垢清洗、 不适对污垢量较多， 无机类污垢清洗。 Another new method is UV cleaning (Ultraviolet Rays is abbreviated to UV) is a section of electromagnetic radiation other than visible purple light, the wavelength is in the range of l (T400rai. UV cleaning technology is the use of photosensitive oxidation of organic compounds to achieve adhesion removal The organic matter on the surface of the material, the surface of the material after light cleaning can achieve "atomic cleanliness". However, since the light cleaning removes the surface of the object by photosensitization and oxidation reaction Carbon and organic compounds, so the surface that is prone to oxidation is not suitable for light cleaning. It is only suitable for surface dirt cleaning, unsuitable for dirt, and inorganic soil cleaning.
为解决以上问题， 本发明的目的在于提供一种高效、 简单的清洗光掩模的方 法。 本发明在使用热水冲洗方法的基础上， 引入红外光照射的手段加强去除硫酸 根的能力， 能够更多地去除残留在光掩模表层的污染物， 使得清洗后的光掩模上 硫酸根离子的残留量低于 lppb 发明内容 In order to solve the above problems, an object of the present invention is to provide an efficient and simple method of cleaning a photomask. The invention adopts the method of using the hot water rinsing method, and adopts the means of infrared light irradiation to strengthen the ability to remove sulfate, and can remove more pollutants remaining on the surface layer of the photomask, so that the sulfate mask on the photomask after cleaning The residual amount of ions is less than 1ppb.
本发明提供一种光掩模的清洗方法， 包括用 50-9CTC的去离子水冲洗光掩模， 其特征在于， 在清洗过程中， 同时以波长为 0. 5-100 μ ηι的红外光照射光掩模，时 间为 3-30分钟。 The present invention provides a method of cleaning a photomask, comprising: illuminating the photomask with 50-9 CTC of deionized water, wherein the light is irradiated with infrared light having a wavelength of 0.5-100 μ ηι during the cleaning process. Mask, time is 3-30 minutes.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 所述光掩模以 50-300rpm的转速回转。 According to the cleaning method of the photomask of the present invention, it is preferable that the photomask is rotated at a rotation speed of 50 to 300 rpm during the cleaning process.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 所述光掩模以 50-150rpm的速度转动。 According to the cleaning method of the photomask of the present invention, it is preferable that the photomask is rotated at a speed of 50 to 150 rpm during the cleaning.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 产生所述红外 光的红外光发生装置距离所述光掩模的高度为 10-500mm According to the cleaning method of the photomask of the present invention, it is preferable that the infrared light generating means for generating the infrared light has a height of 10-500 mm from the photomask during the cleaning process.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 产生所述红外 光的红外光发生装置距离所述光掩模的高度为 100-200 According to the cleaning method of the photomask of the present invention, it is preferable that the infrared light generating means for generating the infrared light has a height of 100 to 200 from the photomask during the cleaning process.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 产生所述红外 光的红外光发生装置距离所述光掩模的高度为 10-20mm According to the cleaning method of the photomask of the present invention, it is preferable that the infrared light generating means for generating the infrared light has a height of 10-20 mm from the photomask during the cleaning process.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 所述去离子水 流速为 0. 5-5 l/min 5-5 l/min。 The flow rate of the deionized water is 0. 5-5 l / min
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 所述红外光的 波长为 1-50 μ ΐη According to the cleaning method of the photomask of the present invention, it is preferable that the wavelength of the infrared light is 1-50 μ ΐ during the cleaning process.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 所述红外光的 波长为 2-20 μ ιη According to the cleaning method of the photomask of the present invention, it is preferable that the wavelength of the infrared light is 2-20 μm during the cleaning process.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 所述去离子水 流速为 1. 5-3 1/min, 时间为 15-25分钟。 According to the cleaning method of the photomask of the present invention, it is preferred that the deionized water has a flow rate of 1. 5 - 3 1 / min and a time of 15 - 25 minutes during the cleaning.
根据本发明的光掩模的清洗方法， 优选的是， 在清洗过程中， 所述去离子水 流速为 2-4 1/min, 时间为 3-10分钟。
硫酸根离子被光掩模吸附的机理是由于氢键的作用。 光掩模的基材为石英玻 璃， 在石英玻璃的表面， 硫酸根离子通过羟基以氢键形式和石英玻璃中的二氧化 硅分子结合。 由于氢键的存在， 使得硫酸根离子难以通过分子扩散的方式脱离光 掩模表面， 这是造成冷水冲洗难以清洗干净硫酸根离子的主要原因。 而热水的高 温会增加硫酸根离子的动能， 增加其氢键断裂的机率， 因此热水的效果要远远大 于冷水。 本发明采用红外光照射光掩模， 同时辅以热水冲洗光掩模。 通过计算， 红外光的波长为 1〜5 μ ηι时， 其光子能量与光掩模表面的氢键键能最为接近， 硫 酸根离子和二氧化硅分子在吸收该波长的光子能量后， 它们之间的氢键会发生断 裂， 而成为游离态的硫酸根离子则被热水及时带走。 由此， 在使用热水冲洗方法 的基础上， 引入红外光照射的手段加强去除硫酸根的能力， 使得清洗后的光掩模 上硫酸根离子的残留量低于 lppb， 从而令光掩模在其生命周期内不产生雾状缺陷 问题。 According to the cleaning method of the photomask of the present invention, it is preferable that the deionized water has a flow rate of 2-4 1 / min and a time of 3 - 10 minutes during the cleaning. The mechanism by which sulfate ions are adsorbed by the photomask is due to the action of hydrogen bonds. The substrate of the photomask is quartz glass. On the surface of the quartz glass, sulfate ions are bonded to the silica molecules in the quartz glass by hydrogen bonds in the form of hydrogen bonds. Due to the presence of hydrogen bonds, it is difficult for sulfate ions to escape from the surface of the photomask by molecular diffusion, which is the main reason why it is difficult to clean the sulfate ions by cold water washing. The high temperature of hot water increases the kinetic energy of sulfate ions and increases the probability of hydrogen bond rupture. Therefore, the effect of hot water is much greater than that of cold water. The invention employs infrared light to illuminate the photomask while rinsing the photomask with hot water. By calculation, when the wavelength of infrared light is 1~5 μ ηι, the photon energy is the closest to the hydrogen bond energy of the photomask surface. After the sulfate ion and the silica molecule absorb the photon energy of the wavelength, they The hydrogen bond between the two will break, and the free sulfate ion will be taken away by the hot water in time. Therefore, on the basis of using the hot water washing method, the infrared light irradiation method is introduced to enhance the ability to remove sulfate, so that the residual amount of sulfate ions on the cleaned photomask is less than 1 ppb, thereby making the photomask There is no fog defect in its life cycle.
光掩模转速： 50rpm~500rpm在清洗过程中， 产生红外光的红外光发生装置距离 光掩模的高度为 10-20mm， 同时光掩模以 50_300rpm的转速高速旋转， 有利于光 掩模表层的较强氢键对红外能量的充分吸收， 使硫酸根和水之间的氢键断裂， 并 随去离子水移出光掩模的表面， 从而有效去除硫酸残留。 Photomask rotation speed: 50 rpm~500 rpm During the cleaning process, the infrared light generating device that generates infrared light has a height of 10-20 mm from the photomask, and the photomask rotates at a high speed of 50-300 rpm, which is beneficial to the surface layer of the photomask. The strong hydrogen bond absorbs the infrared energy sufficiently, and the hydrogen bond between the sulfate and the water is broken, and the deionized water is removed from the surface of the photomask, thereby effectively removing the sulfuric acid residue.
根据本发明， 高温去离子水即高纯水， 一次性使用，不会有交叉沾污。 因其高 电阻， 可用于电子行业的清洗过程。 According to the present invention, high-temperature deionized water, i.e., high-purity water, is used at one time without cross-contamination. Due to its high electrical resistance, it can be used in the cleaning process in the electronics industry.
本发明的有益效果为： The beneficial effects of the invention are:
本发明在使用热水冲洗方法的基础上， 引入红外光照射的手段加强去除硫酸 根的能力， 由于湿法清洗的成本相对来说较低， 工艺技术又比较成熟， 在此基础 上进行改进， 能够更多地去除残留在光掩模表层的污染物， 使得清洗后的光掩模 The invention adopts the method of infrared light irradiation to strengthen the ability to remove sulfate by using the hot water rinsing method. Since the cost of the wet cleaning is relatively low, the process technology is relatively mature, and the improvement is performed on the basis of the method. Can remove more contaminants remaining on the surface of the photomask, making the photomask after cleaning
附图说明 DRAWINGS
图 1表示采用本发明的清洗方法清洗前光掩模上硫酸根离子的残留 图 2表示采用本发明的清洗方法清洗后光掩模上硫酸根离子的残留 具体实施方式 1 shows the residue of sulfate ion on the photomask before cleaning by the cleaning method of the present invention. FIG. 2 shows the residue of sulfate ion on the photomask after cleaning by the cleaning method of the present invention.
以下用实施例结合附图对本发明作更详细的描述。 这些实施例仅仅是对本发
明最佳实施方式的描述， 并不对本发明的范围有任何限制。 实施例 1 The invention will now be described in more detail with reference to the embodiments and drawings. These examples are only for the hair The description of the preferred embodiment is not intended to limit the scope of the invention. Example 1
将光掩模放在清洗机的专用卡盘上， 用温度为 50-7CTC的去离子水冲洗光掩 模， 流速为 0. 5-2 1/min, 时间为 20-30分钟。 光掩模以 50_200rpm速度转动， 去离子水可沿喷头轴心作水平移动， 同时用红外线发生器产生红外光波对光掩模 进行照射， 红外线发生器距离光掩模高度为 10-100mm， 功率为 100W, 波长为 0. 5-40 μ m。 The photomask was placed on a special chuck of the washing machine, and the photomask was rinsed with deionized water at a temperature of 50-7 CTC at a flow rate of 0. 5-2 1 / min for 20-30 minutes. The photomask rotates at a speed of 50-200 rpm, and the deionized water can be horizontally moved along the axis of the nozzle, and the infrared light wave is generated by the infrared generator to irradiate the photomask. The height of the infrared ray generator is 10-100 mm from the photomask, and the power is 100-40微米。 The wavelength is 0. 5-40 μ m.
光掩模表层的硫酸根离子和二氧化硅分子在吸收该波长的光子能量后， 其间 的氢键断裂， 游离态的硫酸根离子以及表面污物随热去离子水移出光掩模表层。 实施例 2 After the sulfate ion and the silica molecule of the photomask surface absorb the photon energy of the wavelength, the hydrogen bond between them breaks, and the free sulfate ion and surface dirt move out of the photomask surface with the hot deionized water. Example 2
将光掩模放在清洗机的专用卡盘上， 用温度为 60-80°C的去离子水冲洗光掩 模， 流速为 2-5 1/min, 时间为 10-20分钟， 光掩模以 50-200rpm速度转动， 产 生红外光波的红外线发生器安装在清洗机上， 并相对于光掩模作水平运动， 距离 光掩模高度 100-300腿， 该红外线辐射器的功率为 200W, 波长为 1-50 μ πι Place the photomask on the special chuck of the washing machine, rinse the photomask with deionized water at 60-80 ° C, flow rate is 2-5 1 / min, time is 10-20 minutes, photomask Rotating at 50-200 rpm, the infrared generator that generates infrared light waves is mounted on the washing machine and horizontally moved relative to the photomask. The height of the photomask is 100-300 legs. The power of the infrared radiator is 200 W, and the wavelength is 1. -50 μ πι
光掩模表层的硫酸根离子和二氧化硅分子在吸收该波长的光子能量后， 其间 的氢键断裂， 游离态的硫酸根离子以及表面污物随热去离子水移出光掩模表层。 实施例 3 After the sulfate ion and the silica molecule of the photomask surface absorb the photon energy of the wavelength, the hydrogen bond between them breaks, and the free sulfate ion and surface dirt move out of the photomask surface with the hot deionized water. Example 3
将光掩模放在清洗机的专用卡盘上， 用温度为 70-90 的去离子水冲洗光掩 模， 流速为 2-4 1/min, 时间为 3-10分钟， 光掩模以 150_300rpm的速度转动， 产生红外光波的红外线发生器安装在清洗机上， 距离光掩模高度 200-400mm， 其 功率为 300W, 波长为 2-30 μ πι。 Place the photomask on the special chuck of the washing machine, rinse the photomask with deionized water at 70-90, the flow rate is 2-4 1/min, the time is 3-10 minutes, and the photomask is 150_300rpm. The speed of rotation, the infrared generator that generates infrared light waves is installed on the washing machine, the distance from the photomask is 200-400mm, the power is 300W, and the wavelength is 2-30 μπι.
光掩模表层的硫酸根离子和二氧化硅分子在吸收该波长的光子能量后， 其间 的氢键断裂， 游离态的硫酸根离子以及表面污物随热去离子水移出光掩模表层。 实施例 4 After the sulfate ion and the silica molecule of the photomask surface absorb the photon energy of the wavelength, the hydrogen bond between them breaks, and the free sulfate ion and surface dirt move out of the photomask surface with the hot deionized water. Example 4
将光掩模放在清洗机的专用卡盘上， 用温度为 80-9CTC的去离子水冲洗光掩 模， 流速为 1. 5-3 1/min, 时间为 15-25分钟， 光掩模以 50_150rpm的速度转动， 产生红外光波的红外线发生器安装在清洗机上， 并相对于光掩模作水平运动， 距
离光掩模高度 300-500mm， 其功率为 500W， 波长为 2-20 μ m。 The photomask is placed on a special chuck of the cleaning machine, and the photomask is rinsed with a deionized water having a temperature of 80-9 CTC at a flow rate of 1.5-3 lbs. Rotating at a speed of 50_150 rpm, an infrared generator that generates infrared light waves is mounted on the washing machine and horizontally moved relative to the photomask. The height of the photomask is 300-500mm, its power is 500W, and the wavelength is 2-20 μm.
光掩模表层的硫酸根离子和二氧化硅分子在吸收该波长的光子能量后， 其间 的氢键断裂， 游离态的硫酸根离子以及表面污物随热去离子水移出光掩模表层。 实施例 5 After the sulfate ion and the silica molecule of the photomask surface absorb the photon energy of the wavelength, the hydrogen bond between them breaks, and the free sulfate ion and surface dirt move out of the photomask surface with the hot deionized water. Example 5
除了所述红外线波长为 40-60 μ πι之外， 其他如同实施例 1，进行光掩模的 清洗。 实施例 6 The photomask was cleaned as in Example 1, except that the infrared wavelength was 40-60 μm. Example 6
除了所述红外线波长为 60-100 μ m之外， 其他如同实施例 1，进行光掩模的 清洗。 实施例 7 Other than Example 1, the photomask was cleaned except that the infrared wavelength was 60-100 μm. Example 7
除了所述红外线波长为 5-20 μ ηι之外， 其他如同实施例 1，进行光掩模的清 洗。 实施例 8 The photomask was cleaned as in Example 1, except that the infrared wavelength was 5-20 μηη. Example 8
除了所述红外光发生装置距离所述光掩模的高度为 10-20mm之外，其他如同 实施例 1，进行光掩模的清洗。 实施例 9 The photomask was cleaned as in Example 1, except that the height of the infrared light generating means was 10-20 mm from the photomask. Example 9
除了所述红外线波长为 5-20 μ ηι之外， 其他如同实施例 3，进行光掩模的清 洗。 实施例 10 The photomask was cleaned as in Example 3 except that the infrared wavelength was 5-20 μηη. Example 10
除了所述红外线波长为 2-10 μ m之外， 其他如同实施例 4，进行光掩模的清 洗。 从图 1与图 2对比可以看出， 采用本发明的清洗方法可使清洗后的光掩模上 硫酸根离子的残留量低于 lppb， 能提高光掩模的制作水平。 The photomask was cleaned as in Example 4 except that the infrared wavelength was 2 - 10 μm. As can be seen from the comparison between Fig. 1 and Fig. 2, the cleaning method of the present invention can reduce the residual amount of sulfate ions on the photomask after cleaning to less than 1 ppb, which can improve the fabrication level of the photomask.
根据本发明的光掩模的清洗方法， 在使用热水冲洗方法的基础上， 引入红外
光照射的手段加强去除硫酸根的能力， 由于湿法清洗的成本相对来说较低， 工艺 技术又比较成熟， 在此基础上进行改进， 能够更多地去除残留在光掩模表层的污 染物， 使得清洗后的光掩模上硫酸根离子的残留量低于 lppb。
According to the cleaning method of the photomask of the present invention, infrared light is introduced based on the hot water rinsing method The means of light irradiation enhances the ability to remove sulfate. The cost of wet cleaning is relatively low, and the process technology is relatively mature. Based on this improvement, it can remove more pollutants remaining on the surface of the photomask. , so that the residual amount of sulfate ions on the cleaned photomask is less than 1 ppb.
Claims
1. 一种光掩模的清洗方法， 包括用 50-9CTC的去离子水冲洗光掩模， 其特征 在于，在清洗过程中，同时以波长为 0. 5-100 μ m的红外光照射光掩模，时间为 3-30 分钟。 The method of illuminating a photomask with 50-9 CTC of deionized water, wherein the photomask is irradiated with infrared light having a wavelength of 0.5-100 μm during the cleaning process. Mode, the time is 3-30 minutes.
2.如权利要求 1所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 所 述光掩模以 50-300rpm的转速回转。 The method of cleaning a photomask according to claim 1, wherein the photomask is rotated at a rotational speed of 50 to 300 rpm during the cleaning.
3.如权利要求 2所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 所 述光掩模以 50-150rpm的速度转动。 The method of cleaning a photomask according to claim 2, wherein the photomask is rotated at a speed of 50 to 150 rpm during the cleaning.
4.如权利要求 1所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 产 生所述红外光的红外光发生装置距离所述光掩模的高度为 10-500mm。 The method of cleaning a photomask according to claim 1, wherein in the cleaning process, the infrared light generating means for generating the infrared light has a height of from 10 to 500 mm from the photomask.
5.如权利要求 4所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 产 生所述红外光的红外光发生装置距离所述光掩模的高度为 100-200讓。 The method of cleaning a photomask according to claim 4, wherein in the cleaning process, the infrared light generating means for generating the infrared light has a height of 100 to 200 from the photomask.
6.如权利要求 4所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 产 生所述红外光的红外光发生装置距离所述光掩模的高度为 10-20讓。 The method of cleaning a photomask according to claim 4, wherein in the cleaning process, the infrared light generating means for generating the infrared light has a height of 10-20 from the photomask.
7.如权利要求 1所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 所 述去离子水流速为 0. 5-5 l/min。 5-5 l/min。 The flow rate of the deionized water is 0. 5-5 l / min.
8.如权利要求 1所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 所 述红外光的波长为 1-50 μ ηι。 The method of cleaning a photomask according to claim 1, wherein the wavelength of the infrared light is 1-50 μηη during the cleaning process.
9.如权利要求 7所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 所 述去离子水流速为 1. 5-3 1/min, 时间为 15-25分钟。 The method of cleaning a photomask according to claim 7, wherein during the cleaning, the deionized water has a flow rate of 1. 5 - 3 1 / min and a time of 15 - 25 minutes.
10.如权利要求 7所述的光掩模的清洗方法， 其特征在于， 在清洗过程中， 所 述去离子水流速为 2-4 1/min, 时间为 3_10分钟。
The method of cleaning a photomask according to claim 7, wherein the deionized water has a flow rate of 2-4 1 / min and a time of 3 - 10 minutes during the cleaning.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2009/070303 WO2010083655A1 (en) | 2009-01-23 | 2009-01-23 | Cleaning method for photomask |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2009/070303 WO2010083655A1 (en) | 2009-01-23 | 2009-01-23 | Cleaning method for photomask |
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| WO2010083655A1 true WO2010083655A1 (en) | 2010-07-29 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071376A (en) * | 1997-12-02 | 2000-06-06 | Mitsubishi Denki Kabushiki Kaisha | Method and apparatus for cleaning photomask |
| US20020155360A1 (en) * | 2001-04-18 | 2002-10-24 | Mitsubishi Denki Kabushiki Kaisha | Cleaning process for photomasks |
| US20060254611A1 (en) * | 2005-04-12 | 2006-11-16 | Harald Koster | Acid-free cleaning process for substrates, in particular masks and mask blanks |
| US20080057411A1 (en) * | 2006-08-31 | 2008-03-06 | Carpenter Craig M | Methods for forming and cleaning photolithography reticles |
| CN101414117A (en) * | 2008-12-04 | 2009-04-22 | 常州瑞择微电子科技有限公司 | Method for cleaning photo mask by wet method |
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- 2009-01-23 WO PCT/CN2009/070303 patent/WO2010083655A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071376A (en) * | 1997-12-02 | 2000-06-06 | Mitsubishi Denki Kabushiki Kaisha | Method and apparatus for cleaning photomask |
| US20020155360A1 (en) * | 2001-04-18 | 2002-10-24 | Mitsubishi Denki Kabushiki Kaisha | Cleaning process for photomasks |
| US20060254611A1 (en) * | 2005-04-12 | 2006-11-16 | Harald Koster | Acid-free cleaning process for substrates, in particular masks and mask blanks |
| US20080057411A1 (en) * | 2006-08-31 | 2008-03-06 | Carpenter Craig M | Methods for forming and cleaning photolithography reticles |
| CN101414117A (en) * | 2008-12-04 | 2009-04-22 | 常州瑞择微电子科技有限公司 | Method for cleaning photo mask by wet method |
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