CN109941967A - One-step production process for ultra-clean and high-purity microelectronic grade hydrogen peroxide - Google Patents
One-step production process for ultra-clean and high-purity microelectronic grade hydrogen peroxide Download PDFInfo
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Abstract
本发明涉及一种一步法生产超净高纯微电子级过氧化氢的生产工艺,包括将H2O2原料用泵输送至树脂塔内进行物理法离子交换进行提纯净化、此工艺步骤循环进行四次步骤,得到超净高纯微电子级H2O2,该生产工艺在运行时运行压力控制在0.5‑1.5Mpa,温度控制在3‑42℃。与现有生产提纯净化技术相比,本发明生产工艺及设计合理简单,成本低,所生产的H2O2纯度高,产品净化后,质量可以达到1ppb以上的产品。
The invention relates to a production process for producing ultra-clean and high - purity microelectronic grade hydrogen peroxide by one-step method. step to obtain ultra-clean and high-purity microelectronic grade H 2 O 2 , and the operating pressure of the production process is controlled at 0.5-1.5Mpa, and the temperature is controlled at 3-42°C. Compared with the existing production purification technology, the production process and design of the invention are reasonable and simple, the cost is low, the produced H 2 O 2 has high purity, and after the product is purified, the quality can reach a product of more than 1 ppb.
Description
技术领域technical field
本发明是属于电子信息化工材料制造领域,产品用途是使用该产品清除芯片、硅晶片、大型集成电路、各种显示面板和太阳能面板上的微量杂质和细小的尘埃颗粒,本发明涉及一种超净高纯微电子级过氧化氢(H2O2)的生产工艺。The invention belongs to the field of electronic information chemical material manufacturing, and the product purpose is to use the product to remove trace impurities and fine dust particles on chips, silicon wafers, large integrated circuits, various display panels and solar panels. Production process of net high-purity microelectronic grade hydrogen peroxide (H 2 O 2 ).
背景技术Background technique
超净高纯微电子级H2O2是微电子、半导体、超大规模集成电路(IC)、以及航空航天精密仪器设备的不可缺的重要的电子化学清洁产品和腐蚀剂。这是因为H2O2的纯度和洁净度对IC的成品率、电性能的可靠性有着极其重大的影响。Ultra-clean and high-purity microelectronic grade H 2 O 2 is an indispensable and important electronic chemical cleaning product and corrosive agent for microelectronics, semiconductors, ultra-large-scale integrated circuits (IC), and aerospace precision instruments. This is because the purity and cleanliness of H 2 O 2 have an extremely significant impact on the yield of IC and the reliability of electrical properties.
随着IC存储的不断提高,但产品面积越做越小、各类芯片以及印刷电路板、包括各类平板显示面板的清晰度要求不断提高,包括航天航空器也是越做越小但功能越来越强大,随着科技的发展大都向着微小面积发展,其产品容量和功能也在不断地增大增强,其需要清洁的产品表面的氧化膜也变得更薄。但是使用微电子级H2O2清洗产品洁净度的质量要求越来越高,否则使用微电子级H2O2清洗电子印刷电路板以及芯片的同时,和腐蚀剂中的碱金属杂质,像钙钠等杂质会融进氧化膜中去,从而导致IC、印刷电路板以及芯片等耐绝缘性的性能下降,进而使重金属杂质如铁离子、银离子、络离子、铜离子等附着在印刷电路板以及芯片、IC、的表面上,将使P-N结的耐电压大大降低,直接影响产品的合格率及存储容量。With the continuous improvement of IC storage, the product area is getting smaller and smaller, and the definition requirements of various chips and printed circuit boards, including various flat panel display panels, have been continuously improved, including aerospace vehicles. Powerful, with the development of science and technology, most of them are developing towards small areas, and their product capacity and functions are also increasing and enhancing, and the oxide film on the surface of products that need to be cleaned is also becoming thinner. However, the quality requirements of cleaning products with microelectronics - grade H2O2 are getting higher and higher, otherwise, when cleaning electronic printed circuit boards and chips with microelectronics - grade H2O2 , alkali metal impurities in corrosive agents , such as calcium Impurities such as sodium will melt into the oxide film, which will cause the insulation resistance of ICs, printed circuit boards and chips to decline, and then make heavy metal impurities such as iron ions, silver ions, complex ions, copper ions, etc. adhere to the printed circuit board. And on the surface of chips, ICs, etc., the withstand voltage of the PN junction will be greatly reduced, which will directly affect the qualification rate and storage capacity of the product.
目前比较先进的就是世界上通用的树脂离子交换法提纯净化生产的电子级H2O2生产工艺;吸附、阴阳树脂离子交换法,此方法虽可以生产出纯度较高的产品,成本也可以掌控,产品中单一阴阳离子可以做到小于5ppb,但是该生产工艺比较繁琐,使用该生产工艺很难做到自动化的生产线;因为此种生产工艺过程由吸附系统,阳离子系统,阴离子系统、混合工艺系统,膜分离工艺系统等组成,系统多、且每个系统的工艺要求数据也各不相同,因此很难整合成自动化生产线。At present, the most advanced is the electronic-grade H 2 O 2 production process that is commonly used in the world for purification and production of resin ion exchange method; adsorption, anion-cation resin ion exchange method, although this method can produce high-purity products, the cost can also be controlled. , the single anion and cation in the product can be less than 5ppb, but the production process is cumbersome, and it is difficult to achieve an automated production line using this production process; because this production process consists of adsorption system, cation system, anion system, mixed process system , membrane separation process system, etc. There are many systems, and the process requirements data of each system are also different, so it is difficult to integrate into an automated production line.
中国专利CN1699144A公开了一种高纯过氧化氢纯化连续生产工艺,以工业级H2O2为原料,利用大孔吸附树脂柱吸附有机碳(TOC),后经阴、阳单个离子交换柱进行离子交换,再经阴阳离子混合柱的离子交换,去除阴、阳离子杂质,最后通过微孔过滤器(PVDF材质),去除尘埃颗粒。按照该专利的报道称可以生产出符合国际半导体设备和材料组织制订的SEMI-C8的产品,(以下简称SEMI-C12)但该产品质量和纯度达不到SEMI-C12的产品质量要求,生产工艺复杂及繁琐。Chinese patent CN1699144A discloses a continuous production process for the purification of high-purity hydrogen peroxide, using industrial grade H 2 O 2 as raw material, using macroporous adsorption resin column to adsorb organic carbon (TOC), and then passing through anion and cation single ion exchange column to carry out Ion exchange, and then ion exchange of anion and cation mixed column to remove anion and cation impurities, and finally pass through a microporous filter (PVDF material) to remove dust particles. According to the report of the patent, it is possible to produce a product that meets the SEMI-C8 formulated by the International Semiconductor Equipment and Materials Organization (hereinafter referred to as SEMI-C12), but the quality and purity of the product cannot meet the product quality requirements of SEMI-C12. The production process Complex and cumbersome.
中国专利CN1330035A公开了一种高纯过氧化氢生产的方法,其工艺简单,纯化效率高,但由于生产工艺过于复杂和繁琐,生产设备和生产线过于繁长,导致生产线设备经常需要维修和维护,因设备和生产线经常需要停车维修维护,其产量就大打折扣,因此,H2O2原料的起始浓度通常还需要高达40%以上,而且为了抑制H2O2氧化和分解的还要采用低温5℃或以下的低温工艺,但低温生产环境带来的是设备投资大,能源消耗大及操作更趋复杂,生产工艺过程对环境同样没有任何的改进和减缓。Chinese patent CN1330035A discloses a method for producing high-purity hydrogen peroxide. The process is simple and the purification efficiency is high. However, because the production process is too complicated and cumbersome, and the production equipment and production line are too long, the production line equipment often needs to be repaired and maintained. Because equipment and production lines often need to be shut down for maintenance, their output is greatly reduced. Therefore, the initial concentration of H 2 O 2 raw materials usually needs to be as high as 40% or more, and in order to inhibit the oxidation and decomposition of H 2 O 2 , low temperature should be used. The low temperature process of 5 °C or below, but the low temperature production environment brings about large equipment investment, large energy consumption and more complicated operation. The production process also does not have any improvement or slowdown on the environment.
中国专利CN1919724公开了一种超高纯H2O2的制备方法,以工业级H2O2为原料,先经过离子交换法或蒸馏法预处理,再采用大孔径吸附树脂去除有机碳,经离子交换树脂柱两段离子交换去除杂质离子,膜过滤去除尘埃颗粒。按照以上公开报道的生产工艺可以得到高纯H2O2水溶液的产品,但他还同时增加了低温,也是同样使用繁杂的生产工艺提纯净化。Chinese patent CN1919724 discloses a preparation method of ultra - high - purity H2O2, which uses industrial - grade H2O2 as raw material, first undergoes pretreatment by ion exchange method or distillation method, and then uses large-pore adsorption resin to remove organic carbon. Two-stage ion exchange of ion exchange resin column removes impurity ions, and membrane filtration removes dust particles. According to the above publicly reported production process, the product of high-purity H 2 O 2 aqueous solution can be obtained, but it also increases the low temperature at the same time, and also uses the complicated production process to purify and purify.
以上专利尽管都是提纯净化工艺的生产技术,因为生产工艺过程极为复杂繁琐,操作人员稍微大意就会造成阴阳树脂柱的树脂装填错误,使用工作量同时增大了数倍。此现象屡见不鲜,结果导致装卸树脂工作量不但增大,水电耗费量增大、以及人工及能源浪费时有发生,因错误操作极易导致树脂失效的事故也是经常发生,不但浪费资源还对生产设备造成损害。Although the above patents are all production technologies for purification and purification processes, because the production process is extremely complicated and tedious, the operator's slight carelessness will cause the resin filling of the yin and yang resin columns to be wrong, and the workload will increase several times at the same time. This phenomenon is not uncommon. As a result, the workload of loading and unloading resin not only increases, but also increases the consumption of water and electricity, as well as labor and energy waste. Accidents that can easily lead to resin failure due to wrong operations also occur frequently, which not only wastes resources, but also affects production equipment. cause damage.
发明内容SUMMARY OF THE INVENTION
为了克服上述现有技术存在的缺陷而提供一种提纯净化效果好、产品稳定度好、成本较低的超净高纯微电子级H2O2的制造生产工艺,此生产工艺操作简单易掌握,不但可以节省四分之三的生产工艺程序,还可以节省水电等人工,具体包括以下步骤:In order to overcome the above-mentioned defects in the prior art, a manufacturing process of ultra-clean and high-purity microelectronic grade H 2 O 2 with good purification effect, good product stability and low cost is provided. The operation of this production process is simple and easy to grasp. Three-quarters of the production process can be saved, and labor such as water and electricity can also be saved, including the following steps:
第一步:将原料储罐中含杂质较多的工业级原料H2O2水溶液,通过动力输送泵进入第一树脂塔。The first step: The industrial grade H 2 O 2 aqueous solution containing more impurities in the raw material storage tank is fed into the first resin tower through the power transfer pump.
第二步:在所述第一树脂塔中进行初级提纯净化,去除50%左右的金属阳离子和阴离子以及杂质。The second step: carry out primary purification in the first resin column to remove about 50% of metal cations and anions and impurities.
将去除50%的原料H2O2液体通过第一树脂塔的动力压力、将提纯净化后的原料液体流入第二树脂塔内,进行阴阳离子和杂质的去除净化,经第二树脂塔的提纯净化,可以去除原料中的50%金属阴阳离子和杂质。The raw material H 2 O 2 liquid with 50% removed is passed through the dynamic pressure of the first resin tower, and the purified and purified raw material liquid flows into the second resin tower for removal and purification of anions and impurities, and the purification of the second resin tower is carried out. Purification can remove 50% of metal anions and impurities in raw materials.
然后通过第二树脂塔的自身运行压力,将第二树脂塔内的原料液体通过自身的压力,流入第三树脂塔内,进行阴阳离子和杂质的提纯净化后,再将第三树脂塔内的液体、通过自身的压力,流入第四树脂塔内进行最后一道提纯净化。Then, through the operating pressure of the second resin tower, the raw material liquid in the second resin tower flows into the third resin tower through its own pressure, and after purification of anions and impurities, the liquid in the third resin tower is purified. The liquid, through its own pressure, flows into the fourth resin tower for final purification.
第三步:将原料液体中剩余的微量金属阴阳离子和杂质去除干净后,通过第四树脂塔内的压力,所述原料液体流入膜分离系统,经过膜分离系统滤除0.2μm尘埃颗粒杂质后,再流入成品接收储罐,整个提纯净化的生产工艺流程结束。The third step: after removing the remaining trace metal anions and impurities in the raw material liquid, the raw material liquid flows into the membrane separation system through the pressure in the fourth resin tower, and the 0.2 μm dust particles are filtered out through the membrane separation system. , and then flow into the finished product receiving storage tank, and the entire purification and purification production process ends.
得到超净高纯微电子级H2O2的高质量产品,产品质量达到0.5ppb质量级别。High-quality products of ultra-clean and high-purity microelectronic grade H 2 O 2 are obtained, and the product quality reaches the quality level of 0.5ppb.
整个生产过程采用一步法生产工艺,上述生产工艺过程的运行压力控制在0.5-1.5Mpa,温度控制在3-42℃。The whole production process adopts a one-step production process, the operating pressure of the above-mentioned production process is controlled at 0.5-1.5Mpa, and the temperature is controlled at 3-42°C.
可优选的,所述原料H2O2水溶液的浓度为27.5-35%。Preferably, the concentration of the raw material H 2 O 2 aqueous solution is 27.5-35%.
可优选的,工作液流速控制在400L/h-500L/h。Preferably, the flow rate of the working fluid is controlled at 400L/h-500L/h.
可优选的,所述原料H2O2水溶液在树脂塔中接触的是采用极少溶出杂质的高抗氧化氟树脂材料。Preferably, the H 2 O 2 aqueous solution of the raw material is contacted in the resin tower using a high anti-oxidative fluororesin material with very few dissolved impurities.
本发明的有益技术效果:Beneficial technical effects of the present invention:
本发明采用了一步法的生产工艺流程,将现有生产工艺技术过多的繁杂工艺流程,整合成一步法生产工艺流程,克服了操作工繁重的劳动和复杂的装填树脂的劳动,既能减轻操作工的劳动量,又能减少三分之二的耗能生产工艺,每吨产品可以节省30%的水电,35%的人力资源。The present invention adopts the one-step production process flow, integrates the complicated and complicated process flow of the existing production technology into a one-step production process flow, overcomes the heavy labor of the operator and the complicated labor of filling resin, and can reduce the The labor of the operator can also reduce the energy-consuming production process by two-thirds, and each ton of product can save 30% of water and electricity and 35% of human resources.
同时一步法生产工艺的混合型树脂塔内的、提纯净化混合型阴阳树脂,在提纯净化的生产工艺过程中,又可以看作是无数道单级阴阳树脂离子交换、因其数量多,提纯净化效果特别好,所得到的微电子级H2O2纯度更高、成本低、稳定度更好,生产效益可以提高20%左右,产品质量可以提高到二个以上级别等级,产品价值可提高35%以上。At the same time, the mixed anion and cation resin in the mixed resin tower of the one-step production process can be purified and purified. The effect is particularly good, the obtained microelectronic grade H 2 O 2 has higher purity, lower cost and better stability, the production efficiency can be increased by about 20%, the product quality can be improved to more than two grades, and the product value can be increased by 35%. %above.
附图说明Description of drawings
图1为本发明的工艺流程图;Fig. 1 is the process flow diagram of the present invention;
图2为本发明树脂塔的结构图;Fig. 2 is the structural drawing of resin tower of the present invention;
其中1-原料储罐,2-动力输送泵,3-膜分离系统,4-成品接收储罐,5-控制阀门,6-管道,7-第一树脂塔,8-第二树脂塔,9-第三树脂塔,10-第四树脂塔,11-塔桶,12-进料口,13-出料口。Among them 1- raw material storage tank, 2- power delivery pump, 3- membrane separation system, 4- finished product receiving storage tank, 5- control valve, 6- pipeline, 7- first resin tower, 8- second resin tower, 9 -The third resin tower, 10- the fourth resin tower, 11- tower barrel, 12- feed port, 13- discharge port.
具体实施方式Detailed ways
下面结合附图及具体实施例,对本发明作进一步详细说明:Below in conjunction with the accompanying drawings and specific embodiments, the present invention is described in further detail:
图1所示的工艺生产线为:原料储罐1→动力输送泵2→第一树脂塔→第二树脂塔→第三树脂塔→第四树脂塔→膜分离系统3→成品接收储罐4,通过管道6依次连接,管道6上设有控制阀门5。The process production line shown in Figure 1 is: raw material storage tank 1→power transfer pump 2→first resin tower→second resin tower→third resin tower→fourth resin tower→membrane separation system 3→finished product receiving storage tank 4, They are connected in sequence through a pipeline 6, and a control valve 5 is arranged on the pipeline 6.
在实施例中,将原料储罐1中含杂质较多的工业级原料H2O2水溶液,通过动力输送泵2与控制阀门5,从第一树脂塔7进料口12进入到塔桶11内进行提纯净化,再将经过第一树脂塔7的原料液体流入第二树脂塔8,然后将第二树脂塔8的原料液流入第三树脂塔9,再将第三树脂塔9的原料液流入第四树脂塔10进行最后一道工序的提纯净化后,将第四树脂塔10的经过提纯净化后的产品流入膜分离系统3除去颗粒杂质后流入成品接收储罐4。In the embodiment, the industrial-grade raw material H 2 O 2 aqueous solution containing more impurities in the raw material storage tank 1 is passed through the power delivery pump 2 and the control valve 5 from the feed port 12 of the first resin tower 7 into the tower barrel 11 Purification is carried out inside, and then the raw material liquid passing through the first resin tower 7 flows into the second resin tower 8, then the raw material liquid of the second resin tower 8 flows into the third resin tower 9, and then the raw material liquid of the third resin tower 9 is After flowing into the fourth resin tower 10 for purification in the last process, the purified product of the fourth resin tower 10 flows into the membrane separation system 3 to remove particulate impurities and then flows into the finished product receiving storage tank 4 .
在本实施例中,运行的压力在0.5Mpa-1.5Mpa,温度控制在3℃-42℃,每小时生产量控制在400L-500L,经过四座树脂塔的提纯净化,从该树脂塔内流出的H2O2已经得到彻底的净化,但是H2O2液体中的颗粒杂质尚未去除,在以前认知中,H2O2的不稳定因素认为是由金属离子、光线、热量所造成,并未意识到颗粒杂质对H2O2的危害。由于颗粒杂质巨大的表面积使H2O2产生分解现象,而不适合长距离运输和存储。In this embodiment, the operating pressure is 0.5Mpa-1.5Mpa, the temperature is controlled at 3°C-42°C, and the output per hour is controlled at 400L-500L. H 2 O 2 has been thoroughly purified, but the particulate impurities in the H 2 O 2 liquid have not been removed. In previous cognition, the unstable factors of H 2 O 2 were considered to be caused by metal ions, light, heat, and Not aware of the hazard of particulate impurities to H2O2 . H 2 O 2 is not suitable for long-distance transportation and storage due to the huge surface area of particulate impurities.
图1中膜分离系统3的分离精度为0.2μm。此时微电子级H2O2溶液得到全面的净化和分离后,大于0.2μm的颗粒状每毫升小于20个,稳定度得到极大的改善,可以进入成品接收储罐4再经过包装线进行产品包装。The separation accuracy of the membrane separation system 3 in FIG. 1 is 0.2 μm. At this time, after the microelectronic grade H 2 O 2 solution is fully purified and separated, the particles larger than 0.2 μm are less than 20 per ml, and the stability is greatly improved, and can enter the finished product receiving tank 4 and then pass through the packaging line for processing. Product packaging.
在本实施例中,原料H2O2的利用率大于99%,上述所用树脂塔、动力输送泵2以及控制阀门5采用极少溶出杂质的聚四氟乙烯、pp、pe、epdf材料制成。In this embodiment, the utilization rate of the raw material H 2 O 2 is greater than 99%, and the resin tower, power delivery pump 2 and control valve 5 used above are made of polytetrafluoroethylene, pp, pe, and epdf materials with very few impurities. .
表1为不同含量H2O2原料在本发明的生产工艺和老工艺提纯净化后各种杂质含量的对比,可从表1中看出本发明的生产工艺实施例1-3对比老工艺,各种杂质含量得到了很大的降低,大大提高了H2O2的纯度。Table 1 is the comparison of various impurity contents after the production process of the present invention and the old process purification and purification of raw materials with different contents of H 2 O , it can be seen from Table 1 that the production process examples 1-3 of the present invention contrast the old process, The content of various impurities has been greatly reduced, and the purity of H 2 O 2 has been greatly improved.
表1:检测报告,单位:ppbTable 1: Test report, unit: ppb
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制,尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should Modifications are made to the technical solutions described in the foregoing embodiments, or some technical features thereof are equivalently replaced, and these modifications or replacements do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
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