CN100429142C - Method for adjusting and controlling configuration of self-assembling block copolymer template oriented to nano micro machining - Google Patents
Method for adjusting and controlling configuration of self-assembling block copolymer template oriented to nano micro machining Download PDFInfo
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
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- B81C2201/0147—Film patterning
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Abstract
面向纳米微加工嵌段共聚物模板自组装形态调控方法，它涉及一种在纳米微加工时所需要的模板图案的调控方法。目前能调控嵌段共聚物形态的处理方法具有调控能力有限、处理工艺比较复杂、所需时间很长的缺点。本发明的操作方法为：将嵌段共聚物溶解在二甲苯溶剂中配制成溶液，将溶液浇铸在基片表面自然挥发成膜，然后将基片放置于密闭容器内，再向密闭容器内滴加有机溶剂后密封，取出即为模板。本发明具有调控出来模板的形态多样性、调控过程高度可控、模板形态高度有序、调控不需复杂设备，工艺简单，成本低，效率高、能在基片上得到几百纳米尺度的各种图案等诸多优点，用本发明的方法还可以得到类似于圆锥齿轮形状的自组装模板图案。
The invention relates to a method for regulating the self-assembly morphology of a nano-microprocessing block copolymer template, which relates to a method for regulating template patterns required in nano-microprocessing. The current treatment methods that can control the morphology of block copolymers have the disadvantages of limited control ability, complicated treatment process, and long time required. The operation method of the present invention is: dissolving the block copolymer in xylene solvent to prepare a solution, casting the solution on the surface of the substrate to volatilize naturally to form a film, then placing the substrate in an airtight container, and then dripping After adding an organic solvent, it is sealed and taken out as a template. The invention has the morphological diversity of the regulated templates, highly controllable regulated process, highly orderly morphological templates, no complex equipment for regulation, simple process, low cost, high efficiency, and can obtain various hundreds of nanometer scales on the substrate. Patterns and many other advantages, the method of the present invention can also be used to obtain self-assembled template patterns similar to the shape of bevel gears.
Description
技术领域： Technical field:
本发明涉及一种在纳米微加工时所需要的模板图案的调控方法。The invention relates to a control method for a template pattern required in nanometer micromachining.
背景技术： Background technique:
目前，制备加工纳米结构有三种不同的途径：一种是用宏观的块体物质，通过去掉多余的部分，加工成纳米结构，通常称之为自上向下方法，属于传统的微细加工技术，包括光刻技术和分子束外延技术；另一种是把微观体系的物质单元组装成纳米器件，通常称之为自下向上方法，属于正在兴起的微细加工技术，包括扫描探针的操纵装配技术、分子模板技术与化学合成技术。以上两种纳米加工都存在一个无法回避问题：即当材料包含纳米结构时，其结构单元数量是惊人的。如果沿用传统的加工方式对逐个结构进行加工，即使工艺上可行，从所需的时间与成本角度去考虑则根本行不通。难怪有人感叹：纳米材料是科学家的梦想，工程师的梦魇。第三种途径是把第一种与第二种方法结合在一起“自组装”技术。所谓自组装是一种无外来因素条件下形成超分子结构或介观超结构的过程。自组装制造过程是绿色的、环境友好的，效率是极高的。由于以上诸多优点并源于纳米科技发展的需要，源于生物的自组装技术近年来已引起科学家高度重视并迅速成为最热门的研究领域。1996年，Whitesides等人(发表于Science)首先利用离子刻蚀技术将嵌段共聚物的球形微区图案复制到50nm厚的SiN2模板材料上，得到每平方厘米具有1011个微孔的SiN2膜材料(见图1)，标志着利用嵌段共聚物自组装模板技术进行纳米微加工新技术技术的开始。At present, there are three different ways to prepare and process nanostructures: one is to use macroscopic bulk materials to process them into nanostructures by removing excess parts, which is usually called the top-down method, which belongs to the traditional microfabrication technology. Including photolithography and molecular beam epitaxy; the other is to assemble the material units of the microscopic system into nano-devices, which is usually called the bottom-up method, which belongs to the emerging microfabrication technology, including the manipulation and assembly technology of scanning probes , Molecular template technology and chemical synthesis technology. There is an unavoidable problem in the above two kinds of nanofabrication: that is, when the material contains nanostructures, the number of its structural units is amazing. If the traditional processing method is used to process the structures one by one, even if it is technically feasible, it will not work at all from the perspective of the required time and cost. No wonder some people sigh: Nanomaterials are the dream of scientists and the nightmare of engineers. The third approach is to combine the first and second methods together with "self-assembly" technology. The so-called self-assembly is a process of forming a supramolecular structure or a mesoscopic superstructure without external factors. The self-assembly manufacturing process is green and environmentally friendly, and the efficiency is extremely high. Due to the above advantages and the needs of the development of nanotechnology, self-assembly technology derived from biology has attracted great attention from scientists in recent years and has quickly become the most popular research field. In 1996, Whitesides et al. (published in Science) first used ion etching technology to replicate the spherical micro-region pattern of the block copolymer to the 50nm thick SiN 2 template material, and obtained SiN with 10 11 micropores per square centimeter 2 Membrane materials (see Figure 1), marking the beginning of new nano-micro-processing technology using block copolymer self-assembly template technology.
对于自组装技术作为加工方法而言，新的机遇与挑战并存：一方面是是如何利用自组装模板制备相应结构纳米材料(模板图案的复制)；另一方面的是如何人为调控自组装模板图案以调控希望构造的纳米结构(模板图案的调控)。图案的复制已知可以通过刻蚀技术实现(离子、臭氧、紫外线选择性地除去部分材料)。模板图案的调控技术目前还亟待提高，因为它是模板纳米加工技术的关键：只有调控出所需图案的模板才有可能复制出理想的结构。目前能调控嵌段共聚物形态的处理方法主要有：高温退火处理、外加电场处理、剪切处理等三种方法。其中剪切处理由于对处理样品厚度有要求，不适用于涉及模板应用的形态调控。剩余的两种方法一方面对于形态调控能力有限，调控得到的有序形态是唯一的，更谈不上进行几百纳米微小模板调控；另一方面处理工艺比较复杂，所需时间很长。For self-assembly technology as a processing method, new opportunities and challenges coexist: on the one hand, how to use self-assembly templates to prepare nanomaterials with corresponding structures (replication of template patterns); on the other hand, how to artificially control self-assembly template patterns To control the desired structure of the nanostructure (template pattern control). Replication of patterns is known to be achieved by etching techniques (ions, ozone, ultraviolet rays selectively remove part of the material). The regulation technology of the template pattern still needs to be improved urgently, because it is the key to the template nanofabrication technology: only the template with the required pattern can be adjusted to reproduce the ideal structure. At present, the treatment methods that can regulate the morphology of block copolymers mainly include three methods: high temperature annealing treatment, external electric field treatment, and shear treatment. Among them, the shearing treatment is not suitable for morphological regulation involving template application due to the requirement for processing sample thickness. On the one hand, the remaining two methods have limited ability to regulate the morphology, and the ordered morphology obtained by the regulation is unique, not to mention regulating the micro-template of hundreds of nanometers; on the other hand, the processing process is relatively complicated and takes a long time.
发明内容： Invention content:
本发明的目的在于提供一种简单、高效的面向纳米微加工嵌段共聚物模板自组装形态调控方法，具体操作方法为：将聚苯乙烯-饱和聚丁二烯-聚苯乙烯嵌段共聚物或聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物溶解在二甲苯溶剂中配制成0.1～1wt％浓度的溶液，室温条件下浇铸在原子水平级平整的基片表面上，自然挥发成膜，将此浇铸膜与附着的基片放置于密闭容器内，密闭容器内垫有具有吸附溶剂蒸汽能力的材料，然后在室温下向密闭容器底部的具有吸附溶剂蒸汽能力的材料上滴加嵌段共聚物材料的良溶剂或选择性溶剂后迅速盖好盖子密封，良溶剂或选择性溶剂的滴加量为足以使溶剂蒸汽压达到饱和，1小时～7天后取出即为面向纳米微加工嵌段共聚物模板。模板形态的自由调控是实现按人的意愿进行纳米微加工的前提与基础，本发明丰富了嵌段共聚物纳米模板的调控技术，与现有的调控技术相比，它具有如下优点：1.它具有调控参数的多样性：本发明可以针对不同的需要使用不同类型的有机溶剂；通过调控温度改变溶剂蒸汽压；另外，溶剂与模板接触时间的不同也会产生不同的效果，从而影响着模板的调控结果。总之，调控参数的多样性决定着调控出来模板的形态具有多样性；2.调控过程高度可控；3.调控模板形态高度有序；4.调控不需复杂设备，工艺简单，成本低，效率高；5.在调控的同时溶剂蒸汽还具有刻蚀的功能，能在基片上得到几百纳米尺度的各种图案，这一点对于未来纳米零件的加工技术有重要意义；6.通过局部刻蚀与调控，用本发明的方法还可以得到类似于圆锥齿轮形状的自组装模板图案(见图6)，这意味着将来利用这类模板可以加工纳米齿轮(见图7)。The purpose of the present invention is to provide a simple and efficient method for regulating the self-assembly morphology of nano-microprocessing block copolymer templates. The specific operation method is: polystyrene-saturated polybutadiene-polystyrene block copolymer Or polystyrene-polybutadiene-polystyrene block copolymer is dissolved in xylene solvent to prepare a solution with a concentration of 0.1 to 1 wt%. To form a film, place the cast film and the attached substrate in a closed container, which is lined with a material capable of absorbing solvent vapor, and then add it dropwise to the material capable of absorbing solvent vapor at the bottom of the closed container After the good solvent or selective solvent of the block copolymer material, quickly cover the lid and seal it. The amount of good solvent or selective solvent added dropwise is enough to saturate the solvent vapor pressure. Take it out after 1 hour to 7 days to face nano-micro-processing Block copolymer template. The free control of the template shape is the premise and basis for realizing nano-micro-processing according to people's wishes. The present invention enriches the control technology of block copolymer nano-templates. Compared with the existing control technology, it has the following advantages: 1. It has the diversity of control parameters: the present invention can use different types of organic solvents according to different needs; the vapor pressure of the solvent can be changed by regulating the temperature; in addition, the difference in contact time between the solvent and the template will also produce different effects, thus affecting the template. control results. In short, the diversity of control parameters determines the diversity of the regulated template shape; 2. The regulation process is highly controllable; 3. The regulation template shape is highly orderly; 4. The regulation does not require complex equipment, the process is simple, the cost is low, and the efficiency is high. High; 5. Solvent vapor also has the function of etching while regulating and controlling, and various patterns of hundreds of nanometers can be obtained on the substrate, which is of great significance for the processing technology of nano parts in the future; 6. Through local etching And regulation, the method of the present invention can also be used to obtain a self-assembled template pattern similar to the shape of a bevel gear (see Figure 6), which means that nano-gears can be processed using this type of template in the future (see Figure 7).
附图说明： Description of drawings:
图1是利用离子刻蚀技术将嵌段共聚物SBS的球形微区图案复制到50nm厚的SiN2模板材料上，得到每平方厘米具有1011个微孔的SiN2膜材料的结构示意图，图2(尺寸800×800nm)是原子力显微镜(AFM)关于SEBS或SBS嵌段共聚物溶于二甲苯之后浇铸在基片上自然挥发成膜的形态图，图3是用具体实施方式二或三方法调控所得模板的AFM形态图(尺寸800×800nm)，图4是用具体实施方式四方法调控所得模板的AFM形态图(尺寸800×800nm)，图5是用具体实施方式五方法调控所得模板的AFM形态图(尺寸500×500nm)，图6是是用具体实施方式六方法调控兼刻蚀的微小尺寸模板AFM形态图(尺寸800×800nm)，图7是由图6模板所能加工微小零件的示意图。Figure 1 is a schematic diagram of the structure of a SiN 2 membrane material with 10 11 micropores per square centimeter obtained by replicating the spherical micro-region pattern of the block copolymer SBS onto a 50nm-thick SiN 2 template material by ion etching technology. 2 (size 800×800nm) is an atomic force microscope (AFM) morphological diagram of SEBS or SBS block copolymer dissolved in xylene and cast on the substrate to form a film after being naturally volatilized. Figure 3 is regulated by the second or third method of the specific embodiment The AFM morphology diagram (size 800×800nm) of the obtained template, Fig. 4 is the AFM morphology diagram (size 800×800nm) of the obtained template regulated by the fourth method of the specific embodiment, and Fig. 5 is the AFM of the regulated template obtained by the fifth method of the specific embodiment Morphological diagram (size 500×500nm), Fig. 6 is the AFM morphological diagram (dimension 800×800nm) of the micro-sized template controlled and etched by the sixth method of the specific embodiment, and Fig. 7 is the tiny parts that can be processed by the template in Fig. 6 schematic diagram.
具体实施方式一：嵌段共聚物自组装模板一般需要溶剂浇铸制备，模板的厚度需控制在纳米尺度以内。我们发现将厚度控制在100纳米以内嵌段共聚物薄膜，在室温下，利用有机良溶剂或选择性溶剂进行熏蒸，可以对模板的自组装图案进行全面的调控。将聚苯乙烯-饱和聚丁二烯-聚苯乙烯嵌段共聚物或聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物溶解在二甲苯溶剂中配制成0.1～1wt％浓度的溶液，室温条件下浇铸在原子水平级平整的基片表面上，自然挥发成膜，将此浇铸膜与附着的基片放置于密闭容器内，密闭容器内垫有具有吸附溶剂蒸汽能力的材料，然后在室温下向密闭容器底部的具有吸附溶剂蒸汽能力的材料上滴加嵌段共聚物材料的良溶剂或选择性溶剂后迅速盖好盖子密封，有机溶剂的滴加量为足以使溶剂蒸汽压达到饱和，1小时～7天后取出即为面向纳米微加工嵌段共聚物模板。用这种方法调控的模板图案形态丰富、高度有序。Embodiment 1: Block copolymer self-assembled templates generally need to be prepared by solvent casting, and the thickness of the templates needs to be controlled within the nanometer scale. We found that controlling the thickness of the block copolymer film within 100 nm, at room temperature, using organic good solvent or selective solvent for fumigation can fully control the self-assembly pattern of the template. Dissolving polystyrene-saturated polybutadiene-polystyrene block copolymer or polystyrene-polybutadiene-polystyrene block copolymer in xylene solvent to prepare a solution with a concentration of 0.1 to 1 wt % , cast on the surface of the atomically flat substrate at room temperature, and naturally volatilize to form a film. The cast film and the attached substrate are placed in a closed container, and the closed container is lined with a material capable of absorbing solvent vapor, and then Add a good solvent or a selective solvent of the block copolymer material to the material with the ability to absorb solvent vapor at the bottom of the closed container at room temperature, and then quickly cover the lid and seal it. The amount of organic solvent added is sufficient to make the solvent vapor pressure reach Saturation, take it out after 1 hour to 7 days, it will be the block copolymer template for nano-microprocessing. The template patterns regulated by this method are rich in morphology and highly ordered.
具体实施方式二：本实施方式模板的调控方法为：将聚苯乙烯-饱和聚丁二烯-聚苯乙烯(SEBS)嵌段共聚物溶解在二甲苯溶剂中配制成0.1wt％浓度的溶液，20-30℃条件下浇铸在云母片上自然挥发成膜，膜的厚度最好要小于100纳米，模板形态如图2所示，将此浇铸膜与附着的云母片放置于垫有滤纸的培养皿内恒温在25℃，滴加良溶剂甲苯于培养皿底部的滤纸上，迅速盖好盖子，甲苯的滴加量为足以使溶剂蒸汽压达到饱和，3小时后将所得产品取出，调控后模板形态如图3所示。然后再通过水面将嵌段共聚物薄膜(即模板)转移到要复型材料表面进行复型。Specific embodiment 2: The regulation method of the template in this embodiment is: dissolving polystyrene-saturated polybutadiene-polystyrene (SEBS) block copolymer in xylene solvent to prepare a solution with a concentration of 0.1 wt%, Cast on the mica sheet at 20-30°C to naturally volatilize to form a film. The thickness of the film should preferably be less than 100 nanometers. The form of the template is shown in Figure 2. Place the cast film and the attached mica sheet on a petri dish lined with filter paper The internal temperature is kept at 25°C, drop the good solvent toluene on the filter paper at the bottom of the petri dish, and quickly cover the lid. The amount of toluene added is enough to saturate the solvent vapor pressure. After 3 hours, the obtained product is taken out, and the shape of the template is adjusted. As shown in Figure 3. Then transfer the block copolymer film (ie template) to the surface of the material to be replicated through the water surface for replication.
具体实施方式三：本实施方式模板的调控方法为：将聚苯乙烯-聚丁二烯-聚苯乙烯(SBS)三嵌段共聚物溶解在二甲苯溶剂中配制成1wt％浓度的溶液，将单晶硅片放置于垫有绵花的培养皿内，室温条件下滴加二甲苯于培养皿底部的绵花上，然后将足以使溶剂蒸汽压达到饱和量的二甲苯浇铸在单晶硅片上，迅速盖好盖，10小时后将产品取出即得模板，调控后模板形态如图3所示，然后可以通过水面将嵌段共聚物模板转移到要复型材料表面进行复型即可。Specific embodiment three: the regulation and control method of the template in this embodiment is: dissolving polystyrene-polybutadiene-polystyrene (SBS) triblock copolymer in xylene solvent and preparing a solution with a concentration of 1wt%, and dissolving The monocrystalline silicon wafer is placed in a petri dish with a cotton pad, and xylene is dropped on the cotton at the bottom of the petri dish at room temperature, and then enough xylene is cast on the single crystal silicon wafer to saturate the vapor pressure of the solvent. After 10 hours, the product is taken out to obtain the template. The shape of the template after adjustment is shown in Figure 3, and then the block copolymer template can be transferred to the surface of the replicating material through the water surface for replicating.
具体实施方式四：本实施方式模板的调控方法为：将美国Shell公司生产的SEBS嵌段共聚物溶解在二甲苯溶剂中配制成0.5wt％浓度的溶液，20-30℃条件下浇铸在云母片上自然挥发成膜，膜的厚度为20纳米，模板形态如图2所示，将此浇铸膜与附着的云母片放置于垫有滤纸的培养皿内恒温在25℃，然后将足以使溶剂蒸汽压达到饱和量的选择性溶剂庚烷滴加于培养皿底部的滤纸上，迅速盖好盖，1小时后将产品取出即得调控后模板，所得模板形态如图4所示，然后可以通过水面将嵌段共聚物薄膜(即为所得模板)转移到要复型材料表面进行复型即可。Specific embodiment four: the regulating method of the template in this embodiment is: dissolving the SEBS block copolymer produced by the American Shell company in a xylene solvent to prepare a solution with a concentration of 0.5 wt%, and casting it on a mica sheet at a temperature of 20-30°C Naturally volatilize to form a film. The thickness of the film is 20 nanometers. The template shape is shown in Figure 2. The cast film and the attached mica sheet are placed in a petri dish lined with filter paper at a constant temperature of 25 ° C, and then enough to make the solvent vapor pressure Add the saturated selective solvent heptane dropwise on the filter paper at the bottom of the petri dish, quickly cover the lid, and take out the product after 1 hour to obtain the regulated template. The block copolymer film (that is, the obtained template) is transferred to the surface of the material to be replicated for replication.
具体实施方式五：本实施方式模板的调控方法为：将美国Shell公司生产的SBS三嵌段共聚物溶解在二甲苯溶剂中配制成0.2wt％浓度的溶液，室温条件下浇铸在单晶硅片上自然挥发成膜，所得膜的厚度为40纳米，模板形态如图2所示，将此浇铸膜与附着的单晶硅片放置于垫有滤纸的培养皿内恒温在25℃，滴加足以使溶剂蒸汽压达到饱和量的环己烷于培养皿底部的滤纸上，迅速盖好盖，24小时后将产品取出即得调控后模板，所得模板形态如图5所示，然后可以通过水面将嵌段共聚物薄膜(即用本发明方法所得模板)转移到要复型材料表面进行复型即可。Embodiment 5: The regulation method of the template in this embodiment is as follows: dissolving the SBS tri-block copolymer produced by the American Shell company in a xylene solvent to prepare a solution with a concentration of 0.2 wt%, and casting it on a single crystal silicon wafer at room temperature The film was naturally volatilized to form a film, the thickness of the obtained film was 40 nm, and the form of the template was shown in Figure 2. The cast film and the attached monocrystalline silicon wafer were placed in a petri dish with filter paper at a constant temperature of 25°C, and enough Make the solvent vapor pressure reach the saturated amount of cyclohexane on the filter paper at the bottom of the petri dish, quickly cover the lid, and take out the product after 24 hours to obtain the adjusted template. The block copolymer film (ie the template obtained by the method of the invention) is transferred to the surface of the material to be replicated for replication.
具体实施方式六：本实施方式模板的调控方法为：将聚苯乙烯-饱和聚丁二烯-聚苯乙烯嵌段共聚物溶解在二甲苯溶剂中配制成0.8wt％浓度的溶液，20-30℃条件下浇铸在云母片上自然挥发成膜，模板形态如图2所示，将此浇铸膜放置带有磨口密闭性能非常好的称量瓶中，样品距离称量瓶底部1cm，滴加足以使溶剂蒸汽压达到饱和量的二甲苯于称量瓶底部迅速盖好盖，恒温25℃ 7天后将产品取出即得调控后模板，所得模板形态如图6所示，此时溶剂蒸汽已将大部分嵌段共聚物模板腐蚀掉，留下局部微小尺寸的模板图案，为利用此模板加工微纳米零件提供了条件。Specific embodiment six: The regulation method of the template in this embodiment is: dissolving polystyrene-saturated polybutadiene-polystyrene block copolymer in xylene solvent to prepare a solution with a concentration of 0.8wt%, 20-30 Under the condition of ℃, it is casted on the mica sheet to form a film by natural volatilization. The form of the template is shown in Figure 2. Quickly cover the bottom of the weighing bottle with the xylene whose solvent vapor pressure reaches saturation, and take out the product after 7 days at a constant temperature of 25°C to obtain the adjusted template. The shape of the template obtained is shown in Figure 6. Part of the block copolymer template is corroded, leaving a template pattern with a small local size, which provides conditions for the use of this template to process micro-nano parts.
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