CN1562730A - Method for adjusting and controlling configuration of self-assembling block copolymer template oriented to nano micro machining - Google Patents

Abstract

Translated fromChinese

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

Towards the little processing block copolymer template of nanometer self assembly morphology control method

Technical field: the present invention relates to a kind of at the little regulate and control method that adds needed die plate pattern in man-hour of nanometer.

Background technology: at present, preparation processing nanostructured has three kinds of different approach: a kind of is with macroscopical block material, by removing unnecessary part, be processed into nanostructured, usually be referred to as method from up to down, belong to traditional Micrometer-Nanometer Processing Technology, comprise photoetching technique and molecular beam epitaxy technique; Another kind is that the urstoff of microsystem is assembled into nano-device, is referred to as bottom-up method usually, belongs to the Micrometer-Nanometer Processing Technology of rising, and comprises manipulation mounting technology, molecular template technology and the chemical synthesising technology of scan-probe.More than two kinds of nanoprocessings all exist one can't evade the question: promptly when material comprised nanostructured, its construction unit quantity was surprising.If continue to use traditional processing mode structure is one by one processed,, go to consider then unworkable at all from required time and cost angle even feasible on the technology.No wonder the someone sighs with feeling: nano material is scientist's a dream, engineer's nightmare.The third approach be first kind with second method " self assembly " technology that combines.So-called self assembly is a kind of process that forms the supramolecular structure or the sight superstructure that is situated between under the foeign element condition of not having.The self assembly manufacture process is green, eco-friendly, and efficient is high.Because above plurality of advantages also comes from the needs that nanosecond science and technology develop, biogenic self-assembling technique has caused that in recent years scientist pays much attention to and become the most popular research field rapidly.1996, people such as Whitesides (being published in Science) at first utilized the ion etching technology that the spherical microcell pattern of block copolymer is copied to the thick SiN of 50nm₂On the mould material, obtain every square centimeter and have 10¹¹The SiN of individual micropore₂The membrane material (see figure 1) indicates and utilizes block copolymer self assembly mould plate technique to carry out the beginning of the little New Machining Technology technology of nanometer.

As for the processing method, new Opportunity coexists with challenge for self-assembling technique: be how to utilize the self assembly template to prepare corresponding construction nano material (duplicating of die plate pattern) on the one hand; On the other hand be how artificial adjustment self assembly die plate pattern is wished the nanostructured (regulation and control of die plate pattern) of structure with regulation and control.Pattern duplicate known can the realization (ion, ozone, remove to ultraviolet selecting part material) by lithographic technique.The control technique of die plate pattern is at present also in urgent need to be improved, because it is the key of template nanofabrication technique: have only the template of regulating and control out required pattern just might copy desirable structure.The processing method that can regulate and control the block copolymer form at present mainly contains: three kinds of methods such as The high temperature anneal, extra electric field processing, shear treatment.Wherein shear treatment is not suitable for the morphology control that relates to template applications owing to handling thickness of sample requirement is arranged.Remaining two kinds of methods are limited in one's ability for morphology control on the one hand, and the orderly form that regulation and control obtain is unique, let alone carries out the small template to regulate of hundreds of nanometer; Treatment process more complicated on the other hand, required time is very long.

Summary of the invention: the object of the present invention is to provide a kind of simple, efficiently towards the little processing block copolymer template of nanometer self assembly morphology control method, concrete operation method is: block copolymer is dissolved in the solution that is mixed with 0.1～1wt% concentration in the xylene solvent, cast under the room temperature condition on the smooth substrate surface of atomic level level, naturally the volatilization film forming, this cast membrane and the substrate that adheres to are positioned in the closed container, be lined with material in the closed container with adsorption solvent steam ability, at room temperature behind good solvent that drips block copolymer material on the material with adsorption solvent steam ability of closed container bottom or selective solvent, build the lid sealing then rapidly, the dripping quantity of organic solvent reaches capacity vapor pressure solvent for being enough to, and takes out after 1 hour～7 days to be towards the little processing block copolymer template of nanometer.Freely regulating and control of template form is to realize carrying out micro-machined prerequisite of nanometer and basis by people's wish, the present invention has enriched the control technique of block copolymer nano template, compare with existing control technique, it has following advantage: 1. it has the diversity of regulation and control parameter: the present invention can use dissimilar organic solvents at different needs; Change vapor pressure solvent by regulating and controlling temperature; In addition, solvent also can produce different effects with the different of template time of contact, thereby affects the regulation and control result of template.In a word, the diversity of regulation and control parameter is determining the come out form of template of regulation and control to have diversity; 2. the regulation process height is controlled; 3. regulate and control template form high-sequential; 4. regulation and control do not need complex device, and technology is simple, and cost is low, the efficient height; 5. solvent vapo(u)r also has the function of etching in regulation and control, can obtain the various patterns of hundreds of nanoscale on substrate, and this point is significant for the process technology of following nanometer part; 6. by local etching and regulation and control, can also obtain being similar to the self assembly die plate pattern (see figure 6) of conical gear shape with method of the present invention, this means and utilize this class template can process the nanogears (see figure 7) in the future.

Description of drawings: Fig. 1 utilizes the ion etching technology that the spherical microcell pattern of block copolymer SBS is copied to the thick SiN of 50nm₂On the mould material, obtain every square centimeter and have 10¹¹The SiN of individual micropore₂The structural representation of membrane material, (size 800 * 800nm) is that AFM (AFM) is dissolved in the aspect graph that dimethylbenzene casts in the film forming of volatilizing naturally on the substrate afterwards about SEBS or SBS block copolymer to Fig. 2, Fig. 3 is the AFM aspect graph (size 800 * 800nm) with the specific embodiment three methods regulation and control gained template, Fig. 4 is the AFM aspect graph (size 800 * 800nm) with specific embodiment four directions method regulation and control gained template, Fig. 5 is the AFM aspect graph (size 500 * 500nm) with the specific embodiment five methods regulation and control gained template, Fig. 6 holds concurrently with the regulation and control of the specific embodiment six methods that (size 800 * 800nm), Fig. 7 is the schematic diagram that can be processed micro parts by Fig. 6 template for the microsize template AFM aspect graph of etching.

The specific embodiment one: block copolymer self assembly template generally needs the solvent cast preparation, and the thickness of template need be controlled in the nanoscale.We find THICKNESS CONTROL in 100 nanometers at room temperature, to utilize organic good solvent or selective solvent to fumigate with interior block copolymer film, can comprehensively regulate and control the self assembly pattern of template.Block copolymer is dissolved in the solution that is mixed with 0.1～1wt% concentration in the xylene solvent, cast under the room temperature condition on the smooth substrate surface of atomic level level, naturally the volatilization film forming, this cast membrane and the substrate that adheres to are positioned in the closed container, be lined with material in the closed container with adsorption solvent steam ability, at room temperature behind good solvent that drips block copolymer material on the material with adsorption solvent steam ability of closed container bottom or selective solvent, build the lid sealing then rapidly, the dripping quantity of organic solvent reaches capacity vapor pressure solvent for being enough to, and takes out after 1 hour～7 days to be towards the little processing block copolymer template of nanometer.Abundant, the high-sequential of Tiao Kong die plate pattern form in this way.

The specific embodiment two: the regulate and control method of present embodiment template is: polystyrene-saturated polybutadiene-polystyrene (SEBS) block copolymer is dissolved in the solution that is mixed with 0.1wt% concentration in the xylene solvent, cast in the film forming of volatilizing naturally on the mica sheet under the 20-30 ℃ of condition, the thickness of film preferably is less than 100 nanometers, the template form as shown in Figure 2, this cast membrane and the mica sheet that adheres to are positioned in the culture dish that is lined with filter paper constant temperature at 25 ℃, drip good solvent toluene on the filter paper of culture dish bottom, build lid rapidly, the dripping quantity of toluene reaches capacity vapor pressure solvent for being enough to, after 3 hours products obtained therefrom is taken out, regulation and control rear pattern plate form as shown in Figure 3.And then by the water surface block copolymer film (being template) is transferred to and to be wanted the replica material surface to carry out replica.

The specific embodiment three: the regulate and control method of present embodiment template is: polystyrene-poly butadiene-polystyrene (SBS) triblock copolymer is dissolved in the solution that is mixed with 1wt% concentration in the xylene solvent, monocrystalline silicon piece is positioned in the culture dish that is lined with continuous flower, room temperature condition drips dimethylbenzene down and takes in the silk floss of culture dish bottom, to be enough to make the dimethylbenzene of the vapor pressure solvent amount of reaching capacity to cast on the monocrystalline silicon piece then, build lid rapidly, after 10 hours the product taking-up is promptly got template, regulation and control rear pattern plate form can be transferred to block copolymer template by the water surface then and want the replica material surface to carry out replica to get final product as shown in Figure 3.

The specific embodiment four: the regulate and control method of present embodiment template is: the SEBS block copolymer that U.S. Shell company is produced is dissolved in the solution that is mixed with 0.5wt% concentration in the xylene solvent, cast in the film forming of volatilizing naturally on the mica sheet under the 20-30 ℃ of condition, the thickness of film is 20 nanometers, the template form as shown in Figure 2, this cast membrane and the mica sheet that adheres to are positioned in the culture dish that is lined with filter paper constant temperature at 25 ℃, to be enough to make the selective solvent heptane droplets of the vapor pressure solvent amount of reaching capacity to be added on the filter paper of culture dish bottom then, build lid rapidly, after 1 hour the product taking-up is promptly got rear pattern plate, gained template form can be transferred to block copolymer film (being the gained template) by the water surface then and want the replica material surface to carry out replica to get final product as shown in Figure 4.

The specific embodiment five: the regulate and control method of present embodiment template is: the SBS triblock copolymer that U.S. Shell company is produced is dissolved in the solution that is mixed with 0.2wt% concentration in the xylene solvent, cast in the film forming of volatilizing naturally on the monocrystalline silicon piece under the room temperature condition, the thickness of gained film is 40 nanometers, the template form as shown in Figure 2, this cast membrane and the monocrystalline silicon piece that adheres to are positioned in the culture dish that is lined with filter paper constant temperature at 25 ℃, dropping is enough to make the cyclohexane of the vapor pressure solvent amount of reaching capacity on the filter paper of culture dish bottom, build lid rapidly, after 24 hours the product taking-up is promptly got rear pattern plate, gained template form can be transferred to block copolymer film (promptly using the inventive method gained template) by the water surface then and want the replica material surface to carry out replica to get final product as shown in Figure 5.

The specific embodiment six: the regulate and control method of present embodiment template is: polystyrene-saturated polybutadiene-polystyrene block copolymer is dissolved in the solution that is mixed with 0.8wt% concentration in the xylene solvent, cast in the film forming of volatilizing naturally on the mica sheet under the 20-30 ℃ of condition, the template form as shown in Figure 2, this cast membrane placement is had in the extraordinary measuring cup of ground airtight performance, sample is apart from measuring cup bottom 1cm, dropping is enough to make the dimethylbenzene of the vapor pressure solvent amount of reaching capacity to build lid rapidly in the measuring cup bottom, 25 ℃ of constant temperature after 7 days take out product and promptly get rear pattern plate, gained template form as shown in Figure 6, this moment, solvent vapo(u)r eroded most of block copolymer template, stay local minute sized die plate pattern, provide condition for utilizing this template to process micro-nano part.

Claims (7)

Translated fromChinese

1、一种面向纳米微加工嵌段共聚物模板自组装形态调控方法，其特征在于将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。1. A method for regulating self-assembly morphology of block copolymer templates for nano-microprocessing, characterized in that the block copolymer is dissolved in xylene solvent to prepare a solution with a concentration of 0.1 to 1 wt%, and cast at the atomic level at room temperature On the level flat substrate surface, it will naturally volatilize to form a film. Place the cast film and the attached substrate in a closed container. The closed container is filled with a material capable of absorbing solvent vapor, and then pour it to the bottom of the closed container at room temperature. Add the good solvent or selective solvent of the block copolymer material to the material with the ability to absorb solvent vapor, and then quickly cover and seal it. The amount of organic solvent added is enough to saturate the solvent vapor pressure, and take it out after 1 hour to 7 days. That is, it is a block copolymer template for nano-microprocessing.2、根据权利要求1所述的面向纳米微加工嵌段共聚物模板自组装形态调控方法，其特征在于所述嵌段共聚物为聚苯乙烯—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。2. The method for regulating the self-assembly morphology of nano-microprocessed block copolymer templates according to claim 1, wherein the block copolymer is polystyrene-saturated polybutadiene-polystyrene block copolymerization or polystyrene-polybutadiene-polystyrene block copolymers.3根据权利要求1或2所述的面向纳米微加工嵌段共聚物模板自组装形态调控方法，其特征在于二甲笨溶液浇涛于基片上挥发成膜的厚度小于100纳米。3. According to claim 1 or 2, the nano-microprocessing-oriented block copolymer template self-assembly morphology control method is characterized in that the thickness of the xylene solution poured on the substrate and volatilized to form a film is less than 100 nanometers.4、根据权利要求1或2所述的面向纳米微加工嵌段共聚物模板自组装形态调控方法，其特征在于所述原子水平级平整的基片为云母片或单晶硅。4. The method for regulating self-assembly morphology of nano-micro-processing block copolymer templates according to claim 1 or 2, characterized in that the atomically flat substrate is a mica sheet or a single crystal silicon.5、根据权利要求1或2所述的面向纳米微加工嵌段共聚物模板自组装形态调控方法，其特征在于所述密闭容器为培养皿或称量瓶。5. The method for regulating the self-assembly morphology of nano-microprocessing block copolymer templates according to claim 1 or 2, characterized in that the airtight container is a petri dish or a weighing bottle.6、根据权利要求1或2所述的面向纳米微加工嵌段共聚物模板自组装形态调控方法，其特征在于所述具有吸附溶剂蒸汽能力的材料为滤纸或绵花。6. The method for regulating the self-assembly morphology of nano-microprocessed block copolymer templates according to claim 1 or 2, characterized in that the material capable of absorbing solvent vapor is filter paper or cotton.7、根据权利要求1或2所述的面向纳米微加工嵌段共聚物模板自组装形态调控方法，其特征在于良溶剂为甲苯或二甲苯，选择性溶剂为环乙烷或庚烷。7. The method for regulating the self-assembly morphology of nano-microprocessed block copolymer templates according to claim 1 or 2, characterized in that the good solvent is toluene or xylene, and the selective solvent is cycloethane or heptane.

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