TWI395775B - Self-assembly method for manufacturing nano/micro structure - Google Patents
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本發明是有關於一種微奈米結構之製造方法，且特別是有關於一種製造微奈米結構之自組裝方法。This invention relates to a method of making a micro-nanostructure, and more particularly to a self-assembly method for making a micro-nanostructure.
目前，一種在基板上形成自組裝微奈米結構的製程係採用為蘭慕爾-布羅吉(Langmuir-Blodgett；以下簡稱“LB”)薄膜法技術。在LB薄膜技術的製程中，先將許多兩性分子散布在具揮發性溶液的液面上，以使這些兩性分子均勻分布在空氣與溶液之界面上。接著，當有機溶劑揮發後，兩性分子分布在水和空氣的界面之間，其中兩性分子之親水基向下和水接觸，而其疏水基則朝上遠離水層。此時，必須小心地擠壓液體表面上的這層兩性分子，以藉由擠壓的方式來縮減分子和分子之間的距離，進而形成緊密堆積的單分子層。然後，將平板狀基板浸入或移出布滿單分子層的液面，在此同時利用機械手臂等電動機具維持液面的表面壓，如此一來即可使液面上之單分子層轉移至基板表面上，而在基板表面上形成一層緊密排列、規則且具方向性的分子薄膜。At present, a process for forming a self-assembled micro-nano structure on a substrate is a Langmuir-Blodgett (hereinafter referred to as "LB") thin film method. In the process of the LB thin film technology, a plurality of amphiphilic molecules are first dispersed on the surface of the volatile solution to uniformly distribute the amphiphilic molecules at the interface between the air and the solution. Then, when the organic solvent is volatilized, the amphiphilic molecules are distributed between the interface of water and air, wherein the hydrophilic groups of the amphiphilic molecules are in contact with water downward, and the hydrophobic groups thereof are directed upwards away from the water layer. At this point, the layer of amphiphilic molecules on the surface of the liquid must be carefully squeezed to reduce the distance between the molecules and the molecules by extrusion, thereby forming a tightly packed monolayer. Then, the flat substrate is immersed or removed from the liquid surface of the monolayer, and at the same time, the surface pressure of the liquid surface is maintained by a motor device such as a robot arm, so that the monolayer on the liquid surface can be transferred to the substrate. On the surface, a tightly arranged, regular and directional molecular film is formed on the surface of the substrate.
然而，此種LB薄膜製程仍存在以下的缺點，包含：需耗費冗長的時間來等待溶液中之揮發性溶劑揮發；兩性分子在液面上的分布係一固定量，而隨著基板的向上拉伸，使得兩性分子附著至基板表面上，如此一來，必須不斷地擠壓液面之兩性分子，以維持其緊密性；此外，受到於兩性分子在溶液中之數量固定的限制，基板之尺寸也會受到限制；再者，必須準確控制液面的表面壓；而且，在LB膜上排列移轉之固體表面的速率慢，商業價值低。However, the LB film process still has the following disadvantages, including: it takes a long time to wait for the volatile solvent in the solution to volatilize; the distribution of the amphiphilic molecules on the liquid surface is a fixed amount, and the substrate is pulled up. Stretching, so that the amphiphilic molecules adhere to the surface of the substrate, so that the liquid molecules must be continuously squeezed to maintain the tightness; in addition, the size of the substrate is limited by the fixed amount of the amphiphilic molecules in the solution. It is also limited; in addition, the surface pressure of the liquid surface must be accurately controlled; moreover, the rate of moving the solid surface on the LB film is slow and the commercial value is low.
因此，本發明之一態樣是在提供一種製造微奈米結構之自組裝方法，其係將具有疏水表面的粒子與短親油基之溶劑混合後，再將所形成之混合物注入水中，粒子藉由其上之短親油基溶劑與水的交換而可在溶液與空氣界面之間形成自組裝單層結構。故，此製程不需使用兩性分子，也無須精準控制溶液之表面壓，即可快速形成高密度排列的微奈米結構，且粒子可在製程期間持續補充，因而更可提高製程的方便性。Accordingly, an aspect of the present invention provides a self-assembly method for fabricating a micro-nano structure by mixing particles having a hydrophobic surface with a solvent of a short lipophilic group, and then injecting the formed mixture into water, the particles. A self-assembled monolayer structure can be formed between the solution and the air interface by the exchange of the short lipophilic solvent thereon with water. Therefore, the process does not need to use amphiphilic molecules, and does not need to accurately control the surface pressure of the solution, and can quickly form a high-density array of micro-nano structures, and the particles can be continuously replenished during the process, thereby further improving the process convenience.
本發明之另一態樣是在提供一種製造微奈米結構之自組裝方法，其係將具有親水表面的粒子與極性溶劑混合後，再將所形成之混合物注入非極性溶劑中，粒子藉由包覆其表面之極性溶劑與非極性溶劑的交換而可在溶液與空氣界面之間形成自組裝單層結構。因此，此自組裝製程不需使用兩性分子，也無須精準控制溶液之表面壓，即可快速形成高密度排列的微奈米結構。此外，粒子可在製程期間持續補充，因此具有極高的製程便利性。Another aspect of the present invention provides a self-assembly method for fabricating a micro-nano structure by mixing particles having a hydrophilic surface with a polar solvent, and then injecting the formed mixture into a non-polar solvent by using particles. The exchange of a polar solvent overlying its surface with a non-polar solvent results in a self-assembled monolayer structure between the solution and the air interface. Therefore, the self-assembly process does not require the use of amphiphilic molecules, and does not require precise control of the surface pressure of the solution to rapidly form a high-density array of micro-nanostructures. In addition, the particles can be continuously replenished during the process, thus providing extremely high process convenience.
根據本發明之上述目的，提出一種製造微奈米結構之自組裝方法，包含：混合複數個粒子與一短親油基溶劑而形成一混合物，其中每一粒子具有一疏水表面；將此混合物注入一水中，以使這些粒子之一部分浮在水之一液面上；將一基板置入水中；以及將基板自水中拉出，以使這些粒子之前述部分附著而排列在基板之一表面上。According to the above object of the present invention, a self-assembly method for fabricating a micro-nano structure is provided, comprising: mixing a plurality of particles with a short lipophilic solvent to form a mixture, wherein each particle has a hydrophobic surface; injecting the mixture a water such that one of the particles is partially floated on one of the water surfaces; a substrate is placed in the water; and the substrate is pulled out of the water so that the aforementioned portions of the particles are attached to be arranged on one surface of the substrate.
依據本發明之一實施例，上述粒子與水之接觸角大於60度。According to an embodiment of the invention, the contact angle of the particles with water is greater than 60 degrees.
依據本發明之另一實施例，上述粒子之材料為經一矽烷類處理劑處理後之物質。According to another embodiment of the present invention, the material of the particles is a substance treated with a decane treating agent.
在一示範實施例中，上述之矽烷類處理劑為一矽烷化合物，且此矽烷化合物具有通式R1 R2 R3 R4 Si，其中R1 、R2 、R3 及R4 為相同或不同之一基團，且基團為鹵素、具4到22個碳原子之直鏈或支鏈之烷基、OR5 、苯基、苯烷氧基、苯甲氧基、或苯烷基，其中R5 為H或具1至6個碳原子之烷基，且此矽烷化合物包含有1至3個鹵素與具4到22個碳原子之直鏈或支鏈之烷基、或OR5 取代基與具4到22個碳原子之直鏈或支鏈之烷基。In an exemplary embodiment, the above decane treating agent is a monodecane compound, and the decane compound has the formula R 1 R 2 R 3 R 4 Si, wherein R 1 , R 2 , R 3 and R 4 are the same or a different group, and the group is a halogen, a linear or branched alkyl group having 4 to 22 carbon atoms, OR 5 , phenyl, phenylalkoxy, benzyloxy, or phenylalkyl, Wherein R 5 is H or an alkyl group having 1 to 6 carbon atoms, and the decane compound contains 1 to 3 halogens and a linear or branched alkyl group having 4 to 22 carbon atoms, or an OR 5 substitution And a straight or branched alkyl group having 4 to 22 carbon atoms.
在另一示範實施例中，上述之矽烷類處理劑為一矽烷化合物，且此矽烷化合物具有通式R1 R2 R3 R4 Si，其中R1 、R2 、R3 及R4 分別為相同或不同之一基團，且此基團係OR5 、1至22個碳原子之直鏈或支鏈之烷基，其中R5 為H或具1至6個碳原子之烷基，且矽烷化合物含有1至3個OR5 取代基。In another exemplary embodiment, the above decane treating agent is a monodecane compound, and the decane compound has the formula R 1 R 2 R 3 R 4 Si, wherein R 1 , R 2 , R 3 and R 4 are respectively a group of the same or different, and the group is a straight or branched alkyl group of OR 5 , 1 to 22 carbon atoms, wherein R 5 is H or an alkyl group having 1 to 6 carbon atoms, and The decane compound contains 1 to 3 OR 5 substituents.
根據本發明之上述目的，另提出一種製造微奈米結構之自組裝方法，包含：混合複數個粒子與一極性溶劑而形成一混合物，其中每一粒子具有一親水表面；將前述混合物注入一非極性溶劑中，以使這些粒子之一部分浮在此非極性溶劑之一液面上；將一基板置入非極性溶劑中；以及將此基板自非極性溶劑中拉出，以使這些粒子之前述部分附著而排列在基板之一表面上。According to the above object of the present invention, a self-assembly method for fabricating a micro-nano structure is further provided, comprising: mixing a plurality of particles with a polar solvent to form a mixture, wherein each particle has a hydrophilic surface; and injecting the mixture into a non- a polar solvent such that one of the particles is partially floated on one of the non-polar solvents; a substrate is placed in the non-polar solvent; and the substrate is pulled from the non-polar solvent to cause the particles to be Partially attached and arranged on one surface of the substrate.
依據本發明之一實施例，上述之粒子為圓球型、方形、棍型、長條型或三角形。According to an embodiment of the invention, the particles are spherical, square, stick, strip or triangle.
依據本發明之另一實施例，上述之粒子為基板為平板或圓柱，其中此圓柱可為空心或實心。According to another embodiment of the invention, the particles are a plate or a cylinder, wherein the cylinder may be hollow or solid.
請參照第1圖與第2A圖至第2C圖，其中第1圖係繪示依照本發明一實施方式的一種製造微奈米結構之自組裝方法的流程圖，第2A圖至第2C圖則係繪示依照本發明一實施方式的一種製造微奈米結構之自組裝方法的裝置流程示意圖。在本實施方式中，進行製造微奈米結構之自組裝方法時，先提供數個粒子200與溶劑202(請先參照第2A圖)，其中這些粒子200之尺寸可例如為微米級或奈米級。在一實施例中，這些粒子200之粒徑可例如介於實質100nm與實質100μm之間。此外，這些粒子200的形狀可例如為圓球型、方形、棍型、長條型或三角形。而後，如第1圖所示之步驟100，進行混合步驟，以混合這些粒子200與溶劑202，而形成混合物204。接著，提供裝有溶劑208之容置槽206，再如第1圖所示之步驟102，可利用例如滴管210，將所形成之混合物204注入容置槽206的溶劑208中。Please refer to FIG. 1 and FIG. 2A to FIG. 2C , wherein FIG. 1 is a flow chart showing a self-assembly method for fabricating a micro-nano structure according to an embodiment of the present invention, and FIG. 2A to FIG. 2C are diagrams. A schematic diagram of a device for fabricating a self-assembly method of a micro-nano structure according to an embodiment of the present invention is shown. In the present embodiment, when the self-assembly method for fabricating the micro-nano structure is performed, a plurality of particles 200 and a solvent 202 are first provided (please refer to FIG. 2A first), wherein the size of the particles 200 may be, for example, micron or nanometer. level. In one embodiment, the particle size of the particles 200 can be, for example, between substantially 100 nm and substantially 100 μm. Further, the shape of these particles 200 may be, for example, a sphere, a square, a stick, a strip, or a triangle. Then, as in step 100 shown in Fig. 1, a mixing step is performed to mix the particles 200 with the solvent 202 to form a mixture 204. Next, a accommodating tank 206 containing a solvent 208 is provided. As in step 102 shown in FIG. 1, the formed mixture 204 can be injected into the solvent 208 of the accommodating tank 206 by, for example, a dropper 210.
在第一示範實施例中，這些粒子200具有疏水表面220，此溶劑202為具短親油基溶劑，且溶劑208為水。具短親油基之溶劑202可為1~10碳之醇、烷、或酮類溶劑，例如甲醇。在一實施例中，粒子200與水的接觸角例如可大於60度。藉由包覆在粒子200之表面220上的短親油基溶劑202與水的動態交換，這些粒子200的一部分可浮在溶劑208與空氣之界面上，亦即溶劑208之液面214上。粒子200之材料可例如為無機材料、有機材料、或有機材料與無機材料之混合物。在本示範實施例之一實施樣態中，粒子200本身可為由疏水材料，例如聚二甲基矽氧烷、聚甲基氫矽氧烷、聚二乙基矽氧烷、甲基苯基矽氧烷、聚矽酸鹽、聚甲基倍半矽氧烷或其混合物所組成。In a first exemplary embodiment, the particles 200 have a hydrophobic surface 220, the solvent 202 is a short lipophilic based solvent, and the solvent 208 is water. The solvent 202 having a short lipophilic group may be a 1 to 10 carbon alcohol, an alkane, or a ketone solvent such as methanol. In an embodiment, the contact angle of the particles 200 with water can be, for example, greater than 60 degrees. By dynamic exchange of the short lipophilic solvent 202 over the surface 220 of the particle 200 with water, a portion of the particles 200 can float on the interface of the solvent 208 with air, i.e., the level 214 of the solvent 208. The material of the particles 200 may be, for example, an inorganic material, an organic material, or a mixture of an organic material and an inorganic material. In one embodiment of the present exemplary embodiment, the particles 200 may themselves be composed of a hydrophobic material such as polydimethyl methoxy alkane, polymethylhydroquinone, polydiethyl decane, methyl phenyl. It consists of a siloxane, a polyphthalate, a polymethylsesquioxane or a mixture thereof.
在本示範實施例之另一實施樣態中，粒子200本身之材料可為非疏水材料，但粒子200之材料可為經矽烷類處理劑處理後之物質，其中在進行矽烷類處理劑處理之前，可先利用例如紫外線、電漿或酸鹼物質來對這些粒子200之表面220進行表面處理。在一實施例中，前述之矽烷類處理劑可為矽烷化合物，且此矽烷化合物具有通式R1 R2 R3 R4 Si，其中R1 、R2 、R3 及R4 可為相同基團或不同基團，且此基團可例如為鹵素、具4到22個碳原子之直鏈或支鏈之烷基、OR5 、苯基、苯烷氧基、苯甲氧基、或苯烷基，其中R5 為H或具1至6個碳原子之烷基，且此矽烷化合物較佳係包含有1至3個鹵素與具4到22個碳原子之直鏈或支鏈之烷基、或OR5 取代基與具4到22個碳原子之直鏈或支鏈之烷基。在另一實施例中，前述之矽烷類處理劑可為矽烷化合物，且該矽烷化合物具有通式R1 R2 R3 R4 Si，其中R1 、R2 、R3 及R4 分別為相同基團或不同基團，且此基團係OR5 、1至22個碳原子之直鏈或支鏈之烷基，其中R5 為H或具1至6個碳原子之烷基，且此矽烷化合物包含有1至3個OR5 取代基。In another embodiment of the exemplary embodiment, the material of the particle 200 itself may be a non-hydrophobic material, but the material of the particle 200 may be a substance treated with a decane treating agent, before being treated with a decane treating agent. The surface 220 of these particles 200 may be surface treated with, for example, ultraviolet light, plasma or an acid-base material. In one embodiment, the aforementioned decane treating agent may be a decane compound, and the decane compound has the formula R 1 R 2 R 3 R 4 Si, wherein R 1 , R 2 , R 3 and R 4 may be the same group. a group or a different group, and this group may, for example, be a halogen, a linear or branched alkyl group having 4 to 22 carbon atoms, OR 5 , phenyl, phenylalkoxy, benzyloxy, or benzene An alkyl group, wherein R 5 is H or an alkyl group having 1 to 6 carbon atoms, and the decane compound preferably contains 1 to 3 halogens and a linear or branched alkane having 4 to 22 carbon atoms a substituent, or an OR 5 substituent, with a straight or branched alkyl group having 4 to 22 carbon atoms. In another embodiment, the aforementioned decane treating agent may be a decane compound, and the decane compound has the formula R 1 R 2 R 3 R 4 Si, wherein R 1 , R 2 , R 3 and R 4 are respectively the same a group or a different group, and this group is a straight or branched alkyl group of OR 5 , 1 to 22 carbon atoms, wherein R 5 is H or an alkyl group having 1 to 6 carbon atoms, and this The decane compound contains from 1 to 3 OR 5 substituents.
在本示範實施例之又一實施樣態中，粒子200之表面220可利用例如電漿處理方式來進行疏水化處理，其中在此電漿處理過程中所利用之電漿氣體可例如為含氟類氣體、含矽烷、1至10個碳原子之烷類、1至10個碳原子之烯類、1至10個碳原子之炔類或其混合物。在一實施例中，粒子200之疏水表面220可例如包含含氟材料。In still another embodiment of the exemplary embodiment, the surface 220 of the particle 200 may be subjected to a hydrophobization treatment by, for example, a plasma treatment method, wherein the plasma gas utilized in the plasma treatment may be, for example, fluorine-containing. Gas-like, decane-containing, alkane of 1 to 10 carbon atoms, olefin of 1 to 10 carbon atoms, acetylene of 1 to 10 carbon atoms or a mixture thereof. In an embodiment, the hydrophobic surface 220 of the particle 200 can comprise, for example, a fluorine-containing material.
在第二示範實施例中，這些粒子200具有親水之表面220，此溶劑202為極性溶劑，且溶劑208為非極性溶劑。藉由包覆在粒子200之表面220上的極性溶劑202與非極性溶劑208的動態交換，這些粒子200的一部分可浮在溶劑208與空氣之界面上，亦即溶劑208之液面214上。In a second exemplary embodiment, the particles 200 have a hydrophilic surface 220, the solvent 202 is a polar solvent, and the solvent 208 is a non-polar solvent. By dynamic exchange of polar solvent 202 and non-polar solvent 208 coated on surface 220 of particle 200, a portion of these particles 200 can float at the interface of solvent 208 and air, i.e., liquid level 214 of solvent 208.
接下來，如第1圖之步驟104所示，將基板212置入溶劑208中，使部分或全部之基板212浸入溶劑208中，如第2A圖所示。基板212可為任意形狀的結構，例如平板結構或圓柱結構，其中此圓柱可為實心或空心結構。此外，基板212可為由單一材料層所構成之單一層結構。基板212亦可為由至少二材料層所構成之複合結構。Next, as shown in step 104 of FIG. 1, the substrate 212 is placed in the solvent 208, and some or all of the substrate 212 is immersed in the solvent 208 as shown in FIG. 2A. The substrate 212 can be of any shape, such as a flat or cylindrical structure, wherein the cylinder can be a solid or hollow structure. Further, the substrate 212 may be a single layer structure composed of a single material layer. The substrate 212 may also be a composite structure composed of at least two material layers.
接著，如第1圖之步驟106所示，可朝著箭頭218所指的方向，將基板212自溶劑208中拉出。在將基板212拉出溶劑208中時，由於注入溶劑208中的大部分粒子200朝液面214移動，因此這些粒子202例如可藉由毛細現象而附著排列在基板212之表面216上，如第2B圖所示。Next, as shown in step 106 of FIG. 1, the substrate 212 can be pulled out of the solvent 208 in the direction indicated by the arrow 218. When the substrate 212 is pulled out of the solvent 208, since most of the particles 200 injected into the solvent 208 move toward the liquid surface 214, the particles 202 may be attached to the surface 216 of the substrate 212 by capillary action, for example, Figure 2B shows.
如第2C圖所示，將基板212拉出溶劑208的同時，可將粒子200與溶劑202所混成之混合物204持續注入溶劑208中，以補充溶劑208之液面214上的粒子200數量，來使液面214具有足夠密度的粒子200，如此可使粒子200以自組裝方式排列在基板212之所需表面216上。As shown in FIG. 2C, while the substrate 212 is pulled out of the solvent 208, the mixture 204 of the particles 200 and the solvent 202 can be continuously injected into the solvent 208 to supplement the amount of particles 200 on the liquid surface 214 of the solvent 208. The liquid level 214 is provided with particles 200 of sufficient density such that the particles 200 are arranged in self-assembly on the desired surface 216 of the substrate 212.
由上述本發明實施方式可知，本發明之一優點就是因為在本發明之製造微奈米結構之自組裝方法中，粒子可藉由包覆其表面上之短親油基溶劑與水的交換而可在溶液與空氣界面之間形成自組裝單層結構，因此不需使用兩性分子，也無須精準控制溶液之表面壓，即可快速形成高密度排列的微奈米結構，且粒子可在製程期間持續補充，因而更可提高製程的方便性。According to the above embodiments of the present invention, it is an advantage of the present invention that in the self-assembly method for fabricating a micro-nano structure of the present invention, particles can be exchanged with water by coating a short lipophilic solvent on the surface thereof. The self-assembled monolayer structure can be formed between the solution and the air interface, so that the micro-nano structure with high density can be quickly formed without using the amphiphilic molecules and the surface pressure of the solution can be accurately controlled, and the particles can be processed during the process. Continuous replenishment, thus increasing the convenience of the process.
由上述本發明實施方式可知，本發明之另一優點就是因為在本發明之製造微奈米結構之自組裝方法中，粒子可藉由包覆其表面之極性溶劑與非極性溶劑的交換而可在溶液與空氣界面之間形成自組裝單層結構，因此不需使用兩性分子，也無須精準控制溶液之表面壓，即可快速形成高密度排列的微奈米結構。此外，粒子可在製程期間持續補充，因此具有極高的製程便利性。It can be seen from the above embodiments of the present invention that another advantage of the present invention is that in the self-assembly method for manufacturing a micro-nano structure of the present invention, particles can be exchanged with a non-polar solvent by coating a surface of a polar solvent. A self-assembled monolayer structure is formed between the solution and the air interface, so that the high-density array of micro-nanostructures can be quickly formed without using the amphiphilic molecules and without precisely controlling the surface pressure of the solution. In addition, the particles can be continuously replenished during the process, thus providing extremely high process convenience.
雖然本發明已以一較佳實施例揭露如上，然其並非用以限定本發明，任何在此技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been described above in terms of a preferred embodiment, it is not intended to limit the invention, and it is intended that various modifications may be made without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.
100．．．步驟100. . . step
102．．．步驟102. . . step
104．．．步驟104. . . step
106．．．步驟106. . . step
200．．．粒子200. . . particle
202．．．溶劑202. . . Solvent
204．．．混合物204. . . mixture
206．．．容置槽206. . . Locating slot
208．．．溶劑208. . . Solvent
210．．．滴管210. . . dropper
212．．．基板212. . . Substrate
214．．．液面214. . . Liquid level
216．．．表面216. . . surface
218．．．箭頭218. . . arrow
220．．．表面220. . . surface
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下：The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.
第1圖係繪示依照本發明一實施方式的一種製造微奈米結構之自組裝方法的流程圖。1 is a flow chart showing a self-assembly method for fabricating a micro-nano structure in accordance with an embodiment of the present invention.
第2A圖至第2C圖則係繪示依照本發明一實施方式的一種製造微奈米結構之自組裝方法的裝置流程示意圖。2A to 2C are schematic views showing the flow of a device for fabricating a self-assembly method of a micro-nano structure according to an embodiment of the present invention.
200．．．粒子200. . . particle
202．．．溶劑202. . . Solvent
204．．．混合物204. . . mixture
206．．．容置槽206. . . Locating slot
208．．．溶劑208. . . Solvent
210．．．滴管210. . . dropper
212．．．基板212. . . Substrate
214．．．液面214. . . Liquid level
216．．．表面216. . . surface
218．．．箭頭218. . . arrow
220．．．表面220. . . surface
Claims (16)
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