本發明涉及一種奈米奈米壓印方法，尤其涉及一種能夠在室溫下進行的奈米壓印方法。The present invention relates to a nanoimprinting method, and more particularly to a nanoimprinting method which can be carried out at room temperature.
在先前技術中，製作各種半導體設備時，常需要製作具有數十奈米到數百奈米的微細結構的奈米圖形。具有上述微細結構的奈米圖形的製作方法主要有光或電子束的光刻方法：首先，經過掩模或者掃描聚焦的輻射線或者電子束，輻射光致抗蝕劑組合物或光罩，上述輻射線或電子束將會改變被曝光區域的抗蝕劑的化學結構；然後，再通過刻蝕的方法除去被曝光區域或者被曝光區域外的抗蝕劑，從而獲得特定的圖案。In the prior art, when manufacturing various semiconductor devices, it is often required to fabricate a nano pattern having a fine structure of several tens of nanometers to several hundreds of nanometers. A method for fabricating a nano pattern having the above fine structure mainly includes a photolithography method of light or electron beam: first, irradiating a photoresist composition or a photomask through a mask or scanning a focused radiation or an electron beam, The radiation or electron beam will change the chemical structure of the resist in the exposed area; then, the exposed area or the resist outside the exposed area is removed by etching to obtain a specific pattern.
為了適應積體電路技術的迅猛發展，在先前的光學光刻技術上努力突破解析度極限的同時，下一代光刻技術在近幾年內獲得大量的研究。例如，深紫外光刻技術採用波長13~14nm的光源和精度極高的反射式光學系統，有效降低了折射系統中強烈的光吸收，但工藝繁雜、造價昂貴的光刻系統，限制了該技術的應用。In order to adapt to the rapid development of integrated circuit technology, while the previous optical lithography technology strives to break through the resolution limit, the next generation lithography technology has obtained a lot of research in recent years. For example, deep ultraviolet lithography uses a light source with a wavelength of 13 to 14 nm and a highly accurate reflective optical system, which effectively reduces the strong light absorption in the refractive system, but the lithography system, which is complicated and expensive, limits the technology. Applications.
上世紀九十年代以來，一種新的奈米圖形的製作工藝得到了發展（請參見Chou S Y, Krauss P R, Renstorm P. Imprint of sub 25 nm vias and trenches in polymers. Appl. Phys. Lett., 1995, 67(21): 3114-3116）。上述製作奈米圖形的新技術，在本領域中被稱作奈米壓印或者奈米壓印平板印刷術。奈米壓印是指採用繪有奈米圖形的模板將基片上的抗蝕劑（resist）薄膜壓印奈米圖形，再對基片上的奈米圖形進行處理，如刻蝕、剝離等，最終製成具有奈米結構的圖形和半導體器件。以奈米壓印技術形成奈米圖案的方法，藉由採用具有奈米圖形的硬性模板壓印抗蝕劑層形成奈米圖案，而不需要依賴任何輻射曝光形成。所以，奈米壓印技術可以消除在常規的光刻方法中所必須的比如對光的波長的限制，以及在抗蝕劑和基底內粒子的反向散射，和光干擾等限制條件，以實現更高的解析度。因此，相對於光刻技術，奈米壓印技術具有製作成本低、簡單易行、效率高的優點，具有廣泛的應用前景。Since the 1990s, a new nano-patterning process has been developed (see Chou SY, Krauss PR, Renstorm P. Imprint of sub 25 nm vias and trenches in polymers. Appl. Phys. Lett., 1995 , 67(21): 3114-3116). The above new techniques for making nanographs are known in the art as nanoimprint or nanoimprint lithography. Nano imprinting refers to imprinting a resist film on a substrate with a template drawn with a nano-pattern, and then processing the nano-pattern on the substrate, such as etching, stripping, etc., and finally A pattern and a semiconductor device having a nanostructure are fabricated. A method of forming a nano pattern by a nanoimprint technique by forming a nano pattern by using a hard template imprint resist layer having a nano pattern without relying on any radiation exposure formation. Therefore, nanoimprint technology can eliminate the limitations of wavelengths such as light in the conventional photolithography method, as well as backscattering of particles in the resist and substrate, and light interference and other constraints to achieve more High resolution. Therefore, compared with the lithography technology, the nano imprint technology has the advantages of low fabrication cost, simplicity, and high efficiency, and has broad application prospects.
由於奈米壓印技術藉由機械方式使聚合物抗蝕劑變形，而不是通過改變平板印刷術的抗蝕劑的化學性能實現。因此，奈米壓印技術對聚合物抗蝕劑具有較高的要求，即該聚合物抗蝕劑應為熱塑型或光固化型，且具有良好的成膜性，模量高，保持形變能力，且固化後容易脫模，使得模板與抗蝕劑分離後，該抗蝕劑仍然可以保留在基底。先前技術中，奈米壓印的抗蝕劑主要有，矽橡膠系列，環氧樹脂系列，丙烯酸酯系列，聚苯乙烯系列等。Because nanoimprint technology mechanically deforms the polymer resist, rather than by changing the chemical properties of the lithographic resist. Therefore, nanoimprint technology has high requirements for polymer resists, that is, the polymer resist should be thermoplastic or photocurable, and has good film forming properties, high modulus, and deformation. The ability, and easy to demold after curing, allows the resist to remain on the substrate after the template is separated from the resist. In the prior art, nano-imprinted resists mainly include tantalum rubber series, epoxy resin series, acrylate series, polystyrene series and the like.
1998年6月30日公告的美國專利5,772,905，公開了一種聚甲基丙烯酸甲酯（PMMA）作為奈米壓印抗蝕劑的技術方案，將聚甲基丙烯酸甲酯在矽片上旋轉澆鑄成膜，再採用熱壓的方法在基底上形成奈米圖形。所公開的奈米壓印方法要求加熱奈米壓印抗蝕劑（約200℃）使之產生塑性形變，然後再將奈米壓印抗蝕劑冷卻（低於PMMA的玻璃化轉變溫度Tg，約105℃）固化成型後，除去模板從而形成奈米級圖形。但是，由於聚甲基丙烯酸甲酯的玻璃化轉變溫度較高，使得該方法中的加熱溫度過高，使得該奈米壓印抗蝕劑的力學穩定性降低，與模板的黏附性強，難以脫模，得到的圖形不平整，使獲得的奈米圖形的解析度較低。先前技術中，為了提高奈米圖形的解析度，在壓印之前，常常需要對模板進行預處理，但是模板的預處理過程繁雜，因此提高了奈米壓印的工藝複雜度，以及成本，該方法不利於實際應用。U.S. Patent No. 5,772,905, issued toK. The film is then formed into a nanopattern on the substrate by hot pressing. The disclosed nanoimprint method requires heating a nanoimprint resist (about 200 ° C) to cause plastic deformation, and then cooling the nanoimprint resist (below the glass transition temperature Tg of PMMA, After curing at about 105 ° C), the template was removed to form a nanoscale pattern. However, due to the high glass transition temperature of polymethyl methacrylate, the heating temperature in the method is too high, so that the mechanical stability of the nanoimprint resist is lowered, and the adhesion to the template is strong, which is difficult. Demolding, the resulting pattern is not flat, so that the resolution of the obtained nano-pattern is low. In the prior art, in order to improve the resolution of the nano-pattern, it is often necessary to pre-treat the template before imprinting, but the pre-processing of the template is complicated, thereby improving the process complexity and cost of the nanoimprint. The method is not conducive to practical applications.
有鑒於此，有必要提供一種獲得的圖形的保真度好，解析度較高，且在室溫下即能進行壓印的奈米壓印方法。In view of the above, it is necessary to provide a nanoimprint method in which the obtained pattern has good fidelity, high resolution, and can be imprinted at room temperature.
一種奈米壓印方法，其包括以下步驟：步驟a，提供一基底和一表面具有奈米圖形的模板，所述基底的一表面形成有有機第一抗蝕層；步驟b，藉由壓印抗蝕劑HSQ貼合所述基底和模板，貼合時所述壓印抗蝕劑HSQ直接接觸所述模板的具有奈米圖形的表面，並將壓印抗蝕劑HSQ夾持於該基底的第一抗蝕層與所述模板的所述表面之間，以形成第二抗蝕層；步驟c，在室溫下、通過在該基底和模板施加壓力，將模板表面的奈米圖形複製到所述第二抗蝕層，在所述第二抗蝕層形成奈米圖形；以及步驟d，將所述第二抗蝕層上的奈米圖形轉移至基底，在所述基底表面形成奈米圖形。A nanoimprinting method comprising the steps of: step a, providing a substrate and a template having a nanopattern on a surface thereof, one surface of the substrate being formed with an organic first resist layer; and step b, by imprinting The resist HSQ is applied to the substrate and the template, and the imprinted resist HSQ directly contacts the surface of the template having a nano pattern, and the imprint resist HSQ is sandwiched between the substrate and the template. a first resist layer is formed between the first resist layer and the surface of the template to form a second resist layer; and step c is performed by applying pressure to the substrate and the template at room temperature to copy the nanopattern of the template surface to a second resist layer forming a nano pattern on the second resist layer; and a step d, transferring a nano pattern on the second resist layer to a substrate, forming a nano surface on the surface of the substrate Graphics.
一種奈米壓印方法，其包括以下步驟：步驟a，提供一基底，在所述基底的一表面依次形成一有機第一抗蝕層、一過渡層及一由壓印抗蝕劑HSQ構成的第二抗蝕層；步驟b，提供一表面具有奈米圖形的模板，並將該模板表面的奈米圖形，在室溫下複製到所述第二抗蝕層；步驟c，將所述第二抗蝕層上的奈米圖形轉移至基底，在所述基底表面形成奈米圖形。A nanoimprinting method comprising the steps of: step a, providing a substrate, sequentially forming an organic first resist layer, a transition layer and a stamping resist HSQ on a surface of the substrate; a second resist layer; step b, providing a template having a surface pattern on the surface, and copying the nano pattern of the surface of the template to the second resist layer at room temperature; step c, The nanopattern on the two resist layers is transferred to the substrate, and a nano pattern is formed on the surface of the substrate.
一種奈米壓印方法，其包括以下步驟：步驟a，提供一基底和一表面具有奈米圖形的模板，所述基底的一表面形成有有機第一抗蝕層；步驟b，提供一表面具有奈米圖形的模板，在該模板具有奈米圖形的表面形成壓印抗蝕劑HSQ，以形成一第二抗蝕層；步驟c，將基底覆蓋於模板，使所述基底的過渡層與所述模板的覆蓋有壓印抗蝕劑HSQ的表面接觸，常溫下壓所述模板及基底，並脫模；以及步驟d，將所述第二抗蝕層上的奈米圖形轉移至基底，在所述基底表面形成奈米圖形。A nanoimprinting method comprising the steps of: step a, providing a substrate and a template having a nanopattern on a surface, a surface of the substrate being formed with an organic first resist; and step b providing a surface having a template of a nano pattern in which an imprint resist HSQ is formed on a surface of the template to form a second resist layer; and in step c, the substrate is overlaid on the template to make the transition layer of the substrate Covering the template with the surface contact of the imprint resist HSQ, pressing the template and the substrate at a normal temperature, and demolding; and step d, transferring the nano pattern on the second resist layer to the substrate, The surface of the substrate forms a nanograph.
與先前技術相比較，本發明奈米壓印方法具有以下優點：其一，該所述第二抗蝕層由壓印抗蝕劑HSQ構成，其可以在室溫下進行壓印，該壓印抗蝕劑HSQ在後續製造工藝中固化產生交聯，提高了模量。其二，由於該壓印抗蝕劑HSQ在室溫下黏附性小較易脫膜，可確保圖形的完整性及解析度。其三，基底與第二抗蝕層之間形成有有機第一抗蝕層，將所述第二抗蝕層上的奈米圖形轉移至基底過程中，對有機第一抗蝕層刻蝕過程對由壓印抗蝕劑HSQ構成的第二抗蝕層只會發生固化交聯，對第一抗蝕層起到有效的光罩作用，減少了第一抗蝕層的奈米圖形產生缺陷，確保了第一抗蝕層的奈米圖形的解析度和保真性。其四，本發明提供的奈米壓印方法，其可在室溫下進行壓印，且模板無須預先處理，使得該方法工藝簡單，成本低。Compared with the prior art, the nanoimprinting method of the present invention has the following advantages: First, the second resist layer is composed of an imprint resist HSQ, which can be imprinted at room temperature, the imprint The resist HSQ cures in a subsequent manufacturing process to produce cross-linking, which increases the modulus. Second, since the imprinted resist HSQ has a small adhesion at room temperature and is relatively easy to release the film, the integrity and resolution of the pattern can be ensured. Third, an organic first resist layer is formed between the substrate and the second resist layer, and the nano pattern on the second resist layer is transferred to the substrate during the etching process of the organic first resist layer. The second resist layer composed of the imprint resist HSQ only undergoes curing cross-linking, and functions as an effective mask for the first resist layer, thereby reducing defects in the nano-pattern of the first resist layer. The resolution and fidelity of the nano-pattern of the first resist layer are ensured. Fourthly, the nanoimprinting method provided by the invention can be imprinted at room temperature, and the template does not need to be pre-treated, so that the method is simple in process and low in cost.
以下將結合附圖詳細說明本發明實施例的奈米光學天線的製造方法。Hereinafter, a method of manufacturing a nano optical antenna according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
請參閱圖1及圖2，採用本發明提供的奈米壓印方法的第一實施例，其包括以下步驟：Referring to FIG. 1 and FIG. 2, a first embodiment of the nanoimprinting method provided by the present invention includes the following steps:
步驟S11，提供一基底10，在所述基底10的一表面(未標示)依次形成一第一抗蝕層110、一過渡層120及一第二抗蝕層130。In step S11, a substrate 10 is provided, and a first resist layer 110, a transition layer 120 and a second resist layer 130 are sequentially formed on a surface (not labeled) of the substrate 10.
首先，在所述基底10的所述表面形成該第一抗蝕層110。First, the first resist layer 110 is formed on the surface of the substrate 10.
提供一基底10，清洗該基底10；在基底10的一表面沉積有機抗蝕劑，後烘乾以形成所述第一抗蝕層110。所述有機抗蝕劑可以採用絲網印刷法或旋塗法等沉積於所述基底10上，形成所述第一抗蝕層110。本實施例中，所述有機抗蝕劑為正性抗蝕劑ZEP520。A substrate 10 is provided to clean the substrate 10; an organic resist is deposited on a surface of the substrate 10, and then dried to form the first resist layer 110. The organic resist may be deposited on the substrate 10 by screen printing or spin coating to form the first resist layer 110. In this embodiment, the organic resist is a positive resist ZEP520.
所述基底10的材料可為硬性材料，如矽、氧化矽、氮化矽或氮化鎵，所述基底10的材料還可為柔性材料，如PSP、PMMA或PET。The material of the substrate 10 may be a hard material such as tantalum, yttria, tantalum nitride or gallium nitride, and the material of the substrate 10 may also be a flexible material such as PSP, PMMA or PET.
本實施例中，所述基底10的材料為矽，採用標準工藝清洗基底10後，於基底10的一表面旋塗ZEP520，旋塗轉速為500轉/分鐘~6000轉/分鐘，時間為0.5分鐘~1.5分鐘，然後在140℃~180℃烘烤3~5分鐘。從而在所述基底10的所述表面形成該第一抗蝕層110。該第一抗蝕層110的厚度為100奈米~500奈米。本實施例中，所述標準工藝為超淨間標準清洗工藝。In this embodiment, the material of the substrate 10 is germanium. After the substrate 10 is cleaned by a standard process, ZEP520 is spin-coated on a surface of the substrate 10, and the spin coating speed is 500 rpm to 6000 rpm, and the time is 0.5 minutes. ~1.5 minutes, then bake at 140 ° C ~ 180 ° C for 3 to 5 minutes. Thereby, the first resist layer 110 is formed on the surface of the substrate 10. The first resist layer 110 has a thickness of 100 nm to 500 nm. In this embodiment, the standard process is a clean room standard cleaning process.
其次，在第一抗蝕層110的遠離所述基底10的表面形成一過渡層120，以覆蓋所述第一抗蝕層110。Next, a transition layer 120 is formed on the surface of the first resist layer 110 away from the substrate 10 to cover the first resist layer 110.
所述過渡層120的材料為氧化矽。可通過濺射法或沉積法，在所述第一抗蝕層110上形成所述過渡層120。The material of the transition layer 120 is ruthenium oxide. The transition layer 120 may be formed on the first resist layer 110 by a sputtering method or a deposition method.
本實施例中，所述第一抗蝕層110上沉積玻璃態氧化矽，形成一厚度為10奈米~100奈米的氧化矽薄膜。In this embodiment, the glassy yttria is deposited on the first resist layer 110 to form a yttria thin film having a thickness of 10 nm to 100 nm.
最後，形成一第二抗蝕層130覆蓋所述過渡層120。Finally, a second resist layer 130 is formed to cover the transition layer 120.
採用無機類壓印抗蝕劑(hydrogen silsesquioxane，HSQ)，通過液滴塗佈、旋塗法等方法沉積於所述過渡層120，以形成第二抗蝕層130。本實施例中，將所述壓印抗蝕劑HSQ採用旋塗的方式塗佈於所述過渡層120，旋塗轉速為2500轉/分鐘~7000轉/分鐘，旋塗時間為0.5分鐘~2分鐘，該壓印抗蝕劑HSQ的旋塗在高壓下進行。該第二抗蝕層130的厚度為100奈米~500奈米，優選的為100奈米~300奈米。該第二抗蝕層130的厚度的控制也相當的重要：經實驗得知該壓印抗蝕劑HSQ固化後，其類似氧化矽材料，若其厚度過厚，則在後續工藝中刻蝕與去除較難；若其厚度過薄，則在後續工藝中難以滿足足夠的刻蝕選擇比。The transition layer 120 is deposited by a droplet coating, a spin coating method or the like using an inorganic silsesquioxane (HSQ) to form a second resist layer 130. In this embodiment, the imprint resist HSQ is applied to the transition layer 120 by spin coating, and the spin coating speed is 2500 rpm to 7000 rpm, and the spin coating time is 0.5 minutes 〜2. In minutes, the spin coating of the imprint resist HSQ was carried out under high pressure. The second resist layer 130 has a thickness of 100 nm to 500 nm, preferably 100 nm to 300 nm. The control of the thickness of the second resist layer 130 is also quite important: it is experimentally known that the imprinted resist HSQ is similar to a cerium oxide material after curing, and if the thickness is too thick, etching is performed in a subsequent process. Removal is difficult; if the thickness is too thin, it is difficult to satisfy a sufficient etching selectivity ratio in subsequent processes.
該壓印抗蝕劑HSQ具有可在室溫下壓印、結構穩定性較佳、以及壓印解析度可達到10nm以下之高解析度等特性。The imprint resist HSQ has characteristics such as embossing at room temperature, good structural stability, and high resolution of an imprint resolution of 10 nm or less.
步驟S12，提供一表面具有奈米圖形的模板20，並將該模板20表面的奈米圖形複製到所述第二抗蝕層130。In step S12, a template 20 having a nanoscopic pattern on the surface is provided, and a nano pattern on the surface of the template 20 is copied to the second resist layer 130.
首先，提供一表面具有奈米圖形的模板20。First, a template 20 having a nanographic pattern on its surface is provided.
該模板20的材料可為硬性材料，如鎳、矽或者氧化矽。該模板20的材料也可為柔性材料，如PET、PMMA、PS、PDMS等。該模板20可以通過電子束曝光製備，模板20的表面形成有奈米圖形，該奈米圖形由模板20的表面的複數第一凸部24和複數第一凹槽26構成。本實施例中，該模板20的材料為氧化矽。The material of the template 20 may be a hard material such as nickel, ruthenium or ruthenium oxide. The material of the template 20 can also be a flexible material such as PET, PMMA, PS, PDMS, and the like. The template 20 can be prepared by electron beam exposure, and the surface of the template 20 is formed with a nano pattern composed of a plurality of first protrusions 24 and a plurality of first grooves 26 on the surface of the template 20. In this embodiment, the material of the template 20 is ruthenium oxide.
其次，將模板20形成有奈米圖形的表面與所述基底10上的第二抗蝕層130貼合，常溫下壓所述模板20與基底10後，脫模。Next, the surface on which the template 20 is formed with a nano pattern is bonded to the second resist layer 130 on the substrate 10, and the template 20 and the substrate 10 are pressed at normal temperature, and then released.
在常溫下，可通過模板20向基底10施加壓力，使得所述模板20上的奈米圖形轉移到第二抗蝕層130。具體地，使模板20形成有奈米圖形的表面與所述基底10上的第二抗蝕層130貼合，並在真空度為1×10-1mbar~1×10-5mbar，施加壓力為2磅/平方英尺~100磅/平方英尺（Psi）的壓印條件下，保持2~30分鐘，最後將模板20與基底10分離，從而該模板20表面的奈米圖形複製到所述第二抗蝕層130。所述第二抗蝕層130形成的奈米圖形包括複數第二凹槽16和第二凸部14。且該第二凹槽16與所述第一凸部24對應，所述第二凸部14與所述第一凹槽26對應。At normal temperature, pressure may be applied to the substrate 10 through the template 20 such that the nano pattern on the template 20 is transferred to the second resist layer 130. Specifically, the surface on which the template 20 is formed with the nano pattern is bonded to the second resist layer 130 on the substrate 10, and the pressure is applied at a degree of vacuum of 1 × 10-1 mbar to 1 × 10-5 mbar. For 2 to 30 minutes under imprint conditions of 2 psi to 100 psi (Psi), the template 20 is finally separated from the substrate 10 so that the nanopattern of the surface of the template 20 is copied to the Two resist layers 130. The nano pattern formed by the second resist layer 130 includes a plurality of second grooves 16 and second protrusions 14. And the second groove 16 corresponds to the first convex portion 24, and the second convex portion 14 corresponds to the first groove 26.
步驟S13，將所述奈米圖形轉移至基底10，在所述基底10表面形成奈米圖形。In step S13, the nano pattern is transferred to the substrate 10, and a nano pattern is formed on the surface of the substrate 10.
首先，刻蝕去除所述第二抗蝕層130的奈米圖形的第二凹槽16底部殘留的壓印抗蝕劑HSQ和第二凹槽16底部的所述過渡層120，露出第一抗蝕層110。First, the imprint resist HSQ remaining at the bottom of the second recess 16 of the nano pattern of the second resist layer 130 and the transition layer 120 at the bottom of the second recess 16 are etched away to expose the first anti-etching Eclipse layer 110.
刻蝕去除所述第二凹槽16底部殘留的壓印抗蝕劑HSQ和第二凹槽16底部的過渡層120可藉由電漿刻蝕的方法。Etching and removing the imprint resist HSQ remaining at the bottom of the second recess 16 and the transition layer 120 at the bottom of the second recess 16 may be by plasma etching.
本實施例中，採用碳氟(CF4)反應性電漿刻蝕去除第二凹槽16底部殘留的壓印抗蝕劑HSQ和第二凹槽16底部的所述過渡層120，露出第一抗蝕層110。具體地，將上述形成有奈米圖形的基底10放置於反應性電漿刻蝕系統中，該反應性電漿刻蝕系統的一感應功率源產生CF4電漿，CF4電漿以較低的離子能量從產生區域擴散並漂移至所述基底10的第二抗蝕層130，此時該第二抗蝕層的第二凹槽16底部殘留的壓印抗蝕劑HSQ和第二凹槽16底部的所述過渡層120幾乎同步被所述CF4電漿刻蝕。CF4電漿系統的功率是10瓦~150瓦，CF4電漿的通入速率為2~100標況毫升每分 (standard-state cubic centimeter per minute，sccm)，形成的氣壓為1~15帕，採用CF4電漿刻蝕時間為2秒~4分鐘。通過上述方法，第二凹槽16底部殘留的該壓印抗蝕劑HSQ和第二凹槽16底部的所述過渡層120刻蝕掉，露出第一抗蝕層110，且所述第二抗蝕層130的第二凸部14也同時被刻蝕變薄，進而能夠保持所述第二抗蝕層130和過渡層120的奈米圖形的完整態。In this embodiment, the embossed resist HSQ remaining at the bottom of the second recess 16 and the transition layer 120 at the bottom of the second recess 16 are removed by fluorocarbon (CF4 ) reactive plasma etching to expose the first The resist layer 110. Specifically, the substrate 10 having the nanopattern formed thereon is placed in a reactive plasma etching system, and an inductive power source of the reactive plasma etching system generates CF4 plasma, and the CF4 plasma is lower. The ion energy diffuses from the generation region and drifts to the second resist layer 130 of the substrate 10, at which time the imprint resist HSQ and the second recess remaining at the bottom of the second recess 16 of the second resist layer The transition layer 120 at the bottom of the 16 is almost simultaneously etched by the CF4 plasma. The power of CF4 plasma system is 10 watts to 150 watts. The inlet rate of CF4 plasma is 2 to 100 standard cent centmeter per minute (sccm), and the pressure is 1~15. Pa, using CF4 plasma etching time is 2 seconds ~ 4 minutes. By the above method, the imprint resist HSQ remaining at the bottom of the second recess 16 and the transition layer 120 at the bottom of the second recess 16 are etched away to expose the first resist layer 110, and the second anti-resistance The second protrusions 14 of the etch layer 130 are also simultaneously etched and thinned, thereby maintaining the integrity of the nanopattern of the second resist layer 130 and the transition layer 120.
其次，去除第二凹槽16底部的第一抗蝕層110，露出基底10。Next, the first resist layer 110 at the bottom of the second recess 16 is removed to expose the substrate 10.
可以採用氧電漿去除第二凹槽16底部的第一抗蝕層110，從而露出基底10。氧電漿系統的功率是10瓦~150瓦，氧電漿的通入速率為2~100sccm，形成的氣壓為0.5帕~15帕，採用氧電漿刻蝕時間為5秒~1分鐘。通過上述方法，第二凹槽16底部的第一抗蝕層110被去除，露出基底10。採用氧電漿刻蝕第一抗蝕層110過程中，與第二凹槽16對應的第一抗蝕層110被氧化而刻蝕掉，由壓印抗蝕劑HSQ構成的所述第二抗蝕層130在氧電漿的作用下發生交聯，與所述過渡層120一併對所述第一抗蝕層110的與第二凹槽16對應部份以外的區域起到良好的光罩作用，進而刻蝕過程中有效保持第一抗蝕層110的解析度。The first resist layer 110 at the bottom of the second recess 16 may be removed by oxygen plasma to expose the substrate 10. The power of the oxygen plasma system is 10 watts to 150 watts, the oxygen plasma inlet rate is 2 to 100 sccm, the gas pressure is 0.5 kPa to 15 kPa, and the oxygen plasma etching time is 5 seconds to 1 minute. By the above method, the first resist layer 110 at the bottom of the second recess 16 is removed to expose the substrate 10. During the etching of the first resist layer 110 by the oxygen plasma, the first resist layer 110 corresponding to the second recess 16 is oxidized and etched away, and the second anti-resistance composed of the imprint resist HSQ The etch layer 130 is cross-linked under the action of the oxygen plasma, and the transition layer 120 and the region of the first resist layer 110 other than the corresponding portion of the second recess 16 serve as a good mask. The effect is to effectively maintain the resolution of the first resist layer 110 during the etching process.
最後，刻蝕第二凹槽16底部的基底10，並用有機溶劑去除殘留的有機材料，從而獲得一具有奈米圖形的基底100。Finally, the substrate 10 at the bottom of the second recess 16 is etched, and the residual organic material is removed with an organic solvent to obtain a substrate 100 having a nano pattern.
將上述基底10放置在一感應耦合電漿系統中，此時第二凹槽16底部的基底10沒有第一抗蝕層110的保護；以四氯化矽和氯氣為刻蝕氣體對基底10進行刻蝕，第二凹槽16底部的部份基底將被去除；用丙酮洗去殘留的有機殘留物，該第一抗蝕層110為有機物，從而被洗掉，覆蓋於第一抗蝕層110上的過渡層120和第二抗蝕層130也一併被除去，從而獲得具有奈米圖形的基底100。本實施例中，電漿系統的功率是100瓦，氯氣的通入速率為20sccm ~60sccm，四氯化矽的通入速率為20sccm~60sccm，形成氣壓為4帕~15帕，刻蝕第二凹槽16底部的基底10。The substrate 10 is placed in an inductively coupled plasma system, and the substrate 10 at the bottom of the second recess 16 is not protected by the first resist layer 110; the substrate 10 is treated with ruthenium tetrachloride and chlorine as an etching gas. Etching, a portion of the substrate at the bottom of the second recess 16 is removed; the residual organic residue is washed away with acetone, and the first resist 110 is organic, thereby being washed away, covering the first resist 110. The upper transition layer 120 and the second resist layer 130 are also removed together, thereby obtaining the substrate 100 having a nano pattern. In this embodiment, the power of the plasma system is 100 watts, the access rate of chlorine gas is 20 sccm ~ 60 sccm, the access rate of ruthenium tetrachloride is 20 sccm ~ 60 sccm, the gas pressure is 4 Pa ~ 15 Pa, and the second etching is performed. The substrate 10 at the bottom of the recess 16.
請參閱圖3及圖4，採用本發明的奈米壓印抗飾劑的奈米壓印的方法的第二實施例，其包括以下步驟：Referring to Figures 3 and 4, a second embodiment of the method of nanoimprinting using the nanoimprinting resist of the present invention comprises the following steps:
步驟S21，提供一基底30，在該基底30的表面依次形成第一抗蝕層310以及一過渡層320。In step S21, a substrate 30 is provided, and a first resist layer 310 and a transition layer 320 are sequentially formed on the surface of the substrate 30.
本實施例中，基底30的材料與第一實施中的基底10的材料完全相同，第一抗蝕層310及過渡層320的製作方法、結構、材料以及位置關係分別與第一實施例中的第一抗蝕層110及過渡層120的製作方法、結構、材料以及位置關係完全相同。In this embodiment, the material of the substrate 30 is completely the same as the material of the substrate 10 in the first embodiment, and the manufacturing method, structure, material and positional relationship of the first resist layer 310 and the transition layer 320 are respectively different from those in the first embodiment. The manufacturing method, structure, material, and positional relationship of the first resist layer 110 and the transition layer 120 are completely the same.
步驟S22，提供一表面具有奈米圖形的模板60，在該模板60具有奈米圖形的表面形成一第二抗蝕層330。In step S22, a template 60 having a nano-pattern on the surface is provided, and a second resist layer 330 is formed on the surface of the template 60 having the nano-pattern.
本實施例中，所述具有奈米圖形的模板60與第一實施例中的模板20完全相同，該模板60的奈米圖形由複數第一凹槽66以及第一凸部64構成。所述採用的第二抗蝕層330同第一實施例中採用的第二抗蝕層130完全相同。具體地，可取一定量的壓印抗蝕劑HSQ，採用液滴塗佈方法，緩慢滴在所述模板60具有奈米圖形的表面，於密閉的環境下靜置1~2個小時。In the embodiment, the template 60 having a nano pattern is completely the same as the template 20 in the first embodiment, and the nano pattern of the template 60 is composed of a plurality of first grooves 66 and a first convex portion 64. The second resist layer 330 used is identical to the second resist layer 130 employed in the first embodiment. Specifically, a certain amount of the imprint resist HSQ may be taken, and the droplet coating method is used to slowly drop the surface of the template 60 having a nano-pattern, and it is allowed to stand in a closed environment for 1 to 2 hours.
步驟S23，將基底30覆蓋於模板60，使所述基底30的過渡層320與所述模板60的覆蓋有壓印抗蝕劑HSQ的表面接觸，常溫下壓所述模板60及基底30，並脫模。Step S23, covering the substrate 30 with the template 60, contacting the transition layer 320 of the substrate 30 with the surface of the template 60 covered with the imprint resist HSQ, pressing the template 60 and the substrate 30 at a normal temperature, and Demoulding.
具體地，將基底30覆蓋於模板60，使所述基底30的過渡層320與所述模板60覆蓋有由壓印抗蝕劑HSQ構成的第二抗蝕層330的表面接觸，並將所述覆蓋有基底30的模板60放置於壓印機中；設置該壓印機的真空度為真空度為1×10-1mbar~1×10-5mbar，施加壓力為2磅/平方英尺~100磅/平方英尺（Psi）的壓印條件下，保持2~30分鐘，使壓印抗蝕劑HSQ充滿模板60的奈米圖形中的第一凹槽66並黏附到基底30的過渡層320表面，將模板60與基底30分離，從而在基體30的過渡層320上形成一由第二抗蝕層330構成的奈米圖形。該由第二抗蝕層330構成的奈米圖形包括複數第二凹槽36以及第二凸部34。Specifically, the substrate 30 is covered on the template 60 such that the transition layer 320 of the substrate 30 and the template 60 are covered with the surface of the second resist layer 330 composed of the imprint resist HSQ, and the The template 60 covered with the substrate 30 is placed in the embossing machine; the vacuum of the embossing machine is set to a vacuum of 1×10-1 mbar to 1×10-5 mbar, and the applied pressure is 2 psi to 100 Å. The embossed resist HSQ is filled with the first recess 66 in the nano pattern of the template 60 and adhered to the surface of the transition layer 320 of the substrate 30 under embossing conditions of pounds per square foot (Psi) for 2 to 30 minutes. The template 60 is separated from the substrate 30 to form a nano pattern formed by the second resist layer 330 on the transition layer 320 of the substrate 30. The nano pattern formed by the second resist layer 330 includes a plurality of second grooves 36 and second protrusions 34.
步驟S24，通過刻蝕的方法，將所述奈米圖形轉移至基底30，在所述基底30表面形成奈米圖形。In step S24, the nano pattern is transferred to the substrate 30 by etching to form a nano pattern on the surface of the substrate 30.
首先，刻蝕去除第二抗蝕層330構成的奈米圖形第二凹槽36底部殘留的壓印抗蝕劑HSQ和第二凹槽36底部的過渡層320，露出第一抗蝕層310。First, the imprint resist HSQ remaining at the bottom of the second recess 36 of the nano pattern formed by the second resist layer 330 and the transition layer 320 at the bottom of the second recess 36 are etched away to expose the first resist layer 310.
其次，去除第二凹槽36底部的第一抗蝕層310，露出基底30。Next, the first resist layer 310 at the bottom of the second recess 36 is removed to expose the substrate 30.
最後，刻蝕第二凹槽36底部的基底30，並用有機溶劑去除殘留的有機材料，從而獲得一具有奈米圖形的基底300。Finally, the substrate 30 at the bottom of the second recess 36 is etched, and the residual organic material is removed with an organic solvent to obtain a substrate 300 having a nano pattern.
本實施例中，上述將所述奈米圖形轉移至基底30，在所述基底30表面刻蝕出奈米圖形的方法與第一實施例中的方法相同。In the embodiment, the method of transferring the nano pattern to the substrate 30 and etching the nano pattern on the surface of the substrate 30 is the same as that in the first embodiment.
與先前技術相比較，本發明奈米壓印方法具有以下優點：其一，該所述第二抗蝕層由壓印抗蝕劑HSQ構成，其可於室溫下進行壓印，該壓印抗蝕劑HSQ在後續製造工藝中固化產生交聯，提高了模量，且形變較小。其二，由於該壓印抗蝕劑HSQ在室溫下黏附性小較易脫膜，保證了圖形的完整性及辨率。其三，基底與第二抗蝕層之間形成有有機第一抗蝕層，將所述第二抗蝕層上的奈米圖形轉移至基底過程中，對有機第一抗蝕層刻蝕過程對由壓印抗蝕劑HSQ構成的第二抗蝕層只會發生固化交聯，對第一抗蝕層起到有效的光罩作用，減少了第一抗蝕層的奈米圖形產生缺陷，保證了第一抗蝕層的奈米圖形的解析度和保真性。其四，本發明提供的奈米壓印方法，其可在室溫下進行壓印，且模板無須預先處理，使得該方法工藝簡單，成本低。Compared with the prior art, the nanoimprinting method of the present invention has the following advantages: First, the second resist layer is composed of an imprint resist HSQ, which can be imprinted at room temperature, the imprint The resist HSQ is cured in a subsequent manufacturing process to produce cross-linking, which increases the modulus and has a small deformation. Second, since the imprinted resist HSQ has a small adhesion at room temperature, it is easy to release the film, thereby ensuring the integrity and resolution of the pattern. Third, an organic first resist layer is formed between the substrate and the second resist layer, and the nano pattern on the second resist layer is transferred to the substrate during the etching process of the organic first resist layer. The second resist layer composed of the imprint resist HSQ only undergoes curing cross-linking, and functions as an effective mask for the first resist layer, thereby reducing defects in the nano-pattern of the first resist layer. The resolution and fidelity of the nano-pattern of the first resist layer are ensured. Fourthly, the nanoimprinting method provided by the invention can be imprinted at room temperature, and the template does not need to be pre-treated, so that the method is simple in process and low in cost.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡習知本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.
10,30‧‧‧基底10,30‧‧‧Base
110,310‧‧‧第一抗蝕層110,310‧‧‧First resist
120,320‧‧‧過渡層120,320‧‧‧Transition layer
130,330‧‧‧第二抗蝕層130,330‧‧‧second resist
20,60‧‧‧模板20,60‧‧‧ template
24,64‧‧‧第一凸部24,64‧‧‧First convex
26,66‧‧‧第一凹槽26,66‧‧‧first groove
14,34‧‧‧第二凸部14,34‧‧‧second convex
16,36‧‧‧第二凹槽16,36‧‧‧second groove
100,300‧‧‧具有奈米圖形的基底100,300‧‧‧Base with a nano graphic
圖1為本發明奈米壓印方法的第一實施例的流程圖。1 is a flow chart of a first embodiment of a nanoimprint method of the present invention.
圖2為本發明奈米壓印方法的第一實施例的工藝流程示意圖。2 is a schematic view showing the process flow of the first embodiment of the nanoimprinting method of the present invention.
圖3為本發明奈米壓印方法的第二實施例的流程圖。3 is a flow chart of a second embodiment of the nanoimprint method of the present invention.
圖4為本發明奈米壓印方法的第二實施例的工藝流程示意圖。4 is a schematic view showing the process flow of a second embodiment of the nanoimprint method of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| TW99120723ATWI386304B (en) | 2010-06-25 | 2010-06-25 | Nano imprint method |
| Application Number | Priority Date | Filing Date | Title |
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| TW99120723ATWI386304B (en) | 2010-06-25 | 2010-06-25 | Nano imprint method |
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| TW201200342A TW201200342A (en) | 2012-01-01 |
| TWI386304Btrue TWI386304B (en) | 2013-02-21 |
| Application Number | Title | Priority Date | Filing Date |
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| TW99120723ATWI386304B (en) | 2010-06-25 | 2010-06-25 | Nano imprint method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003332211A (en)* | 2002-05-14 | 2003-11-21 | Mitsubishi Electric Corp | Resist pattern forming method and device |
| TW200728923A (en)* | 2005-09-09 | 2007-08-01 | Tokyo Ohka Kogyo Co Ltd | Film forming composition for nanoimprint and pattern forming method |
| JP2008053666A (en)* | 2006-08-28 | 2008-03-06 | Meisho Kiko Kk | Pattern formation method and pattern formation object |
| TW200822185A (en)* | 2006-11-02 | 2008-05-16 | Applied Materials Inc | Etching of nano-imprint templates using an etch reactor |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003332211A (en)* | 2002-05-14 | 2003-11-21 | Mitsubishi Electric Corp | Resist pattern forming method and device |
| TW200728923A (en)* | 2005-09-09 | 2007-08-01 | Tokyo Ohka Kogyo Co Ltd | Film forming composition for nanoimprint and pattern forming method |
| JP2008053666A (en)* | 2006-08-28 | 2008-03-06 | Meisho Kiko Kk | Pattern formation method and pattern formation object |
| TW200822185A (en)* | 2006-11-02 | 2008-05-16 | Applied Materials Inc | Etching of nano-imprint templates using an etch reactor |
| Publication number | Publication date |
|---|---|
| TW201200342A (en) | 2012-01-01 |
| Publication | Publication Date | Title |
|---|---|---|
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