WO2018196320A1 - 水溶性负性电子束光刻胶及其成像方法 - Google Patents

水溶性负性电子束光刻胶及其成像方法 Download PDF

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WO2018196320A1
WO2018196320A1 PCT/CN2017/109465 CN2017109465W WO2018196320A1 WO 2018196320 A1 WO2018196320 A1 WO 2018196320A1 CN 2017109465 W CN2017109465 W CN 2017109465W WO 2018196320 A1 WO2018196320 A1 WO 2018196320A1
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water
electron beam
soluble
negative electron
photoresist
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PCT/CN2017/109465
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English (en)
French (fr)
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翁雨燕
陈高健
李志运
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苏州大学
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Definitions

  • the present invention relates to the field of photoresists, and in particular to a water-soluble negative electron beam resist and an image forming method thereof.
  • photoresist has been the focus of research, such as its sensitivity, spatial resolution, and physicochemical stability.
  • the photoresist usually crosslinks or degrades before and after exposure, and the solubility changes in the developer. After etching and removing the film, a specific high-precision pattern can be transferred to the surface of the target substrate.
  • the improvement or decrease of the dissolution rate in the developer after exposure it can be divided into positive and negative photoresists, and the photosensitive resin in the exposure position of the negative photoresist is no longer dissolved in the developer and is retained.
  • the photosensitive resin in the unexposed position is washed away.
  • the photoresist solution used is mostly Chlorobenzene, ethyl lactate; developer is mostly methyl isobutyl ketone and isopropanol, both have certain biological toxicity and environmental hazard, and the price is high; 3, must introduce a strong photo-initiating catalyst to make light Engraving is expensive.
  • the invention aims to provide a water-soluble negative electron beam resist and an image forming method thereof, and the water-soluble polymer containing a hydroxyl side chain is applied to an electron beam lithography system, thereby solving the problems of high cost, pollution to the environment and human body. .
  • a water-soluble negative electron beam photoresist comprising:
  • a a water-soluble polymer for self-crosslinking under an electron beam, the side chain of which has a hydroxyl group
  • b a solvent: water
  • water soluble polymer is a sugar-containing polymer.
  • the sugar-containing polymer is a glucose homopolymer, a mannose homopolymer, a grape A copolymer of sugar and methacrylic acid, or a copolymer of glucose and sodium p-styrenesulfonate.
  • the mass ratio of the water-soluble polymer to water is 1:10 to 1,000,000.
  • the structure of the water-soluble polymer is as follows:
  • R 1 H, CH 3 ;
  • R 2 or R 3 H, CH 3 ,
  • R 4 H, OH (linear or cyclic hydroxyl molecule, 1-5 hydroxyl groups);
  • R 5 H, CH 3 ;
  • R 6 or R 7 H, CH 3 ,
  • Another technical solution of the present invention is: a method for imaging a water-soluble negative electron beam photoresist, comprising the steps of: (1) dissolving a water-soluble polymer in water to prepare a water-soluble photoresist solution; (2) depositing the water-soluble photoresist solution on the surface of the substrate to be processed to form an electron beam resist film; (3) performing electron beam exposure, and self-crosslinking occurs in the exposed region under the action of the electron beam.
  • the water-soluble polymer in the exposed region is crosslinked and insoluble in water; (4) water is used as a developing solution, and the water-soluble polymer in the non-exposed region is washed away to form a developed image.
  • the concentration of the water-soluble photoresist solution is from 0.1 mg/L to 100 g/L.
  • the method of coating the water-soluble photoresist solution on the surface of the substrate to be processed is any one of a tantalum method, a deposition method, a spin coating method or a drop coating method, and the substrate It is a silicon wafer, an ITO glass, a quartz plate having a gold plating layer on its surface, and an SiO 2 sheet having a silver plating layer on its surface.
  • the electron beam exposure conditions are: a voltage of 5 kV to 30 kV, a working distance of 5 mm to 20 mm, an aperture of 5 ⁇ m to 30 ⁇ m, and an exposure measurement of 100 to 10000 ⁇ C/cm 2 .
  • step (4) water is used as the developing solution, and the water-soluble polymer in the non-exposed area is washed away: the substrate after the electron beam is exposed is immersed in water for 1 to 30 minutes to remove the unexposed area. Water soluble polymer.
  • the water-soluble polymer according to the present invention comprises industrially mature polyvinyl alcohol, which is inexpensive and stable in performance, and can be applied to actual production in the future.
  • FIG. 1 is a schematic view showing the steps of an image forming method of a water-soluble negative electron beam resist of the present invention
  • FIG. 2 is a SEM comparison diagram of a water-soluble negative electron beam resist and a PMMA photoresist of the present invention
  • 3 is an SEM image of a photoresist pattern of the water-soluble negative electron beam resist of the present invention.
  • the present invention provides a water-soluble negative electron beam resist comprising a, a water-soluble polymer for self-crosslinking under an electron beam, the side chain having a hydroxyl group; b, a solvent: water.
  • the water-soluble polymer is a sugar-containing polymer such as a glucose homopolymer, a mannose homopolymer, a copolymer of glucose and methacrylic acid, or a copolymer of glucose and sodium p-styrenesulfonate.
  • Water soluble polymer The water mass ratio is 1:10 to 1000000, and the structure of the water-soluble polymer is as follows:
  • R 1 H, CH 3 ;
  • R 2 or R 3 H, CH 3 ,
  • R 4 H, OH (linear or cyclic hydroxyl molecule, 1-5 hydroxyl groups);
  • R 5 H, CH 3 ;
  • R 6 or R 7 H, CH 3 ,
  • the first structural formula is a homopolymer with a hydroxyl group
  • the second structural formula is a copolymer obtained by copolymerization of a monomer having a hydroxyl group and another monomer.
  • R 4 is H
  • X is O
  • the polymer has -OH
  • the unlabeled portion (both ends) of the structural formula is a chain end group.
  • the polymerization method used may be different, and the terminal group may be other groups such as a RAFT chain transfer agent or an ATRP initiator.
  • m, n is the number of repeating units of the polymer.
  • FIG. 1 is a schematic diagram showing the steps of an image forming method of a water-soluble negative electron beam resist of the present invention.
  • the image forming method of the water-soluble negative electron beam resist comprises:
  • Step 1 dissolving the water-soluble polymer in water to prepare a water-soluble photoresist solution
  • the step may be specifically carried out by dissolving the water-soluble polymer in water to prepare a water-soluble photoresist solution having a concentration of from 0.1 mg/L to 100 g/L.
  • Step 2 depositing the water-soluble photoresist solution 1 on the surface of the substrate 2 to be processed to form an electron beam photoresist film.
  • the step may be performed by: depositing the water-soluble photoresist solution on the surface of the substrate to be processed to form an electron beam photoresist film, wherein the water-soluble photoresist solution is spread
  • the method of the surface of the substrate to be treated is any one of a tantalum method, a deposition method, a spin coating method or a drop coating method, and the substrate is a silicon wafer, an ITO glass, a quartz sheet having a gold film plating on the surface, and a silver surface. Any of the SiO 2 sheets of the film coating.
  • Step 3 performing electron beam exposure, under the action of the electron beam, the exposed region self-crosslinks, so that the water-soluble polymer in the exposed region is crosslinked and insoluble in water.
  • the step may be specifically performed by electron beam exposure using an electron beam having a voltage of 5 kV to 30 kV, a working distance of 5 mm to 20 mm, a pupil of 5 ⁇ m to 30 ⁇ m, and an exposure measurement of 100 to 10000 ⁇ C/cm 2 .
  • the exposed region is self-crosslinked, so that the water-soluble polymer in the exposed region is crosslinked and insoluble in water.
  • Step 4 Using water as a developing solution, the water-soluble polymer in the non-exposed area is washed away to form a developed image.
  • the step may be specifically performed by immersing the substrate after electron beam exposure in water for 1 to 30 minutes to remove the water-soluble polymer in the unexposed region to form a developed image.
  • FIG. 2 is a SEM comparison diagram of the water-soluble negative electron beam resist and the PMMA photoresist of the present invention, wherein a is a sugar-containing polymer and b is a PMMA.
  • the method lithographs a grating having a slit width of 20 nm, and obtains a sugar-containing polymer grating with a clear boundary after washing, and has a higher resolution than a PMMA grating.
  • 3 is an SEM image of a photoresist pattern of the water-soluble negative electron beam resist of the present invention.
  • various types of patterns such as square, grating and circular patterns, can be photolithographically used with electron beams to have higher resolution. It can be seen that the sugar-containing polymer is a good photoresist water-soluble material.
  • an embodiment or “an embodiment” as used herein refers to a particular feature, structure, or characteristic that can be included in at least one implementation of the invention.
  • Film formation and preparation method of water-soluble negative electron beam photoresist preparing a sugar-containing polymer aqueous solution with a mass ratio of 1:10, as a water-soluble negative electron beam photoresist, with a gold film at a speed of 3000 rpm
  • the surface of the quartz was spin-coated with a photoresist having a film thickness of about 60 nm. Then, it was exposed by electron beam, and the working voltage was 20 kV, the working distance was 10 mm, the aperture was 30 ⁇ m, and the exposure was measured at 160 ⁇ C/cm 2 . After the end, the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm.
  • Film formation and preparation method of water-soluble negative electron beam photoresist preparing a sugar-containing polymer aqueous solution with a mass ratio of 1:100 as a water-soluble negative electron beam photoresist at a speed of 3000 rpm with a silver film
  • the SiO 2 surface was spin-coated with the photoresist to a film thickness of about 30 nm. Then, it was exposed by an electron beam, and the working voltage was 20 kV, the working distance was 10 mm, the aperture was 30 ⁇ m, and the exposure measurement was 800 ⁇ C/cm 2 . After the end, the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm.
  • Film formation and use method of water-soluble negative electron beam photoresist preparing a sugar-containing polymer aqueous solution with a mass ratio of 1:1000 as a water-soluble negative electron beam resist, spinning at a speed of 2000 rpm on the surface of the silicon wafer The photoresist was applied to a film thickness of about 40 nm. Then, it was exposed by an electron beam, and the working voltage was 20 kV, the working distance was 10 mm, the aperture was 30 ⁇ m, and the exposure was measured at 1000 ⁇ C/cm 2 . After the end, the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm.
  • Film formation and preparation method of water-soluble negative electron beam photoresist preparing polyvinyl alcohol aqueous solution with mass ratio of 1:10000, as water-soluble negative electron beam photoresist, spin coating on ITO glass surface at 2000 rpm
  • the photoresist has a film thickness of about 20 nm. Then, it was exposed by electron beam, and the working voltage was 20 kV, the working distance was 10 mm, the aperture was 15 ⁇ m, and the exposure measurement was 1500 ⁇ C/cm 2 . After the end, the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm.
  • Film formation and preparation method of water-soluble negative electron beam photoresist preparing a sugar-containing polymer aqueous solution with a mass ratio of 1:100,000 as a water-soluble negative electron beam photoresist, spinning on the surface of ITO glass at a speed of 1000 rpm The photoresist was applied to a film thickness of about 30 nm. Then, it was exposed by an electron beam, and the working voltage was 5 kV, the working distance was 5 mm, the aperture was 10 ⁇ m, and the exposure measurement was 2000 ⁇ C/cm 2 . After the end, the substrate was fully immersed in deionized water to develop an image with a single dot resolution of ⁇ 50 nm.
  • Film formation and preparation method of water-soluble negative electron beam photoresist preparing a sugar-containing polymer aqueous solution with a mass ratio of 1:1000000, as a water-soluble negative electron beam photoresist, dripping on the surface of the silicon wafer, and rapidly drying Dry moisture, film thickness of about 80nm. Then, it was exposed by an electron beam, and the working voltage was 30 kV, the working distance was 10 mm, the aperture was 5 ⁇ m, and the exposure measurement was 3000 ⁇ C/cm 2 . After the end, the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm.
  • the present invention discloses a water-soluble negative electron beam photoresist, and firstly proposes the application of a water-soluble polymer containing a hydroxyl side chain in an electron beam lithography system, and has experimentally produced a high resolution environmental protection.
  • Type electron beam photoresist It can reduce the biological toxicity of traditional photoresist and improve the comfort of human body during the lithography process.
  • the photosensitive resin is a high molecular polymer having water-soluble characteristics, and its self-crosslinking action under electron beam exposure is used to change the difference in water solubility before and after exposure to realize image development.
  • the water-soluble photosensitive resin is a water-soluble polymer having one or more OH groups in its side chain, and both the solvent and the developer are water, and therefore it is environmentally friendly to use such a photoresist in semiconductor manufacturing. And some of the water-soluble polymers with such OH groups in the side chain have already had very mature industrial production capacity, which will greatly reduce the cost of the electron beam photoresist, and the present invention can be applied to industrial production in the future.
  • the invention discloses a water-soluble negative electron beam resist imaging method, which completely uses water as a solvent and a developing solution of a photoresist, and has no pollution to the environment and the human body, and has a good application prospect.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
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Abstract

公开了一种水溶性负性电子束光刻胶，包括：a，用于电子束下自交联的水溶性聚合物，其侧链具有羟基，和b，溶剂：水。同时公开了该水溶性负性电子束光刻胶的成像方法。该光刻胶以水作为溶剂和显影液，对环境和人体无污染，具有良好的应用前景。

Description

水溶性负性电子束光刻胶及其成像方法 技术领域
本发明涉及光刻胶领域，具体涉及一种水溶性负性电子束光刻胶及其成像方法。
背景技术
大规模集成电路自上世纪60年代至今已经历了半个多世纪的发展，单片晶圆的存储量也成摩尔定律增长。目前由于光刻精度的日益提高，电子束光刻技术也在工业生产中得到了广泛的应用。作为大规模集成电路工业中的关键性功能材料，光刻胶一直是研究的重点，譬如，它的灵敏度、空间分辨率以及物理化学稳定性。光刻胶在曝光前后通常会发生交联或者降解，在显影液中溶解度发生变化，再经历刻蚀、去膜，就可以将特定的高精度图形转移到目标基片表面了。根据曝光后在显影液中溶解速度的提升或者降低可分为正性和负性光刻胶，负性光刻胶在显影过程中曝光位置的感光树脂不再溶于显影液从而被保留下来，未曝光位置的感光树脂则被洗去，目前光刻胶产业存在几方面的问题：1、光酸产生剂使用过程中的有机酸腐蚀金属，污染环境；2、使用的光刻胶溶液多为氯苯，乳酸乙酯；显影液则多为甲基异丁基甲酮和异丙醇，都存在一定的生物毒性和环境危害性，而且价格不菲；3、必须引入强效光引发催化剂，使得光刻胶成本昂贵。随着生产技术的日益更新，人们对自身和环境的保护意识日益加强，在提升光刻胶性能的同时，优化光刻工艺过程中的操作环境也是迫在眉睫的命题。
发明内容
本发明目的是提供水溶性负性电子束光刻胶其及成像方法，采用含有羟基侧链的水溶性聚合物应用于电子束光刻系统，解决了成本高、对环境、人体有污染的问题。
本发明的一种技术方案是：一种水溶性负性电子束光刻胶，包括：
a，用于电子束下自交联的水溶性聚合物，其侧链具有羟基；b，溶剂：水。
进一步的，所述水溶性聚合物为含糖聚合物。
进一步的，所述含糖聚合物为葡萄糖均聚合物、甘露糖均聚合物、葡萄 糖与甲基丙烯酸的共聚物、葡萄糖与对苯乙烯磺酸钠的共聚物中的任意一种。
进一步的，所述水溶性聚合物与水的质量比为1：10～1000000。
进一步的，所述水溶性聚合物的结构如下：
Figure PCTCN2017109465-appb-000001
其中，R1：H、CH3；
R2或者R3：H、CH3，
R4：H、OH(线性或环形羟基分子，1-5个羟基)；
X：O、C、─CO─、─CO─N─、─Ph─O─、
Figure PCTCN2017109465-appb-000002
R5：H、CH3；
R6或R7：H、CH3，
R8：─COOH、─Ph─SO3-Na+。
本发明的另一种技术方案是：一种水溶性负性电子束光刻胶的成像方法，其包括步骤：(1)将水溶性聚合物溶于水，制得水溶性光刻胶溶液；(2)将所述水溶性光刻胶溶液铺在待处理基板表面，做成电子束光刻胶薄膜；(3)进行电子束曝光，在电子束的作用下，曝光区域发生自交联，使得曝光区域的水溶性高分子发生交联而不溶于水；(4)将水作为显影液，洗去非曝光区域的水溶性聚合物，形成显影图像。
进一步的，步骤(1)中，所述水溶性光刻胶溶液的浓度为0.1mg/L～100g/L。
进一步的，步骤(2)中，将所述水溶性光刻胶溶液铺在待处理基板表面的方法为甩胶法、沉积法、旋涂法或滴涂法中的任意一种，所述基板为硅片、ITO玻璃、表面具有金膜镀层的石英片、表面具有银膜镀层的SiO2片中的任意一种。
进一步的，步骤(3)中，所述电子束曝光的条件为：电压为5kV～30kV、 工作距离为5mm～20mm、光阑为5μm-30μm、曝光计量为100～10000μC/cm2。
进一步的，步骤(4)中，将水作为显影液，洗去非曝光区域的水溶性聚合物具体为：将电子束曝光以后的基片，放在水中浸泡1～30min以去除未曝光的区域的水溶性聚合物。
本发明优点是：
(1)将带有羟基侧链的水溶性聚合物溶于水，配成光刻胶溶液，并在待处理基板上形成光刻胶薄膜，免去了传统光刻胶溶液以氯苯或者乳酸乙酯作为溶剂所带来的刺激性和不稳定性；
(2)同时后期仍以水作为显影液，代替了甲基异丁基甲酮或异丙醇，且无需定影，水洗以后即可以得到显影图像；
(3)整个过程只涉及水溶性聚合物和水，绿色环保无污染；
(4)本发明所涉及的水溶性聚合物包含工业化成熟的聚乙烯醇，其价格低廉，性能稳定，未来可以适用于实际生产。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。其中，
图1为本发明的水溶性负性电子束光刻胶的成像方法的步骤示意图；
图2为本发明的水溶性负性电子束光刻胶与PMMA光刻胶的SEM对比图；
图3为本发明的水溶性负性电子束光刻胶的光刻胶图案的SEM图。
具体实施方式
本发明提供水溶性负性电子束光刻胶，包括a，用于电子束下自交联的水溶性聚合物，其侧链具有羟基；b，溶剂：水。其中，水溶性聚合物为含糖聚合物，如：葡萄糖均聚合物、甘露糖均聚合物、葡萄糖与甲基丙烯酸的共聚物、葡萄糖与对苯乙烯磺酸钠的共聚物中的任意一种。水溶性聚合物与 水的质量比为1：10～1000000，水溶性聚合物的结构如下：
Figure PCTCN2017109465-appb-000003
其中，R1：H、CH3；
R2或者R3：H、CH3，
R4：H、OH(线性或环形羟基分子，1-5个羟基)；
X：O、C、─CO─、─CO─N─、─Ph─O─、
Figure PCTCN2017109465-appb-000004
R5：H、CH3；
R6或R7：H、CH3，
R8：─COOH、─Ph─SO3-Na+。
需提醒注意的是：第一个结构式是带有羟基的均聚物，第二个结构式是带有羟基的单体和另一单体共聚后得到的共聚物。当R4为H时，X为O，聚合物中带有-OH，结构式中未标出的部分(两端)为链端基。所用聚合方法不同，端基可为RAFT链转移剂或ATRP引发剂等其它基团。m，n是聚合物的重复单元个数。
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施方式对本发明作进一步详细的说明。
请参阅图1，图1为本发明的水溶性负性电子束光刻胶的成像方法的步骤示意图。如图1所示，所述水溶性负性电子束光刻胶的成像方法，包括：
步骤一：将水溶性聚合物溶于水，制得水溶性光刻胶溶液；
在一个实施例中，该步骤可以具体如下执行：将水溶性聚合物溶于水，制得浓度为0.1mg/L～100g/L的水溶性光刻胶溶液。
步骤二：将所述水溶性光刻胶溶液1铺在待处理基板2表面，做成电子束光刻胶薄膜。
在一个实施例中，该步骤可以具体如下执行：将所述水溶性光刻胶溶液铺在待处理基板表面，做成电子束光刻胶薄膜，其中，将所述水溶性光刻胶 溶液铺在待处理基板表面的方法为甩胶法、沉积法、旋涂法或滴涂法中的任意一种，所述基板为硅片、ITO玻璃、表面具有金膜镀层的石英片、表面具有银膜镀层的SiO2片中的任意一种。
步骤三：进行电子束曝光，在电子束的作用下，曝光区域发生自交联，使得曝光区域的水溶性高分子发生交联而不溶于水。
在一个实施例中，该步骤可以具体如下执行：用电压为5kV～30kV、工作距离为5mm～20mm、光阑为5μm-30μm、曝光计量为100～10000μC/cm2的电子束进行电子束曝光，曝光区域发生自交联，使得曝光区域的水溶性高分子发生交联而不溶于水。
步骤四：将水作为显影液，洗去非曝光区域的水溶性聚合物，形成显影图像。
在一个实施例中，该步骤可以具体如下执行：将电子束曝光以后的基片，放在水中浸泡1～30min以去除未曝光的区域的水溶性聚合物，形成显影图像。
上述步骤所得实验结果请参阅图2-图3，图2为本发明的水溶性负性电子束光刻胶与PMMA光刻胶的SEM对比图，其中，a为含糖聚合物，b为PMMA，从图2可知，本方法光刻出狭缝宽为20nm的光栅，水洗后得到边界较为清晰的含糖聚合物光栅，与PMMA光栅对比，其具有较高的分辨率。图3为本发明的水溶性负性电子束光刻胶的光刻胶图案的SEM图。从图3可知，用电子束可以光刻出多种类型的图案，如：方形、光栅和圆形图案，具有较高的分辨率。由此可知，含糖聚合物是一种较好的光刻胶水溶性材料。
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和实施例进一步说明本发明的技术方案。但是本发明不限于所列出的实施例，还应包括在本发明所要求的权利范围内其他任何公知的改变。
首先，此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例，也不是单独的或选择性的与其他实施例互相排斥的实施例。
其次，本发明利用结构示意图等进行详细描述，在详述本发明实施例时，为便于说明，示意图会不依一般比例作局部放大，而且所述示意图只是实例，其在此不应限制本发明保护的范围。此外，在实际制作中应包含长度、宽度 及深度的三维空间。
另外，本发明中所讲的字母简称，均为本领域固定简称，其中部分字母文解释如下：SEM图：电子扫描显像图。
实施例一
水溶性负性电子束光刻胶的成膜及制备方法：配制含糖聚合物水溶液，质量比为1：10，作为水溶性负性电子束光刻胶，以3000rpm的速度在带有金膜的石英表面旋涂该光刻胶，膜厚约60nm。然后用电子束曝光，工作电压为20kV，工作距离10mm，光阑30μm，曝光计量160μC/cm2。结束后将基片至于去离子水中充分浸泡，显影图像，图像单点分辨率<20nm。
实施例二
水溶性负性电子束光刻胶的成膜及制备方法：配制含糖聚合物水溶液，质量比为1：100，作为水溶性负性电子束光刻胶，以3000rpm的速度在带有银膜的SiO2表面旋涂该光刻胶，膜厚约30nm。然后用电子束曝光，工作电压为20kV，工作距离10mm，光阑30μm，曝光计量800μC/cm2。结束后将基片至于去离子水中充分浸泡，显影图像，图像单点分辨率<20nm。
实施例三
水溶性负性电子束光刻胶的成膜及使用方法：配制含糖聚合物水溶液，质量比为1：1000，作为水溶性负性电子束光刻胶，以2000rpm的速度在硅片表面旋涂该光刻胶，膜厚约40nm。然后用电子束曝光，工作电压为20kV，工作距离10mm，光阑30μm，曝光计量1000μC/cm2。结束后将基片至于去离子水中充分浸泡，显影图像，图像单点分辨率<20nm。
实施例四
水溶性负性电子束光刻胶的成膜及制备方法：配制聚乙烯醇水溶液，质量比为1：10000，作为水溶性负性电子束光刻胶，以2000rpm的速度在ITO玻璃表面旋涂该光刻胶，膜厚约20nm。然后用电子束曝光，工作电压为20kV，工作距离10mm，光阑15μm，曝光计量1500μC/cm2。结束后将基片至于去离子水中充分浸泡，显影图像，图像单点分辨率<20nm。
实施例五
水溶性负性电子束光刻胶的成膜及制备方法：配制含糖聚合物水溶液，质量比为1：100000，作为水溶性负性电子束光刻胶，以1000rpm的速度在ITO玻璃表面旋涂该光刻 胶，膜厚约30nm。然后用电子束曝光，工作电压为5kV，工作距离5mm，光阑10μm，曝光计量2000μC/cm2。结束后将基片至于去离子水中充分浸泡，显影图像，图像单点分辨率<50nm。
实施例六
水溶性负性电子束光刻胶的成膜及制备方法：配制含糖聚合物水溶液，质量比为1：1000000，作为水溶性负性电子束光刻胶，滴涂在硅片表面，迅速烘干水分，膜厚约80nm。然后用电子束曝光，工作电压为30kV，工作距离10mm，光阑5μm，曝光计量3000μC/cm2。结束后将基片至于去离子水中充分浸泡，显影图像，图像单点分辨率<20nm。
综上所述，本发明公开了水溶性负性电子束光刻胶，首次提出了含有羟基侧链的水溶性聚合物在电子束光刻系统中的应用，试制出了具有高分辨率的环保型电子束光刻胶。可以降低传统光刻胶的生物毒性，提高光刻工艺过程中人体的舒适度。所述感光树脂为具有水溶性特征的高分子聚合物，利用其在电子束曝光下的自交联作用，改变曝光前后的水溶性差异，实现图像显影。该水溶性感光树脂是侧链含1个或多个OH基的水溶性聚合物，溶剂和显影液都为水，因此在半导体制造中使用这种光刻胶将是环保的。且此类侧链带有OH基的水溶性聚合物中有一些已经具有很成熟的工业化生产能力，这将大大降低电子束光刻胶的成本，未来可应用于工业化生产中本发明还提供了一种水溶性负性电子束光刻胶成像方法，完全以水作为光刻胶的溶剂和显影液，对环境和人体完全无污染，其具有良好的应用前景。
应说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。

Claims (10)

  1. 水溶性负性电子束光刻胶，其特征在于，包括：
    a，用于电子束下自交联的水溶性聚合物，其侧链具有羟基；
    b，溶剂：水。
  2. 根据权利要求1所述的水溶性负性电子束光刻胶，其特征在于：所述水溶性聚合物为含糖聚合物。
  3. 根据权利要求2所述的水溶性负性电子束光刻胶，其特征在于：所述含糖聚合物为葡萄糖均聚合物、甘露糖均聚合物、葡萄糖与甲基丙烯酸的共聚物、葡萄糖与对苯乙烯磺酸钠的共聚物中的任意一种。
  4. 根据权利要求1所述的水溶性负性电子束光刻胶，其特征在于：所述水溶性聚合物与水的质量比为1：10～1000000。
  5. 根据权利要求1所述的水溶性负性电子束光刻胶，其特征在于：所述水溶性聚合物的结构如下：
    Figure PCTCN2017109465-appb-100001
    其中，R1：H、CH3；
    R2或者R3：H、CH3，
    R4：H、OH(线性或环形羟基分子，1-5个羟基)；
    X：O、C、─CO─、─CO─N─、─Ph─O─、
    Figure PCTCN2017109465-appb-100002
    R5：H、CH3；
    R6或R7：H、CH3，
    R8：─COOH、─Ph─SO3-Na+。
  6. 根据权利要求1～5所述的水溶性负性电子束光刻胶的成像方法，其特征在于，包括步骤：(1)将水溶性聚合物溶于水，制得水溶性光刻胶溶液；(2)将所述水溶性光刻胶溶液铺在待处理基板表面，做成电子束光刻胶薄膜；(3)进行电子束曝光，在电子束的作用下，曝光区域发生自交联，使得曝光区域的水溶性高分子发生交联而不溶于水；(4)将水作为显影液， 洗去非曝光区域的水溶性聚合物，形成显影图像。
  7. 根据权利要求6所述的水溶性负性电子束光刻胶的成像方法，其特征在于，步骤(1)中，所述水溶性光刻胶溶液的浓度为0.1mg/L～100g/L。
  8. 根据权利要求6所述的水溶性负性电子束光刻胶的成像方法，其特征在于，步骤(2)中，将所述水溶性光刻胶溶液铺在待处理基板表面的方法为甩胶法、沉积法、旋涂法或滴涂法中的任意一种，所述基板为硅片、ITO玻璃、表面具有金膜镀层的石英片、表面具有银膜镀层的SiO2片中的任意一种。
  9. 根据权利要求6所述的水溶性负性电子束光刻胶的成像方法，其特征在于，步骤(3)中，所述电子束曝光的条件为：电压为5kV～30kV、工作距离为5mm～20mm、光阑为5μm-30μm、曝光计量为100～10000μC/cm2。
  10. 根据权利要求6所述的水溶性负性电子束光刻胶的成像方法，其特征在于，步骤(4)中，将水作为显影液，洗去非曝光区域的水溶性聚合物具体为：将电子束曝光以后的基片，放在水中浸泡1～30min以去除未曝光的区域的水溶性聚合物。
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