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WO2018196319A1 - 具有荧光效应的碳纳米点光刻胶及其成像方法 - Google Patents

具有荧光效应的碳纳米点光刻胶及其成像方法 Download PDF

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WO2018196319A1
WO2018196319A1 PCT/CN2017/109454 CN2017109454W WO2018196319A1 WO 2018196319 A1 WO2018196319 A1 WO 2018196319A1 CN 2017109454 W CN2017109454 W CN 2017109454W WO 2018196319 A1 WO2018196319 A1 WO 2018196319A1
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carbon nano
sugar
containing polymer
photoresist
electron beam
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陈高健
翁雨燕
李志运
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Suzhou University
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only

Definitions

  • quantum dots With the development of optoelectronic technology, the device size has been gradually reduced, and nano-sized quantum dots can be used as a good base material in the next few decades.
  • the synthesis of quantum dots is mainly divided into two types: “top-down method” and “bottom-up method", that is, large-sized materials are ground, or small molecules are used as precursors.
  • top-down method and “bottom-up method”
  • bottom-up method that is, large-sized materials are ground, or small molecules are used as precursors.
  • the positioning and laying of quantum dots play a more important role in the realization of functions.
  • the object of the invention is to provide a carbon nano-dot photoresist with fluorescence effect and an imaging method thereof, and to complete the preparation and laying of quantum dots by one-step method, to break the bottleneck of precise positioning of quantum dots, and to solve the precise control of quantum dot positioning and configuration.
  • the problem is completed in one step.
  • a carbon nano-dot photoresist having a fluorescent effect comprising:
  • the mass ratio of the sugar-containing polymer to water is 1:10 to 1,000,000.
  • the sugar-containing polymer has a molecular weight of 800 to 1,000,000.
  • the structure of the sugar-containing polymer is as follows:
  • R 1 H, ⁇ CH 3 ;
  • R 2 or R 3 H, ⁇ CH 3 ,
  • R 4 a sugar ring (glucose ring, galactose ring, mannose ring and other polyhydroxy compounds conforming to the sugar definition);
  • R 5 H, ⁇ CH 3 ;
  • the concentration of the sugar-containing polymer photoresist solution is 0.1 mg/L to 100 g/L.
  • the method of coating the photoresist solution on the surface of the substrate to be processed is any one of a spin coating method and a dropping coating method, wherein the substrate is a silicon wafer, an ITO glass, and the surface has A gold plated quartz plate and a SiO 2 plate having a silver film plating 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 1000 to 100,000 ⁇ C/cm 2 .
  • the sugar-containing polymer film forms carbon nano-dots at the exposure point, and the carbon nano-dots have a corresponding quantum fluorescence effect, and the fluorescence is generated under the excitation of the corresponding wavelength ultraviolet or visible light.
  • the position of the carbon nano-dots in the photoresist can be precisely positioned by the electron beam
  • the carbon dots are combined into an arbitrary pattern by electron beam exposure, and the exposed region has blue fluorescence under excitation of a specific wavelength.
  • FIG. 1 is a schematic view showing the steps of an image forming method of a carbon nano-dot photoresist having a fluorescent effect
  • FIG. 2 is an AFM characterization diagram of a carbon nano-dot photoresist pattern having a fluorescent effect of the present invention
  • Figure 3 is a precise map of the carbon nanodots with fluorescence effect of the present invention (SEM image and optical diagram at 405 nm excitation);
  • FIG. 4 is a block array fluorescence confocal diagram based on a sugar-containing polymer carbon dot of the present invention, and an ultraviolet absorption spectrum thereof and a fluorescence emission spectrum thereof.
  • the present invention provides a carbon nano-dot photoresist having a fluorescent effect, comprising a, a sugar-containing polymer for self-crosslinking under electron beam, a side chain having a sugar ring; b, a solvent: water.
  • the sugar-containing polymer is any one of a glucose homopolymer, a mannose homopolymer, a copolymer of glucose and methacrylic acid, and a copolymer of glucose and sodium p-styrenesulfonate.
  • the mass ratio of the sugar-containing polymer to water is 1:10 to 1,000,000, and the structure of the sugar-containing polymer is as follows:
  • R 1 H, ⁇ CH 3 ;
  • R 2 or R 3 H, ⁇ CH 3 ,
  • R 4 a sugar ring (glucose ring, galactose ring, mannose ring and other polyhydroxy compounds conforming to the sugar definition);
  • R 5 H, ⁇ CH 3 ;
  • R 6 or R 7 H, ⁇ CH 3 ,
  • Step 1 dissolving the sugar-containing polymer in water to obtain a sugar-containing polymer photoresist solution
  • the step may be specifically carried out by dissolving the sugar-containing polymer in water to prepare a sugar-containing polymer photoresist solution having a concentration of from 0.1 mg/L to 100 g/L.
  • Step 2 depositing the photoresist solution on the surface of the substrate to be processed to form an electron beam photoresist film
  • the step may be performed by depositing the photoresist solution on the surface of the substrate to be processed to form an electron beam photoresist film, wherein the photoresist solution is deposited on the substrate to be processed.
  • the surface method is any one of a spin coating method and a drop coating method
  • the substrate is any one of a silicon wafer, an ITO glass, a quartz sheet having a gold film plating layer on the surface, and a SiO 2 sheet having a silver film plating layer on its surface. .
  • Step 4 Place it under a wavelength source of 300-800 nm wavelength range, which has a fluorescent effect.
  • the step may be specifically performed as follows: the sugar-containing polymer film forms carbon nano-dots at the exposure point, and the carbon nano-dots of a specific size have a corresponding quantum fluorescence effect, under the excitation of the corresponding wavelength ultraviolet or visible light , producing fluorescence.
  • FIG. 2 is an AFM characterization diagram of a carbon nano-dot photoresist pattern having a fluorescent effect according to the present invention.
  • FIG. 2 an enlarged scan of the exposed region can be found.
  • the surface contains dense nano-sized lattices (carbon dots).
  • Figure 3 is a precise map of the carbon nanodots with fluorescence effect of the present invention (SEM image and 405 nm excitation) Under the optical map).
  • a Au point (coated with a sugar film, the same below) SEM photograph
  • b optical image of Au point (405 nm excitation, dark color)
  • c SEM of the sugar-containing polymer carbon spot positioned at the lower right corner of the Au point Photograph
  • d Optical image of the sugar-containing polymer carbon spot positioned at the lower right corner of the Au spot (excitation at 405 nm, bright color at the lower right corner).
  • FIG. 3c is a block array fluorescence confocal diagram based on a sugar-containing polymer carbon dot of the present invention, and an ultraviolet absorption spectrum thereof and a fluorescence emission spectrum thereof.
  • a Confocal fluorescence pattern excited by 405nm wavelength light (this picture is not developed by ion water in the past, the gray point is the blue fluorescent area, which is the electron beam exposure area, and the rest is not exposed by electron beam)
  • b The ultraviolet absorption spectrum of the sugar polymer carbon dots (c line) and the fluorescence emission spectrum (d line 405 nm excitation), as shown in Fig. 4, the sample was placed in an ultraviolet-visible absorption spectrometer for testing, and the ultraviolet absorption of the film was obtained.
  • Spectrogram (c-line) we found a strong UV absorption peak at 360 nm.
  • 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 carbon nano-dot photoresist with fluorescence effect preparing poly(acrylamide-based) glucose polymer aqueous solution (PAGA) with a mass ratio of 1:100 as a water-soluble negative electron beam photoresist,
  • PAGA poly(acrylamide-based) glucose polymer aqueous solution
  • the photoresist was spin-coated on the surface of the silicon wafer at a speed of 2000 rpm to a film thickness of about 40 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 2000 ⁇ 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. Under a confocal microscope, excitation with 400 nm wavelength light, the exposed region has blue fluorescence.
  • the substrate was fully immersed in deionized water to develop an image with a single dot resolution of ⁇ 50 nm. Under a confocal microscope, it was excited with a light of 360 nm wavelength and developed with a fluorescent pattern.
  • Film formation and preparation method of carbon nano-dot photoresist with fluorescence effect preparing (methacrylamide-based) glucose and sodium p-styrenesulfonate copolymer (P(MAG-co-SS)) aqueous solution, mass ratio It is 1:100,000, as a water-soluble negative electron beam photoresist, which is applied onto the surface of the silicon wafer to quickly dry the water, and the film thickness is about 80 nm. 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 was measured at 1000 ⁇ C/cm 2 .
  • P(MAG-co-SS) sodium p-styrenesulfonate copolymer
  • the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm.
  • excitation with a light of 390 nm wavelength the exposed area has blue fluorescence.
  • Film formation and preparation method of carbon nano-dot photoresist with fluorescence effect preparing (methacrylamide-based) mannose (PMAM) aqueous solution with a mass ratio of 1:10000 as a water-soluble negative electron beam photoresist,
  • the photoresist was spin-coated at a speed of 2000 rpm on a quartz surface with a gold film to a film thickness of about 20 nm.
  • the working voltage was 20 kV
  • the working distance was 10 mm
  • the aperture was 30 ⁇ m
  • the exposure measurement was 20000 ⁇ C/cm 2 .
  • the substrate was fully immersed in deionized water to develop an image with a single point resolution of ⁇ 20 nm. Under a confocal microscope, excitation with 380 nm wavelength light, the exposed region has blue fluorescence.
  • the present invention discloses a carbon nano-dot photoresist having a fluorescent effect and an image forming method thereof, which is a novel photosensitive resin based on a sugar-containing polymer and an electron beam etching technique to generate fluorescent carbon nano-dots in situ and
  • the photosensitive resin is a sugar-containing polymer, and its carbonized nano-point preparation with nanometer-scale precise positioning is realized by controlled carbonization and self-crosslinking in a certain electron beam exposure dose range.
  • Fluorescent properties under wavelength illumination for fluorescence development and other applications. Water is the only solvent used in this patent. It has the characteristics of green environmental protection, and can form fluorescent carbon nano-dots with arbitrary nano patterns at any specified position.
  • One step is to solve the problems of fluorescent particle preparation and nano-scale precise positioning in semiconductor manufacturing. And the biological field has broad application prospects.

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  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
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Abstract

具有荧光效应的碳纳米点光刻胶及其成像方法，所述感光树脂为含糖聚合物，利用其在一定电子束曝光剂量范围内的可控碳化及自交联作用，实现具有纳米尺度精确定位的碳纳米点制备，在特定波长光照下具有荧光特性，实现荧光显影及其他应用。水是其中唯一使用的溶剂，具有绿色环保的特点，同时可在任意指定位置形成具有任意纳米图案的荧光碳纳米点，一步解决荧光粒子制备与纳米尺度精确定位两个问题，在半导体制造以及生物领域具广泛的应用前景。

Description

具有荧光效应的碳纳米点光刻胶及其成像方法 技术领域
本发明涉及光刻胶领域，具体涉及一种具有荧光效应的碳纳米点光刻胶及其成像方法。
背景技术
随着光电技术的发展，器件尺寸逐步缩小，具有纳米尺寸的量子点在将来的数十年中可作为一种较好的基础材料。在这个领域中量子点的合成和定位一直是非常重要的问题，大多数情况下，这两个问题是被分别处理的。量子点的合成主要分为两种类型：“自上而下法”和“自下而上法”即大尺寸的材料研碎，或是以小分子为前驱体制得。然而，在科学研究和工业制造领域中，量子点的定位和铺设在功能实现方面具有更重要的作用。例如，量子计算机中三维量子点的构建，表面等离激元的精确分析和光子晶体的选频特性都有赖于量子点的精确定位和有序排列。纳米尺度下，在任意位置精确铺设单个或一系列量子点将是该领域一种革命性的突破。目前大量的研究都集中于如何精确铺设已经制备好的量子点上，但是对于量子点剂量和位置的精确控制仍面临较大的挑战。量子点的自组装是目前报道的主要定位方法。光镊和电渗微流控制是在微米粒子的精确定位方面也起到了很明显的作用。然而由于光学梯度会随着颗粒体积的变小而衰减，通过光镊精确定位尺寸较小的纳米粒子是比较困难的。同样由于纳米粒子的布朗运动明显，电渗微流控制技术在微米尺度的控制中更适合。那么我们提出一种完全不同的量子点制备和定位的方法，将传统分立的两个步骤糅合，即精确控制，原位生成量子点。与其相关的例子是在宽能隙带材料中引入点缺陷，从而实现金刚色心的发光，相关报道已经在金刚石和碳化硅材料中实现。而且随着激光直写技术的发展，空间分辨率可以超越光学衍射极限。然而，这种方法尚未应用到量子点的制备当中。
发明内容
本发明目的是提供具有荧光效应的碳纳米点光刻胶其及成像方法，采用一步法完成量子点的制备和铺设，打破量子点精确定位的瓶颈，解决量子点定位与构型的精确控制难以一步完成的问题。
本发明的一种技术方案是：一种具有荧光效应的碳纳米点光刻胶，包括：
a，用于电子束下自交联的含糖聚合物，其侧链具有糖环；
b，溶剂：水。
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，所述含糖聚合物与水的质量比为1：10～1000000。
进一步的，所述含糖聚合物的分子量为800-1000000。
进一步的，所述含糖聚合物的结构如下：
Figure PCTCN2017109454-appb-000001
其中，R1：H、─CH3；
R2或者R3：H、─CH3，
R4：糖环(葡萄糖环，半乳糖环，甘露糖环以及其他符合糖定义的多羟基化合物)；
X：O、C、─CO─、─CO─N─、─Ph─O─、
Figure PCTCN2017109454-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：一种具有荧光效应的碳纳米点光刻胶的成像方法，其包括步骤：(1)将含糖聚合物溶于水，制得含糖聚合物光刻胶溶液；(2)将所述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，使得所述曝光区域的含糖聚合物发生交联而不溶于水；并且在电子束曝光的位置形成纳米级的碳点；(4)将其放到300-800nm波长范围的波长光源下，具有荧光效应。
进一步的，步骤(1)中，所述含糖聚合物光刻胶溶液的浓度为 0.1mg/L～100g/L。
进一步的，步骤(2)中，将所述光刻胶溶液铺在待处理基板表面的方法为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1000～100000μC/cm2。
进一步的，步骤(4)中，含糖聚合物薄膜在曝光点处形成碳纳米点，碳纳米点具有对应的量子荧光效应，在其对应波长紫外或可见光的激发下，产生荧光。
本发明优点是：
(1)将带有糖环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)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)可通过电子束精确定位光刻胶中碳纳米点的位置；
(5)由电子束曝光将碳点组合成任意图案，在特定波长激发下，曝光区域具有蓝色荧光。
(6)通过电子束辐照含糖聚合物光刻胶一步解决荧光粒子制备与纳米尺度精确定位两个问题。
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为本发明的具有荧光效应的碳纳米点光刻胶的成像方法的步骤示意图；
图2为本发明的具有荧光效应的碳纳米点光刻胶图案的AFM表征图；
图3为本发明的具有荧光效应的碳纳米点的精确定位图(SEM图和405nm激发下光学图)；
图4为本发明的基于含糖聚合物碳点的方块阵列荧光共聚焦图、及其紫外吸收光谱图和荧光发射光谱图。
具体实施方式
本发明提供具有荧光效应的碳纳米点光刻胶，包括a，用于电子束下自交联的含糖聚合物，其侧链具有糖环；b，溶剂：水。其中，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。含糖聚合物与水的质量比为1：10～1000000，含糖聚合物的结构如下：
Figure PCTCN2017109454-appb-000003
其中，R1：H、─CH3；
R2或者R3：H、─CH3，
R4：糖环(葡萄糖环，半乳糖环，甘露糖环以及其他符合糖定义的多羟基化合物)；
X：O、C、─CO─、─CO─N─、─Ph─O─、
Figure PCTCN2017109454-appb-000004
R5：H、─CH3；
R6或R7：H、─CH3，
R8：─COOH、─Ph─SO3-Na+。
需说明的是：第一个结构式为含糖均聚物，第二个结构式是含糖共聚物，两个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为本发明的具有荧光效应的碳纳米点光刻胶的成像方法的步骤示意图。如图1所示，所述具有荧光效应的碳纳米点光刻胶的成像方法，包括：
步骤一：将含糖聚合物溶于水，制得含糖聚合物光刻胶溶液；
在一个实施例中，该步骤可以具体如下执行：将含糖聚合物溶于水，制得浓度为0.1mg/L～100g/L的含糖聚合物光刻胶溶液。
步骤二：将所述光刻胶溶液铺在待处理基板表面，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，将所述光刻胶溶液铺在待处理基板表面的方法为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，使得所述曝光区域的含糖聚合物发生交联而不溶于水；并且在电子束曝光的位置形成纳米级的碳点；
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：将其放到300-800nm波长范围的波长光源下，具有荧光效应。
在一个实施例中，该步骤可以具体如下执行：含糖聚合物薄膜在曝光点处形成碳纳米点，特定大小的碳纳米点具有对应的量子荧光效应，在其对应波长紫外或可见光的激发下，产生荧光。
上述步骤所得实验结果请参阅图2-图4，图2为本发明的具有荧光效应的碳纳米点光刻胶图案的AFM表征图，从图2可知，对曝光后的区域进行放大扫描可以发现，表面上含有密密麻麻的纳米尺寸的点阵(碳点)。图3为本发明的具有荧光效应的碳纳米点的精确定位图(SEM图和405nm激发 下光学图)。其中，a：Au点(已覆有糖膜，下同)的SEM照片，b：Au点的光学图片(405nm激发，暗色)，c：含糖聚合物碳点定位于Au点右下角的SEM照片，d：含糖聚合物碳点定位于Au点右下角的光学图片(405nm激发，右下角亮色)。从图3可知，在旋涂有PMAG的ITO片(带有金点)上SEM照片(图3a)，用电子束定位碳点在金点的右下角(图3c)，在超分辨显微镜405nm的光激发下，可以明显的观察到经过电子束曝光的位置(右下角)发出亮光，即荧光(图3d)。说明利用电子束曝光可以直接实现碳量子点的精确定位操作。图4为本发明的基于含糖聚合物碳点的方块阵列荧光共聚焦图、及其紫外吸收光谱图和荧光发射光谱图。其中，a：405nm波长光激发下的共聚焦荧光图案(本图未经过去离子水显影，灰色的点为蓝色荧光区域，其为电子束曝光区域，其余未经电子束曝光)b：含糖聚合物碳点的紫外吸收光谱图(c线)和荧光发射光谱图(d线405nm激发)，从图4可知，将样品放到紫外-可见光吸收光谱仪中进行测试，得到该薄膜的紫外吸收光谱图(c线)，我们发现在360nm波长处具有较强的紫外吸收峰。在此基础上我们进行了共聚焦显微镜测试，用405nm的波长光进行激发，可以明显观察到曝光后的薄膜区域可以发射出蓝色的荧光(图4a)。同时在共聚焦显微镜下，对该区域进行了荧光发射光谱测试，得到荧光发射光谱图(d线)，在480nm处具有最大荧光发射峰值。
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；AFM图：原子力显微镜图。
实施例一
具有荧光效应的碳纳米点光刻胶的成膜及制备方法：配制聚(甲基丙烯酰胺基)葡萄糖聚合物(PMAG)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ITO玻璃表面旋涂该光刻胶，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10000μC/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。在共聚焦显微镜下，用405nm波长光激发，曝光区域具有蓝色荧光。
实施例二
具有荧光效应的碳纳米点光刻胶的成膜及制备方法：配制聚(丙烯酰胺基)葡萄糖聚合物水溶液(PAGA)，质量比为1：100，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15μm，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<20nm。在共聚焦显微镜下，用400nm波长光激发，曝光区域具有蓝色荧光。
实施例三
具有荧光效应的碳纳米点光刻胶的成膜及使用方法：配制(甲基丙烯酰胺基)葡萄糖与甲基丙烯酸共聚合物(P(MAG-co-MAA))水溶液，质量比为1：1000，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50nm。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5000μC/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。在共聚焦显微镜下，用360nm波长光激发，具有荧光图案显影。
实施例四
具有荧光效应的碳纳米点光刻胶的成膜及制备方法：配制(甲基丙烯酰胺基)葡萄糖与对苯乙烯磺酸钠共聚合物(P(MAG-co-SS))水溶液，质量比为1：100000，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。在共聚焦显微镜下，用390nm波长光激发，曝光区域具有蓝色荧光。
实施例五
具有荧光效应的碳纳米点光刻胶的成膜及制备方法：配制(甲基丙烯酰胺基)甘露糖(PMAM)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，在带有金膜的石英表面旋涂该光刻胶，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30μm，曝光计量20000μC/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。在共聚焦显微镜下，用380nm波长光激发，曝光区域具有蓝色荧光。
实施例六
具有荧光效应的碳纳米点光刻胶的成膜及制备方法：配制聚(丙烯酰胺基)葡萄糖与甲基丙烯酸共聚合物(P(AGA-co-MAA))水溶液聚合物水溶液，质量比为1：1000000，作为水溶性负性电子束光刻胶，滴涂在带有银膜的SiO2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20kV，工作距离10mm，光阑30μm，曝光计量50000μC/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。在共聚焦显微镜下，用375nm波长光激发，曝光区域具有蓝色荧光。
综上所述，本发明公开了具有荧光效应的碳纳米点光刻胶及其成像方法，是一种基于含糖聚合物的新型感光树脂以及电子束刻蚀技术原位生成荧光碳纳米点并且进行精确定位的方法，所述感光树脂为含糖聚合物，利用其在一定电子束曝光剂量范围内的可控碳化及自交联作用，实现具有纳米尺度精确定位的碳纳米点制备，在特定波长光照下具有荧光特性，实现荧光显影及其他应用。水是本专利中唯一使用的溶剂，具有绿色环保的特点，同时可在任意指定位置形成具有任意纳米图案的荧光碳纳米点，一步解决荧光粒子制备与纳米尺度精确定位两个问题，在半导体制造以及生物领域具广泛的应用前景。
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. 具有荧光效应的碳纳米点光刻胶，其特征在于，包括：
    a，用于电子束下自交联的含糖聚合物，其侧链具有糖环；
    b，溶剂：水。
  2. 根据权利要求1所述的具有荧光效应的碳纳米点光刻胶，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。
  3. 根据权利要求1所述的具有荧光效应的碳纳米点光刻胶，其特征在于：所述含糖聚合物与水的质量比为1：10～1000000。
  4. 根据权利要求1所述的具有荧光效应的碳纳米点光刻胶，其特征在于：所述含糖聚合物的分子量为800-1000000。
  5. 根据权利要求1所述的具有荧光效应的碳纳米点光刻胶，其特征在于：所述含糖聚合物的结构如下：
    Figure PCTCN2017109454-appb-100001
    其中，R1：H、─CH3；
    R2或者R3：H、─CH3，
    R4：糖环；
    X：O、C、─CO─、─CO─N─、─Ph─O─、
    Figure PCTCN2017109454-appb-100002
    R5：H、─CH3；
    R6或R7：H、─CH3，
    R8：─COOH、─Ph─SO3-Na+。
  6. 根据权利要求1～5所述的具有荧光效应的碳纳米点光刻胶的成像方法，其特征在于，包括步骤：(1)将含糖聚合物溶于水，制得含糖聚合物光刻胶溶液；(2)将所述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，使得所述曝光区域的含糖聚合物发生交联而不溶于水；并且在电子束曝 光的位置形成纳米级的碳点；(4)将其放到300-800nm波长范围的波长光源下，具有荧光效应。
  7. 根据权利要求6所述的具有荧光效应的碳纳米点光刻胶的成像方法，其特征在于，步骤(1)中，所述含糖聚合物光刻胶溶液的浓度为0.1mg/L～100g/L。
  8. 根据权利要求6所述的具有荧光效应的碳纳米点光刻胶的成像方法，其特征在于，步骤(2)中，将所述光刻胶溶液铺在待处理基板表面的方法为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所述的具有荧光效应的碳纳米点光刻胶的成像方法，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1000～100000μC/cm2。
  10. 根据权利要求6所述的具有荧光效应的碳纳米点光刻胶的成像方法，其特征在于，步骤(4)中，含糖聚合物薄膜在曝光点处形成碳纳米点，碳纳米点具有对应的量子荧光效应，在其对应波长紫外或可见光的激发下，产生荧光。
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