WO2012055086A1 - 制备微观数密度或尺寸梯度金属纳米粒子点阵的方法 - Google Patents

制备微观数密度或尺寸梯度金属纳米粒子点阵的方法 Download PDF

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WO2012055086A1
WO2012055086A1 PCT/CN2010/078066 CN2010078066W WO2012055086A1 WO 2012055086 A1 WO2012055086 A1 WO 2012055086A1 CN 2010078066 W CN2010078066 W CN 2010078066W WO 2012055086 A1 WO2012055086 A1 WO 2012055086A1
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substrate
nanoparticle
gradient
lattice
metal
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French (fr)
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贺龙兵
韩民
宋凤麒
王广厚
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Nanjing University
Nanjing Tech University
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Nanjing Tech University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/042—Coating on selected surface areas, e.g. using masks using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/221—Ion beam deposition

Definitions

  • the present invention relates to the field of nanomaterials and nanodevices, micro/nano processing, self-assembly, bio/chemical sensors, and the like, and more particularly to controllable preparation of micro-gradient nanoparticle lattices.
  • Gradient nanoparticle lattices have additional degrees of freedom over traditional uniform nanoparticle lattices. Since the structure of the gradient nanoparticle lattice can be continuously changed in its gradient direction, the gradient nanoparticle lattice provides more structural variables than the uniform nanoparticle lattice, such as the numerical density gradient of the nanoparticles formed along the gradient direction or The size gradient of the nanoparticles. This is of great value in the study of the nature and application of nanoparticle lattice structures. For example, gradient nanoparticle lattices have greater latitude and response range as sensors; for gradient precious metal nanoparticle lattices, different assembly structures along the gradient direction can broadly control the plasmon of localized regions of nanoparticle lattices.
  • the meta-resonance frequency has important application value in the fields of plasmon-enhanced spectroscopy and photovoltaic cells.
  • the gradient nanoparticle lattice has more than the traditional uniform nanoparticle lattice. Higher efficiency and sensitivity.
  • the controllable preparation of gradient nanoparticle lattices has not been effectively solved.
  • some researches have been carried out on the preparation of gradient nanoparticle lattices at home and abroad, for example, the adsorption of colloidal nanoparticles by surface organic grafting method to prepare gradient colloidal nanoparticle lattices on the scale of several millimeters to several centimeters (RR Bhat, J. Genzer ,
  • This method can be applied to the common gas phase preparation process of nano materials and devices, and has the characteristics of low cost, simple process, high efficiency, and easy scale.
  • the technical solution of the present invention is: a method for preparing a micro-number density or size-graded metal nanoparticle dot matrix, characterized in that the preparation steps are as follows:
  • the equivalent deposition rate is 0.1 nm/s; the beam baffle (3) is opened to beam-deposit the substrate and the substrate holder (6) is rotated to uniformly reduce the angle between the substrate surface and the nanoparticle beam or Gradually reduce to ⁇ 2 and close the beam baffle (3), that is, a continuous gradient nanoparticle lattice or a step gradient gradient nanoparticle lattice with a span of L at the edge of the mask, and deposition of different regions of the gradient nanoparticle lattice
  • the mass is controlled by the rotational speed or rotational step of the substrate holder (6); the gradient nanoparticle lattice prepared on the substrate coated with the polymer film has a number density gradient characteristic; the substrate coated with the amorphous carbon film
  • the gradient nanoparticle lattice prepared above has a size gradient feature.
  • the high polymer film described in the step (a) is preferably a prismatic film or a PMMA film, more preferably a prismatic film (polyvinyl formal).
  • Fanghua membrane has good stability and is easy to prepare ultra-thin film.
  • the present invention utilizes a mask of height h to decorate the substrate and rotate it and deposit it uniformly or stepwise in a beam of collimated collimated nanoparticles, by controlling the angle between the surface of the substrate and the beam of nanoparticles to be controlled.
  • Deposition quality of different regions of the substrate to construct micro-gradient nanoparticle lattices, through high polymer film or amorphous carbon film The surface of the modified substrate controls the migration and assembly of the nanoparticles on the surface of the substrate to achieve the regulation of the gradient characteristics of the gradient nanoparticle lattice (ie, the number density or average size of the nanoparticles).
  • the method provides a high-efficiency, low-cost method for preparing micro-gradient nanoparticle lattices, and achieves independent control of gradient characteristics (nanoparticle number density and average size) through modification of the substrate surface, and is easy to implement. And build micro-nano devices.
  • the method works by changing a substrate having a height of several micrometers to several hundreds of micrometers on a modified substrate and rotating the substrate holder in a stream of nanoparticles to change the surface of the substrate and the beam of nanoparticles.
  • the angle between the angles of the shadows formed on the surface of the substrate by the mask is used to construct a gradient nanoparticle lattice.
  • FIG 2 Paste the mask onto the substrate (optional polymer film or amorphous carbon film can be used to coat the surface of the substrate to regulate the migration of nanoparticles on the substrate surface) and placed to collimate
  • the surface of the substrate is at an angle to the beam of the nanoparticle; the mask along the direction of the beam of the nanoparticle has a certain shaded area on the surface of the substrate and does not deposit nanoparticles.
  • the shadow area of the mask changes on the substrate, forming a gradient in the shadow span region.
  • Deposition quality for example, when the angle between the surface of the substrate and the beam of nanoparticles is (Fig. 2(c)), c in the shadow of the mask. The region will not deposit nanoparticles, and the deposition quality in the ⁇ and distal regions is ⁇ ! ⁇ , where V represents the deposition rate of the nanoparticle beam, ⁇ represents the deposition time; when the substrate surface and nanoparticles The angle of the beam is time, c.
  • DM x(i+1) DM xi +v-At sin( ⁇ - ⁇ ) (1)
  • xi hl tan( ⁇ - ⁇ ) -hi tan ⁇ ⁇ (2)
  • a periodic gradient nanoparticle lattice can be prepared using a periodic mask. As shown in Fig. 2(d), each gradient nanoparticle lattice in a periodic gradient nanoparticle lattice has a highly uniform gradient characteristic. Therefore, the spatial gradient distribution of deposition quality generated by the method of mask and dynamic nanoparticle beam deposition in this scheme is universal, that is, the directional nanoparticle beam can be used for any material.
  • a mass thickness gradient film is prepared by the present scheme.
  • the polymer film can effectively bind the nanoparticles deposited on the surface thereof, so that the metal nanoparticles in the lattice remain isolated from each other, rarely occurring Migration, collision and growth, the prepared gradient metal nanoparticle lattice has a particle number density gradient characteristic; when the substrate is coated with an amorphous carbon film, the metal nanoparticles deposited on the surface of the substrate easily migrate on the surface and Collision growth occurs, so in the region where the deposition quality is large, the probability of collision growth between the nanoparticles is large, and the nanoparticles after the collision growth have a large size, and thus the gradient nanoparticle lattice obtained by the preparation has a size gradient characteristic.
  • the two-dimensional gradient metal nanoparticle lattice can be prepared by rotating the mask at a certain angle (between 5 and 90 degrees) and performing gradient deposition again.
  • the invention provides a method for preparing a micro-number density or size-graded metal nanoparticle lattice: the substrate is decorated with a mask and rotated and deposited in a collimated nanoparticle beam at a constant speed or stepwise, by changing the substrate
  • the angle between the surface and the metal nanoparticle beam is controlled to control the deposition quality in different regions of the substrate to construct a micro-gradient metal nanoparticle lattice, and the surface of the substrate is modified by a high polymer film or an amorphous carbon film to modulate the metal nanoparticles in the lining.
  • the migration and assembly of the bottom surface enables the regulation of gradient nanoparticle lattice gradient features (ie, the number density or average size of the nanoparticles).
  • the prepared gradient nanoparticle lattice can precisely adjust the gradient characteristics and gradient span, and it is easy to construct a micro-nano device. Therefore, the present invention provides a general method for preparing a gradient nanoparticle lattice with high efficiency, low cost and easy scale, and fills the gap that the current micro-gradient nanoparticle lattice is difficult to control and is technically and modern device fabrication process. Has good compatibility. Fourth, the description of the drawings
  • Figure 1 A device for producing and depositing a beam of nanoparticles for carrying out the preparation method of the present invention.
  • Figure 2 Schematic diagram of the principle of deposition preparation of a gradient nanoparticle array: (a) collimated nanoparticle beam and substrate with mask, (b) rotating substrate to obtain gradient deposition quality, (c) substrate surface and nano The deposition area of the particle beam at different angles, (d) The periodic gradient nanoparticle array is prepared using a periodic mask.
  • Figure 3 Optical microscopy image of a continuous gradient nanoparticle lattice with a gradient span of 25 ⁇ m.
  • Figure 4 (a) The relationship between the number density, average size and coverage of nanoparticles in a gradient silver nanoparticle lattice prepared on a coated Chinese film substrate, (c) - (h) in turn (a TEM structure of silver nanoparticle lattices with corresponding coverage; (b) Number density, average size and coverage of nanoparticle lattices in gradient silver nanoparticle lattices prepared on amorphous carbon film substrates coated with The relationship, (i) - (n) is the transmission electron microscopy structure of the corresponding coverage silver nanoparticle lattice in (b).
  • Figure 5 Optical microscopy of a lattice of stepped gradient silver nanoparticles prepared on (a) a substrate coated with a bi-membrane film and a substrate coated with an amorphous carbon film, respectively.
  • Figure 6 (a) Transmission electron microscopy structure of each strip in a stepped gradient silver nanoparticle lattice (Fig. 5 (a)) prepared on a coated ceramic substrate; (b) No coating A transmission electron microscope structure diagram of each strip in a stepped gradient silver nanoparticle lattice (Fig. 5(b)) prepared on a shaped carbon film substrate.
  • Figure 7 Optical microscopy of a two-dimensional stepped gradient silver nanoparticle lattice with an angle of 70° prepared on a coated Chinese film substrate.
  • Figure 8 (a) Optical micrograph of a continuous gradient silver nanoparticle lattice, (b) Average intensity curve of the 610 wavenumber Raman peak of the rhodamine 6G molecule corresponding to the position in the gradient silver nanoparticle lattice, (c) Rhodamine The spatial distribution of the average intensity of the 6G molecule 610 wavenumber Raman peak in the rectangular frame region in (a), and (d) the structural scale of the gradient silver nanoparticle lattice. V. Specific implementation methods
  • the basic flow of the method is illustrated by taking various gradient metal nanoparticle arrays as an example.
  • the metal target is, for example, gold, silver, copper, chromium, or the like, and different metal targets have different sputtering powers, and a silver target is used here.
  • the thickness of the prismatic film described in the preparation step (1) is 8-15 nm ; and the thickness of the amorphous carbon film is 5-8 nm ;
  • the mask height is 10 ⁇ m 1 1 100 ⁇ ;
  • the substrate is an arbitrary flat non-metal substrate such as a quartz glass plate or a silicon wafer.
  • the divergence angle of the collimated nanoparticle beam described in the preparation step (2) of the invention is less than 5°.
  • the vacuum deposition degree of the high vacuum deposition chamber 11 described in the preparation step (3) is 10 - 4 Pa 10 - 5 P a is filled into the condensation chamber 9 with an inert gas of 90 200 Pa; the metal nanoparticle beam in the nanometer
  • the particles have an average diameter of 8 to 20 nm, and their size is controlled by changing the distance between the atomizer 1 and the aerodynamic nozzle 2, or by changing the gas pressure of the inert gas charged into the condensation chamber 9.
  • step (4) in the angle between the substrate surface and the nano-particle beam 61 is 60 ° -90 °; angle ⁇ of the surface of the substrate and the nano-particle beam 2 is O ez Si;
  • the gradient span L is determined by h 6i and ⁇ 2 , 1 ⁇ ⁇ 380 ⁇
  • the beam baffle 3 is opened to beam-deposit the substrate and the substrate holder 6 is rotated at an angular velocity of 0.2 ° / s to make the substrate surface
  • the beam baffle 3 is closed after the angle formed by the beam of nanoparticles is reduced to 30°;
  • the substrate holder is heated and maintained at 200 ° C to open the beam baffle 3
  • the substrate is subjected to beam deposition and the substrate holder 6 is rotated at an angular velocity of 0.05 s to reduce the angle between the substrate surface and the nanoparticle beam to a uniform angle of 30°, and then the beam baffle 3 is closed; the span at the edge of the mask is formed.
  • FIG. 3 A gradient silver nanoparticle dot matrix of 25 ⁇ ; an optical microscope photograph is shown in Fig. 3.
  • Figure 4 shows the relationship between the gradient silver nanoparticle lattice structure and the nanoparticle coverage of two different gradient features prepared.
  • the average size of the silver nanoparticles remains substantially unchanged at 10 nm (the dot in Fig. 4 (a)).
  • Silver nanoparticles The degree of monotony increases (Fig. 4 (a) the Chinese point), so the gradient nanoparticle lattice has a number density gradient feature; on the substrate covering the amorphous carbon film, as the coverage increases (Fig.
  • Stepped gradient silver nanoparticle array with several density gradient features or size gradient features with several density gradient features or size gradient features
  • the beam baffle 3 is opened and the substrate is deposited for 30 seconds, then the beam baffle 3 is closed, and the substrate holder 6 is rotated to make the substrate surface and silver.
  • the angle of the beam of the nanometer beam is reduced by 6° and the beam baffle 3 is opened for 30 s.
  • the beam baffle is closed again and the substrate holder 6 is rotated to reduce the angle between the substrate surface and the nanoparticle beam by 6°, and then deposit again. After 7 cycles, the final surface of the substrate and the beam of the nanoparticle are at an angle of 28°, and 8 lattices of stepped gradient nanoparticles of different deposition qualities are formed on the substrate, as shown in Fig.
  • a substrate coated with an amorphous carbon film A substrate coated with an amorphous carbon film, the substrate holder is heated and maintained at 200 ° C, the beam baffle 3 is opened, the beam baffle 3 is closed after deposition for 60 s on the substrate, and the substrate holder 6 is rotated to make the substrate surface and the silver nanoparticle bundle
  • the flow angle is reduced by 6° and the beam baffle 3 is opened for 60 s, the beam baffle is closed again and the substrate holder 6 is rotated.
  • the angle between the substrate surface and the nanoparticle beam is reduced by 6° and deposited again, and 7 cycles are sequentially performed.
  • the final surface of the substrate and the nanobeam beam are at an angle of 28°, and 8 different deposition qualities are formed on the substrate.
  • a stepped gradient nanoparticle lattice as shown in Fig. 5(b); a stepped gradient nanoparticle lattice prepared on a substrate coated with a diurnal film has a number density gradient characteristic, and the structure of each strip is as Figure 6 (a); painted The stepped gradient nanoparticle lattice prepared on the amorphous carbon film substrate has a size gradient characteristic, and the structure of each strip is as shown in Fig. 6(b).
  • the beam baffle 3 is opened to form a beam deposition on the substrate for 30 seconds, and then the beam baffle 3 is closed, and the substrate holder 6 is rotated to reduce the angle between the substrate surface and the nanoparticle beam.
  • the beam baffle 3 6° and open the beam baffle 3 for 30s, close the beam baffle again and rotate the substrate holder 6 to reduce the angle between the substrate surface and the nanoparticle beam by 6°, and then re-deposit, and then perform 4 cycles, the final substrate.
  • the angle between the surface and the beam of the nanoparticle is 36°, and five lattices of stepped gradient silver nanoparticles with different deposition qualities are formed on the substrate; the substrate is taken out and the mask is removed by 70° and pasted to the original place, repeating Steps (2) and (3), closing the beam baffle, rotating the connecting rod 8 of the substrate holder 6, so that the surface of the substrate and the silver nanoparticle beam are at an angle of 60°, adjusting the input power of the sputtering power source to control the silver nanometer.
  • the equivalent deposition rate of the particle beam is 0.1 nm/s; the beam baffle 3 is opened to beam the substrate After the flow deposition for 30 s, the beam baffle is closed, the substrate holder 6 is rotated to reduce the angle between the substrate surface and the silver nanoparticle beam by 6°, and the beam baffle 3 is opened for deposition for 30 s, and the beam baffle is closed again and the substrate holder is rotated. 6 The angle between the surface of the substrate and the beam of silver nanoparticles is reduced by 6°, and then deposited, and three cycles are sequentially performed. The final surface of the substrate and the beam of the nanoparticle are at an angle of 42°, and the other side of the substrate is formed into four.
  • a stepped gradient silver nanoparticle lattice with different deposition qualities that is, a two-dimensional stepped gradient silver nanoparticle lattice with an angle of 70° is obtained, as shown in Fig. 7.
  • the continuous gradient silver nanoparticle lattice is used to detect the optimal assembly structure to achieve the maximum Raman enhancement.
  • Figure 8 shows the optimal Raman substrate structure using the prepared continuous gradient silver nanoparticle dot matrix with several density gradient features. Applications. By uniformly adsorbing Rhodamine 6G molecules onto the gradient silver nanoparticle lattice, the average intensity of the Raman peak of Rhodamine 6G 610 wavenumber is selected and measured by the dotted rectangular frame area shown in Fig. 8(a). c) The spatial distribution of the Raman intensity shown (light color indicates high intensity, dark color indicates low intensity), and the intensity curve shown by white line in Fig. 8(c) is shown in Fig. 8(b), at 9.
  • the maximum value corresponds to the optimal Raman-enhanced optimal silver nanoparticle structure.
  • the "structural ruler" of the gradient silver nanoparticle lattice as shown in Fig. 8(d) (short line indicates the relative content of the neighboring silver nanoparticle pairs with a pitch smaller than the average radius of the silver nanoparticles, and the black dot indicates the gradient nanoparticle lattice
  • the localized plasmon resonance wavelength of the region can quickly obtain the structural characteristics of the silver nanoparticle lattice corresponding to the maximum Raman enhancement of the Rhodamine 6G molecule.

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Description

说明书 制备微观数密度或尺寸梯度金属纳米粒子点阵的方法 一、 技术领域
本发明涉及纳米材料与纳米器件， 微纳加工， 自组装， 生物 /化学传感器等 技术领域， 具体地说是涉及微观梯度纳米粒子点阵的可控制备。
二、 背景技术
梯度纳米粒子点阵比传统的均一纳米粒子点阵具有额外的自由度。由于梯度 纳米粒子点阵的结构在其梯度方向上可连续变化，因而梯度纳米粒子点阵比均一 纳米粒子点阵提供了更多的结构变量，例如沿着梯度方向形成纳米粒子的数密度 梯度或者纳米粒子的尺寸梯度。这在研究和纳米粒子点阵结构关联的性质和应用 上具有重要的价值。例如，梯度纳米粒子点阵作为传感器具有更大的宽容度和响 应范围；对于梯度贵金属纳米粒子点阵，沿着梯度方向的不同组装结构可宽范围 调控纳米粒子点阵局域区域的等离激元共振频率，在等离激元增强光谱以及光伏 电池等领域有重要的应用价值； 另外， 在质量输运、 存储、 医学检测与诊断上， 梯度纳米粒子点阵比传统均一纳米粒子点阵具有更高的效率和灵敏度。然而，梯 度纳米粒子点阵的可控制备一直没有得到有效地解决。虽然国内外在梯度纳米粒 子点阵的制备上开展了一定的研究，例如通过表面有机物嫁接的方法吸附胶体纳 米粒子制备数毫米至数厘米尺度的梯度胶体纳米粒子点阵（R. R. Bhat, J. Genzer,
B. N. Chaney, H. W. Sugg, A. Liebm纖- Vinson, Nanotechnology, 14， 1145 (2003) )， 通过狭缝遮挡楔形衬底在原子气中沉积制备数毫米的厚度梯度薄膜（T. W. H. Oates , S. Noda, Appl ied Physics Letters , 94, 053106 ( 2009) )以及通过纳米 粒子在掩模阴影中的自由扩散制备亚微米尺寸的梯度纳米粒子点阵 （M. Han，
C. H. Xu, D. Zhu, L. Yang, J. L. Zhang, Y. P. Chen, K. Ding, F. Q. Song, G. H. Wang, Adv Mater, 19, 2979 ( 2007 ) ), 但是这类方法难以精确控制纳米粒子的数密度， 梯度跨度也只能在宏观尺寸或者在亚微米尺寸，在微米到数百微米范围的微观尺 寸无法有效制备梯度纳米粒子点阵结构， 因而难以构建微纳器件，很大程度限制 了梯度纳米粒子点阵的应用； 另一方面， 电子束刻蚀和离子束刻蚀理论上也具备 制备梯度纳米粒子点阵的能力，但是其成本高、效率低，尤其在制备直径小于 30nm 的纳米粒子点阵上代价更加昂贵，难以满足工业要求。在微观梯度纳米粒子点阵 的可控制备上， 当前仍然缺乏有效的制备手段，尤其对于微观梯度纳米粒子点阵 梯度特征 （纳米粒子点阵的颗粒数密度或平均尺寸） 的调控， 当前仍然是空白。 总之， 对于梯度特征（颗粒数密度或颗粒平均尺寸）可独立调控的微观梯度纳米 粒子点阵的制备， 目前尚未有高效低成本的通用制备方法。 三、 发明内容
1.发明目的
本发明的目的在于提供一种可实现颗粒数密度或颗粒平均尺寸独立调控的 微观梯度金属纳米粒子点阵的制备方法。此方法可通用于常见的纳米材料和器件 的气相制备工艺流程中， 具有低成本、 工艺简单、 高效率、 易于规模化等特点。
2.技术方案
本发明的技术方案是：一种制备微观数密度或尺寸梯度金属纳米粒子点阵的 方法， 其特征在于制备步骤如下：
(a) 在衬底上涂覆一层均匀的高聚物膜或无定形碳膜， 把高度为 h的掩模粘贴 到衬底 （7) 表面， 然后把带有掩模的衬底固定到可旋转衬底座 （6) 上；
(b)将衬底座 （6)安装到纳米粒子束流沉积系统的高真空沉积室 （11) 中， 使 得衬底座 （6) 上的衬底 （7) 处于准直纳米粒子束流 （5) 的中心；
(c) 利用抽气系统罗兹泵 （12) 和分子泵 （13) 对沉积室 （11) 抽真空， 并从 惰性气体入口 （14) 向气相聚集法团簇束流源的冷凝室 （9) 内充入氩气， 采用 气相聚集法团簇束流源 （10) 中的原子化器 （1) 产生高密度金属靶材原子气， 靶材原子气在冷凝室 （9) 中的惰性气体中生长成为金属纳米粒子， 金属纳米粒 子随惰性气体通过喷嘴 （2) 等熵膨胀形成金属纳米粒子束流 （5)， 金属纳米粒 子束流经过准直器 （4) 进入高真空沉积室 （11) 内， 形成高度定向的金属纳米 粒子束流 （5);
(d)旋转连真空沉积室 （11) 内衬底座（6) 的连接杆（8)， 使衬底表面与 纳米粒子束流成夹角 调节溅射电源的输入功率控制金属纳米粒子束流的等效 沉积速率为 0.1 nm/s;打开束流挡板（3)对衬底进行束流沉积并旋转衬底座（6) 使衬底表面与纳米粒子束流所成的夹角匀速减小或逐步减小到 θ2后关闭束流挡 板 （3)， 即在掩模边缘构成跨度为 L 的连续梯度纳米粒子点阵或阶梯状梯度纳 米粒子点阵， 梯度纳米粒子点阵不同区域的沉积质量由衬底座 （6) 的转动速度 或转动步长控制;在涂覆高聚物膜的衬底上制备的梯度纳米粒子点阵具有数密度 梯度特征;在涂覆无定形碳膜的衬底上制备的梯度纳米粒子点阵具有尺寸梯度特 征。
步骤（a) 中所述的高聚物膜优选为方华膜或 PMMA膜， 更优选为方华膜（聚 乙烯醇縮甲醛）。 方华膜稳定性好， 容易制备超薄的薄膜。
本发明是利用高度为 h 的掩模装饰衬底并使其在定向准直的纳米粒子束流 中匀速或逐步旋转并沉积，通过改变衬底表面与纳米粒子束流之间的夹角控制在 衬底不同区域的沉积质量构建微观梯度纳米粒子点阵，通过高聚物膜或无定形碳 膜 修饰衬底表面调控纳米粒子在衬底表面的徙动和组装，实现对梯度纳米粒子点阵 的梯度特征（即纳米粒子的数密度或平均尺寸）的调控。 因此， 该法提供了一种 高效、低成本制备微观梯度纳米粒子点阵的通用方法，并通过衬底表面的修饰实 现对梯度特征（纳米粒子数密度和平均尺寸）的独立调控， 易于实现功能化并构 建微纳器件。
本方法的工作原理是：通过在修饰过的衬底上粘贴高度为数微米至数百微米 的掩模并在纳米粒子束流中匀速或逐步转动衬底座改变衬底表面与纳米粒子束 流之间的夹角，利用掩模在衬底表面构成的阴影区域随夹角的变化构建梯度纳米 粒子点阵。通过在衬底上涂覆超薄高聚物膜或者无定形碳膜调控纳米粒子在衬底 表面的徙动从而实现梯度纳米粒子点阵梯度特征的调控，即调控纳米粒子的数密 度和平均尺寸。 具体原理如图 2所示： 把掩模粘贴到衬底上（可选用高聚物膜或 无定形碳膜涂覆衬底表面以调控纳米粒子在衬底表面的徙动）并放置到准直纳米 粒子束流中， 如图 2 (a) 所示， 使衬底表面与纳米粒子束流成一夹角； 沿纳米 粒子束流方向掩模在衬底表面有一定的阴影区域不会沉积纳米粒子， 如图 2 (b) 所示， 随着衬底的转动 （即改变衬底表面与纳米粒子束流的夹角）， 掩模在衬底 上的阴影区域发生改变， 在阴影跨度区域形成梯度沉积质量； 例如， 当衬底表面 与纳米粒子束流的夹角为 时（图 2(c) )，处于掩模阴影中的 c。区域将不会沉积 纳米粒子， 而处于^及远端区域具有沉积质量 ^^^二 ^!!^， 其中 V表示纳米 粒子束流的沉积速率， ^表示沉积时间； 当衬底表面与纳米粒子束流的夹角为 时， c。和 ^区域不会沉积纳米粒子， 处于 及远端区域具有沉积质量 DMx2 =vt2 sin θ2+ DM xl 依次类推， 当衬底表面与纳米粒子束流的夹角为 时， 处于 C;的区域具有沉积质量 ^k^ = ^ 8¾1 + ¾1^(;— D。 因此， 沉积制备的梯度 纳米粒子点阵位置对应的沉积质量关系为
DMx(i+1) = DMxi +v-At sin(^ -ΪΑΘ) (1) xi = hl tan(^ - ίΑΘ) -hi tan θγ (2) 其中 A为掩模的高度， 为衬底座转动的步进角度， = 0,1,2,3···并且 θγ - ΪΑΘ≡θ2 >{), 梯度跨度 L =
Figure imgf000005_0001
-Λ/tan^。 当采用逐步转动， 制备的梯度 纳米粒子点阵呈阶梯状条带， 每个条带中的沉积质量及条带宽度由上述 （1) 和 (2) 式决定； 当采用连续匀速转动， 则制备得到连续梯度纳米粒子点阵， 纳米 粒子点阵中不同位置对应的沉积质量以及梯度纳米粒子点阵的梯度跨度同样由 上述（1)和 （2)式决定。 采用周期性掩模可制备周期性梯度纳米粒子点阵， 如 图 2 (d) 所示， 周期性梯度纳米粒子点阵中每个梯度纳米粒子点阵都具有高度 一致的梯度特征。因而本方案中通过掩模和动态纳米粒子束流沉积的方法产生沉 积质量的空间梯度分布是普适性的，即对于任意材料的定向纳米粒子束流都可以 通过本方案制备质量厚度梯度薄膜。对于金属纳米粒子束流， 当采用高聚物膜涂 覆衬底时， 高聚物膜能够有效束缚沉积到其表面的纳米粒子， 因而点阵中金属纳 米粒子相互之间保持孤立， 很少发生徙动、碰撞和生长， 制备得到的梯度金属纳 米粒子点阵具有颗粒数密度梯度特征； 当采用无定形碳膜涂覆衬底时， 沉积到衬 底表面的金属纳米粒子容易在表面徙动并发生碰撞生长，因而在沉积质量较大的 区域， 纳米粒子之间碰撞生长的几率大， 碰撞生长后的纳米粒子具有较大尺寸， 因而制备获得的梯度纳米粒子点阵具有尺寸梯度特征。另外， 在制备获得的一维 梯度纳米粒子点阵的基础上， 旋转掩模一定角度 （5-90度之间）， 再次进行梯度 沉积， 可制备二维梯度金属纳米粒子点阵。
3.有益效果
本发明提出了一种制备微观数密度或尺寸梯度金属纳米粒子点阵的方法：利 用掩模装饰衬底并使其在准直的纳米粒子束流中匀速或逐步旋转并沉积，通过改 变衬底表面与金属纳米粒子束流之间的夹角控制在衬底不同区域的沉积质量构 建微观梯度金属纳米粒子点阵，通过高聚物膜或无定形碳膜修饰衬底表面调控金 属纳米粒子在衬底表面的徙动和组装， 实现对梯度纳米粒子点阵梯度特征（即纳 米粒子的数密度或平均尺寸）的调控。所制备的梯度纳米粒子点阵可精确调控梯 度特征和梯度跨度，易于构建微纳器件。因此本发明提供了一种高效率、低成本、 易于规模化制备梯度纳米粒子点阵的通用方法，填补了当前微观梯度纳米粒子点 阵难以可控制备的空白并且在技术上与现代器件制作工艺具有很好的兼容性。 四、 附图说明
图 1 : 用于实现本发明制备方法的纳米粒子束流的产生与沉积装置。
附图标记：
1-原子化器 (磁控溅射、 高温蒸发等）；
2-气体动力学喷嘴；
3-可上下移动的纳米粒子束流挡板；
4-准直器；
5-金属纳米粒子束流；
6-可旋转衬底座；
7-粘贴掩模的衬底；
8-衬底座连接杆；
9-生长金属纳米粒子的冷凝室；
10-气相聚集法团簇束流源； 11-高真空沉积室；
12-罗兹泵；
13-分子泵；
14-惰性气体入口。
图 2: 沉积制备梯度纳米粒子阵列的原理示意图： （a)准直纳米粒子束流与带有 掩模的衬底， （b )旋转衬底获得梯度沉积质量， （c )衬底表面与纳米粒子束流不 同夹角时的沉积区域， （d) 利用周期掩模制备周期性梯度纳米粒子阵列。
图 3: 梯度跨度为 25μηι的连续梯度纳米粒子点阵的光学显微镜像。
图 4: ( a)在涂覆方华膜衬底上制备的梯度银纳米粒子点阵中纳米粒子点阵数密 度、 平均尺寸与覆盖率的关系， （c ) - ( h) 依次为 （a) 中相应覆盖率银纳米粒 子点阵的透射电镜结构图； （b )在涂覆无定形碳膜衬底上制备的梯度银纳米粒子 点阵中纳米粒子点阵数密度、 平均尺寸与覆盖率的关系， （i ) - ( n)依次为 （b ) 中相应覆盖率银纳米粒子点阵的透射电镜结构图。
图 5: 分别在涂覆方华膜的衬底上 （a)和涂覆无定形碳膜的衬底上 （b )制备的 阶梯状梯度银纳米粒子点阵的光学显微像。
图 6: ( a) 在涂覆方华膜衬底上制备的阶梯状梯度银纳米粒子点阵 （图 5 ( a) ) 中每个条带的透射电镜结构图； （b )在涂覆无定形碳膜衬底上制备的阶梯状梯度 银纳米粒子点阵 （图 5 (b ) ) 中每个条带的透射电镜结构图。
图 7:在涂覆方华膜衬底上制备的夹角 70° 的二维阶梯状梯度银纳米粒子点阵的 光学显微像。
图 8: ( a)连续梯度银纳米粒子点阵的光学显微像， （b )梯度银纳米粒子点阵中 位置对应的罗丹明 6G分子 610波数拉曼峰平均强度曲线， （c ) 罗丹明 6G分子 610 波数拉曼峰在 （a) 中矩形框区域平均强度的空间分布， （d) 梯度银纳米粒 子点阵的结构标尺。 五、 具体实施方式
以下以制备各种梯度金属纳米粒子阵列为例， 说明本方法的基本流程。所述 金属靶材例如为金、 银、 铜、 铬等， 不同的金属靶材所对应的溅射功率不同， 此 处选用银靶。
制备微观数密度或尺寸梯度金属纳米粒子点阵的方法， 发明制备步骤 （1 ) 中所述的方华膜的厚度为 8-15nm; 所述的无定形碳膜的厚度为 5-8nm; 所述的掩 模高度为 10μηι 1ι 100μιη; 所述的衬底为任意平整非金属基片， 如石英玻璃片 或者硅片等。
发明制备步骤 （2) 中所述的准直纳米粒子束流的发散角小于 5° 。 发明制备步骤 （3 ) 中所述的高真空沉积室 11 的真空度为 10— 4Pa 10— 5Pa 向冷凝室 9充入 90 200Pa的惰性气体；所述的金属纳米粒子束流中纳米粒子的 平均直径为 8-20nm， 其尺寸大小通过改变原子化器 1与气体动力学喷嘴 2之间 的距离， 或改变充入冷凝室 9内惰性气体的气压来控制。
发明步骤 （4) 中所述的衬底表面与纳米粒子束流的夹角 61为60°-90°； 所述 的衬底表面与纳米粒子束流的夹角 θ2为 O ez Si； 所述的梯度跨度 L受 h 6i 和 θ2决定， 1μηι<ί <380μιη 实施例 1
具有数密度梯度特征或尺寸梯度特征的连续梯度银纳米粒子阵列
( 1 )在石英玻璃片上涂覆一层均匀的方华膜 （膜厚为 8-15nm) 并在另一片 石英玻璃片上涂覆一层均匀的无定形碳膜（膜厚 5-8nm)，把高度为 25μηι的掩模 分别粘贴到涂覆方华膜和无定形碳膜的石英玻璃片表面，然后把带有掩模的石英 玻璃片四角涂抹 704真空硅橡胶固定到可旋转衬底座 6上；
( 2 ) 将带有衬底的衬底座 6通过螺丝固定安装到纳米粒子束流沉积系统的 高真空沉积室 11中， 使得衬底座 7上的衬底处于银纳米粒子束流 5的中心；
( 3 ) 利用抽气系统罗兹泵 12和分子泵 13对沉积室 11抽真空， 真空度为 5 X 10— 5Pa，从惰性气体入口 14向气相聚集法团簇束流源的冷凝室 9内充入 lOOPa 氩气， 在此气压下气相聚集法团簇束流源 10中的原子化器 1通过磁控溅射产生 高密度银原子气，银原子气在冷凝室 9中的惰性气体中生长成为银纳米粒子， 银 纳米粒子随惰性气体通过 2mm直径的喷嘴 2发生等熵膨胀，形成银纳米粒子束流， 银纳米粒子束流经过 2 直径的准直器 4进入真空度为 5 X 10— 5Pa的高真空沉积 室 11内， 形成高度定向的银纳米粒子束流 5;
( 4)关闭束流挡板 3， 旋转衬底座 6的连接杆 8， 使衬底表面与纳米粒子束流成 60° 夹角， 调节溅射电源的输入功率控制银纳米粒子束流的等效沉积速率为 0. 1 nm/s ; 对于涂覆方华膜的衬底， 打开束流挡板 3对衬底进行束流沉积并以 0.2°/s 的角速度匀速旋转衬底座 6 使衬底表面与纳米粒子束流所成的夹角匀速减小到 30° 后关闭束流挡板 3; 对于涂覆无定形碳膜的衬底， 衬底座加热并维持 200 °C 打开束流挡板 3对衬底进行束流沉积并以 0.05 s的角速度旋转衬底座 6使衬底 表面与纳米粒子束流所成的夹角匀速减小到 30° 后关闭束流挡板 3; 在掩模边缘 构成跨度为 25μηι的梯度银纳米粒子点阵； 光学显微镜照片如图 3所示。 图 4所 示为制备的两种不同梯度特征的梯度银纳米粒子点阵结构与纳米粒子覆盖度之 间的关系。 在覆盖方华膜的衬底上， 随着覆盖度的增大 （图 4 ( c ) - ( h) ) 银纳 米粒子的平均尺寸基本维持 10nm不变 （图 4 ( a) 中圆点）， 而银纳米粒子数密 度成单调增加（图 4 ( a)中方点）， 因而梯度纳米粒子点阵具有数密度梯度特征； 在覆盖无定形碳膜的衬底上， 随着覆盖度的增大 （图 4 ( i ) - ( n) ) 银纳米粒子 的平均尺寸从 10nm单调增加至 28nm (图 4 (b ) 中圆点）， 而纳米粒子数密度没 有增加 （图 4 (b ) 中方点）， 因而梯度银纳米粒子点阵具有尺寸梯度特征。 实施例 2
具有数密度梯度特征或尺寸梯度特征的阶梯状梯度银纳米粒子阵列
( 1 )在石英玻璃片上涂覆一层均匀的方华膜 （膜厚为 8_15nm) 并在另一片 石英玻璃片上涂覆一层均匀的无定形碳膜（膜厚 5_8nm)，把高度为 35μηι的掩模 分别粘贴到涂覆方华膜和无定形碳膜的石英玻璃片表面，然后把带有掩模的石英 玻璃片四角涂抹 704真空硅橡胶固定到可旋转衬底座 6上；
( 2 ) 将带有衬底的衬底座 6通过螺丝固定安装到纳米粒子束流沉积系统的 高真空沉积室 11中， 使得衬底座 6上的衬底处于银纳米粒子束流 5的中心；
( 3 )利用抽气系统罗兹泵 12和分子泵 13对沉积室 11抽真空， 真空度为 5 X 10— 5Pa， 从惰性气体入口 14向气相聚集法团簇束流源的冷凝室 9内充入 150Pa 氩气， 在此气压下气相聚集法团簇束流源 10中的原子化器 1通过磁控溅射产生 高密度银原子气，银原子气在冷凝室 9中的惰性气体中生长成为银纳米粒子， 银 纳米粒子随惰性气体通过 2mm直径的喷嘴 2发生等熵膨胀，形成银纳米粒子束流， 银纳米粒子束流经过 2mm直径的准直器 4进入真空度为 5 X 10— 5Pa的高真空沉积 室 11内， 形成高度定向的银纳米粒子束流 5;
( 4)关闭束流挡板 3， 旋转衬底座 6的连接杆 8， 使衬底表面与银纳米粒子束流 成 70° 夹角， 调节溅射电源的输入功率控制银纳米粒子束流的等效沉积速率为 0. 1 nm/s ; 对于涂覆方华膜的衬底， 打开束流挡板 3对衬底沉积 30s后关闭束流 挡板 3， 旋转衬底座 6使衬底表面与银纳米粒子束流夹角减小 6° 并打开束流挡 板 3沉积 30s， 再次关闭束流挡板并旋转衬底座 6使衬底表面与纳米粒子束流夹 角减小 6° 再次沉积， 依次进行 7次循环， 最终衬底表面与纳米粒子束流夹角为 28° ， 在衬底上构成 8条不同沉积质量的阶梯状梯度纳米粒子点阵， 如图 5 ( a) 所示； 对于涂覆无定形碳膜的衬底， 衬底座加热并维持 200°C， 打开束流挡板 3 对衬底沉积 60s后关闭束流挡板 3， 旋转衬底座 6使衬底表面与银纳米粒子束流 夹角减小 6° 并打开束流挡板 3沉积 60s， 再次关闭束流挡板并旋转衬底座 6使 衬底表面与纳米粒子束流夹角减小 6° 再次沉积， 依次进行 7次循环， 最终衬底 表面与纳米粒子束流夹角为 28° ， 在衬底上构成 8条不同沉积质量的阶梯状梯 度纳米粒子点阵， 如图 5 (b ) 所示； 在涂覆方华膜的衬底上制备的阶梯状梯度 纳米粒子点阵具有数密度梯度特征， 其每个条带的结构如图 6 ( a) 所示； 在涂 覆无定形碳膜衬底上制备的阶梯状梯度纳米粒子点阵具有尺寸梯度特征， 其 每个条带的结构如图 6 (b ) 所示。 实施例 3
二维阶梯状梯度银纳米粒子阵列
( 1 ) 在石英玻璃片上涂覆一层均匀的方华膜 （膜厚为 8-15nm)， 把高度为 30μηι的掩模粘贴到涂覆方华膜的石英玻璃片表面， 然后把带有掩模的石英玻璃 片四角涂抹 704真空硅橡胶固定到可旋转衬底座 6上；
( 2 ) 将带有衬底的衬底座 6通过螺丝固定安装到纳米粒子束流沉积系统的 高真空沉积室 11中， 使得衬底座 6上的衬底处于银纳米粒子束流 5的中心；
( 3 ) 利用抽气系统罗兹泵 12和分子泵 13对沉积室 11抽真空， 真空度为 5 X 10— 5Pa，从惰性气体入口 14向气相聚集法团簇束流源的冷凝室 9内充入 120Pa 氩气， 在此气压下气相聚集法团簇束流源 10中的原子化器 1通过磁控溅射产生 高密度银原子气，银原子气在冷凝室 9中的惰性气体中生长成为银纳米粒子， 银 纳米粒子随惰性气体通过 2mm直径的喷嘴 2发生等熵膨胀，形成银纳米粒子束流， 银纳米粒子束流经过 2隱直径的准直器 4进入真空度为 5 X 10— 5Pa的高真空沉积 室 11内， 形成高度定向的银纳米粒子束流 5;
( 4)关闭束流挡板 3， 旋转衬底座 6的连接杆 8， 使衬底表面与银纳米粒子 束流成 60° 夹角， 调节溅射电源的输入功率控制银纳米粒子束流的等效沉积速 率为 0. 1 nm/s ; 打开束流挡板 3对衬底进行束流沉积 30s后关闭束流挡板 3， 旋 转衬底座 6使衬底表面与纳米粒子束流夹角减小 6° 并打开束流挡板 3沉积 30s， 再次关闭束流挡板并旋转衬底座 6使衬底表面与纳米粒子束流夹角减小 6° 再次 沉积， 依次进行 4次循环， 最终衬底表面与纳米粒子束流夹角为 36° ， 在衬底 上构成 5条不同沉积质量的阶梯状梯度银纳米粒子点阵；取出衬底并取下掩模旋 转 70° 后粘贴到原处， 重复步骤 （2 ) 和 （3)， 关闭束流挡板， 旋转衬底座 6的 连杆 8， 使衬底表面与银纳米粒子束流成 60° 夹角， 调节溅射电源的输入功率控 制银纳米粒子束流的等效沉积速率为 0. 1 nm/s ; 打开束流挡板 3对衬底进行束 流沉积 30s后关闭束流挡板，旋转衬底座 6使衬底表面与银纳米粒子束流夹角减 小 6° 并打开束流挡板 3沉积 30s， 再次关闭束流挡板并旋转衬底座 6使衬底表 面与银纳米粒子束流夹角减小 6° 继而沉积， 依次进行 3次循环， 最终衬底表面 与纳米粒子束流夹角为 42° ， 在衬底另外一方向上构成 4条不同沉积质量的阶 梯状梯度银纳米粒子点阵， 即获得夹角为 70° 的二维阶梯状梯度银纳米粒子点 阵， 如图 7所示。 六、 应用例
连续梯度银纳米粒子点阵用于探测最佳组装结构实现最大拉曼增强 图 8 所示的是利用制备的具有数密度梯度特征的连续梯度银纳米粒子点阵 探测最优拉曼衬底结构的应用实例。 通过把罗丹明 6G分子均匀地吸附到梯度银 纳米粒子点阵上， 选择如图 8 ( a) 所示的虚线矩形框区域对罗丹明 6G 610波数 的拉曼峰平均强度跟踪测量得到图 8 ( c ) 所示的拉曼强度空间分布图 （浅色表 示强度高， 暗色表示强度低）， 图 8 ( c ) 中白色直线所示的强度曲线如图 8 (b ) 所示， 在 9. 7μπι处成最大值， 对应最大拉曼增强的最优银纳米粒子结构。通过标 定梯度银纳米粒子点阵的 "结构尺"， 如图 8 ( d) 所示 （短线表示间距小于银纳 米粒子平均半径的近邻银纳米粒子对的相对含量，黑点表示梯度纳米粒子点阵该 区域的局域等离激元共振波长），可快速得到对应罗丹明 6G分子最大拉曼增强的 银纳米粒子点阵的结构特征。

Claims

权利要求书
1.一种制备微观数密度或尺寸梯度金属纳米粒子点阵的方法，其特征在于制备步 骤如下：
(a) 在衬底上涂覆一层均匀的高聚物膜或无定形碳膜， 把高度为 h的掩模粘贴 到衬底 （7) 表面， 然后把带有掩模的衬底固定到可旋转衬底座 （6) 上；
(b)将衬底座 （6)安装到纳米粒子束流沉积系统的高真空沉积室 （11) 中， 使 得衬底座 （6) 上的衬底 （7) 处于准直纳米粒子束流 （5) 的中心；
(c) 利用抽气系统罗兹泵 （12) 和分子泵 （13) 对沉积室 （11) 抽真空， 并从 惰性气体入口 （14) 向气相聚集法团簇束流源的冷凝室 （9) 内充入氩气， 通过 气相聚集法团簇束流源 （10) 中的原子化器 （1) 产生高密度金属靶材原子气， 靶材原子气在冷凝室 （9) 中的惰性气体中生长成为金属纳米粒子， 金属纳米粒 子随惰性气体通过喷嘴（2)等熵膨胀形成 金属纳米粒子束流（5)， 金属纳米粒 子束流经过准直器 （4) 进入高真空沉积室 （11) 内， 形成高度定向的金属纳米 粒子束流 （5);
(d) 旋转连接真空沉积室 （11) 内衬底座 （6) 的连接杆 （8)， 使衬底表面与纳 米粒子束流成夹角 调节溅射电源的输入功率控制金属纳米粒子束流的等效沉 积速率为 0.1 nm/s; 打开束流挡板 （3) 对衬底进行束流沉积并旋转衬底座 （6) 使衬底表面与纳米粒子束流所成的夹角匀速减小或逐步减小到 θ2后关闭束流挡 板（3)， 即在掩模边缘构成跨度为 L的连续梯度纳米粒子点阵或阶梯状梯度纳米 粒子点阵， 梯度纳米粒子点阵不同区域的沉积质量由衬底座 （6) 的转动速度或 转动步长控制；在涂覆高聚物膜的衬底上制备的梯度纳米粒子点阵具有数密度梯 度特征； 在涂覆无定形碳膜的衬底上制备的梯度纳米粒子点阵具有尺寸梯度特 征。
2. 根据权利要求 1所述的制备微观数密度或尺寸梯度金属纳米粒子点阵的方法， 其特征在于步骤 （a) 中所述的高聚物膜的厚度为 8-15nm; 所述的无定形碳膜的 厚度为 5-8nm; 所述的掩模高度为 10μηι 1 100μηι; 所述的衬底为任意平整非 金属材料的基片。
3. 根据权利要求 2所述的制备微观数密度或尺寸梯度金属纳米粒子点阵的方法， 其特征在于步骤 （a) 中所述的高聚物膜为方华膜或 PMMA膜。
4. 根据权利要求 3 所述的制备微观数密度或尺寸梯度金属纳米粒子点阵的方 法， 其特征在于步骤 （a) 中所述的高聚物膜为方华膜。
5. 根据权利要求 2所述的衬底为任意平整基片， 其中所述的任意平整基片选自 石英玻璃片或者硅片。
6. 根据权利要求 1所述的制备微观数密度或尺寸梯度金属纳米粒子点阵的方法， 其特征在于步骤（b ) 中所述的金属纳米粒子束流（5 )为定向纳米粒子束流并可 精确调节束流大小。
7. 根据权利要求 1 所述的制备微观数密度或尺寸梯度金属纳米粒子点阵的方 法，其特征在于步骤（c )中所述的高真空沉积室（11 )的真空度为 10— 4Pa〜10— 5pa; 所述的金属纳米粒子束流中纳米粒子的平均直径为 8_20nm，通过控制冷凝室（9) 中的气压调控。
8. 根据权利要求 1 所述的制备微观数密度或尺寸梯度金属纳米粒子点阵的方 法，其特征在于步骤（d)中所述的衬底表面与纳米粒子束流的夹角 61为60°-90°； 所述的衬底表面与纳米粒子束流的夹角 62为 0 Sz Si；所述的梯度跨度 L受 h、 Θ^ΒΘ2决定， l m<L <380μηι。
PCT/CN2010/078066 2010-10-25 2010-10-25 制备微观数密度或尺寸梯度金属纳米粒子点阵的方法 Ceased WO2012055086A1 (zh)

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CN1810629A (zh) * 2006-01-24 2006-08-02 南京大学 具有直径和数密度一维梯度的纳米粒子阵列的气相合成方法
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