WO2015176272A1 - 正负相移双金属波带片 - Google Patents

正负相移双金属波带片 Download PDF

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Publication number
WO2015176272A1
WO2015176272A1 PCT/CN2014/078122 CN2014078122W WO2015176272A1 WO 2015176272 A1 WO2015176272 A1 WO 2015176272A1 CN 2014078122 W CN2014078122 W CN 2014078122W WO 2015176272 A1 WO2015176272 A1 WO 2015176272A1
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Prior art keywords
zone plate
positive
negative phase
bimetallic
phase shift
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PCT/CN2014/078122
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English (en)
French (fr)
Inventor
吴自玉
陈健
高昆
刘刚
王志立
胡仁芳
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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Priority to US15/311,879 priority Critical patent/US10436722B2/en
Priority to PCT/CN2014/078122 priority patent/WO2015176272A1/zh
Publication of WO2015176272A1 publication Critical patent/WO2015176272A1/zh
Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
    • G01N23/06—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption
    • G01N23/083—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption the radiation being X-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005—Spin coating
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/42—Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect
    • G02B27/44—Grating systems; Zone plate systems
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—HANDLING OF PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
    • G21K1/06—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—HANDLING OF PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
    • G21K1/06—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators
    • G21K1/067—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators using surface reflection, e.g. grazing incidence mirrors, gratings
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—HANDLING OF PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K7/00—Gamma- or X-ray microscopes

Definitions

  • This invention relates to the field of X-ray microscopy, and more particularly to a positive and negative phase shifting double metal zone plate. Background technique
  • the zone plate is one of the most commonly used diffractive optics in the X-ray band and is often used to focus X-rays and to act as an objective for imaging systems.
  • the zone plate is essentially a circular diffractive optical element consisting of a concentric ring of light and dark phases with a linear increase in linear density (as shown in Figure 1).
  • ⁇ (n is the number of rings, ⁇ is the wavelength
  • the circular hole is continuously divided into individual ring bands, and the odd or even ring bands are covered to form a Fresnel zone plate.
  • the band forming the zone plate is called a half-band, and the optical path difference of any two adjacent half-bands reaching the focus is ⁇ /2. This means that the phase difference when the light waves passing through two adjacent half-wave bands reach the focus is ⁇ , and mutual weakening interference occurs at the focus. Therefore, the zone plate consists of a half-waveband between the transparent and the opaque phase to achieve the purpose of coherence enhancement.
  • the two most important parameters of the zone plate are the outermost ring width and the ring thickness.
  • the diffraction efficiency of the zone plate increases as the thickness of the ring increases.
  • an important factor limiting the development of zone plates is the aspect ratio. Due to processing techniques and other factors, there is a contradiction between the outermost ring width of the zone plate and the ring thickness. At this stage, the outermost loop width of the zone plate cannot be made smaller, or the high-resolution zone plate efficiency cannot be made very high. Therefore, the spatial resolution of the zone plate imaging system has a bottleneck (hard X-ray: 30 nm; water window: 10 nm).
  • a positive and negative phase shift bimetallic zone plate comprising:
  • the first metal material having a positive phase shift
  • a second metal material having a negative phase shift at a working energy point; the first metal material and the second metal material being alternately arranged such that the second metal material replaces a conventional zone plate A blank part of a cycle.
  • the positive and negative phase shift bimetallic zone plates are annular, and the first metal material and the second metal material form an alternating ring structure.
  • the first metallic material is often selected from the group consisting of nickel, gold, ruthenium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, and the like.
  • the second metal material is selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, ruthenium, osmium, tungsten, ruthenium, osmium, and the like.
  • the positive and negative phase shift bimetallic zone plate has the same diffraction thickness as the ordinary single metal phase zone plate, and the diffraction efficiency of the positive and negative phase shift bimetallic zone plate Higher than the diffraction efficiency of the conventional single metal phase zone plate.
  • the positive and negative phase shift bimetallic zone plate is a vanadium nickel bimetal novel zone plate.
  • the thickness of the positive and negative phase shift bimetallic zone plate is
  • the structure of the positive and negative phase shift bimetallic zone plate does not have a hollow portion, and this structure can avoid the problem that the ordinary zone plate may collapse.
  • the efficiency of the positive and negative phase shift bimetallic zone plate is directly related to the ring thickness, and within a certain range, the diffraction efficiency of the zone plate increases as the ring thickness increases.
  • the ring height cannot be too high temporarily and the diffraction efficiency is limited.
  • the working energy of the positive and negative phase shift bimetallic zone plate The amount is limited to different energy points depending on the zone of the zone plate. The reason is that the negative phase shift of different metals occurs in different narrow energy segments (several eV).
  • Another aspect of the present invention provides a method of preparing a positive and negative phase shift bimetallic zone plate, the method comprising the following steps:
  • the photoresist is applied by spin coating and then subjected to electron beam exposure to form a photoresist having a zone plate structure.
  • the etching in step d is performed by argon ion etching and various reactive ion etching.
  • the method further includes opening a window on the back side of the positive and negative phase shift bimetallic zone plate structure obtained in step e to obtain a positive and negative phase shift bimetallic zone plate.
  • Figure 1 is a schematic view showing the structure of a conventional zone plate
  • FIG. 2 is a schematic structural view of a positive-negative phase-shifted bimetallic wave strip
  • Fig. 3 is a graph showing the relationship between the primary diffraction efficiency and the material thickness of a common nickel zone plate and a vanadium-nickel double-metal zone plate when the energy is 511.9 eV;
  • Figure 4 is a graph showing the relationship between the first-order diffraction efficiency and the energy of a vanadium-nickel bimetal zone plate with a thickness of 140 nm.
  • the invention provides a novel phase wave band piece, which can achieve two effects: 1) can reduce the metal thickness required to reach the maximum first-order diffraction efficiency; 2) improve the wave band without increasing the ring height
  • the diffraction efficiency of the sheet is to replace the traditional single metal zone plate with two metal alternating structures. At the working energy point, the phase shift of one of the metals is positive. The other metal phase shift is negative. We call it "positive and negative phase shift bimetallic zone plate". Different from the traditional zone plate, we use another material to replace the blank part of the traditional zone plate. The selected alternative material requires a negative phase shift at the working energy point, so that the phase is reached.
  • the thickness of the material required to produce a phase difference of ⁇ in the adjacent ring band can be reduced, thereby reducing the difficulty in fabricating the zone plate.
  • the new zone plate structure is shown in Figure 2.
  • metals exhibit negative phase shifts at specific energies, which are referred to herein as working energy points.
  • Metals such as ⁇ (1217eV), ⁇ (1661eV), tungsten (1809eV), ⁇ (1883eV), and ⁇ (1960eV) all exhibit a negative phase shift near the corresponding energy.
  • these metals can be used to make positive and negative phase shift bimetallic zone plates that work at different energies.
  • the positive and negative phase-shifted bimetallic zone strips have lower metal thickness required for the first-order diffraction efficiency peak, and can maintain their peak efficiency equivalent to the single metal peak efficiency. . Therefore, we have achieved a high degree of diffraction efficiency while reducing the difficulty of making the zone plate. Moreover, at the same strip thickness (resolution better than 150 nm), positive and negative phase shift bimetallic strips are more efficient than ordinary strips. Therefore, the present invention can effectively improve the diffraction efficiency of the fine zone plate.
  • the commonly used nickel zone plate reaches a maximum first-order diffraction efficiency of about 22% at a thickness of about 250 nm, and the novel zone plate proposed by the present invention has a thickness of The maximum first order diffraction efficiency was 24% at 140 nm.
  • the thickness of the zone plate can be reduced to about 56%.
  • the nickel-phase phase-type zone plate which is well-made internationally for the water window can reach the outermost ring width of 13 nm and the ring height is 5 nm [Towards 10-nm soft X-ray zone plate fabrication] incubated at 511.9eV amount of 0, which is a theoretical value of the diffraction efficiency of 1.6% while the theoretical efficiency of the same width and thickness of the nickel vanadium new bimetallic zone plate can reach 4.3%, increased by nearly 170%.
  • Example The zone plate proposed by the present invention can be fabricated by using any metal capable of exhibiting a negative phase shift at a specific energy in combination with any other metal.
  • a new phase-type zone plate with vanadium and nickel as an example is taken as an example.
  • Metal vanadium exhibits a maximum negative phase shift at 511.9eV, and this energy is just around the usual “water window” energy, so we can use vanadium and nickel (the band metal commonly used in “water windows”). To produce positive and negative phase shift bimetallic zone plates at 511.9eV energy.
  • the first-order diffraction efficiency of the ordinary phase zone plate is [P/ifl ⁇ zone plates for x rays and the extreme uv]:
  • the dotted line in Fig. 3 is the first-order diffraction efficiency of the ordinary nickel phase zone plate, and the solid line is the first-order diffraction efficiency of the novel phase-wave zone plate of vanadium-nickel bimetal (in which the metal thickness of vanadium and nickel are the same).
  • the solution used in the present invention reduces the metal thickness of the zone plate by nearly half.
  • the scheme used in the present invention can greatly improve the diffraction efficiency of the zone plate. Taking a zone plate with a maximum outer ring width of 13 nm and a ring height of 35 nm as an example, the new bi-directional zone plate has improved the diffraction efficiency from 1.6% to 4.3% of the ordinary zone plate.
  • the novel phase shift zone plate of the present invention can only be used at a specific energy.
  • an energy of about 500eV, such as 520eV the same can also choose 511.9eV, has no significant impact on the imaging results.
  • the novel phase shift zone plate proposed by the present invention is not limited by the conditions under which it can be used only at a specific energy.
  • Figure 4 shows the first-order diffraction efficiency and energy of vanadium-nickel bimetallic zone plate with a thickness of 140 nm.
  • the new zone plate made of vanadium and nickel has an energy of between 510.3 and 512.leV at a thickness of 140 nm and a first-order diffraction efficiency of more than 20%.
  • the general energy dispersion is better than the O.leV magnitude.
  • the energy range of the BL08U line station of Shanghai light source is 250 ⁇ 2500eV
  • the energy resolution capability ⁇ / ⁇ is 2500 6000.
  • the U41-FSGM line station of the II source has an energy range of 250 to 1500 eV and an energy resolution of ⁇ / ⁇ of up to 10,000. This means that the same-radiation X-ray imaging system can achieve the working energy accuracy of 1 ⁇ 2eV.
  • the first-order diffraction efficiency of the ordinary nickel zone plate and the titanium-nickel bimetal zone plate at 453.6 eV is also calculated.
  • the results show that the thickness can be reduced from 210 nm to 130 nm, and the maximum first-order diffraction efficiency is substantially unchanged.
  • the new titanium-titanium bimetallic zone plate has improved the diffraction efficiency from 2.0% of the ordinary zone plate to 4.6%.
  • phase-shifted bimetallic zone plates for example, a vanadium-nickel bimetal having a thickness of 100 nm
  • Electron beam exposure forms a band plate nanostructure
  • the ion beam etch is used to transfer the zone plate structure to the metal film to form a metal vanadium zone plate structure.
  • the sample is immersed in acetone to remove the photoresist PMMA to form a metal vanadium and nickel interphase zone sheet structure;

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Abstract

提供一种正负相移双金属波带片及其制备方法，所述正负相移双金属波带片包含：第一金属材料，所述第一金属材料具有正相移；第二金属材料，所述第二金属材料在工作能量点具有负相移；所述第一金属材料与所述第二金属材料交替排列，以使得所述第二金属材料替代传统波带片的一个周期中的空白部分。

Description

正负相移双金属波带片 技术领域
本发明涉及 X射线显微成像领域， 更具体地涉及一种正负相移双金 属波带片。 背景技术
波带片是 X射线波段最常用的衍射光学元件之一， 常用来聚焦 X射 线以及充当成像系统的物镜。 波带片实质上就是一圆形的衍射光学元件， 它是由线密度径向增加的明暗相间的同心圆环构成 （如图一所示）。 根据 菲涅尔圆孔衍射理论， 如果半径按式子^ = (n为环数， λ为波长，
/为焦距）， 把圆孔连续分割成一个个环带， 把奇数或者偶数环带遮住， 就构成一个菲涅尔波带片。构成波带片的环带称为半波带， 任意两个相邻 半波带到达焦点的光程差为 λ/2。 这意味着通过两个相邻半波带的光波到 达焦点时的相位差为 π， 在焦点处会发生相互减弱的干涉。 因此， 波带片 由透明和不透明相间的半波带构成， 达到相干增强的目的。如果把波带片 不透明半波带变成相移 π的透明半波带，即产生光程为 λ/2的透明半波带， 这样通过两个相邻半波带的光波到达焦点时的相位差不是 0就是 2π， 通 过波带片的光将全部在焦点处形成相互加强的干涉，这就是普通相位型波 带片的原理。 [参考： 同歩辐射光源及其应用， 下册， Ρ686]
波带片两个最重要的参数是最外环宽度以及环厚度。波带片成像系统 的空间分辨率 (Δ)由波带片的最外环宽度 （drN) 决定， A=1.22drN。 在一定 范围内， 波带片的衍射效率随着环厚度的增加而提高。 然而， 目前限制波 带片发展的一个重要因素是高宽比， 由于加工技术等因素， 波带片的最外 环宽度与环厚度之间存在矛盾。现阶段波带片的最外环宽度无法做到更小， 或者高分辨的波带片效率无法做到很高。 因此， 波带片成像系统的空间分 辨率出现了瓶颈 （硬 X射线： 30nm; 水窗： 10nm)。
物质的折射率可表示为 n = 1 - δ + 1β，其中 δ为相位项， β为吸收项。 在某些特定的能量下， 一种物质的 δ和 β都会发生突变， 而其中的相位项 δ可能会出现负值。 对于利用元素相移特性制作的相位型波带片来说， 负 值相移的出现， 很可能带来新的突破。 发明内容
在本发明的一个方面， 提供一种正负相移双金属波带片， 所述正负相 移双金属波带片包含：
第一金属材料， 所述第一金属材料具有正相移；
第二金属材料， 所述第二金属材料在工作能量点具有负相移； 所述第一金属材料与所述第二金属材料交替排列，以使得所述第二金 属材料替代传统波带片的一个周期中的空白部分。
在本发明的另一个实施方案中，所述正负相移双金属波带片是环形的， 所述第一金属材料与所述第二金属材料形成交替的环结构。
在本发明的另一个实施方案中，所述第一金属材料常选自镍、金、锗、 钛、 钒、 铬、 锰、 铁、 钴、 铜、 锌等。
在本发明的另一个实施方案中， 所述第二金属材料选自钛、 钒、 铬、 锰、 铁、 钴、 镍、 铜、 锌、 镓、 锗、 铪、 钨、 铼和锇等。
在本发明的另一个实施方案中，所述正负相移双金属波带片在与普通 单金属相位波带片厚度相同的情况下，所述正负相移双金属波带片的衍射 效率高于所述普通单金属相位波带片的衍射效率。
在本发明的另一个实施方案中，所述正负相移双金属波带片为钒镍双 金属新型波带片。
在本发明的另一个实施方案中，所述正负相移双金属波带片的厚度为
10~500nm, 因波带片分辨率不同而不同， 在加工条件允许的情况下尽可 能选择高的厚度。
在本发明的另一个实施方案中，所述正负相移双金属波带片的结构中 不存在空心部分， 这种结构可以避免普通波带片可能坍塌的问题。
在本发明的另一个实施方案中，所述正负相移双金属波带片的效率与 环厚度直接相关， 在一定范围内， 波带片的衍射效率随着环厚度的增加而 提高。 对于高分辨 （30nm以下） 波带片， 由于高宽比的限制， 环高度暂 时无法做到太高， 衍射效率受到限制。
在本发明的另一个实施方案中，所述正负相移双金属波带片的工作能 量根据波带片材料不同而限定于不同的能量点。其原因是不同金属的负相 移出现在不同狭窄能量段 （几个 eV)。
本发明的另一个方面提供一种制备正负相移双金属波带片的方法，所 述方法包括以下歩骤：
a. 在基片上沉积第一金属材料的薄膜；
b. 在第一金属材料的薄膜上形成具有波带片结构的光刻胶； c 经由所形成的具有波带片结构的光刻胶进行刻蚀，将波带片结构转 移至所述第一金属材料的薄膜上， 形成第一金属材料的波带片结构； d. 在刻蚀出的空隙处沉积第二金属材料；
e. 去除光刻胶， 形成正负相移双金属波带片结构。
在本发明的另一个实施方案中， 所述光刻胶通过旋涂涂布， 之后对其 进行电子束曝光， 从而形成具有波带片结构的光刻胶。
在本发明的另一个实施方案中，所述歩骤 d中的刻蚀通过氩离子刻蚀 和各种反应离子刻蚀进行。
在本发明的另一个实施方案中，所述方法还包括在歩骤 e得到的正负 相移双金属波带片结构背面开窗， 获得正负相移双金属波带片。 附图说明
图 1是传统波带片结构示意图；
图 2是正负相移双金属波带片结构示意图；
图 3是能量为 511.9eV时，普通镍波带片和钒镍双金属波带片一级衍 射效率与材料厚度关系；
图 4是厚度为 140nm情况下， 钒镍双金属波带片一级衍射效率与能 量的关系图。 具体实施方式
本发明提出一种新型相位波带片， 该波带片能达到两种效果： 1 ) 能 够降低达到最大一级衍射效率时所需金属厚度； 2) 在不增加环高度的情 况下提高波带片的衍射效率。本发明的主要创新点是利用两种金属交替的 结构取代传统的单金属波带片， 在工作能量点， 其中一种金属的相移为正 数而另一种金属相移为负值。 我们称之为"正负相移双金属波带片"。 不同于传统的波带片，我们利用另一种材料替代了传统波带片一个周 期中的空白部分， 所选的替代材料要求在工作能量点出现负值相移， 这样 一来， 要达到相邻环带产生的相位差为 π所需的材料厚度可以降低， 从而 降低制作波带片的难度。该新型波带片结构如图二所示， 其环半径同样由 公式 r„ = ^Of ( n为环数， λ为波长， /为焦距）计算得出。从结构上看， 与图一所示传统波带片相比，图二增加了一种在工作能量处相移为负值的 材料， 其中负值相移材料可以为结构图中的任意一种。
多数金属在特定的能量会出现负数相移的情况，这些能量点在本文被 称为工作能量点。例如钛（453eV)、钒（512eV)、铬（574eV)、锰（638eV)、 铁 （706eV)、 钴 （778eV)、 镍 （852eV)、 铜 （932eV)、 锌 （1022eV)、 镓（1116eV)、锗（1217eV)、铪（1661eV)、钨（1809eV)、铼（1883eV)、 锇 （1960eV ) 等金属都会在对应的能量附近出现负数相移。 理论上这些 金属都可以用来制作工作在不同能量的正负相移双金属波带片。
计算表明， 相比于传统的单金属相位波带片， 正负相移双金属波带片 出现一级衍射效率峰值所需的金属厚度更低，并且能保持其峰值效率与单 金属峰值效率相当。 因此， 我们实现降低制作波带片难度的同时， 保持了 高的衍射效率。 而且， 在相同的波带片厚度下 （分辨率优于 150nm的情 况）， 正负相移双金属波带片比普通波带片效率更高。 因此， 本发明可以 有效的提高精细波带片的衍射效率。
以钒镍双金属新型波带片为例， 在 511.9eV能量下， 常用的镍波带片 在厚度为 250nm左右达到最大一级衍射效率 22%， 而本发明提出的新型 波带片在厚度为 140nm时就达到了最大一级衍射效率 24%。 可以将波带 片的厚度降低到原来的 56%左右。 由于加工工艺的限制， 目前国际上制作 较好的用于水窗的镍金属相位型波带片能达到最外环宽度 13nm， 环高度 为 5nm[Towards 10-nm soft X-ray zone plate fabrication] 0在 511.9eV育量 下， 其一级衍射效率的理论值为 1.6%， 而同样宽度和厚度的钒镍双金属 新型波带片的理论效率能达到 4.3%， 提高了将近 170%。 实施例 本发明提出的波带片可利用任何能在特定能量下出现负数相移的金 属结合其他任意金属制作而成。
以钒和镍两种金属的新型相位型波带片为例来说明。
金属钒在 511.9eV能量下出现最大负数相移，而这个能量恰好在常用 的"水窗"能量附近， 因此我们能够利用钒和镍 （"水窗" 中常用的波带片 金属） 两种金属来制作 511.9eV能量下的正负相移双金属波带片。
普通相位波带片的一级衍射效率为 [P/ifl^ zone plates for x rays and the extreme uv]：
Figure imgf000007_0001
由此可推导出由两种不同材料制作而成的正负相移双金属波带片一 级衍射效率为：
Eff = + exp(_2A ¾t2) _ 2exp卜 + ¾t2)]cos[ :(i¾ - S2t2)]]
Figure imgf000007_0002
其中 = 2 r / /l， t! , t2分别为两种材料的厚度。 由此， 我们可以计算 出双金属新型相位波带片的一级衍射效率， 如图三所示（其中两种金属的 厚度取为相同）。
图三中虚线是普通镍相位波带片的一级衍射效率，实线是钒镍双金属 新型相位波带片（其中钒和镍的金属厚度相同） 的一级衍射效率。 由此可 见， 本发明所用方案可使波带片的金属厚度降低将近一半。 另外， 在相同 环高度（小于 150nm)的情况下， 本发明所用方案可大幅提高波带片的衍 射效率。 以最外环宽度为 13nm， 环高度为 35nm的波带片为例， 双金属 新型波带片将衍射效率从普通波带片的 1.6%提高到了 4.3%。
由于金属负值相移系数只出现在某一狭窄的能量段，所以本发明所提 的新型相移波带片只能在特定的能量下使用。 但是在绝大多数的 X射线 成像情况下， 只需要在一个能量下观察样品即可， 对这个能量并没有太苛 刻的要求。 比如在 "水窗 "波段的含水细胞成像，一般都在 500eV左右任选 一个能量， 例如 520eV， 同样的也可以选择 511.9eV， 对成像的结果并无 太大的影响。从这个角度出发， 本发明提出的新型相移波带片并不因其只 能在特定能量下使用的条件而受限制。
图四为厚度为 140nm情况下， 钒镍双金属波带片一级衍射效率与能 量的关系图。 从图四可知， 钒和镍制作的新型波带片， 在 140nm厚度情 况下， 能量在 510.3~512.leV之间， 一级衍射效率大于 20%。 在同歩辐射 显微成像系统中， 一般的能量色散优于 O.leV 量级， 例如上海光源的 BL08U 线站的能量范围为 250~2500eV， 而能量分辨能力 Ε/ΔΕ为 2500 6000，德国 BESSY II光源的 U41-FSGM线站能量范围为 250~1500eV， 而能量分辨能力 Ε/ΔΕ高达 10000。这意味着， 同歩辐射 X射线成像系统能 够达到工作能量精确到 l~2eV的要求。
另外， 也计算了在 453.6eV能量下， 普通镍波带片和钛镍双金属波带 片的一级衍射效率， 结果表明厚度可以从 210nm降到 130nm， 而最大一 级衍射效率基本不变。 另外， 对于最外环宽度为 13nm， 环高度为 35nm 的波带片， 钛镍双金属新型波带片将衍射效率从普通波带片的 2.0%提高 到了 4.6%。
下面提供一种可以加工正负相移双金属波带片的加工工艺（以厚度为 lOOnm的钒镍双金属为例）：
1、 利用离子束溅射在氮化硅基片上沉积 100纳米厚金属钒薄膜；
2、 旋涂 400纳米厚电子束光刻胶 PMMA, 180度烘干；
3、 电子束曝光形成波带片纳米结构；
4、 利用离子束刻蚀将波带片结构转移到金属薄膜上， 形成金属钒波 带片结构。 氩离子刻蚀， 能量： 500eV， 束流密度 0.5mA/cm2;
5、 利用离子束溅射在样品上沉积 100纳米厚金属镍薄膜；
6、 将样品放入丙酮中浸泡， 除去光刻胶 PMMA, 形成金属钒、 镍相 间波带片结构；
7、 在样品背面开窗（30%KOH、 80°C )， 获得高度为 100纳米的金属 钒、 镍相间波带片。

Claims

权 利 要 求
1.一种正负相移双金属波带片， 所述正负相移双金属波带片包含： 第一金属材料， 所述第一金属材料具有正相移；
第二金属材料， 所述第二金属材料在工作能量点具有负相移； 所述第一金属材料与所述第二金属材料交替排列， 以使得所述第二金 属材料替代传统波带片的一个周期中的空白部分。
2. 权利要求 1所述的正负相移双金属波带片，所述正负相移双金属波 带片是环形的，所述第一金属材料与所述第二金属材料形成交替的环结构。
3. 权利要求 1所述的正负相移双金属波带片，所述第一金属材料选自 镍、 金、 锗、 钛、 钒、 铬、 锰、 铁、 铜、 锌。
4. 权利要求 1所述的正负相移双金属波带片，所述第二金属材料选自 钛、 钒、 铬、 锰、 铁、 钴、 镍、 铜、 锌、 镓、 锗、 铪、 钨、 铼和锇。
5. 权利要求 1所述的正负相移双金属波带片，所述正负相移双金属波 带片在与普通单金属相位波带片厚度相同的情况下，所述正负相移双金属 波带片的衍射效率在常用范围内高于所述普通单金属相位波带片的衍射 效率。
6. 权利要求 1所述的正负相移双金属波带片，所述正负相移双金属波 带片为钒镍、 钛镍、 钒金双金属波带片。
7. 一种制备正负相移双金属波带片的方法， 所述方法包括以下歩骤： a. 在基片上沉积第一金属材料的薄膜；
b. 在第一金属材料的薄膜上形成具有波带片结构的光刻胶；
c 经由所形成的具有波带片结构的光刻胶进行刻蚀，将波带片结构转 移至所述第一金属材料的薄膜上， 形成第一金属材料的波带片结构；
d. 在刻蚀出的空隙处沉积第二金属材料；
e. 去除光刻胶， 形成正负相移双金属波带片结构。
8. 权利要求 7所述的方法，所述光刻胶通过旋涂涂布，之后对其进行 电子束曝光或干涉光刻， 从而形成具有波带片结构的光刻胶。
9. 权利要求 7所述的方法，所述歩骤 d中的刻蚀通过氩离子刻蚀或反 应离子刻蚀进行。
10. 权利要求 7所述的方法， 所述方法还包括在歩骤 e得到的正负相 移双金属波带片结构背面开窗， 获得正负相移双金属波带片。
PCT/CN2014/078122 2014-05-22 2014-05-22 正负相移双金属波带片 Ceased WO2015176272A1 (zh)

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