WO2015043104A1 - 一种高灵敏度的热电子热辐射探测计及其制备方法 - Google Patents

一种高灵敏度的热电子热辐射探测计及其制备方法 Download PDF

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WO2015043104A1
WO2015043104A1 PCT/CN2014/000157 CN2014000157W WO2015043104A1 WO 2015043104 A1 WO2015043104 A1 WO 2015043104A1 CN 2014000157 W CN2014000157 W CN 2014000157W WO 2015043104 A1 WO2015043104 A1 WO 2015043104A1
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boron nitride
film
electrode
disordered
graphene film
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PCT/CN2014/000157
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French (fr)
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吴孝松
韩琪
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北京大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation

Definitions

  • the invention relates to a high sensitivity thermal electron thermal radiation detector and a preparation method thereof. Background technique
  • graphene As a new two-dimensional material, graphene has high carrier mobility and good electrical, optical, thermal, mechanical and other properties, making it more and more widely used in various devices in recent years.
  • Graphene has a unique Dirac electron band structure, and the density near the Dirac point is close to zero, which makes the graphene have a small electron heat capacity.
  • graphene itself has weak electron-phonon coupling at normal temperature and good thermal response to different wavelengths of light radiation, which has led to how to achieve high sensitivity and high response speed heat from graphene in recent years. Research on radiation detectors has received increasing attention.
  • the object of the present invention is to provide a high-sensitivity thermal electron thermal radiation detector and a preparation method thereof.
  • the invention can reduce the device resistance and increase the light absorption rate of the device by stacking a plurality of layers of boron nitride-disordered graphene film. , resulting in faster response times and more sensitive thermal radiation detection.
  • the method for preparing an electronic thermal radiation detector provided by the invention comprises the following steps:
  • the boron nitride-disordered graphene film is a composite film sequentially superposed by a boron nitride film and a disordered graphene film, and the disordered graphene film is provided on the SiO ⁇ i vapor-deposited with the electrode On the end face of the bottom;
  • the boron nitride-disordered graphene film is prepared according to the method comprising the following steps: under the condition of 800 ° C to 1200 ° C, using NH 3 BH 3 as a precursor on the substrate The single-layer boron nitride film is grown thereon; then, under the condition of 800 ° C to 120 (TC), a carbon source is grown on the single-layer boron nitride film, and the flow rate of controlling the 3 ⁇ 4 and Ar can be 10 sccm respectively.
  • the growth pressure may be 100 Pa to 150 Pa, and the disordered graphene film is obtained, and thus the boron nitride-disordered graphene film is obtained.
  • the carbon source may be benzoic acid
  • the boron nitride-disordered graphene film is grown on a Cu foil substrate.
  • the conditions of the electron beam exposure are as follows:
  • the acceleration voltage is 10KV-30KV, specifically 25KV, the aperture is 15 ⁇ 50 ⁇ , specifically 30 ⁇ , the beam spot size (Spotsize) It can be 1 ⁇ 5, specifically 5, the exposure dose is 160 ⁇ 40 (C/cm 2 , specifically 30 ( C/cm 2 ;
  • the developing solution used for the development is a mixture of MIBK (methyl isobutyl ketone) and isopropyl alcohol, and the volume ratio of MIBK to isopropyl alcohol is 1:3, and the development time may be 30 seconds to 90 seconds. , such as 60s.
  • the electrode in the step (1), may be an Au electrode or a Ti/Au electrode; and the pattern is a six-electrode structure.
  • the boron nitride film and the disordered graphene film are both monoatomic layers each having a thickness of 0.3 nm.
  • the boron nitride-disordered graphene film is grown on a Cu foil substrate to facilitate transfer of the boron nitride-disordered graphene film, and transfer The damage to the boron nitride-disordered graphene film structure is reduced.
  • the step (2) preparing the boron nitride-disorder graphene film on the boron nitride-disorder graphene film before transferring the boron nitride-disorder graphene film onto the SiO 2 substrate
  • the PMMA layer acts as a protective layer to reduce damage to the boron nitride-disordered graphene film.
  • the conditions of the electron beam exposure are as follows:
  • the acceleration voltage is 10KV-30KV, specifically 25KV, the aperture is 15 ⁇ 50 ⁇ , specifically 30 ⁇ , the spot size (Spotsize) It can be 1 to 5, specifically 5, and the exposure dose is 160 to 40 (C/cm 2 ) .
  • the etching conditions are: etching in a 15 sccm air plasma for 30 s to 60 s, such as 30 s, as in a Femto Plasma Cleaner (Plasma cleaning machine). .
  • the present invention further provides an electron thermal radiation detector prepared by the above method.
  • FIG. 1 is a schematic view showing the structure of a device and a six-electrode structure prepared by the present invention, wherein FIG. 1(a) is a schematic diagram of a six-electrode structure, and FIG. 1(b) is a schematic structural view of the device.
  • Figure 2 is a plot of the Raman spectrum of the disordered graphene and its resistance versus temperature, where Figure 2 (a) is the Raman spectrum of the disordered graphene, and Figure 2 (b) is the Raman spectrum of the disordered graphene. Resistance vs. temperature.
  • Figure 4 shows the differential resistance of the device of the present invention as a function of bias current at different temperatures.
  • Fig. 5 is a graph showing the relationship between the thermal resistance of the device according to the invention and the heating power (a) and the degree of thermal resistance as a function of disorder (b).
  • Figure 6 is a graph comparing the photothermal response and the Joule thermal response of the device of the present invention at different temperatures. detailed description
  • the materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
  • the boron nitride-disorder graphene film used in the following examples was prepared as follows:
  • a SiO 2 /N-Si substrate having a SiO 2 thickness of 285 nm was used, and the substrate was purchased from the Institute of Microelectronics, Peking University. Ultrasonic cleaning of SiO 2 /N-Si substrate with acetone to remove organic residues, followed by deionized water Ultrasonic cleaning was performed to remove impurities such as metal ions, and then the sample was quickly dried by a nitrogen gun.
  • the electron beam exposure machine used in this experiment was modified by installing RaithElphy Plus software on the basis of scanning electron microscope FEI Satran DB235.
  • the scanning electron microscope conditions used were: a high voltage of 25 kV, a pupil of 30 ⁇ m, a Spotsize of 5, and an exposure dose of 30 ( ⁇ C/cm 2 ) .
  • the fixing was washed with high-purity isopropyl alcohol for half a minute to remove the residual developer.
  • a 5 nm/70 nm Ti/Au layer was deposited by electron beam evaporation coating and degummed, thereby preparing a complete electrode structure on the substrate.
  • the Cu substrate layer under the boron nitride-disordered graphene film was dissolved in the FeCl 3 solution, and the suspended boron nitride-disordered graphene film was washed in dilute hydrochloric acid and deionized water for 15 min, respectively, and the bottom residue was removed. Fe 3+ ion.
  • the clean boron nitride-disordered graphene film was transferred to the SiO 2 /N-Si substrate prepared in step 3) and immersed in pure acetone for 15 minutes to remove the PMMA protective layer.
  • the film is processed into a strip of 5 ⁇ > ⁇ 20 ⁇ by a further PMMA, electron beam exposure, and etching step.
  • the etching was performed using a Femto Plasma Cleaner (Plasma Washer) with a 15 sccm air plasma etching for 30 seconds.
  • the silicone and exposure conditions are the same as in the above steps 1) and 2), and the PMMA protective layer is finally removed.
  • Fig. 2(a) shows the Raman spectrum of the disordered graphene used in the present invention, and a distinct D peak can be seen, indicating that the graphene used in the present invention has a high degree of disorder.
  • Figure 2 (b) is the relationship between resistance and temperature of disordered graphene, and linear fitting.
  • the fitting results show that the sample resistance has a significant temperature dependence, RT 1/3 (K 1/3 ) And calculate the localized length to 50nm based on the slope.
  • the electron thermal radiation detector prepared in this example was attached to a chip-carrier, and the electrode was taken out. Place in liquid helium dewar for low temperature testing.
  • the sample is heated by direct current.
  • Fig. 3(b) it can be seen that the differential resistance of the sample has a sharp drop with increasing bias voltage, achieving a thermal response.
  • the electron temperature is calculated along with the heating power.
  • T 1.57, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12K
  • the present invention also investigates the relationship of thermal resistance with the degree of disorder of graphene.
  • the abscissa represents the resistance of graphene with different degrees of disorder. The higher the degree of disorder, the higher the resistance. It can be seen from the figure that the thermal radiation detector prepared by the graphene having stronger disorder has higher thermal resistance.
  • the device was optically responsive for measurement.
  • the absorption power of graphene to light is about 40PW.
  • the photovoltaic response value at different temperatures is calculated, and compared with the Joule thermal radiant heat response, as shown in Fig. 6, it can be seen that The response is very good.
  • thermoelectron thermal radiation detector prepared from disordered graphene
  • the present invention employs a disordered graphene having a much larger sheet resistance than perfect graphene.
  • Disordered graphene exhibits strong localized conductance and can achieve a very strong resistance-temperature relationship, making the device highly sensitive.
  • the disorder of graphene can hinder the electron diffusion heat transfer, highlighting the thermoelectron effect.
  • the electronic thermal radiation detector prepared by the invention not only has a sensitivity of up to lx l7 7 V/W when the current is ⁇ , but the sensitivity is widely adjustable, and the average noise power (NEP) is only l.lfW/(Hz) 1/2 . Lower than reported values from previous literature.
  • the device structure of the present invention is a simple parallel six-electrode structure, and it is not necessary to prepare a complicated superconducting tunnel junction and a double gate structure.
  • the device does not require a particularly high magnetic field during operation, which is very simple to implement.
  • the quality requirements of graphene are very low. It is not necessary to prepare high-quality graphene, but the device can be prepared by using disordered and defective graphene.
  • the invention can work in a common liquid helium refrigerator without operating at a very low temperature, which reduces the cost and is very simple to operate. Sample preparation is highly reproducible and subject to little external interference.
  • the performance test of the device prepared by the present invention is very reproducible, and tests are performed on different samples to obtain substantially repeated results.

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Abstract

一种电子热辐射探测计及其制备方法。制备方法包括如下步骤：（1）在SiO2衬底上进行甩膜得到PMMA层；对PMMA层依次进行电子束曝光和显影得到电极的图形，然后蒸镀电极；（2）去除SiO2衬底上的PMMA层；将氮化硼-无序石墨烯薄膜转移到SiO2衬底上；氮化硼一无序石墨烯薄膜为由氮化硼薄膜和无序石墨烯薄膜依次叠加的复合薄膜，无序石墨烯薄膜设于蒸镀有电极的SiO2衬底的端面上；（3）在氮化硼-无序石墨烯薄膜上进行甩膜得到PMMA层，然后依次经电子束曝光和刻蚀得到与电极相对应的结构，至此即得电子热辐射探测计。与现有的使用超导隧道结制备的石墨烯热辐射探测计相比，不用工作在极低温度下，而是可以工作在普通的液氦制冷机，减少了成本而且操作非常简单。

Description

一种高灵敏度的热电子热辐射探测计及其制备方法
技术领域
本发明涉及一种高灵敏度的热电子热辐射探测计及其制备方法。 背景技术
石墨烯作为一种新型的二维材料， 有着高的载流子迁移率以及良好的电学、 光 学、 热学、 力学等性质， 使其近年来在各种器件中的应用越来越广泛。 石墨烯具有 独特的狄拉克电子能带结构， 在狄拉克点附近态密度接近为零， 从而使石墨烯具有 很小的电子热容。 除此之外， 石墨烯本身在常温下的弱的电子-声子耦合以及对不同 波段的光辐射的很好的热响应， 这使得近年来大家对如何由石墨烯实现高灵敏度高 响应速度热辐射探测计的研究越来越关注。
目前关于石墨烯热辐射探测计的实现方法有很多。 有一种是采用高磁场下的石 墨稀电阻量子霍尔效应 （N. G. Kalugin et al, Graphene-based quantum Hall effect infrared photodetector operating at liquid Nitrogen temperatures. Applied Physics Letters99, 013504 (2011)) 来实现对光的热辐射的探测。 但是这种方式电阻温度关系 非常弱， 器件不仅灵敏度很低， 只有 10_2-10_3V/W， 而且器件的漏热很严重。 为了提 高石墨烯热辐射探测计的灵敏度， 采用铝 -石墨烯超导隧道结 （H. Vora, P. Kumaravadivel, B. Nielsen, X. Du, Bolometric response in graphene based superconducting tunnel junctions. Applied Physics Letters 100， 153507 (2012). )可以实现 响应率〜 105V/W。但是由于超导结的制备工艺复杂，而且器件必须工作在极低温度下， 所以实用性不强。 除此之外， 也有人通过双门压对双层石墨烯带隙进行调控制备出 电子热福射探测计 (J. Yan et al , Dual-gated bilayer graphene hot-electron bolometer. Nat ΝαηοΊ, ΑΊΙ (2012) ) o这种方式虽然响应率可以达到 2x l05V/W， 但是双层石墨烯双栅 结构的器件制备工艺相当复杂， 且器件漏热也比较严重。 同时器件电阻比较大， 影 响了器件的响应速度。 由于单层石墨烯非常薄， 对光的吸收率仅 2.3%， 基于石墨烯 的热电子热辐射探测计面临吸收效率低的问题， 上述结构都无法实现多层结构来提 高吸收率。 发明内容
本发明的目的是提供一种高灵敏度的热电子热辐射探测计及其制备方法， 本发 明通过叠加多层氮化硼 -无序石墨烯薄膜， 可以降低器件电阻， 提高器件的光吸收率 量， 从而实现更快响应速度和更灵敏热辐射探测。 本发明所提供的一种电子热辐射探测计的制备方法， 包括如下步骤：
( 1 ) 在 SiO2衬底上进行甩膜得到 PMMA层； 对所述 PMMA层依次进行电子 束曝光和显影得到电极的图形， 然后蒸镀电极；
(2)去除所述 SiO2衬底上的所述 PMMA层；将氮化硼-无序石墨烯薄膜转移到 所述 SiO2衬底上；
所述氮化硼-无序石墨烯薄膜为由氮化硼薄膜和无序石墨烯薄膜依次叠加的复 合薄膜， 所述无序石墨烯薄膜设于蒸镀有所述电极的所述 SiO^i底的端面上；
(3 )在所述氮化硼 -无序石墨烯薄膜上进行甩膜得到 PMMA层， 然后依次经电 子束曝光和刻蚀， 把复合薄膜加工成所需的形状， 至此即电子热辐射探测计。
上述的制备方法中， 所述氮化硼 -无序石墨烯薄膜是按照包括如下步骤的方法制 备的： 在 800°C〜1200°C的条件下， 以 NH3BH3为先驱物在衬底上生长所述单层氮化 硼薄膜； 然后在 800°C〜120(TC的条件下， 碳源在所述单层氮化硼薄膜上进行生长， 控制 ¾和 Ar的流速分别可为 lOsccm〜30sccm和 40sccm〜60sccm，生长压强可为 100 Pa〜150Pa， 得到所述无序石墨烯薄膜， 至此即得到所述氮化硼 -无序石墨烯薄膜。
上述的制备方法中， 所述碳源可为苯甲酸；
所述氮化硼 -无序石墨烯薄膜生长在一 Cu箔衬底上。
上述的制备方法中， 步骤 （1 ) 中， 所述电子束曝光的条件如下： 加速电压为 10KV-30KV,具体可为 25KV,光阑为 15〜50μηι，具体可为 30μηι，束斑大小（Spotsize) 可为 1〜5， 具体可为 5， 曝光剂量为 160〜40( C/cm2， 具体可为 30( C/cm2;
所述显影所用的显影液为 MIBK (甲基异丁酮） 与异丙醇的混合液， 且 MIBK 与异丙醇的体积比为 1 : 3, 所述显影的时间可为 30秒〜 90秒， 如 60s。
上述的制备方法中， 步骤 （1 ) 中， 所述电极可为 Au电极或 Ti/Au电极； 所述图形为六电极结构。
上述的制备方法中， 步骤（2) 中， 所述氮化硼薄膜和所述无序石墨烯薄膜均为 单原子层， 其厚度均为 0.3nm。
上述的制备方法中， 步骤（2) 中， 所述氮化硼 -无序石墨烯薄膜生长在一 Cu箔 衬底上， 以方便所述氮化硼 -无序石墨烯薄膜的转移， 以及转移时减少对所述氮化硼- 无序石墨烯薄膜结构的破坏。
上述的制备方法中， 步骤 （2) 中， 在将所述氮化硼 -无序石墨烯薄膜转移到所 述 SiO2衬底上之前， 在所述氮化硼-无序石墨烯薄膜上制备 PMMA层作为保护层， 以减少对所述氮化硼 -无序石墨烯薄膜的破坏。
上述的制备方法中， 步骤 （3 ) 中， 所电子束曝光的条件如下： 加速电压为 10KV-30KV,具体可为 25KV,光阑为 15〜50μηι，具体可为 30μηι，束斑大小（Spotsize) 可为 1〜5， 具体可为 5， 曝光剂量为 160〜40( C/cm2。
上述的制备方法中， 步骤 （3 ) 中， 所述刻蚀的条件为： 在 15sccm的空气等离 子体 （plasma) 刻蚀 30s〜60s， 如 30s， 如在 Femto Plasma Cleaner (Plasma清洗机） 中进行。
本发明进一步提供了由上述方法制备得到的电子热辐射探测计。 附图说明
图 1为本发明制备的器件结构示意图和六电极结构示意图， 其中图 1 (a) 为六 电极结构示意图， 图 1 (b ) 为器件结构示意图。
图 2为无序石墨烯的拉曼光谱和其电阻与温度的关系曲线， 其中图 2 ( a) 为无 序石墨烯的拉曼光谱， 图 2 (b ) 为无序石墨烯的拉曼光谱电阻与温度的关系曲线。
图 3为本发明器件的传热示意图 （a)、 在不同磁场下 （B=0T， IT, 5T) 本发明 器件微分电阻随着偏置电流的变化关系 （b ) 以及电子温度随着加热功率的变化关系 ( c)。
图 4为不同温度下本发明器件微分电阻随着偏置电流的变化关系。
图 5为本发明器件热阻随着加热功率的变化关系 （a) 以及热阻随着无序程度的 变化关系 （b)。
图 6为不同温度下本发明的器件的光热响应与焦耳热响应的对比图。 具体实施方式
下述实施例中所使用的实验方法如无特殊说明， 均为常规方法。
下述实施例中所用的材料、 试剂等， 如无特殊说明， 均可从商业途径得到。 下述实施例所用的氮化硼-无序石墨烯薄膜是按照下述方法制备的：
首先在厚度为 25μηι的铜箔上通过低压 CVD (化学气相沉积） 的方法制备的： 在 1000°C下， 利用 NH3BH3 (硼垸铵） 为先驱物在铜箔上生长单层氮化硼薄膜 （约 0.3nm) o 然后通过向生长系统里引入苯甲酸固体碳源直接在氮化硼薄膜上生长无序 石墨烯薄膜， 控制生长温度为 800°C， 生长气压为 120Pa， ¾和 Ar的气流速度分别 为 20sccm和 50sccm, 则在单层氮化硼薄膜上得到单层无序石墨烯薄膜（约 0.3nm)， 进而得到氮化硼 -无序石墨烯薄膜。 实施例 1、 制备无序石墨烯电子热辐射探测计
1 )采用 SiO2厚度为 285nm厚的 SiO2/N-Si衬底， 此衬底购买于北京大学微电子 研究所。 用丙酮对 SiO2/N-Si衬底超声清洗去除有机物残留， 接着用去离子水对它们 进行超声清洗去除金属离子等杂质， 然后用氮气枪迅速吹干样品。
2) 用转速 3000r/min持续时间为 45秒 （启动与停止时间为 15秒） 甩一层分子 量为 950K：、 质量分数为 6%， 厚度约为 300nm的 PMMA, 并用 170°C烘烤 4min。
2)将甩胶后的衬底在选定的位置进行电子束曝光制作出如图 1 (a) 中的间隔为 2.5μηι的六电极结构。
本实验采用的电子束曝光机是在扫描电子显微镜 FEI Satran DB235基础上安装 RaithElphy Plus软件进行改装而成的。 所使用的扫描电镜条件为： 高压为 25KV, 光 阑为 30μηι， Spotsize为 5， 曝光剂量为 30(^C/cm2。
3 ) 显影并镀膜。
显影使用的显影液为 ΜΙΒΚ (甲基异丁酮）： 异丙醇 =1 : 3 (体积比）， 显影时间 为 lmin。 定影采用高纯异丙醇冲洗半分钟， 除去残余的显影液。 显影成功后， 利用 电子束蒸镀的镀膜方法蒸镀 5nm/70nm的 Ti/Au层， 并去胶， 这样就制备出在衬底上 的完整的电极结构。
4)取一 5cmx5cm的生长在 Cu箔衬底上的氮化硼-无序石墨烯薄膜运用第 2)步 中的甩胶工艺甩一层 PMMA, 作为保护层。
用 FeCl3溶液溶解掉氮化硼-无序石墨烯薄膜下的 Cu衬底层，并将悬浮着的氮化 硼-无序石墨烯薄膜在稀盐酸和去离子水中分别清洗 15min， 去掉底部残留的 Fe3+离 子。
最后将干净的氮化硼-无序石墨烯薄膜转移到步骤 3 ) 中制备好电极的 SiO2/N-Si 衬底上， 并用纯净的丙酮浸泡 15min去掉 PMMA保护层。
5 ) 氮化硼-无序石墨烯薄膜转移到衬底之后， 再一次甩胶 （PMMA)、 电子束曝 光、 刻蚀步骤将薄膜加工成 5μηι><20μηι的条带状。
刻蚀使用的是 Femto Plasma Cleaner (Plasma清洗机）， 15sccm的空气 plasma刻 蚀 30s。 甩胶、 曝光条件同上述步骤 1 ) 和 2) 中， 最后去掉 PMMA保护层。
本实施例制备的器件结构图如图 1 (b) 所示。
图 2 (a) 为本发明使用的无序石墨烯的拉曼光谱， 可以看到很明显的 D峰， 说 明本发明所用的石墨烯的无序程度很高。
图 2 (b) 为无序石墨烯的电阻与温度的关系曲线， 并进行线性拟合， 拟合结果 看出样品电阻有一个很明显的温度依赖关系， R T 1/3(K 1/3)， 并根据斜率计算出局域 化长度为 50nm。
将本实施例制备的电子热辐射探测计粘附在 chip-carrier上， 并点悍引出电极。 放入液氦杜瓦中进行低温测试。
为了探究本发明中的热辐射探测计的热响应， 通直流电对样品加热。 如图 3 (b)所示， 可以看到样品的微分电阻随着偏压的增加有一个剧烈的下降， 实现了热响应。 为了排除此响应是由于电子-电子相互作用引起的， 在不同磁场下 (B=0T， IT, 5T) 测试器件的微分电阻随着偏置电流的变化关系， 并计算出电子温 度随着加热功率的变化关系。 如图 3 (b)和图 3 (c)所示， 可以看出在不同磁场下， 器件的电子温度随着加热功率的变化是趋于一致的。 这就证明了本发明的器件实现 了热辐射探测的作用。 除此之外在不同温度 （T=1.57， 2， 3， 4， 5， 6， 7， 8， 9， 10， 11， 12K) 下测量了器件的微分电阻随着偏执电流的变化， 如图 4所示， 可以看 出温度越高， 器件的响应越不明显。
由实验数据计算出本发明器件的热阻 dR/dP随着加热功率 Ρ的关系。如图 5 (a) 所示， 在温度为 2K时， 器件的响应率可达到 ΙΜΩ/nW, 并且在电流 I=10nA时， 灵 敏度可达到 lx l07V/W。
本发明还探究了热阻随着石墨烯无序程度的变化关系。 如图 5 (b) 所示， 横坐 标代表不同无序程度的石墨烯的电阻， 无序度越高电阻越高。 由图可以看出由无序 性越强的石墨烯制备的热辐射探测计其热阻越高。
为了验证本发明器件的实际应用性质， 对器件进行了光响应进行测量。 实验中 石墨烯对光的吸收功率约为 40PW, 在 InA的激发电流下， 计算出不同温度下光伏 响应值， 并与焦耳热辐射热响应相比较， 如图 6所示， 可以看出这两种响应符合的 很好。
上述试验验证了本发明通过焦耳热辐射实现了电子热辐射探测计。 工业应用
( 1 ) 首次实现由无序石墨烯制备的高灵敏度的热电子热辐射探测计
本发明采用一种面电阻比完美石墨烯大很多的无序石墨烯。 无序石墨烯体现出 强局域化电导， 可以实现非常强的电阻温度关系， 使得器件的灵敏度很高。 其次由 于石墨烯的无序可以阻碍电子扩散传热， 突出了热电子效应。 本发明制备的电子热 辐射探测计不仅灵敏度在电流为 ΙΟηΑ时可达 lx l07V/W， 灵敏度大范围可调， 而且 平均噪声功率 （NEP) 只有 l.lfW/(Hz)1/2， 低于之前文献的报道值。
(2) 结构简单， 对石墨烯品质要求低
本发明的器件结构就是简单的平行六电极结构， 不需要制备复杂的超导隧道结 以及双栅结构。 器件工作时也不需要特别高的磁场， 实现起来非常简单。 其次对于 石墨烯的品质要求很低， 不需要准备质量高的石墨烯， 而是采用无序有缺陷的石墨 烯就能实现器件的制备。
(3 ) 成本低， 操作简单 本发明与现有的使用超导隧道结制备的石墨烯热辐射探测计相比， 不用工作在 极低温度下， 而是可以工作在普通的液氦制冷机， 减少了成本而且操作非常简单。 样品制备重复性很高， 受外界干扰很小。
(4 ) 器件性能重复性好
本发明制备的器件性能测试重复性很好， 对于不同的样品进行测试， 得出基本 重复一致的结果。

Claims

权利要求
1、 一种电子热辐射探测计的制备方法， 包括如下步骤：
( 1 ) 在 SiO2衬底上进行甩膜得到 PMMA层； 对所述 PMMA层依次进行电子 束曝光和显影得到电极的图形， 然后蒸镀电极；
(2)去除所述 SiO2衬底上的所述 PMMA层；将氮化硼-无序石墨烯薄膜转移到 所述 SiO2衬底上；
所述氮化硼-无序石墨烯薄膜为由氮化硼薄膜和无序石墨烯薄膜依次叠加的复 合薄膜， 所述无序石墨烯薄膜设于蒸镀有所述电极的所述 SiO2衬底的端面上；
(3 )在所述氮化硼 -无序石墨烯薄膜上进行甩膜得到 PMMA层， 然后依次经电 子束曝光和刻蚀得到与所述电极相对应的结构， 至此即得电子热辐射探测计。
2、 根据权利要求 1 所述的制备方法， 其特征在于： 所述氮化硼-无序石墨烯薄 膜是按照包括如下步骤的方法制备的： 在 800°C〜1200°C的条件下， 以 NH3BH3为先 驱物在衬底上生长所述单层氮化硼薄膜； 然后在 800°C〜120(TC的条件下， 碳源在所 述单层氮化硼薄膜上进行生长， 控制 ¾和 Ar 的流速分别为 lOsccm 〜30sccm和 40sccm〜60sccm， 生长压强为 100 Pa 〜150Pa， 得到所述无序石墨烯薄膜， 至此即得 到所述氮化硼 -无序石墨烯薄膜。
3、 根据权利要求 2所述的制备方法， 其特征在于： 所述碳源为苯甲酸； 所述氮化硼 -无序石墨烯薄膜生长在一 Cu箔衬底上。
4、 根据权利要求 1-3 中任一项所述的制备方法， 其特征在于： 步骤 （1 ) 中， 所述电子束曝光的条件如下： 加速电压为 10KV〜30KV， 光阑为 15〜50μηι， 束斑大小 为 1〜5， 曝光剂量为 160〜40( C/cm2;
所述显影所用的显影液为甲基异丁酮与异丙醇的混合液。
5、 根据权利要求 1-4 中任一项所述的制备方法， 其特征在于： 步骤 （1 ) 中， 所述电极为 Au电极或 Ti/Au电极；
所述图形为六电极结构。
6、 根据权利要求 1-5 中任一项所述的制备方法， 其特征在于： 步骤 （2) 中， 在将所述氮化硼-无序石墨烯薄膜转移到所述 SiO2衬底上之前， 在所述氮化硼 -无序 石墨烯薄膜上制备 PMMA层作为保护层。
7、 根据权利要求 1-6 中任一项所述的制备方法， 其特征在于： 步骤 （3 ) 中， 所电子束曝光的条件如下： 加速电压为 10KV〜30KV， 光阑为 15〜50μηι， 束斑大小为
1-5, 曝光剂量为 160〜40( C/cm2。
8、 根据权利要求 1-7 中任一项所述的制备方法， 其特征在于： 步骤 （3 ) 中， 所述刻蚀的条件为： 在 15sccm的空气等离子体刻蚀 30s〜60s。 、 权利要求 1-8中任一项所述方法制备的电子热辐射探测计。
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