技术领域technical field
本发明属于三族氮化物光电子技术领域，涉及三族氮化物半导体薄膜生长方法，具体涉及一种非极性氮化铟纳米晶薄膜的制备装置和方法。The invention belongs to the technical field of III-nitride optoelectronics, and relates to a method for growing a III-nitride semiconductor thin film, in particular to a preparation device and method for a nonpolar indium nitride nanocrystal thin film.
背景技术Background technique
氮化铟(InN)是一种重要的三族氮化物半导体材料，相对于宽禁带AlN和GaN，InN具有相对较窄的直接带隙(0.7eV)、较小的电子有效质量、良好的稳态和瞬态电学传输特性、最大的电子迁移率等优异的性质。这些特殊的性质使得InN在制备高频高速率晶体管、太赫兹器件，化学传感器、半导体发光二极管、全光谱太阳能电池等光电器件领域具有巨大的应用价值。由于InN具有较低的热稳定性，分解温度低，作为氮源的氨气，其分解温度较高，这与InN的生长相互矛盾，此外，缺少相应匹配的衬底材料，这使得高质量InN薄膜晶体生长特别困难。Indium Nitride (InN) is an important Group III nitride semiconductor material. Compared with AlN and GaN with wide bandgap, InN has a relatively narrow direct bandgap (0.7eV), small electronic effective mass, good Excellent properties such as steady-state and transient electrical transport characteristics, maximum electron mobility, etc. These special properties make InN have great application value in the field of optoelectronic devices such as high-frequency high-speed transistors, terahertz devices, chemical sensors, semiconductor light-emitting diodes, and full-spectrum solar cells. Since InN has low thermal stability and low decomposition temperature, ammonia as a nitrogen source has a high decomposition temperature, which is contradictory to the growth of InN. In addition, the lack of corresponding matching substrate materials makes high-quality InN Thin film crystal growth is particularly difficult.
目前InN薄膜的生长方法主要有金属有机物化学气相沉积(MOCVD)方法、等离子体辅助分子束外延方法(PA-MBE)和磁控溅射方法。MOCVD制备方法使用的反应物为有机源，需要做好防毒措施，并且MOCVD方法需要更高的温度(约750-1000℃)，这个高温不利于InN的热稳定性。PA-MBE方法具有较高的真空度，使用的反应源简单，可以实现高质量InN薄膜外延生长，但是PA-MBE方法由于自身的特点，需要约300W高频的射频功率，而且它成本昂贵，不适合商业化发展。磁控溅射法制备的InN薄膜质量差，结晶差，生长不均匀。At present, the growth methods of InN thin films mainly include metal-organic chemical vapor deposition (MOCVD), plasma-assisted molecular beam epitaxy (PA-MBE) and magnetron sputtering. The reactants used in the MOCVD preparation method are organic sources, and anti-virus measures need to be taken, and the MOCVD method requires a higher temperature (about 750-1000 ° C), which is not conducive to the thermal stability of InN. The PA-MBE method has a high degree of vacuum, the reaction source used is simple, and can achieve high-quality InN film epitaxial growth, but due to its own characteristics, the PA-MBE method requires about 300W of high-frequency radio frequency power, and it is expensive. Not suitable for commercial development. The InN film prepared by magnetron sputtering has poor quality, poor crystallization and uneven growth.
发明内容Contents of the invention
针对现有技术的不足，本发明提供了一种非极性氮化铟纳米晶薄膜的制备装置和方法，该方法利用自行设计的低温等离子体增强与蒸发镀相结合的气相沉积装置，提供一种利用低温等离子体辅助热蒸发方法在硅和石英衬底上直接制备非极性InN纳米晶薄膜的新方法，无需在硅或石英衬底上预先进行催化剂和缓冲层的生长。该工艺方法使用原料简单、成本低，没有添加任何催化剂和模板，易于大尺寸衬底基片上生长，为制备高性能InN光电器件提供实验材料。Aiming at the deficiencies of the prior art, the present invention provides a non-polar indium nitride nanocrystalline thin film preparation device and method. The method uses a self-designed low-temperature plasma enhancement and vapor deposition device combined with evaporation plating to provide a A new method to directly prepare non-polar InN nanocrystalline thin films on silicon and quartz substrates by using low-temperature plasma-assisted thermal evaporation method, without the need for pre-growth of catalyst and buffer layer on silicon or quartz substrates. The process method uses simple raw materials, low cost, does not add any catalyst and template, is easy to grow on a large-scale substrate, and provides experimental materials for preparing high-performance InN photoelectric devices.
本发明采用的技术方案如下：The technical scheme that the present invention adopts is as follows:
本发明的一种非极性氮化铟纳米晶薄膜的制备装置，包括反应腔体，衬底基片样品台、束源炉、射频电极、真空机械泵、分子泵和氮气供给系统；A non-polar indium nitride nanocrystalline film preparation device of the present invention comprises a reaction chamber, a substrate sample stage, a beam source furnace, a radio frequency electrode, a vacuum mechanical pump, a molecular pump and a nitrogen gas supply system;
所述的反应腔体为密闭腔体，其中，衬底基片样品台、束源炉和射频电极均布置在反应腔体内；其中，衬底基片样品台设置在反应腔体上方，束源炉设置在反应腔体下方；The reaction chamber is a closed chamber, wherein the substrate sample stage, the beam source furnace and the radio frequency electrode are all arranged in the reaction chamber; wherein the substrate substrate sample stage is arranged above the reaction chamber, and the beam source The furnace is arranged under the reaction chamber;
反应腔体两侧设置有进气口、出气口和接地口，进气口和接地口相对，出气口设置在反应腔体进气口相对一侧上方，进气口一侧设置有射频电极，射频电极和射频电源相连接，射频电极相对一侧接地，射频电极上设置有气体喷淋头；The two sides of the reaction chamber are provided with an air inlet, an air outlet, and a grounding port. The air inlet and the grounding port are opposite to each other. The radio frequency electrode is connected to the radio frequency power supply, the opposite side of the radio frequency electrode is grounded, and a gas shower head is arranged on the radio frequency electrode;
进气口外接氮气供给系统，出气口外接真空机械泵和分子泵，同时，反应腔体外的出气口部分设置有电动蝶阀，以控制稳定的腔体气压。The air inlet is connected to a nitrogen supply system, and the gas outlet is connected to a vacuum mechanical pump and a molecular pump. At the same time, the gas outlet outside the reaction chamber is equipped with an electric butterfly valve to control the stable chamber air pressure.
所述的衬底基片样品台和束源炉相对位置关系为：所述的衬底基片样品台和束源炉的垂直距离为7～12cm；衬底基片样品台轴线和束源炉轴线呈0～45°夹角。The relative positional relationship between the substrate sample table and the beam source furnace is as follows: the vertical distance between the substrate sample table and the beam source furnace is 7-12 cm; the axis of the substrate sample table and the beam source furnace axis are 0 ~45° included angle.
所述的非极性氮化铟纳米晶薄膜的制备装置，所述的束源炉包括坩埚、金属挡板和加热丝，其中，坩埚采用的材质为氮化硼、氧化铝或石墨中的一种。In the preparation device of the non-polar indium nitride nanocrystalline thin film, the beam source furnace includes a crucible, a metal baffle and a heating wire, wherein the material of the crucible is one of boron nitride, aluminum oxide or graphite. kind.
本发明的非极性氮化铟纳米晶薄膜的制备方法，采用上述装置，包括以下步骤：The preparation method of the nonpolar indium nitride nanocrystalline thin film of the present invention adopts the above-mentioned device, comprising the following steps:
步骤1，衬底基片预处理Step 1, substrate substrate pretreatment
将衬底基片超声清洗，自然风干，得到处理后的衬底基片；Ultrasonic cleaning of the substrate substrate and natural air drying to obtain the processed substrate substrate;
步骤2，组装装置Step 2, Assembling the Device
(1)将处理后的衬底基片固定在衬底基片样品台上；(1) fixing the substrate substrate after processing on the substrate substrate sample stage;
(2)将金属铟颗粒放入束源炉的坩埚中；(2) Putting metal indium particles into the crucible of the beam source furnace;
(3)调整束源炉和衬底基片样品台的垂直距离和轴线角度；(3) Adjust the vertical distance and axis angle between the beam source furnace and the substrate sample stage;
(4)关闭反应腔体，装置密封；(4) close the reaction chamber, and the device is sealed;
步骤3，制备Step 3, Preparation
(1)采用真空机械泵和分子泵对反应装置抽真空，抽至压力≤1.0x10-4Pa，加热衬底基片样品台温度为450～650℃，进行退火，退火时间为10～30min；(1) Use a vacuum mechanical pump and a molecular pump to evacuate the reaction device to a pressure of ≤1.0x10-4 Pa, heat the substrate and the sample stage at a temperature of 450-650°C, and perform annealing for 10-30 minutes;
(2)关闭分子泵，持续通入流量为5～10sccm的氮气，启动电动蝶阀，自动控制反应腔体氮气压力稳定为25～50Pa；(2) Turn off the molecular pump, continuously feed nitrogen with a flow rate of 5-10 sccm, start the electric butterfly valve, and automatically control the nitrogen pressure in the reaction chamber to be stable at 25-50 Pa;
(3)打开射频电极，设定射频电极的射频功率为120～200W，进行辉光清洗衬底基片，清洗时间为5～10min；(3) Turn on the radio-frequency electrode, set the radio-frequency power of the radio-frequency electrode to 120-200W, and perform glow cleaning of the substrate for 5-10 minutes;
(4)启动束源炉，加热至温度为700～800℃，并打开束源炉的金属挡板，维持氮气流量、反应腔体氮气压力和射频功率不变的条件下，反应时间为3～5h；(4) Start the beam source furnace, heat it to a temperature of 700-800°C, and open the metal baffle of the beam source furnace. Under the conditions of maintaining the nitrogen flow rate, nitrogen pressure in the reaction chamber and radio frequency power, the reaction time is 3-800°C. 5h;
步骤4，后处理Step 4, Postprocessing
反应完成后，依次关闭装置束源炉和衬底基片样品台加热电源，关闭射频电源，关闭氮气，样品冷却后，取出，得到沉积在衬底基片的非极性氮化铟纳米晶薄膜。After the reaction is completed, turn off the beam source furnace of the device and the heating power of the substrate sample stage in turn, turn off the radio frequency power supply, and turn off the nitrogen gas. After the sample is cooled, take it out to obtain a non-polar indium nitride nanocrystalline film deposited on the substrate. .
所述的步骤1中，所述的衬底基片为石英片或硅片；In the step 1, the substrate substrate is a quartz wafer or a silicon wafer;
所述的步骤1中，所述的超声清洗为，将衬底基片置于酒精中，超声清洗15～20min。In the step 1, the ultrasonic cleaning includes placing the substrate in alcohol and ultrasonic cleaning for 15-20 minutes.
所述的步骤2中，所述的金属铟的纯度为99.999wt.％以上。In the step 2, the purity of the metal indium is above 99.999wt.%.
所述的步骤3中，所述的步骤3(2)中，控制流量采用的流量计为质量流量计。In the step 3, in the step 3(2), the flowmeter used to control the flow rate is a mass flowmeter.
所述的步骤4中，所述的依次关闭时间间隔为10～15min。In the step 4, the time interval of sequential closing is 10-15 minutes.
所述的非极性氮化铟纳米晶薄膜的XRD图谱中(002)衍射峰没有出现或者极弱，表明氮化铟薄膜的生长是沿着非c轴极性方向，因此制备的产品为非极性氮化铟薄膜。得到的非极性氮化铟薄膜的厚度为400～650nm，InN纳米晶颗粒长度为150～200nm，形貌尺寸均匀。In the XRD spectrum of the nonpolar indium nitride nanocrystalline film, the (002) diffraction peak does not appear or is extremely weak, indicating that the growth of the indium nitride film is along the non-c-axis polar direction, so the prepared product is non-polar Polar indium nitride thin film. The obtained non-polar indium nitride thin film has a thickness of 400-650nm, the length of InN nano crystal particles is 150-200nm, and the shape and size are uniform.
其中，当衬底基片温度为550～650℃时，生成的InN纳米晶颗粒为棱锥状。Wherein, when the temperature of the substrate is 550-650° C., the formed InN nano-crystal particles are pyramid-shaped.
本发明的一种非极性氮化铟纳米晶薄膜的制备装置和方法，相比于现有技术，其有益效果在于：Compared with the prior art, the preparation device and method of a non-polar indium nitride nanocrystalline thin film of the present invention have the beneficial effects of:
1.本发明利用自行设计的沉积系统可以直接在硅和石英衬底上制备较高质量InN纳米晶薄膜，无需在基片上预先进行催化剂或缓冲层。1. The present invention uses a self-designed deposition system to directly prepare higher-quality InN nanocrystalline films on silicon and quartz substrates, without pre-forming catalysts or buffer layers on the substrates.
2.本发明独立控制束源炉蒸发温度和衬底基片的生长温度，无需较高的真空度，相对较低的射频功率提供了充足的活性氮源，具有沉积温度低，克服了InN热稳定性差的生长特点。2. The present invention independently controls the evaporation temperature of the beam source furnace and the growth temperature of the substrate substrate, does not require a high degree of vacuum, relatively low radio frequency power provides sufficient active nitrogen sources, has a low deposition temperature, and overcomes InN heat Growth characteristics of poor stability.
3.本发明抽气管路配备过滤器、压力控制薄膜硅及电动蝶阀，组成智能联动系统，可以提供稳定的工作气压。3. The air extraction pipeline of the present invention is equipped with a filter, a pressure control thin film silicon and an electric butterfly valve to form an intelligent linkage system, which can provide stable working air pressure.
4.本发明使用原料简单、没有添加任何催化剂和模板、易于大尺寸硅和石英衬底上生长，重复性好、可适用于大量的工业化生长InN纳米晶薄膜4. The present invention uses simple raw materials, does not add any catalysts and templates, is easy to grow on large-scale silicon and quartz substrates, has good repeatability, and is applicable to a large number of industrial growth InN nanocrystalline films
5.本发明利用自行设计的低温等离子体增强与蒸发镀相结合的气相沉积系统，采用气相沉积方法，以金属In和N2为反应原料，在25～50Pa的氮气压下，射频功率为120～200W，通过控制蒸发源温度、衬底基片生长温度、蒸发源与衬底基片距离以及沉积时间，实现了InN纳米晶薄膜在硅或石英衬底上的生长。制备的纳米晶薄膜具有形貌尺寸均匀、结晶质量高和纯度高的特点。5. The present invention utilizes a self-designed low-temperature plasma enhanced vapor deposition system combined with evaporation plating, adopts a vapor deposition method, uses metalIn and N as reaction raw materials, and under a nitrogen pressure of 25 to 50 Pa, the radio frequency power is 120 ~200W, by controlling the evaporation source temperature, the growth temperature of the substrate, the distance between the evaporation source and the substrate, and the deposition time, the growth of InN nanocrystalline thin films on silicon or quartz substrates is realized. The prepared nanocrystalline film has the characteristics of uniform shape and size, high crystal quality and high purity.
附图说明Description of drawings
图1为本发明非极性氮化铟纳米晶薄膜的制备装置结构示意图；Fig. 1 is a schematic diagram of the preparation device structure of the nonpolar indium nitride nanocrystalline thin film of the present invention;
其中，1为反应腔体，2为衬底基片样品台，3为束源炉，4为射频电极，5为真空机械泵，6为分子泵，7为氮气供给系统；1-1为进气口，1-2为出气口，1-3为接地口，1-4为电动蝶阀，4-1为射频电源，4-2为气体喷淋头，3-1为金属挡板。Among them, 1 is the reaction chamber, 2 is the substrate sample stage, 3 is the beam source furnace, 4 is the radio frequency electrode, 5 is the vacuum mechanical pump, 6 is the molecular pump, 7 is the nitrogen supply system; 1-1 is the inlet Air port, 1-2 is the air outlet, 1-3 is the grounding port, 1-4 is the electric butterfly valve, 4-1 is the radio frequency power supply, 4-2 is the gas spray head, 3-1 is the metal baffle.
图2为本发明实施例1中制备的InN纳米晶薄膜XRD图谱；Fig. 2 is the XRD spectrum of the InN nanocrystalline film prepared in Example 1 of the present invention;
图3为本发明实施例2中制备的InN纳米晶薄膜XRD图谱；Fig. 3 is the XRD spectrum of the InN nanocrystalline film prepared in Example 2 of the present invention;
图4为本发明实施例1中制备的InN纳米晶薄膜的SEM图；Fig. 4 is the SEM figure of the InN nanocrystalline film prepared in the embodiment of the present invention 1;
图5为本发明实施例2中制备的InN纳米晶薄膜的SEM图；Fig. 5 is the SEM figure of the InN nanocrystalline film prepared in the embodiment 2 of the present invention;
图6为本发明实施例3中制备的InN纳米晶薄膜的SEM图；Fig. 6 is the SEM picture of the InN nanocrystalline film prepared in the embodiment of the present invention 3;
图7为本发明实施例4中制备的InN纳米晶薄膜的SEM图；Fig. 7 is the SEM picture of the InN nanocrystalline film prepared in the embodiment of the present invention 4;
图8为本发明实施例1中制备的InN纳米晶薄膜厚度SEM图；Figure 8 is an SEM image of the thickness of the InN nanocrystalline film prepared in Example 1 of the present invention;
图9为本发明实施例5中制备的InN纳米晶薄膜厚度SEM图。FIG. 9 is an SEM image of the thickness of the InN nanocrystalline film prepared in Example 5 of the present invention.
图10为本发明实施例6中制备的InN纳米晶薄膜厚度SEM图。FIG. 10 is an SEM image of the thickness of the InN nanocrystalline film prepared in Example 6 of the present invention.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步的详细说明。The present invention will be described in further detail below in conjunction with embodiment.
以下实施例，除特殊说明，所用的设备和原料均为市购。In the following examples, unless otherwise specified, all equipment and raw materials used are commercially available.
以下实施例，控制流量采用的流量计为质量流量计。In the following embodiments, the flowmeter used to control the flow rate is a mass flowmeter.
实施例1Example 1
一种非极性氮化铟纳米晶薄膜的制备装置，其结构示意图见图1，具体包括反应腔体1，衬底基片样品台2、束源炉3、射频电极4、真空机械泵5、分子泵6和氮气供给系统7；A preparation device for a non-polar indium nitride nanocrystalline thin film, its structural schematic diagram is shown in Figure 1, specifically including a reaction chamber 1, a substrate substrate sample stage 2, a beam source furnace 3, a radio frequency electrode 4, and a vacuum mechanical pump 5 , molecular pump 6 and nitrogen supply system 7;
所述的反应腔体1为密闭腔体，其中，衬底基片样品台2、束源炉3和射频电极4均布置在反应腔体1内；其中，衬底基片样品台2设置在反应腔体1上方，束源炉3设置在反应腔体1下方；The reaction chamber 1 is a closed chamber, wherein the substrate sample stage 2, the beam source furnace 3 and the radio frequency electrode 4 are all arranged in the reaction chamber 1; wherein the substrate sample stage 2 is arranged on Above the reaction chamber 1, the beam source furnace 3 is arranged below the reaction chamber 1;
反应腔体1两侧设置有进气口1-1、出气口1-2和接地口1-3，进气口1-1和接地口1-3相对，出气口1-2设置在反应腔体进气口1-1相对一侧上方，进气口1-1一侧设置有射频电极4，射频电极4和射频电源4-1相连接，射频电极4-1相对一侧接地，射频电极4-1上设置有气体喷淋头4-2；The two sides of the reaction chamber 1 are provided with an air inlet 1-1, an air outlet 1-2 and a grounding port 1-3, the air inlet 1-1 is opposite to the grounding port 1-3, and the air outlet 1-2 is set in the reaction chamber Above the opposite side of the body air inlet 1-1, the side of the air inlet 1-1 is provided with a radio frequency electrode 4, the radio frequency electrode 4 is connected to the radio frequency power supply 4-1, the opposite side of the radio frequency electrode 4-1 is grounded, and the radio frequency electrode 4 4-1 is provided with a gas shower head 4-2;
进气口1-1外接氮气供给系统7，出气口1-2外接真空机械泵5和分子泵6，同时，反应腔体外的出气口部分设置有电动蝶阀1-4，以控制稳定的腔体气压。The air inlet 1-1 is externally connected to the nitrogen supply system 7, and the gas outlet 1-2 is externally connected to the vacuum mechanical pump 5 and the molecular pump 6. At the same time, the gas outlet part outside the reaction chamber is equipped with an electric butterfly valve 1-4 to control the stable chamber. air pressure.
所述的衬底基片样品台2和束源炉3相对位置关系为：所述的衬底基片样品台和束源炉的垂直距离为10cm；衬底基片样品台轴线和束源炉轴线重合。The relative positional relationship between the substrate sample stage 2 and the beam source furnace 3 is as follows: the vertical distance between the substrate sample stage and the beam source furnace is 10 cm; the axis of the substrate sample stage coincides with the beam source furnace axis.
所述的非极性氮化铟纳米晶薄膜的制备装置，所述的束源炉3包括坩埚、金属挡板3-1和加热丝，其中，坩埚采用的材质为氮化硼。In the preparation device of the non-polar indium nitride nanocrystalline thin film, the beam source furnace 3 includes a crucible, a metal baffle 3-1 and a heating wire, wherein the material of the crucible is boron nitride.
一种非极性氮化铟纳米晶薄膜的制备方法，采用上述装置，包括以下步骤：A method for preparing a nonpolar indium nitride nanocrystalline film, using the above-mentioned device, comprising the following steps:
步骤1，衬底基片预处理Step 1, substrate substrate pretreatment
将硅片作为衬底基片，置于酒精中超声清洗15min后，取出自然风干，得到处理后的硅衬底；The silicon wafer is used as the substrate substrate, and after being ultrasonically cleaned in alcohol for 15 minutes, it is taken out and air-dried naturally to obtain the processed silicon substrate;
步骤2，组装装置Step 2, Assembling the Device
(1)打开反应腔体，将处理后的硅衬底基片固定在衬底基片样品台上；(1) Open the reaction chamber, and fix the processed silicon substrate on the substrate sample stage;
(2)将10g(纯度为5N)的金属铟颗粒放入束源炉的氮化硼坩埚中；(2) Put 10g (purity of 5N) metal indium particles into the boron nitride crucible of the beam source furnace;
(3)调整束源炉和衬底基片样品台的垂直距离和轴线角度；(3) Adjust the vertical distance and axis angle between the beam source furnace and the substrate sample stage;
(4)关闭反应腔体，装置密封；(4) close the reaction chamber, and the device is sealed;
步骤3，制备Step 3, Preparation
(1)采用真空机械泵和分子泵对反应装置抽真空，抽至压力≤1.0x10-4Pa，加热衬底基片样品台温度为550℃，进行退火，退火时间为30min；(1) Use a vacuum mechanical pump and a molecular pump to evacuate the reaction device to a pressure of ≤1.0x10-4 Pa, heat the substrate and the sample stage at a temperature of 550°C, and perform annealing for 30 minutes;
(2)关闭分子泵，持续通入流量为10sccm的氮气，启动电动蝶阀，自动控制反应腔体氮气压力稳定为25Pa；(2) Turn off the molecular pump, continuously feed in nitrogen with a flow rate of 10 sccm, start the electric butterfly valve, and automatically control the nitrogen pressure in the reaction chamber to be stable at 25 Pa;
(3)打开射频电极，设定射频电极的射频功率为150W，进行辉光清洗衬底基片，清洗时间为8min；(3) Turn on the radio frequency electrode, set the radio frequency power of the radio frequency electrode to 150W, and perform glow cleaning of the substrate substrate, and the cleaning time is 8 minutes;
(4)启动束源炉，加热至温度为750℃，并打开束源炉的金属挡板，维持氮气流量、反应腔体氮气压力和射频功率不变的条件下，反应时间为4h；(4) Start the beam source furnace, heat it to a temperature of 750°C, open the metal baffle of the beam source furnace, and keep the nitrogen flow rate, nitrogen pressure in the reaction chamber and radio frequency power constant, and the reaction time is 4 hours;
步骤4，后处理Step 4, Postprocessing
反应完成后，依次关闭装置束源炉和衬底基片样品台加热电源，关闭束源炉的金属挡板，关闭射频电源，关闭真空机械泵，10min后关闭氮气，样品随炉冷却至室温后，取出，得到沉积在衬底基片的非极性氮化铟纳米晶薄膜。After the reaction is completed, turn off the heating power of the beam source furnace and substrate sample stage of the device in turn, close the metal baffle of the beam source furnace, turn off the radio frequency power supply, turn off the vacuum mechanical pump, and turn off the nitrogen gas after 10 minutes, and the sample is cooled to room temperature with the furnace , taken out to obtain a non-polar indium nitride nanocrystalline film deposited on the substrate.
本实施例在硅衬底上制备的InN纳米晶薄膜XRD图谱见图2，从图2中的XRD分析，从图中可以看出到明显的特征峰，分别与(100)、(101)、(102)、(110)、(112)相对应，并且衍射峰明显，为纤锌矿结构的InN晶体，通过Jade软件分析，与标准的InN的衍射峰一致，说明制得的InN纳米晶薄膜结晶质量较高，纯度高，无杂质峰。The XRD spectrum of the InN nanocrystalline thin film prepared on the silicon substrate in this embodiment is shown in Fig. 2, from the XRD analysis in Fig. (102), (110), (112) correspond to, and the diffraction peaks are obvious, it is InN crystal with wurtzite structure, analyzed by Jade software, it is consistent with the standard InN diffraction peak, indicating that the prepared InN nanocrystalline film The crystal quality is high, the purity is high, and there is no impurity peak.
所述的氮化铟纳米晶薄膜的XRD图谱中(002)衍射峰没有出现或者极弱，表明氮化铟薄膜的生长是沿着非c轴极性方向，因此制备的产品为非极性氮化铟薄膜。本实施例在硅衬底上制备的InN纳米晶薄膜SEM图见图4，从图4中，可以看到，制备InN纳米晶薄膜形貌尺寸均匀，在硅衬底上排列紧密，得到的InN纳米晶颗粒长度为200nm，形貌尺寸均匀。其中，形成的非极性氮化铟薄膜的厚度为440nm左右，见图5。The (002) diffraction peak does not appear or is extremely weak in the XRD spectrum of described indium nitride nanocrystalline thin film, shows that the growth of indium nitride thin film is along the non-c-axis polar direction, so the product prepared is nonpolar nitrogen indium thin film. The SEM image of the InN nanocrystalline film prepared on the silicon substrate in this embodiment is shown in Figure 4. From Figure 4, it can be seen that the prepared InN nanocrystalline film has uniform morphology and size, and is closely arranged on the silicon substrate. The length of the nanocrystalline particles is 200nm, and the shape and size are uniform. Wherein, the thickness of the formed non-polar indium nitride thin film is about 440 nm, as shown in FIG. 5 .
实施例2Example 2
一种非极性氮化铟纳米晶薄膜的制备装置，同实施例1。A preparation device for non-polar indium nitride nanocrystalline thin film, same as embodiment 1.
一种非极性氮化铟纳米晶薄膜的制备方法，采用上述装置，包括步骤同实施例1，不同之处在于，采用的衬底基片为石英片。A method for preparing a non-polar indium nitride nanocrystalline thin film, using the above-mentioned device, including the same steps as in Example 1, except that the substrate used is a quartz plate.
本实施例在石英衬底上制备的InN纳米晶薄膜XRD图谱见图3，从图3中的XRD分析，从图中可以看出到明显的特征峰，分别与(100)、(101)、(102)、(110)、(112)相对应，并且衍射峰明显，为纤锌矿结构的InN晶体，通过Jade软件分析，与标准的InN的衍射峰一致，说明制得的InN纳米晶薄膜结晶质量较高，纯度高，无杂质峰。The XRD spectrum of the InN nanocrystalline film prepared on the quartz substrate in this embodiment is shown in Fig. 3, from the XRD analysis in Fig. 3, it can be seen from the figure that there are obvious characteristic peaks, respectively corresponding to (100), (101), (102), (110), (112) correspond to, and the diffraction peaks are obvious, it is InN crystal with wurtzite structure, analyzed by Jade software, it is consistent with the standard InN diffraction peak, indicating that the prepared InN nanocrystalline film The crystal quality is high, the purity is high, and there is no impurity peak.
本实施例在石英衬底上制备的InN纳米晶薄膜SEM图见图6，从图6中，可以看到，制备InN纳米晶薄膜形貌尺寸均匀，在石英衬底上排列紧密。The SEM image of the InN nanocrystalline thin film prepared on the quartz substrate in this embodiment is shown in FIG. 6 . From FIG. 6 , it can be seen that the prepared InN nanocrystalline thin film has uniform shape and size, and is closely arranged on the quartz substrate.
实施例3Example 3
一种非极性氮化铟纳米晶薄膜的制备装置，同实施例1。A preparation device for non-polar indium nitride nanocrystalline thin film, same as embodiment 1.
一种非极性氮化铟纳米晶薄膜的制备方法，采用上述装置，包括步骤同实施例2，不同之处在于，衬底基片样品台温度为450℃。A method for preparing a non-polar indium nitride nanocrystalline thin film, using the above-mentioned device, including the same steps as in Example 2, except that the temperature of the substrate sample stage is 450°C.
本实施例在石英衬底上制备的InN纳米晶薄膜SEM图见图7，从图7中，可以看到，制备InN纳米晶薄膜形貌尺寸均匀，在石英衬底上排列紧密。The SEM image of the InN nanocrystalline thin film prepared on the quartz substrate in this embodiment is shown in FIG. 7 . From FIG. 7 , it can be seen that the prepared InN nanocrystalline thin film has uniform shape and size and is closely arranged on the quartz substrate.
实施例4Example 4
一种非极性氮化铟纳米晶薄膜的制备装置，同实施例1。A preparation device for non-polar indium nitride nanocrystalline thin film, same as embodiment 1.
一种非极性氮化铟纳米晶薄膜的制备方法，采用上述装置，包括步骤同实施例1，不同之处在于，衬底基片样品台温度为650℃。A method for preparing a non-polar indium nitride nanocrystalline thin film, using the above-mentioned device, including the same steps as in Example 1, except that the temperature of the substrate sample stage is 650°C.
本实施例在硅衬底上制备的InN纳米晶薄膜SEM图见图8，从图8中，可以看到，制备InN纳米晶薄膜形貌尺寸均匀，在石英衬底上排列紧密，生成的InN纳米晶颗粒为棱锥状。The SEM image of the InN nanocrystalline film prepared on the silicon substrate in this embodiment is shown in Figure 8. From Figure 8, it can be seen that the prepared InN nanocrystalline film has uniform morphology and size, and is closely arranged on the quartz substrate. Nanocrystalline particles are pyramid-shaped.
通过实施例1～4进行对比分析，制备InN纳米晶薄膜形貌尺寸均匀，随着温度升高，制备的InN纳米晶薄膜更致密。衬底基片温度为550℃时，硅衬底上InN纳米晶颗粒尺寸比石英衬底上InN纳米晶颗粒尺寸相对大，相对稀疏些(见图4(b)和图6(b)对比)。650℃硅衬底上得到棱锥状InN纳米晶颗粒。Through the comparative analysis of Examples 1-4, the prepared InN nanocrystalline thin film has a uniform shape and size, and the prepared InN nanocrystalline thin film is denser as the temperature increases. When the substrate temperature is 550°C, the size of InN nanocrystal particles on the silicon substrate is relatively larger than that on the quartz substrate, and relatively sparse (see Figure 4(b) for comparison with Figure 6(b)) . Pyramidal InN nanocrystalline particles were obtained on a silicon substrate at 650°C.
实施例5Example 5
一种非极性氮化铟纳米晶薄膜的制备装置，同实施例1，不同之处在于，所述的衬底基片样品台2和束源炉3相对位置关系为：所述的衬底基片样品台和束源炉的垂直距离为7cm；衬底基片样品台轴线和束源炉轴线呈45°夹角。A preparation device for a nonpolar indium nitride nanocrystalline thin film, the same as in Example 1, the difference is that the relative positional relationship between the substrate substrate sample stage 2 and the beam source furnace 3 is: the substrate substrate The vertical distance between the sample stage and the beam source furnace is 7cm; the axis of the substrate sample stage and the axis of the beam source furnace form an included angle of 45°.
所述的非极性氮化铟纳米晶薄膜的制备装置，所述的束源炉3包括坩埚、金属挡板和加热丝，其中，坩埚采用的材质为石墨。In the preparation device of the non-polar indium nitride nanocrystalline thin film, the beam source furnace 3 includes a crucible, a metal baffle and a heating wire, wherein the material of the crucible is graphite.
一种非极性氮化铟纳米晶薄膜的制备方法，采用上述装置，包括以下步骤：A method for preparing a nonpolar indium nitride nanocrystalline film, using the above-mentioned device, comprising the following steps:
步骤1，衬底基片预处理Step 1, substrate substrate pretreatment
将硅片作为衬底基片，置于酒精中超声清洗20min后，取出自然风干，得到处理后的硅衬底；The silicon wafer is used as the substrate substrate, and after being ultrasonically cleaned in alcohol for 20 minutes, it is taken out and air-dried naturally to obtain the processed silicon substrate;
步骤2，组装装置Step 2, Assembling the Device
(1)打开反应腔体，将处理后的硅衬底固定在衬底基片样品台上；(1) Open the reaction chamber, and fix the processed silicon substrate on the substrate sample stage;
(2)将10g(纯度为5N)的金属铟颗粒放入束源炉的石墨坩埚中；(2) Put 10g (purity of 5N) metal indium particles into the graphite crucible of the beam source furnace;
(3)调整束源炉和衬底基片样品台的垂直距离和轴线角度；(3) Adjust the vertical distance and axis angle between the beam source furnace and the substrate sample stage;
(4)关闭反应腔体，装置密封；(4) close the reaction chamber, and the device is sealed;
步骤3，制备Step 3, Preparation
(1)采用真空机械泵和分子泵对反应装置抽真空，抽至压力≤1.0x10-4Pa，加热衬底基片样品台温度为500℃，进行退火，退火时间为10min；(1) Use a vacuum mechanical pump and a molecular pump to evacuate the reaction device to a pressure of ≤1.0x10-4 Pa, heat the substrate and the sample stage at a temperature of 500°C, and perform annealing for 10 minutes;
(2)关闭分子泵，持续通入流量为5sccm的氮气，启动电动蝶阀，自动控制反应腔体氮气压力稳定为50Pa；(2) Turn off the molecular pump, continuously feed in nitrogen with a flow rate of 5 sccm, start the electric butterfly valve, and automatically control the nitrogen pressure in the reaction chamber to be stable at 50 Pa;
(3)打开射频电极，设定射频电极的射频功率为200W，进行辉光清洗衬底基片，清洗时间为10min；(3) Turn on the radio frequency electrode, set the radio frequency power of the radio frequency electrode to 200W, and perform glow cleaning of the substrate for 10 minutes;
(4)启动束源炉，加热至温度为800℃，并打开束源炉的金属挡板，维持氮气流量、反应腔体氮气压力和射频功率不变的条件下，反应时间为5h；(4) Start the beam source furnace, heat it to a temperature of 800°C, open the metal baffle of the beam source furnace, and keep the nitrogen flow rate, nitrogen pressure in the reaction chamber and radio frequency power constant, and the reaction time is 5 hours;
步骤4，后处理Step 4, Postprocessing
反应完成后，依次关闭装置束源炉和衬底基片样品台加热电源，关闭束源炉的金属挡板，关闭射频电源，关闭真空机械泵，15min后关闭氮气，样品随炉冷却至室温后，取出，得到沉积在衬底基片的非极性氮化铟纳米晶薄膜。形成的非极性氮化铟薄膜的厚度为610nm左右，见图9。After the reaction is completed, turn off the heating power supply of the beam source furnace and substrate sample stage of the device in turn, close the metal baffle of the beam source furnace, turn off the radio frequency power supply, turn off the vacuum mechanical pump, and turn off the nitrogen after 15 minutes, and the sample is cooled to room temperature with the furnace , taken out to obtain a non-polar indium nitride nanocrystalline film deposited on the substrate. The thickness of the formed non-polar indium nitride thin film is about 610 nm, as shown in FIG. 9 .
实施例6Example 6
一种非极性氮化铟纳米晶薄膜的制备装置，同实施例1。A preparation device for non-polar indium nitride nanocrystalline thin film, same as embodiment 1.
一种非极性氮化铟纳米晶薄膜的制备方法，采用上述装置，包括以下步骤：A method for preparing a nonpolar indium nitride nanocrystalline film, using the above-mentioned device, comprising the following steps:
步骤1，衬底基片预处理Step 1, substrate substrate pretreatment
将硅片作为衬底基片，置于酒精中超声清洗15min后，取出自然风干，得到处理后的硅衬底；The silicon wafer is used as the substrate substrate, and after being ultrasonically cleaned in alcohol for 15 minutes, it is taken out and air-dried naturally to obtain the processed silicon substrate;
步骤2，组装装置Step 2, Assembling the Device
(1)打开反应腔体，将处理后的硅衬底固定在衬底基片样品台上；(1) Open the reaction chamber, and fix the processed silicon substrate on the substrate sample stage;
(2)将10g(纯度为5N)的金属铟颗粒放入束源炉的氮化硼坩埚中；(2) Put 10g (purity of 5N) metal indium particles into the boron nitride crucible of the beam source furnace;
(3)调整束源炉和衬底基片样品台的垂直距离和轴线角度；(3) Adjust the vertical distance and axis angle between the beam source furnace and the substrate sample stage;
(4)关闭反应腔体，装置密封；(4) close the reaction chamber, and the device is sealed;
步骤3，制备Step 3, Preparation
(1)采用真空机械泵和分子泵对反应装置抽真空，抽至压力≤1.0x10-4Pa，加热衬底基片样品台温度为550℃，进行退火，退火时间为30min；(1) Use a vacuum mechanical pump and a molecular pump to evacuate the reaction device to a pressure of ≤1.0x10-4 Pa, heat the substrate and the sample stage at a temperature of 550°C, and perform annealing for 30 minutes;
(2)关闭分子泵，持续通入流量为10sccm的氮气，启动电动蝶阀，自动控制反应腔体氮气压力稳定为30Pa；(2) Turn off the molecular pump, continuously feed in nitrogen with a flow rate of 10 sccm, start the electric butterfly valve, and automatically control the nitrogen pressure in the reaction chamber to be stable at 30 Pa;
(3)打开射频电极，设定射频电极的射频功率为200W，进行辉光清洗衬底基片，清洗时间为5min；(3) Turn on the radio frequency electrode, set the radio frequency power of the radio frequency electrode to 200W, and perform glow cleaning of the substrate for 5 minutes;
(4)启动束源炉，加热至温度为700℃，并打开束源炉的金属挡板，维持氮气流量、反应腔体氮气压力和射频功率不变的条件下，反应时间为3h；(4) Start the beam source furnace, heat it to a temperature of 700°C, open the metal baffle of the beam source furnace, and keep the nitrogen flow rate, nitrogen pressure in the reaction chamber and radio frequency power constant, and the reaction time is 3 hours;
步骤4，后处理Step 4, Postprocessing
反应完成后，依次关闭装置束源炉和衬底基片样品台加热电源，关闭束源炉的金属挡板，关闭射频电源，关闭真空机械泵，10min后关闭氮气，样品随炉冷却至室温后，取出，得到沉积在衬底基片的非极性氮化铟纳米晶薄膜。形成的非极性氮化铟薄膜的厚度为328nm左右，见图10。After the reaction is completed, turn off the heating power of the beam source furnace and substrate sample stage of the device in turn, close the metal baffle of the beam source furnace, turn off the radio frequency power supply, turn off the vacuum mechanical pump, and turn off the nitrogen gas after 10 minutes, and the sample is cooled to room temperature with the furnace , taken out to obtain a non-polar indium nitride nanocrystalline film deposited on the substrate. The thickness of the formed non-polar indium nitride thin film is about 328 nm, as shown in FIG. 10 .
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| CN201711314853.2ACN108060458B (en) | 2017-12-12 | 2017-12-12 | A kind of preparation device and method of non-polar indium nitride nanocrystalline thin film |
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| CN113897677B (en)* | 2021-09-30 | 2023-04-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Indium nitride crystal and method for growing same |
| CN114855270B (en)* | 2022-04-21 | 2023-07-28 | 南昌大学 | Molecular beam-like epitaxy equipment and film preparation method |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308145A (en)* | 2000-11-17 | 2001-08-15 | 武汉大学 | Gallium nitride film preparing technology and special equipment |
| JP2010538949A (en)* | 2007-01-04 | 2010-12-16 | アリゾナ ボード オブ リージェンツ ア ボディー コーポレート アクティング オン ビハーフ オブ アリゾナ ステイト ユニバーシティ | Zirconium and hafnium boride alloy templates for silicon for nitride incorporation |
| CN100549242C (en)* | 2007-05-17 | 2009-10-14 | 浙江大学 | A kind of growing apparatus for preparing IV-VI family semiconductor single crystal thin film |
| CN101423927B (en)* | 2008-12-11 | 2010-10-27 | 四川师范大学 | A kind of preparation method of AlxIn1-xN film |
| Publication number | Publication date |
|---|---|
| CN108060458A (en) | 2018-05-22 |
| Publication | Publication Date | Title |
|---|---|---|
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