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一种氮化镁薄膜及其制备方法 【EN】A kind of nitridation magnesium film and preparation method thereof

申请(专利)号:CN201910139644.1国省代码:吉林 22
申请(专利权)人:【中文】吉林大学【EN】Jilin University
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摘要:
【中文】一种氮化镁(Mg3N2)薄膜及其制备方法,属于无机非金属材料领域。其是将高纯Mg靶和清洗后的衬底(硅、蓝宝石、石英、以六方氮化硼为缓冲层的硅、以六方氮化硼为缓冲层的蓝宝石等)放入射频磁控溅射生长室内,采用反应射频磁控溅射技术,利用高纯N2在强电场下电离形成等离子体与溅射出来的Mg反应,生成Mg3N2沉积在衬底上形成薄膜。本发明方法简单,成本低廉,安全可靠,无毒无害;同时可以通过调节Mg靶的靶距、溅射功率、溅射时间以及衬底温度等参数来控制薄膜的生长速率和薄膜厚度,可获得大面积、高质量的Mg3N2薄膜,实现薄膜的可控性以及重复性生长。 【EN】Paragraph:A kind of magnesium nitride (Mg3N2) film and preparation method thereof, belong to field of inorganic nonmetallic material.It is by high-purity Mg target and cleaning after substrate (silicon, sapphire, quartz, using hexagonal boron nitride as the silicon of buffer layer, using hexagonal boron nitride as sapphire of buffer layer etc.) be put into rf magnetron sputtering growth room, using reactive radio frequency magnetron sputtering technology, high-purity N is utilized2Ionization forms plasma and reacts with the Mg sputtered out under strong electric field, generates Mg3N2It is deposited on substrate to form film.The method of the present invention is simple, low in cost, securely and reliably, nontoxic;The growth rate and film thickness that film can be controlled by parameters such as range, sputtering power, sputtering time and the underlayer temperatures of adjusting Mg target simultaneously, can get the Mg of large area, high quality3N2Film realizes the controllability and repeatability growth of film.Image:201910139644.GIF

主权项:
【中文】1.一种MgN薄膜的制备方法,其步骤如下: (1)将高纯Mg靶材和清洗后的衬底依次放入磁控溅射生长室内,Mg靶材与衬底之间距离为4~6cm; (2)抽真空使生长室本底真空度≤8.0×10Pa,加热使衬底升温至400~600℃;通入高纯N气,N流量为80~120sccm,控制生长室内工作压强为0.8~1.0Pa,并用挡板遮挡在衬底与靶材之间; (3)将Mg靶材与射频电源(频率为13.56MHz)连接,溅射功率为150~200W;选择自动调节模式使得Mg靶材表面出现辉光,先预溅射20~30min;然后打开档板,开始在衬底上沉积MgN薄膜,沉积速率为30~50nm/min,溅射时间为100~150min; (4)生长结束后,关闭挡板,关闭射频电源,关闭衬底加热电源,待衬底冷却10~20分钟后,再依次关闭N气和真空泵系统,自然冷却至室温,从而在衬底上制备得到厚度为5~7μm的MgN薄膜。 【EN】1. a kind of MgNThe preparation method of film, its step are as follows: (1) substrate after high-purity Mg target and cleaning is sequentially placed into Grown by Magnetron Sputtering room, the spacing of Mg target and substrate From for 4~6cm; (2) vacuumizing makes growth room background vacuum≤8.0 × 10Pa, heating make substrate be warming up to 400~600 DEG C;It is passed through height Pure NGas, NFlow is 80~120sccm, and controlling operating pressure in growth room is 0.8~1.0Pa, and is blocked with baffle in substrate Between target; (3) Mg target is connect with radio-frequency power supply (frequency 13.56MHz), sputtering power is 150~200W;Selection is automatic to adjust Section mode makes Mg target material surface aura, first 20~30min of pre-sputtering occur;Then plate washer is opened, starts to deposit on substrate MgNFilm, deposition rate are 30~50nm/min, and sputtering time is 100~150min; (4) after growing, baffle is closed, closes radio-frequency power supply, closes silicon power supply, it is 10~20 minutes cooling to substrate Afterwards, then successively N is closedGas and vacuum pump system, cooled to room temperature, to be prepared on substrate with a thickness of 5~7 μm MgNFilm.


说明书

【中文】

一种氮化镁薄膜及其制备方法

技术领域

本发明属于无机非金属材料技术领域,具体涉及一种氮化镁(Mg3N2)薄膜及其制备方法。

背景技术

Mg3N2是镁和氮的无机化合物。在室温和标准大气压下,工业上生产的Mg3N2是一种黄绿色粉末。Mg3N2的工业用途很广泛,常作为烧结助剂用来制备高硬度、高导热性、耐腐蚀、耐磨损、耐高温的氮化硼、氮化硅等特种陶瓷材料。Mg3N2在储氢材料、核燃料回收、建筑钢材的冶炼等方面也有重要作用。此外,Mg3N2作为触媒,还能在高温高压下促进六方氮化硼转化为立方氮化硼,同时促进生成六方氮化硼的反应。

第一性原理计算表明,常温常压下Mg3N2具有反方铁锰矿结构,属于立方晶系,晶格常数约为为直接带隙半导体材料。根据Mg3N2的紫外可见吸收光谱可以确定其光学带宽约为2.8eV。因此,Mg3N2作为电子功能材料也具有应用前景。为了实现Mg3N2在电子功能材料方面的应用,制备出高质量Mg3N2薄膜是非常关键的。

目前制备Mg3N2的方法主要包括:氧化镁为催化剂下金属镁与氮气直接反应法、在氮气气氛中镁线圈的爆炸法、低压化学气相沉积法、镁与氨气的直接反应法、镁与氮在氮等离子体中的反应法等。上述方法中制备的多为粉末,虽已实现工业化生产,但制备的Mg3N2粉末中含有较多杂质。制备Mg3N2薄膜的相关报道较少,G.Soto等人利用脉冲激光沉积法,在硅衬底上能够制备出镁与氮化学计量比不同的无定型Mg3N2薄膜。上述这些制备方法成本较高、操作较为复杂、Mg3N2产率较低、难以生长出大面积高质量的Mg3N2薄膜。

发明内容

本发明目的在于提供一种成本低廉、安全可靠、易于操作、能够获得高质量大面积Mg3N2薄膜及其制备方法。其是将高纯Mg靶和清洗后的衬底放入射频磁控溅射生长室内,采用反应射频磁控溅射技术,利用高纯N2在强电场下电离形成等离子体与溅射出来的Mg反应,生成Mg3N2沉积在衬底上形成薄膜。

本发明所采用的原料为高纯镁靶材(纯度99.95%以上),氮源为高纯氮气(纯度99.999%以上)。

本发明所述的一种Mg3N2薄膜的制备方法,是反应磁控溅射法,其步骤如下:

(1)将高纯Mg靶材(纯度99.95%以上)和清洗后的衬底依次放入磁控溅射生长室内,一般衬底可以选用硅、蓝宝石、石英、以六方氮化硼(hBN)为缓冲层的硅(hBN/Si)、以六方氮化硼为缓冲层的蓝宝石(hBN/蓝宝石)等;Mg靶材与衬底之间距离为4~6cm;

(2)抽真空使生长室本底真空度≤8.0×10-4Pa,加热使衬底升温至400~600℃;通入高纯(纯度99.999%以上)N2气,N2流量为80~120sccm,控制生长室内工作压强为0.8~1.0Pa,用挡板遮挡在衬底与靶材之间;

(3)将Mg靶材与射频电源连接,射频电源的频率为13.56MHz,最大输出功率为600W;开启连接Mg靶材的射频电源,选择自动调节模式使得Mg靶材表面出现辉光,溅射功率为150~200W,先预溅射20~30min;然后打开遮挡在衬底与靶材之间的挡板,开始在衬底上沉积Mg3N2薄膜;沉积速率为30~50nm/min,溅射时间为100~150min;

(4)生长Mg3N2薄膜结束后,关闭挡板,关闭连接Mg靶材的射频电源,关闭衬底加热电源,待衬底冷却10~20分钟后,再依次关闭N2气和真空泵系统,自然冷却至室温,从而在衬底上制备得到厚度为5~7μm的Mg3N2薄膜。

本发明的优点在于:(1)方法简单,成本低廉;(2)可以通过调节Mg靶的靶距、溅射功率、衬底温度、工作气压和溅射时间等参数来方便地调控Mg3N2薄膜的生长速度和薄膜厚度;(3)可以获得大面积、高质量Mg3N2薄膜,实现薄膜的可控性以及重复性生长,利于批量制备;(4)安全可靠,无毒无害。

附图说明

图1:本发明采用的射频磁控溅射装置结构示意图。1是生长室;2是进气阀;3是加热台;4是衬底;5是高纯Mg靶材。

图2:本发明方法在Si(图a)以及hBN/Si(图b)上制备的Mg3N2薄膜的Raman光谱。

图3:本发明方法在Si(图a)以及hBN/Si(图b)上制备的Mg3N2薄膜的XRD图谱。

图4:本发明方法在蓝宝石(图a)以及hBN/蓝宝石(图b)上制备的Mg3N2薄膜的Raman光谱。

图5:本发明方法在蓝宝石(图a)以及hBN/蓝宝石(图b)上制备的Mg3N2薄膜的XRD图谱。

具体实施方式

实施例1:

将双面抛光的Si(100)晶片衬底用丙酮超声清洗10分钟,去除表面的有机物杂质;然后,用无水乙醇超声清洗10分钟,去除丙酮;最后,用去离子水超声清洗10分钟,去除乙醇,氮气吹干备用。

将纯度为99.95%的高纯Mg靶5和清洗后的Si(100)衬底放置在图1所示的生长室1中。将系统真空度抽到5.0×10-4Pa。将Mg靶5与衬底的距离调整为5cm。打开加热台3的开关,将衬底4升温至500℃。之后打开进气阀2通入流量为100sccm的高纯N2(纯度99.999%以上)。待气流稳定后,将生长室内工作气压调整到1.0Pa。用挡板遮挡住衬底。打开连接Mg靶5的射频电源,将功率调至200W,选择自动调谐模式,使得Mg靶表面出现稳定的辉光。预溅射20分钟,去除靶材表面的沾污。旋开挡板,开始在衬底4上沉积薄膜,沉积时间120min,薄膜厚度约为5μm。生长结束后,用挡板遮挡住衬底,关闭连接Mg靶5的射频电源。冷却10分钟后,依次关闭N2气阀门和真空泵系统,自然冷却至室温,从而在衬底上制备得到Mg3N2薄膜。

本发明方法在Si(100)衬底上制备的Mg3N2薄膜的Raman光谱如图2(a)所示。位于521cm-1的振动峰源于硅衬底。Mg3N2的最强的振动峰位于380cm-1处,半峰宽仅为9cm-1,可以和硅衬底的Raman峰相比拟,说明Mg3N2薄膜的结晶质量很高。同时还有强度相对较弱的一些振动峰分别位于214cm-1、233cm-1、261cm-1、340cm-1、443cm-1、612cm-1等处,它们都是Mg3N2薄膜的特征峰。

本发明方法在Si(100)衬底上制备的Mg3N2薄膜的XRD图谱如图3(a)所示。图3(a)中,Mg3N2(222)的衍射峰最强,其半峰宽仅为0.136°,表明薄膜质量很高。此外,还观测到Mg3N2(332),Mg3N2(211),Mg3N2(321),Mg3N2(622)和Mg3N2(444)等晶面的衍射峰。此外,我们还在33.1°处观测到硅化镁(Mg2Si)(112)晶面衍射峰,这是由于Si衬底与Mg在高温下反应所致,硅化镁主要位于硅衬底与氮化镁薄膜的界面处。

实施例2:

为了避免硅化镁的产生,我们通过低压化学气相沉积方法,在Si(100)衬底表面沉积了一层六方氮化硼(hBN)薄膜(厚度约2μm),制备出带有hBN缓冲层的Si(100)衬底(即:hBN/Si衬底)。由于本发明只涉及Mg3N2薄膜的制备方法,所以有关hBN薄膜的制备过程这里不做说明。

将hBN/Si衬底放在丙酮中浸泡10分钟,去除有机杂质;然后,在无水乙醇中缓慢清洗10分钟;在去离子水中缓慢清洗10分钟;最后用氮气吹干备用。

将纯度为99.95%的高纯Mg靶5和清洗后的hBN/Si衬底4放置在图1所示的生长室1中。将系统真空度抽到6.0×10-4Pa。将Mg靶5与衬底的距离调整为5cm。打开加热台3的开关,将衬底4升温至550℃。之后打开进气阀2通入流量为100sccm的高纯N2(纯度99.999%以上)。待气流稳定后,将生长室内工作气压调整到0.9Pa。用挡板遮挡住衬底。打开连接Mg靶5的射频电源,将功率调至200W,选择自动调谐模式,使得Mg靶表面出现稳定的辉光。预溅射20分钟,去除靶材表面的沾污。旋开挡板,开始在衬底4上沉积薄膜,沉积时间120min,薄膜厚度约为6μm。生长结束后,用挡板遮挡住衬底,关闭连接Mg靶5的射频电源。冷却10分钟后,依次关闭N2气阀门和真空泵系统,自然冷却至室温,从而在衬底上制备得到Mg3N2薄膜。

本发明方法在hBN/Si(100)上制备的Mg3N2薄膜的Raman光谱如图2(b)所示,其Raman峰位分布与图2(a)完全类似。Mg3N2的最强的振动峰位于380cm-1处,半峰宽约为9cm-1,其强度强于位于521cm-1硅衬底的振动峰,也比图2(a)中的振动峰强,说明Mg3N2薄膜的结晶质量很高。同时也发现了位于214cm-1、233cm-1、261cm-1、340cm-1、443cm-1、612cm-1等处Mg3N2薄膜相对较弱的特征峰。

本发明方法在hBN/Si上制备的Mg3N2薄膜的XRD图谱如图3(b)所示。图3(b)中,Mg3N2(222)的衍射峰最强,其半峰宽仅为0.142°,表明薄膜质量很好。此外,还观测到Mg3N2(332),Mg3N2(211),Mg3N2(321)和Mg3N2(444)等晶面的衍射峰。没有观察到Mg2Si(112)的衍射峰,说明hBN缓冲层隔绝了Si衬底与Mg的反应,抑制了Mg2Si的形成。

实施例3:

将抛光的蓝宝石衬底用丙酮超声清洗10分钟;然后,用无水乙醇超声清洗10分钟;用去离子水超声清洗10分钟;最后用氮气吹干备用。

将纯度为99.95%的高纯Mg靶5和清洗后的蓝宝石衬底4放置在图1所示的生长室1中,将系统真空度抽到5.0×10-4Pa,将Mg靶5与衬底的距离调整为5cm,打开加热台3的开关,将衬底4加热至500℃,之后打开进气阀2通入流量为100sccm的高纯N2(纯度99.999%以上),待气流稳定后,将生长室内工作气压调整到1.0Pa,用挡板遮挡住衬底。打开连接Mg靶5的射频电源,将功率调至200W,选择自动调谐模式,使得Mg靶表面出现稳定的辉光。预溅射20分钟,去除靶材表面的沾污。旋开挡板,开始在衬底4上沉积薄膜,沉积时间120min,薄膜厚度约为5μm。生长结束后,用挡板遮挡住衬底,关闭连接Mg靶5的射频电源。冷却10分钟后,依次关闭N2气阀门和真空泵系统,自然冷却至室温,从而在衬底上制备得到Mg3N2薄膜。

本发明方法在蓝宝石衬底上制备的Mg3N2薄膜的Raman光谱如图4(a)所示,与实施例1完全类似,其中,Mg3N2薄膜最强的振动峰位于380cm-1处,半峰宽约为8cm-1,其他相对较弱的Mg3N2振动峰与图3一致。

本发明方法在蓝宝石衬底上制备的Mg3N2薄膜的XRD图谱如图5(a)所示。图5(a)中,沉积在蓝宝石上的Mg3N2薄膜对应于(222)晶面的衍射峰最强,其半峰宽为0.139°,说明Mg3N2薄膜结晶质量很好。还观测到Mg3N2(211)、Mg3N2(332)和Mg3N2(444)等较弱的晶面衍射峰。同时在41.8°处有强基底峰。

实施例4:

利用LPCVD方法在蓝宝石衬底上制备了一层hBN薄膜(厚度约2μm),以hBN/蓝宝石为衬底进行了Mg3N2薄膜的生长。

将hBN/蓝宝石衬底放在丙酮中浸泡10分钟,去除有机杂质;然后,在无水乙醇中缓慢清洗10分钟;在去离子水中缓慢清洗10分钟;最后用氮气吹干备用。

将纯度为99.95%的高纯Mg靶5和清洗后的hBN/蓝宝石衬底4放置在图1所示的生长室1中,将系统真空度抽到5.0×10-4Pa,将Mg靶5与衬底的距离调整为5cm,打开加热台3的开关,将衬底4加热至600℃,之后打开进气阀2通入流量为100sccm的高纯N2(纯度99.999%以上),待气流稳定后,将生长室内工作气压调整到0.8Pa,用挡板遮挡住衬底。打开连接Mg靶5的射频电源,将功率调至150W,选择自动调谐模式,使得Mg靶表面出现稳定的辉光。预溅射20分钟,去除靶材表面的沾污。旋开挡板,开始在衬底4上沉积薄膜,沉积时间120min,薄膜厚度约为5.5μm。生长结束后,用挡板遮挡住衬底,关闭连接Mg靶5的射频电源。冷却10分钟后,依次关闭N2气阀门和真空泵系统,自然冷却至室温。

本发明方法在hBN/蓝宝石上制备的Mg3N2薄膜的Raman光谱如图4(b)所示,与实施例3完全类似,其中,Mg3N2薄膜最强的振动峰位于380cm-1处,半峰宽约为8cm-1,其他相对较弱的Mg3N2振动峰也与图3(a)一致。

本发明方法在hBN/蓝宝石上制备的Mg3N2薄膜的XRD图谱如图5(b)所示。由于hBN缓冲层的作用,使得蓝宝石衬底峰被抑制,得到晶体质量很高的Mg3N2薄膜。最强的衍射峰仍为Mg3N2(222)晶面衍射峰,其半峰全宽约为0.140°,中强衍射峰对应Mg3N2(332)晶面,其半峰全宽为0.177°。还存在Mg3N2(211)、Mg3N2(321)、Mg3N2(444)等较弱的晶面衍射峰。

【EN】

A kind of nitridation magnesium film and preparation method thereof

Technical field

The invention belongs to technical field of inorganic nonmetallic materials, and in particular to a kind of magnesium nitride (Mg3N2) film and its preparation

Method.

Background technique

Mg3N2It is the inorganic compound of magnesium and nitrogen.It is depressed in room temperature and normal atmosphere, the Mg industrially produced3N2It is a kind of

Yellow greenish powder.Mg3N2Industrial use it is very extensive, frequently as sintering aid be used to prepare high rigidity, high-termal conductivity, it is corrosion-resistant,

The special ceramic materials such as boron nitride wear-resistant, resistant to high temperature, silicon nitride.Mg3N2In hydrogen storage material, nuclear fuel recycling, structural steel

Smelting etc. also play an important role.In addition, Mg3N2As catalyst, moreover it is possible to promote hexagonal boron nitride conversion at high temperature under high pressure

For cubic boron nitride, while promoting to generate the reaction of hexagonal boron nitride.

First-principles calculations show Mg under normal temperature and pressure3N2With negative side's Ferromanganese Ore structure, belong to cubic system, lattice

Constant is aboutFor direct band-gap semicondictor material.According to Mg3N2Ultraviolet-visible absorption spectroscopy can determine its light

Learning bandwidth is about 2.8eV.Therefore, Mg3N2Also there is application prospect as electronic functional material.In order to realize Mg3N2In electronic work

Application in terms of energy material, prepares high quality Mg3N2Film is very crucial.

Preparation Mg at present3N2Method specifically include that magnesia be magnesium metal and the direct reaction method of nitrogen under catalyst,

The explosion method of magnesium coil in nitrogen atmosphere, Low Pressure Chemical Vapor Deposition, magnesium and ammonia direct reaction method, magnesium and nitrogen in nitrogen etc.

Reaction method etc. in gas ions.What is prepared in the above method is mostly powder, though realize industrialized production, the Mg of preparation3N2Powder

Contain more impurity in end.Prepare Mg3N2The relevant report of film is less, and G.Soto et al. utilizes pulsed laser deposition, in silicon

Magnesium can be prepared on substrate to measure from nitrogen chemical than different unformed Mg3N2Film.Above-mentioned these preparation methods cost compared with

Height, complicated operation, Mg3N2Yield is lower, is difficult to grow the Mg of large-area high-quality3N2Film.

Summary of the invention

It is an object of that present invention to provide it is a kind of it is low in cost, safe and reliable, easily operated, high quality large area can be obtained

Mg3N2Film and preparation method thereof.It is that the substrate after high-purity Mg target and cleaning is put into rf magnetron sputtering growth room, is adopted

With reactive radio frequency magnetron sputtering technology, high-purity N is utilized2It is anti-with the Mg that sputters out to form plasma for ionization under strong electric field

It answers, generates Mg3N2It is deposited on substrate to form film.

Raw material of the present invention is high purity magnesium target (99.95% or more purity), and nitrogen source is high pure nitrogen (purity

99.999% or more).

A kind of Mg of the present invention3N2The preparation method of film is reactive magnetron sputtering method, and its step are as follows:

(1) substrate after high-purity Mg target (99.95% or more purity) and cleaning is sequentially placed into Grown by Magnetron Sputtering room

It is interior, general substrate can select silicon, sapphire, quartz, with hexagonal boron nitride (hBN) be buffer layer silicon (hBN/Si), with six

Square boron nitride is the sapphire (hBN/ sapphire) etc. of buffer layer;Distance is 4~6cm between Mg target and substrate;

(2) vacuumizing makes growth room background vacuum≤8.0 × 10-4Pa, heating make substrate be warming up to 400~600 DEG C;It is logical

Enter high-purity (99.999% or more purity) N2Gas, N2Flow be 80~120sccm, control growth room in operating pressure be 0.8~

1.0Pa is blocked between substrate and target with baffle;

(3) Mg target is connect with radio-frequency power supply, the frequency of radio-frequency power supply is 13.56MHz, and peak power output is

600W;The radio-frequency power supply of connection Mg target is opened, selects automatic adjustment mode that Mg target material surface is made aura, sputtering power occur

For 150~200W, first 20~30min of pre-sputtering;Then the baffle blocked between substrate and target is opened, is started on substrate

Deposit Mg3N2Film;Deposition rate is 30~50nm/min, and sputtering time is 100~150min;

(4) Mg is grown3N2After film, baffle is closed, closes the radio-frequency power supply of connection Mg target, closes silicon

Power supply to substrate cooling 10~after twenty minutes, then successively closes N2Gas and vacuum pump system, cooled to room temperature, thus

The Mg with a thickness of 5~7 μm is prepared on substrate3N2Film.

The present invention has the advantages that (1) method is simple, it is low in cost;It (2) can be by adjusting the range of Mg target, sputtering

The parameters such as power, underlayer temperature, operating air pressure and sputtering time easily regulate and control Mg3N2The speed of growth and film of film are thick

Degree;(3) large area, high quality Mg can be obtained3N2Film realizes the controllability and repeatability growth of film, is conducive to batch and makes

It is standby;(4) securely and reliably, nontoxic.

Detailed description of the invention

Fig. 1: the rf magnetron sputtering apparatus structure schematic diagram that the present invention uses.1 is growth room;2 be intake valve;3 be to add

Thermal station;4 be substrate;5 be high-purity Mg target.

Fig. 2: the Mg that the method for the present invention is prepared on Si (figure a) and hBN/Si (figure b)3N2The Raman spectrum of film.

Fig. 3: the Mg that the method for the present invention is prepared on Si (figure a) and hBN/Si (figure b)3N2The XRD spectrum of film.

Fig. 4: the Mg that the method for the present invention is prepared on sapphire (figure a) and hBN/ sapphire (figure b)3N2The Raman of film

Spectrum.

Fig. 5: the Mg that the method for the present invention is prepared on sapphire (figure a) and hBN/ sapphire (figure b)3N2The XRD diagram of film

Spectrum.

Specific embodiment

Embodiment 1:

Si (100) wafer substrates of twin polishing acetone is cleaned by ultrasonic 10 minutes, the organic impurities on surface are removed;

Then, it is cleaned by ultrasonic 10 minutes with dehydrated alcohol, removes acetone;Finally, being cleaned by ultrasonic 10 minutes with deionized water, second is removed

Alcohol is dried with nitrogen spare.

High-purity Mg target 5 that purity is 99.95% is placed on growth room 1 shown in FIG. 1 with Si (100) substrate after cleaning

In.System vacuum is extracted into 5.0 × 10-4Pa.Mg target 5 is adjusted to 5cm at a distance from substrate.The switch of warm table 3 is opened,

Substrate 4 is warming up to 500 DEG C.Intake valve 2 is opened later is passed through the high-purity N that flow is 100sccm2(purity 99.999% with

On).After steady air current, operating air pressure in growth room is adjusted to 1.0Pa.Substrate is sheltered from baffle.Open connection Mg target 5

Radio-frequency power supply, power is adjusted to 200W, selects automatic tuning mode, so that stable aura occurs in Mg target surface.Pre-sputtering

20 minutes, remove the contamination of target material surface.Baffle is unscrewed, deposition film, sedimentation time 120min, film on substrate 4 are started

Thickness is about 5 μm.After growth, substrate is sheltered from baffle, closes the radio-frequency power supply of connection Mg target 5.It cools down after ten minutes,

Successively close N2Air valve and vacuum pump system, cooled to room temperature, so that Mg be prepared on substrate3N2Film.

The Mg that the method for the present invention is prepared on Si (100) substrate3N2Shown in Raman spectrum such as Fig. 2 (a) of film.It is located at

521cm-1Vibration peak be derived from silicon substrate.Mg3N2Strongest vibration peak be located at 380cm-1Place, half-peak breadth is only 9cm-1, can be with

It is comparable with the peak Raman of silicon substrate, illustrate Mg3N2The crystalline quality of film is very high.There are also relatively weak some of intensity simultaneously

Vibration peak is located at 214cm-1、233cm-1、261cm-1、340cm-1、443cm-1、612cm-1Etc., they are all Mg3N2It is thin

The characteristic peak of film.

The Mg that the method for the present invention is prepared on Si (100) substrate3N2Shown in the XRD spectrum of film such as Fig. 3 (a).Fig. 3 (a)

In, Mg3N2(222) diffraction maximum is most strong, and half-peak breadth is only 0.136 °, shows that film quality is very high.In addition, also observing

Mg3N2(332), Mg3N2(211), Mg3N2(321), Mg3N2(622) and Mg3N2(444) diffraction maximum of crystal faces such as.In addition, we

Magnesium silicide (Mg is also observed at 33.1 °2Si) (112) crystallographic plane diffraction peak, this is because Si substrate reacts at high temperature with Mg

Caused, magnesium silicide is predominantly located at silicon substrate and nitrogenizes the interface of magnesium film.

Embodiment 2:

In order to avoid the generation of magnesium silicide, we are heavy in Si (100) substrate surface by low-pressure chemical vapor deposition method

One layer of hexagonal boron nitride (hBN) film (about 2 μm of thickness) has been accumulated, has prepared Si (100) substrate with hBN buffer layer (i.e.:

HBN/Si substrate).Since the present invention pertains only to Mg3N2The preparation method of film, so the preparation process in relation to hBN film is here

It is not described.

HBN/Si substrate is put and is impregnated 10 minutes in acetone, organic impurities is removed;Then, slowly clear in dehydrated alcohol

It washes 10 minutes;It slowly cleans 10 minutes in deionized water;It is finally spare with being dried with nitrogen.

High-purity Mg target 5 that purity is 99.95% is placed on growth room 1 shown in FIG. 1 with the hBN/Si substrate 4 after cleaning

In.System vacuum is extracted into 6.0 × 10-4Pa.Mg target 5 is adjusted to 5cm at a distance from substrate.The switch of warm table 3 is opened,

Substrate 4 is warming up to 550 DEG C.Intake valve 2 is opened later is passed through the high-purity N that flow is 100sccm2(purity 99.999% with

On).After steady air current, operating air pressure in growth room is adjusted to 0.9Pa.Substrate is sheltered from baffle.Open connection Mg target 5

Radio-frequency power supply, power is adjusted to 200W, selects automatic tuning mode, so that stable aura occurs in Mg target surface.Pre-sputtering

20 minutes, remove the contamination of target material surface.Baffle is unscrewed, deposition film, sedimentation time 120min, film on substrate 4 are started

Thickness is about 6 μm.After growth, substrate is sheltered from baffle, closes the radio-frequency power supply of connection Mg target 5.It cools down after ten minutes,

Successively close N2Air valve and vacuum pump system, cooled to room temperature, so that Mg be prepared on substrate3N2Film.

The Mg that the method for the present invention is prepared on hBN/Si (100)3N2Shown in Raman spectrum such as Fig. 2 (b) of film,

The distribution of Raman peak position and Fig. 2 (a) all fours.Mg3N2Strongest vibration peak be located at 380cm-1Place, half-peak breadth is about 9cm-1,

Its intensity is better than positioned at 521cm-1The vibration peak of silicon substrate illustrates Mg also than the vibration peak intensity in Fig. 2 (a)3N2The crystallization of film

It is of high quality.It has also discovered simultaneously positioned at 214cm-1、233cm-1、261cm-1、340cm-1、443cm-1、612cm-1Etc. Mg3N2

The relatively weak characteristic peak of film.

The Mg that the method for the present invention is prepared on hBN/Si3N2Shown in the XRD spectrum of film such as Fig. 3 (b).In Fig. 3 (b),

Mg3N2(222) diffraction maximum is most strong, and half-peak breadth is only 0.142 °, shows that film quality is fine.In addition, also observing Mg3N2

(332), Mg3N2(211), Mg3N2(321) and Mg3N2(444) diffraction maximum of crystal faces such as.Mg is not observed2Si (112) spread out

Peak is penetrated, illustrates that hBN buffer layer has completely cut off reacting for Si substrate and Mg, it is suppressed that Mg2The formation of Si.

Embodiment 3:

The Sapphire Substrate of polishing acetone is cleaned by ultrasonic 10 minutes;Then, it is cleaned by ultrasonic 10 minutes with dehydrated alcohol;

It is cleaned by ultrasonic 10 minutes with deionized water;It is finally spare with being dried with nitrogen.

High-purity Mg target 5 that purity is 99.95% is placed on growth room 1 shown in FIG. 1 with the Sapphire Substrate 4 after cleaning

In, system vacuum is extracted into 5.0 × 10-4Mg target 5 is adjusted at a distance from substrate 5cm, opens the switch of warm table 3 by Pa,

Substrate 4 is heated to 500 DEG C, intake valve 2 is opened later and is passed through the high-purity N that flow is 100sccm2(purity 99.999% with

On), after steady air current, operating air pressure in growth room is adjusted to 1.0Pa, shelters from substrate with baffle.Open connection Mg target 5

Radio-frequency power supply, power is adjusted to 200W, selects automatic tuning mode, so that stable aura occurs in Mg target surface.Pre-sputtering

20 minutes, remove the contamination of target material surface.Baffle is unscrewed, deposition film, sedimentation time 120min, film on substrate 4 are started

Thickness is about 5 μm.After growth, substrate is sheltered from baffle, closes the radio-frequency power supply of connection Mg target 5.It cools down after ten minutes,

Successively close N2Air valve and vacuum pump system, cooled to room temperature, so that Mg be prepared on substrate3N2Film.

The Mg that the method for the present invention is prepared on a sapphire substrate3N2Shown in Raman spectrum such as Fig. 4 (a) of film, with implementation

1 all fours of example, wherein Mg3N2The strongest vibration peak of film is located at 380cm-1Place, half-peak breadth is about 8cm-1, other are relatively

Weak Mg3N2Vibration peak is consistent with Fig. 3.

The Mg that the method for the present invention is prepared on a sapphire substrate3N2Shown in the XRD spectrum of film such as Fig. 5 (a).In Fig. 5 (a),

The Mg of deposition on sapphire3N2The diffraction maximum that film corresponds to (222) crystal face is most strong, and half-peak breadth is 0.139 °, explanation

Mg3N2Film crystalline quality is fine.Also observe Mg3N2(211)、Mg3N2(332) and Mg3N2(444) the weaker crystal face diffraction such as

Peak.There is strong basis bottom peak at 41.8 ° simultaneously.

Embodiment 4:

It is prepared for one layer of hBN film (about 2 μm of thickness) on a sapphire substrate using LPCVD method, with hBN/ sapphire

Mg has been carried out for substrate3N2The growth of film.

HBN/ Sapphire Substrate is put and is impregnated 10 minutes in acetone, organic impurities is removed;Then, delay in dehydrated alcohol

Slow cleaning 10 minutes;It slowly cleans 10 minutes in deionized water;It is finally spare with being dried with nitrogen.

High-purity Mg target 5 that purity is 99.95% is placed on life shown in FIG. 1 with the hBN/ Sapphire Substrate 4 after cleaning

In long room 1, system vacuum is extracted into 5.0 × 10-4Mg target 5 is adjusted at a distance from substrate 5cm, opens warm table 3 by Pa

Switch, is heated to 600 DEG C for substrate 4, opens intake valve 2 later and is passed through the high-purity N that flow is 100sccm2(purity 99.999%

More than), after steady air current, operating air pressure in growth room is adjusted to 0.8Pa, shelters from substrate with baffle.Open connection Mg

Power is adjusted to 150W by the radio-frequency power supply of target 5, selects automatic tuning mode, so that stable aura occurs in Mg target surface.It splashes in advance

It penetrates 20 minutes, removes the contamination of target material surface.Baffle is unscrewed, the deposition film on substrate 4 is started, sedimentation time 120min is thin

Film thickness is about 5.5 μm.After growth, substrate is sheltered from baffle, closes the radio-frequency power supply of connection Mg target 5.It is 10 points cooling

Zhong Hou successively closes N2Air valve and vacuum pump system, cooled to room temperature.

The Mg that the method for the present invention is prepared on hBN/ sapphire3N2Shown in Raman spectrum such as Fig. 4 (b) of film, with implementation

3 all fours of example, wherein Mg3N2The strongest vibration peak of film is located at 380cm-1Place, half-peak breadth is about 8cm-1, other are relatively

Weak Mg3N2Vibration peak is also consistent with Fig. 3 (a).

The Mg that the method for the present invention is prepared on hBN/ sapphire3N2Shown in the XRD spectrum of film such as Fig. 5 (b).Since hBN is slow

The effect of layer is rushed, so that Sapphire Substrate peak is suppressed, obtains the very high Mg of crystal quality3N2Film.Strongest diffraction maximum is still

Mg3N2(222) crystallographic plane diffraction peak, full width at half maximum (FWHM) are about 0.140 °, in strong diffraction maximum correspond to Mg3N2(332) crystal face, half-peak

Overall with is 0.177 °.There is also Mg3N2(211)、Mg3N2(321)、Mg3N2(444) the weaker crystallographic plane diffraction peak such as.

图1
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