CN1206703C - Process for growing P-type ZnO crystal film by real-time doping nitrogen - Google Patents

Process for growing P-type ZnO crystal film by real-time doping nitrogen Download PDF

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CN1206703C
CN1206703C CN 02136110 CN02136110A CN1206703C CN 1206703 C CN1206703 C CN 1206703C CN 02136110 CN02136110 CN 02136110 CN 02136110 A CN02136110 A CN 02136110A CN 1206703 C CN1206703 C CN 1206703C
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substrate
nitrogen
doped
zno crystal
type zno
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CN1391259A (en
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黄靖云
叶志镇
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浙江大学
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Abstract

本发明的实时掺氮生长p型ZnO晶体薄膜的方法是采用磁控溅射法,先将衬底表面清洗后放入直流反应磁控溅射装置的反应室中,反应室真空度抽到至少10 The method of the present invention in real time the nitrogen-doped p-type ZnO crystal grown film was deposited by magnetron sputtering, after cleaning the surface of the substrate into the first reaction chamber DC magnetron sputtering apparatus, the reaction chamber pumped to a vacuum of at least 10

Description

实时掺氮生长p型ZnO晶体薄膜的方法 Real-time growth of nitrogen-doped p-type ZnO crystal thin film method

技术领域 FIELD

本发明涉及p型ZnO的掺杂方法。 The present invention relates to a method of doping a p-type ZnO. 具体说是关于实时掺氮生长p型ZnO晶体薄膜的方法。 Particularly to a method of real time nitrogen-doped p-type ZnO crystal grown films.

背景技术 Background technique

要实现ZnO基器件的应用,制备可控的n和p型ZnO晶体薄膜是必须的。 To achieve application of ZnO-based devices, Controllable n and p-type ZnO crystal film is necessary. 目前,人们对于n型ZnO晶体薄膜的研究已经比较充分,通过掺杂III价元素,已经能够实现实时、浓度可控的低阻n型ZnO晶体薄膜的生长。 Currently, people study crystal n-type ZnO films have been more fully, by doping a III valence element, has been able to achieve real-time, concentration controlled crystal growth of the low resistance n-type thin film ZnO. 但要使ZnO晶体薄膜制备出光电子器件,必须制备ZnO pn结。 But for ZnO Films prepared optoelectronic device, it must be prepared ZnO PN junction. 由于ZnO存在诸多的本征施主缺陷,如间隙锌Zni和空位氧Vo,其能级分别位于导带底0.05eV和0.3eV处,对受主产生高度自补偿作用,而且,ZnO受主能级一般很深(N除外),空穴不易于热激发进入价带,受主掺杂的固溶度也很低,因而难以实现p型转变,成为制约ZnO实现产业化的瓶颈。 Due to the presence of many donor defects intrinsic ZnO, such as oxygen vacancy and a gap Zni Vo of zinc, which is located in the bottom of conduction band energy level are 0.05eV and 0.3eV, the height of the self-compensation effect is generated by the master, and, ZnO acceptor level Usually deep (excluding N), the hole is not easily thermally excited into the valence band, acceptor doped solid solubility is very low, making it difficult to realize p-type transition, a constraint ZnO and industrialization bottleneck. 目前ZnO晶体薄膜的p型掺杂研究还处于开始阶段,浓度可控,重复性好的p型ZnO薄膜还难以实现。 Currently crystal doped p-type ZnO film is still in the research stage of the start concentration controllable, repeatable p-type ZnO film further difficult to achieve.

目前文献报道p型ZnO晶体薄膜的掺杂主要有四种方法:(1)利用高活性的氮作为掺杂剂,(2)镓和氮的共掺杂,(3)掺砷,(4)掺磷。 Currently reported p-type ZnO thin film doped crystal are mainly four methods: (1) a high activity by the nitrogen as a dopant, (2) co-doped gallium and nitrogen, (3) doped with arsenic, (4) phosphorus-doped. 后两种由于受主能级较深,固溶度低,所以掺杂效果不理想,并且砷和磷都有毒性。 Since the latter two deep acceptor level, low solubility, so the doping effect is not satisfactory, and phosphorus and arsenic are toxic. 前两种利用高活性的氮掺杂及镓和氮共掺杂,由于氮的活性很低,且原子半径比氧原子大,因此采用化学气相淀积(CVD)和分子束外延(MBE)生长技术,很难替代氧原子的位置,也无法实现实时可控掺氮。 The first two high activity by the nitrogen doping and co-doping gallium and nitrogen, due to the low activity of nitrogen and oxygen is larger than the atomic radius, so a chemical vapor deposition (CVD) and molecular beam epitaxy (MBE) growth technology, difficult to replace the position of an oxygen atom, can not be controlled in real time nitrogen doped.

发明内容 SUMMARY

本发明的目的是提供一种实时掺氮生长p型ZnO晶体薄膜的方法。 Object of the present invention is to provide a real-time method of nitrogen-doped p-type ZnO film crystal growth.

本发明的实时掺氮生长p型ZnO晶体薄膜的方法是采用磁控溅射法,先将衬底表面清洗后放入直流反应磁控溅射装置的反应室中,反应室真空度抽到至少10-3Pa,然后加热衬底,使衬底温度为200~600℃,优选400~550℃,以高纯氨气NH3(99.99%以上)和高纯氧气O2(99.99%以上)为溅射气体,该二种气体分别由流量计控制输入装置的缓冲室,在缓冲室充分混合后引入真空反应室,在1~10Pa压强下,以高纯Zn(99.99%以上)为靶材,进行溅射生长,其中氨气与氧气的分压比根据掺杂浓度调节。 The method of the present invention in real time the nitrogen-doped p-type ZnO crystal grown film was deposited by magnetron sputtering, after cleaning the surface of the substrate into the first reaction chamber DC magnetron sputtering apparatus, the reaction chamber pumped to a vacuum of at least 10-3Pa, and then heating the substrate, the substrate temperature is 200 ~ 600 ℃, preferably 400 ~ 550 ℃, the NH3 to high-purity ammonia (99.99%) and high purity oxygen O2 (99.99%) of the sputtering gas the two gases are controlled by a flow meter input buffer chamber means, introduced into the vacuum chamber after thorough mixing the buffer chamber, at a pressure of 1 ~ 10Pa, high-purity Zn (99.99%) as a target, sputtering growth, wherein adjusting a doping concentration of ammonia and the oxygen partial pressure ratio in accordance with. 根据NH3与O2不同的分压比可以制备不同掺杂浓度p型ZnO晶体薄膜,生长的时间由所需的厚度决定。 Can be prepared by different dopant concentration of the p-type ZnO crystal thin film in accordance with different NH3 and O2 partial pressure ratio, the growth time is determined by the desired thickness.

上述衬底可以采用硅或蓝宝石或玻璃。 Said substrate may be glass or silicon, or sapphire.

本发明的优点:1)可以实现实时掺杂,在ZnO晶体薄膜生长过程中同时实现掺杂;2)掺杂浓度较高,由于NH3在溅射过程中被离化,氮原子被激活,而且NH3的离化能低于N2,所以N的掺杂效率比较高;3)掺杂浓度可以通过调节输入的NH3∶O2不同分压比来控制;4)有较好的重复性和稳定性。 Advantages of the invention: 1) enables real-time doping, while achieving doping during the growth of ZnO crystal thin film; 2) a high doping concentration, since NH3 is ionized during the sputtering process, the nitrogen atom is activated, and NH3 ionization energy lower than N2, so that a relatively high doping efficiency of N; 3) the doping concentration can be controlled by adjusting the voltage dividing ratio NH3:O2 different input; 4) better repeatability and stability.

附图说明 BRIEF DESCRIPTION

附图是根据本发明方法采用的直流反应磁控溅射装置示意图图中1和2分别为氨气和氧气的进气管路;3为流量计;4缓冲室;5样品架;6加热器;7真空计;8自动压强控制仪;9S枪具体实施方式以下结合具体实例进一步说明本发明。 The drawings are reacted according to the method of the present invention employed in a DC magnetron sputtering apparatus in a schematic view of an inlet line 2 and ammonia and oxygen, respectively; flowmeter 3; 4 buffer chamber; sample holder 5; 6 heater; vacuum gauge 7; 8 automatic pressure controller; 9S gun DETAILED DESCRIPTION following detailed examples further illustrate the present invention.

先将衬底经过表面清洗后放入反应室样品架5上,衬底朝下放置,有效防止颗粒状的杂质对衬底的玷污,反应室真空度抽至10-3Pa;利用加热器,加热衬底,衬底温度控制在500℃;溅射气体是高纯的NH3(99.99%以上)和高纯的O2(99.99%以上),两路气体经进气管1和2进入缓冲室4,在缓冲室充分混合后引入到真空室,真空室内的压强由自动压强控制仪8控制,压强约为5Pa左右。 After cleaning the surface of the substrate first reaction chamber into the sample holder 5, the substrate placed face down, effectively prevent the contamination of particulate impurities of the substrate, the reaction chamber is evacuated to a vacuum of 10-3Pa; using a heater, heating the substrate, the substrate temperature is controlled at 500 deg.] C; the NH3 sputtering gas of high purity (99.99%) and O2 of high purity (99.99%), two gas through the inlet pipe 2 into the buffer chamber 1 and 4, in after thorough mixing the buffer chamber is introduced into the vacuum chamber, the vacuum chamber pressure gauge 8 is controlled by an automatic pressure control, the pressure is about 5Pa. NH3与O2分压比根据掺杂需要,可通过流量计3任意调节,此例设NH3∶O2=1∶1;以S枪9上的高纯Zn(99.99%)为靶材进行溅射生长。 NH3 and O2 partial pressure ratio of doping according to needs, can be adjusted by a flow meter 3, this embodiment is provided NH3:O2 = 1:1; highly pure Zn (99.99%) on the S gun grown sputtering target 9 . 溅射功率在32W下生长一定的时间,半小时可以溅射2微米左右。 Growth sputtering power at a certain time 32W, half an hour about 2 microns can be sputtered. 通过调节输入的NH3∶O2分压比,可以获得掺杂浓度可控的p型ZnO晶体薄膜。 NH3:O2 by adjusting the voltage dividing ratio input, the doping concentration can be controlled to obtain p-type ZnO crystal thin film.

生长过程中发生的化学反应如下: Chemical reaction growth process is as follows:

这里,v和s分别代表气态和固态。 Here, v and s represent the gaseous and solid. 在ZnO薄膜中,N取代O位于晶格位置,而H由于原子半径较小,会存在于与N相邻的间隙位置,这可以很大程度上抑制生长过程中间隙Zn的存在,降低自补偿效应。 A ZnO film, the lattice position N-substituted O and H due to the smaller atomic radius, will be present in the gap adjacent to the N-position, which can be largely suppressed during growth there is a gap of Zn, reduced self-compensating effect.

Claims (3)

1.实时掺氮生长p型ZnO晶体薄膜的方法,其特征是采用磁控溅射法,先将衬底表面清洗后放入直流反应磁控溅射装置的反应室中,反应室真空度抽到至少10-3Pa,然后加热衬底,使衬底温度为200~600℃,以高纯氨气和高纯氧气为溅射气体,该二种气体分别由流量计控制输入装置的缓冲室,在缓冲室充分混合后引入真空反应室,在1~10Pa压强下,以高纯Zn为靶材,进行溅射生长,其中氨气与氧气的分压比根据掺杂浓度调节。 A method for real time nitrogen-doped p-type ZnO crystal grown film, which is characterized by using a magnetron sputtering method, after the first cleaning surface of the substrate into the reaction chamber DC magnetron sputtering apparatus, the degree of vacuum of the reaction chamber evacuated at least 10-3Pa, and then heating the substrate, the substrate temperature is 200 ~ 600 ℃, high purity oxygen and high purity ammonia gas as the sputtering gas, the two gases are controlled by a flow meter input buffer chamber means, after thorough mixing introducing the buffer chamber vacuum reaction chamber, at a pressure of 1 ~ 10Pa, high-purity Zn as a target, sputtering growth, wherein adjusting a doping concentration of ammonia and the oxygen partial pressure ratio in accordance with.
2.根据权利要求1所述的实时掺氮生长p型ZnO晶体薄膜的方法,其特征是衬底的温度为400~550℃。 The real-time according to a method of nitrogen-doped p-type ZnO crystal thin film grown claim, wherein the temperature of the substrate is 400 ~ 550 ℃.
3.根据权利要求1所述的实时掺氮生长p型ZnO晶体薄膜的方法,其特征是所说的衬底是硅或蓝宝石或玻璃。 The real time of the nitrogen-doped p-type to a method for growing ZnO crystal thin film as claimed in claim, wherein said substrate is a silicon or glass or sapphire.
CN 02136110 2002-07-17 2002-07-17 Process for growing P-type ZnO crystal film by real-time doping nitrogen CN1206703C (en)

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Publication number Priority date Publication date Assignee Title
CN1293606C (en) * 2004-09-30 2007-01-03 浙江大学 Method or growing N-Al co-blended p type ZnO transistor film by two step method
CN1327042C (en) * 2005-03-28 2007-07-18 中国科学院半导体研究所 Method for growing single-crystal zinc oxide film by using zinc oxide buffer layer
JP4850901B2 (en) 2006-03-17 2012-01-11 Jx日鉱日石金属株式会社 Zinc oxide based transparent conductor and sputtering target for forming the transparent conductor
JP5145228B2 (en) * 2006-07-28 2013-02-13 株式会社アルバック Method for forming transparent conductive film
CN100485892C (en) 2007-03-20 2009-05-06 西安交通大学 A method for manufacturing enhancement type ZnO channel layer thin film transistor by ammonia doping
CN100540756C (en) 2007-10-18 2009-09-16 中国科学院长春光学精密机械与物理研究所 Method for preparing p-type zinc oxide thin film by using n-type zinc oxide
CN100530607C (en) 2007-12-11 2009-08-19 西安交通大学 Method of producing ZnO based transparent film transistor array
CN101599363B (en) 2009-04-09 2011-11-23 上海工程技术大学 Preparation method of nitrogen-doped zinc oxide p-type diluted magnetic semiconductor material
CN102002667A (en) * 2010-11-22 2011-04-06 烟台睿创微纳技术有限公司 Method and equipment for preparing high-repeatability vanadium oxide film

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