CN1278385C - P-ZnO thin film and preparation method thereof - Google Patents

P-ZnO thin film and preparation method thereof Download PDF

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CN1278385C
CN1278385C CN 03116007 CN03116007A CN1278385C CN 1278385 C CN1278385 C CN 1278385C CN 03116007 CN03116007 CN 03116007 CN 03116007 A CN03116007 A CN 03116007A CN 1278385 C CN1278385 C CN 1278385C
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thin film
zno thin
substrate
gas
zno
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CN 03116007
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CN1440053A (en
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叶志镇
袁国栋
黄靖云
曾昱嘉
赵炳辉
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浙江大学
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Abstract

本发明的p-ZnO薄膜是以N为受主掺杂源,以Al为施主掺杂源共掺杂的p-ZnO薄膜,掺杂浓度为1.8×10 p-ZnO film of the present invention is N as an acceptor dopant source, Al as a donor dopant source p-ZnO films co-doped with a doping concentration of 1.8 × 10

Description

一种p-ZnO薄膜及其制备方法 One kind of p-ZnO film and preparation method

技术领域 FIELD

本发明涉及半导体器件,具体说涉及p-ZnO薄膜及其制备方法。 The present invention relates to a semiconductor device, particularly relates to p-ZnO film and preparation method.

背景技术 Background technique

由于ZnO存在诸多的本征施主缺陷,如间隙锌Zni和氧空位V0,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。 Due to the presence of many donor defects intrinsic ZnO, such as a gap Zni zinc and oxygen vacancies V0, the conduction band energy level located at the bottom 0.05eV and 0.3eV, to produce a highly self-compensating effect of acceptor. 因此,很难实现ZnO的p型转变,而且,ZnO的受主能级一般很深(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。 Thus, it is difficult to realize p-type ZnO transition, and, the acceptor level of ZnO is generally deep (excluding N), the hole is not easily thermally excited into the valence band, acceptor doped very low solubility. 可控稳定的p型掺杂一直是ZnO研究中的一个重要课题。 Controllable stable p-type doped ZnO has been an important subject of research. 目前文献报道p型掺杂主要有四种渠道:1.掺N 2.Ga、N共掺3.掺As 4.掺P。 Currently reported p-type dopant, there are four channels: 1-doped N 2.Ga, N co-doped doped 3. As 4. doped P. 后两种受主能级都比较深,掺杂效果不理想,而且As和P都有毒。 The latter two acceptor level deeper than, the doping effect is not satisfactory, and As and P are poisonous. 第一种中活性N源一般来源于NH3、N2或者N2O,但是由于N原子取代O原子时,提高了Madelung能从而引起了N能级的局域化,N能级较深,掺杂效果不是很理想。 A first active N source is generally derived from NH3, N2 or of N2O, but since the N atoms when substituted with an O atom, to improve the Madelung energy to cause a localized level of N, N deeper level doping effect is not very satisfactory. 第二种施主(Ga)、受主(N)共掺杂技术得到的ZnO表面颗粒均匀度较差,而且要用到价格较高的Ga源,通常采用(MBE)分子束外延工艺,设备昂贵,制作成本高。 The second donor (Ga), acceptor (N) co-doped ZnO poor uniformity of the surface of the particles obtained technology, but also more expensive to use a Ga source, usually (MBE) molecular beam epitaxy process, expensive equipment and high production costs.

发明内容 SUMMARY

本发明的目的是提供一种p-ZnO薄膜及其制备方法。 Object of the present invention is to provide a p-ZnO film and preparation method.

本发明的p-ZnO薄膜是以N为受主,以Al为施主共掺杂的p-ZnO薄膜,掺杂浓度为1.8×1015cm-3-4.5×1018cm-3。 p-ZnO film of the present invention is N acceptors, Al as a donor co-doped p-ZnO thin film, a doping concentration of 1.8 × 1015cm-3-4.5 × 1018cm-3.

本发明的p-ZnO薄膜的制备方法是利用磁控溅射法,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1×10-3Pa,然后加热衬底,衬底温度为400-600℃,以含N气体(99.99%以上)和O2或含N气体和Ar(99.99%以上)为溅射气体,将二种气体分别由气体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3-5Pa压强下,以ZnxAl1-x为靶材,式中1>x>0.6,进行溅射生长。 Preparation of p-ZnO film of the invention is the use of 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 pumped to 1 × 10-3Pa and then heating the substrate, the substrate temperature is 400-600 deg.] C, to the N-containing gas (99.99%) or a N-containing gas and O2 and Ar (99.99%) of the sputtering gas, the two gases separately by the gas flow rate Total control input means buffer chamber, the buffer chamber after mixing sufficiently introduced into the vacuum reaction chamber, at a pressure 3-5Pa, as a target to ZnxAl1-x, where 1> x> 0.6, sputtering growth.

上述的含N气体包括NH3、N2O、NO、NO2。 The above-described N-containing gas comprises NH3, N2O, NO, NO2. 含N气体和O2或含N气体和Ar的分压比以及靶材中Al的含量根据掺杂浓度调节,生长的时间由所需的厚度决定。 N-containing gas and a partial pressure ratio of the target and the content of Al in N-containing O2 or Ar gas and doping concentration adjustment in accordance with, the growth time is determined by the desired thickness.

本发明的优点是:1)设备简单,操作方便,Al原料丰富,价格低廉。 Advantage of the present invention are: 1) the device is simple, easy to operate, Al-rich raw materials, low price. 制作成本低。 Low production cost.

2)掺杂浓度可控性、稳定性好,可以通过调节输入的含N气体和高纯O2或Ar不同分压比和靶材中Al的含量来控制。 2) doping concentration controllability, good stability, high purity and the content of the N-containing gas or O2 partial pressure ratio of Ar and different targets of Al can be controlled by adjusting the input.

3)本发明的p-ZnO薄膜表面平整,晶粒大小均匀,具有择优取向。 3) the surface of p-ZnO thin film formation according to the present invention, a uniform grain size, have a preferred orientation.

附图说明 BRIEF DESCRIPTION

图1是根据本发明方法采用的直流反应磁控溅射装置示意图。 1 is a schematic reaction according to the DC magnetron sputtering apparatus employed in the method of the present invention. 图中1和2分别为含N气体和O2或Ar的进气管路;3为流量计;4为缓冲室;5为样品架;6为加热器;7为真空计;8为自动压强控制仪;9为S枪图2是p-ZnO薄膜表面的AFM(原子力显微)照片。 1 and FIG. 2 are the N-containing gas inlet line and O2 or Ar; 3 flowmeter; buffer chamber 4; 5 sample holder; heater 6; 7 is a vacuum gauge; automatic pressure control device 8 ; FIG. 9 is S gun 2 is an AFM surface of the p-ZnO film (atomic force microscopy) photographs.

图3是蓝宝石上沉积的p-ZnO薄膜的XRD(X射线衍射)图。 FIG 3 is a p-ZnO thin film deposited on a sapphire XRD (X-ray diffraction) FIG.

具体实施方式 Detailed ways

以下参照图1,通过实例进一步说明本发明p-ZnO薄膜的制备方法。 Referring now to Figure 1, to further illustrate the preparation of p-ZnO thin film according to the present invention by way of example. 先将衬底经过表面清洗后放入反应室样品架5上,衬底欲沉积表面朝下放置,有效防止颗粒状的杂质对衬底的玷污,反应室真空度抽至1×10-3Pa,利用加热器加热衬底,衬底温度控制在550℃;溅射气体是NH3(99.99%以上)和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,压强为3Pa。 After cleaning the surface of the substrate first reaction chamber into the sample holder 5, the deposition surface of the substrate to be placed down, effectively prevent the contamination of particulate impurities of the substrate, the reaction chamber is evacuated to a vacuum of 1 × 10-3Pa, a heater for heating the substrate, the substrate temperature is controlled at 550 deg.] C; sputtering gas is the NH3 (99.99%) and O2 (99.99%), two gas through the inlet pipe 2 into the buffer chamber 1 and 4, the buffer chamber after thorough mixing into the vacuum chamber, the vacuum chamber by the pressure control device 8 controls the automatic pressure, pressure of 3Pa. NH3与O2分压比根据掺杂需要,可通过流量计3调节,本例为NH3∶O2=60∶40;以S枪9上的ZnxAl1-x,为靶材进行溅射生长,本例为x=0.9。 NH3 and O2 partial pressure ratio of doping according to need, by adjusting the flow meter 3, the present embodiment is NH3:O2 = 60:40; ZnxAl1-x to the gun 9 S, grown by sputtering a target, in this case x = 0.9. 在60W的功率下生长25min。 25min grow at a power of 60W.

生长过程中发生如下反应: The following reaction takes place during growth:

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-Al-N取代O而使N活化,一个N-Al-N相当于一个空位,使Madelung能降低,从而N能级更浅。 A ZnO film, a substituted N-Al-N N O the activation, a N-Al-N corresponds to a vacancy, Madelung enable to reduce to N shallower level. 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。 H due to the smaller atomic radius and 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-compensation effect.

本发明的p-ZnO薄膜表面平整,晶粒大小均匀(见图2),并具有高度C轴择优取向(见图3)。 The surface of p-ZnO film formation according to the present invention, a uniform grain size (see FIG. 2), and having a high degree of C-axis orientation (see FIG. 3).

Claims (4)

1.一种p-ZnO薄膜,其特征在于它是以N为受主,以Al为施主共掺杂的p-ZnO薄膜,掺杂浓度为1.8×1015cm-3-4.5×1018cm-3。 A p-ZnO thin film, characterized in that it is an acceptor is N, Al as a donor co-doped p-ZnO thin film, a doping concentration of 1.8 × 1015cm-3-4.5 × 1018cm-3.
2.权利要求1所述的p-ZnO薄膜的制备方法,其特征是: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1×10-3Pa,然后加热衬底,衬底温度为400-600℃,以含N气体和O2或含N气体和Ar为溅射气体,将二种气体分别由气体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3-5Pa压强下,以ZnxAl1-x为靶材,式中1>x>0.6,进行溅射生长。 Preparation of p-ZnO thin film according to claim 1, wherein: the first surface of the substrate cleaning reaction chamber into a DC magnetron sputtering apparatus, the degree of vacuum evacuated reaction chamber 1 × 10 -3Pa, then heating the substrate, the substrate temperature is 400-600 deg.] C, to the N-containing gas and O2 as the sputtering gas or a gas containing N and Ar, the two gases are controlled by the gas meter input buffer chamber means, after thorough mixing introducing the buffer chamber vacuum reaction chamber, at a pressure 3-5Pa, as a target to ZnxAl1-x, where 1> x> 0.6, sputtering growth.
3.根据权利要求2所述的p-ZnO薄膜的制备方法,其特征是含N气体包括NH3、N2O、NO、NO2。 3. The method for preparing p-ZnO thin film according to claim 2, wherein the N-containing gas comprises NH3, N2O, NO, NO2.
4.根据权利要求2所述的p-ZnO薄膜的制备方法,其特征是所说的衬底是蓝宝石、硅。 4. The method for preparing p-ZnO thin film according to claim 2, wherein said substrate is sapphire, silicon.
CN 03116007 2003-03-25 2003-03-25 P-ZnO thin film and preparation method thereof CN1278385C (en)

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CN1317749C (en) * 2005-04-05 2007-05-23 中国科学院物理研究所 Three-dopant contained P-type zinc oxide film and method for making same
CN100485081C (en) 2005-06-16 2009-05-06 中国科学院物理研究所 Process for preparing boron-doped n-shape high-hardness transparent conductive zinc oxide film
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101548343A (en) * 2007-09-05 2009-09-30 株式会社村田制作所 Transparent conductive film and method for producing transparent conductive film

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