CN105322026B - 一种NiO:Ag/TiOx异质pn结二极管 - Google Patents
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- 229910003087 TiOx Inorganic materials 0.000 title claims abstract description 36
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 10
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 33
- 239000012535 impurity Substances 0.000 description 10
- 239000013077 target material Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
- H01L29/861—Diodes
- H01L29/8613—Mesa PN junction diodes
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66969—Multistep manufacturing processes of devices having semiconductor bodies not comprising group 14 or group 13/15 materials
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Abstract
本发明公开了一种NiO:Ag/TiOx异质pn结二极管，至少包括pn结和欧姆接触电极，所述pn结在Si衬底上生长p型NiO:Ag薄膜以及n型TiOx薄膜得到异质pn结。本发明利用磁控溅射工艺在Si衬底上制备NiO:Ag/TiOx异质pn结二极管，最后采用磁控溅射或热蒸发法在pn结上制作电极。本发明中异质pn结二极管具有较高的反向击穿电压、较大的正向电流密度，而且其制备方法工艺简单。
Description
技术领域
本发明涉及一种NiO:Ag/TiOx异质pn结二极管。属于功能材料和光电子器件领域。
背景技术
强关联材料NiO中含有的d(f)电子的内部自由度如自旋、电荷、轨道之间的相互作用，使得NiO表现出许多奇异的性质，同时也使得材料的物性随着内部参数如温度、压强、掺杂的变化而发生显著改变。截止到目前，NiO因其良好的催化性能、热敏性能而被应用于催化剂、电池电极、电化学电容器等领域的研究，对其光电特性的研究少见报道。半导体异质结易于实现光生电荷分离被广泛应用于薄膜电池等光电子器件的研制和开发。NiO除了上述性质外，还是p型直接宽带隙半透明半导体材料，与间接带隙半导体材料相比，量子效率相对较高。室温下禁带宽度为3.0-4.0eV，3d电子结构的d-d轨道跃迁，使其在可见光区域存在较弱吸收。我们通过NiO基异质结形式研究新型光电子器件。P.Puspharajha等人采用喷雾热解法通过对NiO掺入Li+使NiO薄膜在可见光波段透光率达到90%，薄膜电阻下降到1Ω·cm (见文献P PUSPHARAJAH, S RADHAKRISHNA, A K AROF. Transparent conductinglithium-doped nickel oxide thin films by spray pyrolysis technique. Journalof Materials Science, 1997, 32(11): 3001-3006)。但从长远考虑，Ag金属更为常见。我们将Ag元素引入NiO，制备NiO:Ag基pn结二极管。于此同时，我们选用价格低廉的n型TiOx作为pn结的另一端，从而实现NiO:Ag/TiOx异质pn结二极管。众所周知，TiOx集多种功能于一身，而且在很多领域已被广泛应用。这种选择对于新型器件的开发有着重要意义，而目前对于NiO:Ag/TiOx异质结还未见报道。
发明内容
为提高传统的平面pn结二极管的性能，本发明提供了一种NiO:Ag/TiOx异质pn结二极管，制备的NiO:Ag/TiOx异质pn结二极管具有较高的反向击穿电压和大的正向电流密度。相对于传统的平面pn结二极管，该新型二极管的整流特性得到了提高。本发明的技术方案：NiO:Ag/TiOx异质pn结二极管，至少包括pn结和欧姆接触电极，所述pn结是由p型NiO:Ag和n型TiOx形成异质pn结。
上述NiO:Ag/TiOx异质pn结二极管的制备方法：用磁控溅射工艺在Si衬底上制备NiO:Ag薄膜以及TiOx薄膜形成异质pn结；最后采用溅射或热蒸发法在pn结上制作电极；其中，NiO:Ag和TiOx表面溅射或蒸发银，镍或铝或金电极。本发明采用直径为50mm的NiO:Ag2O陶瓷靶，磁控溅射制备的NiO:Ag薄膜。溅射前的腔体本底真空度优于3x10-4Pa，在此采用的相对氧分压O2/(O2+Ar)=0％-100％。溅射气压为0.5-2Pa，溅射功率100-200W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为20-120min，衬底温度为RT-600oC或者后期退火温度从200oC至700oC时间为0.5至1个小时。本发明采用直径为50mm的TiO2陶瓷靶，磁控溅射制备的TiOx薄膜。溅射前的腔体本底真空度优于3x10-4Pa，在此采用的相对氧分压O2/(O2+Ar)=0％-100％。溅射气压为0.5-2Pa，溅射功率50-200W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为20-120min，衬底温度为RT-600oC或者后期退火温度从200oC至700oC时间为0.5至1个小时。
本发明利用p型NiO:Ag薄膜与n型TiOx薄膜形成了异质pn结二极管。通过对NiO:Ag薄膜以及TiOx薄膜制备等条件的控制、pn结结构的优化等，提高了异质pn结性能，充分发挥半导体NiO:Ag在异质pn结应用方面的独到优势。
附图说明
图1为本发明NiO:Ag/TiOx异质pn结结构图
图2为本发明反映异质结整流特性的I-V曲线(实施例一)
图3为本发明反映异质结整流特性的I-V曲线(实施例二)
图4为本发明反映异质结整流特性的I-V曲线(实施例三)。
具体实施方式
本发明NiO:Ag/TiOx异质pn结二极管，至少包括pn结和欧姆接触电极，所述pn结是在n型Si衬底上沉积NiO:Ag/TiOx形成异质pn结，见图1。其具体制备步骤如下：（1）采用半导体工艺中的清洗方法清洗硅片并用氮气吹干；（2）p-NiO:Ag的制备：溅射前的腔体本底真空度优于3x10-4Pa，采用的相对氧分压O2/(O2+Ar)=0％-100％，溅射气压为0.5-2Pa，溅射功率100-200W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为20-120min，衬底温度为RT-600oC以及温度为200oC至700oC退火0.5至1个小时。（3）n-TiOx的制备：溅射前的腔体本底真空度优于3x10-4Pa，采用的相对氧分压O2/(O2+Ar)=0％-100％，溅射气压为0.5-2Pa，溅射功率50-200W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为20-120min，衬底温度为RT-600oC以及温度为200oC至700oC退火0.5至1个小时。（4）电极的制备：采用热蒸发方法在NiO:Ag和TiOx表面边缘制作Al电极。（5）测试用Keithley 2612A检测电极的欧姆接触特性和异质pn结二极管的I-V特性（整流特性）。
实施例一
（1）采用半导体工艺中的清洗方法清洗硅片并用氮气吹干；（2）p-NiO:Ag的制备：采用直径为50mm的NiO:Ag2O陶瓷靶。磁控溅射制备的NiO:Ag薄膜。溅射前的腔体本底真空度优于3x10-4Pa，采用的相对氧分压O2/(O2+Ar)=30％。溅射气压为2Pa，溅射功率150W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为40min，衬底温度为室温（RTroom temperature）。（3）n-TiOx的制备：采用直径为50mm的TiO2陶瓷靶。溅射前的腔体本底真空度优于3x10-4Pa，采用的相对氧分压O2/(O2+Ar)=0％，溅射气压为1Pa，溅射功率100W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为60min，衬底温度为RT。（4）电极的制备：采用热蒸发方法在NiO:Ag和TiOx表面边缘制作Al电极。（5）测试用Keithley2612A检测电极的欧姆接触特性和异质pn结二极管的I-V特性（整流特性），见图2。
实施例二
（1）采用半导体工艺中的清洗方法清洗硅片并用氮气吹干；（2）p-NiO:Ag的制备：采用直径为50mm的NiO:Ag2O陶瓷靶。磁控溅射制备的NiO:Ag薄膜。溅射前的腔体本底真空度优于3x10-4Pa，采用的相对氧分压O2/(O2+Ar)=30％。溅射气压为2Pa，溅射功率150W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为40min，衬底温度为200oC。（3）n-TiOx的制备：采用直径为50mm的TiO2陶瓷靶。溅射前的腔体本底真空度优于3x10-4Pa，采用的相对氧分压O2/(O2+Ar)=0％，溅射气压为1Pa，溅射功率100W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为60min，衬底温度为RT。（4）电极的制备：采用热蒸发方法在NiO:Ag和TiOx表面边缘制作Al电极。（5）测试用Keithley 2612A检测电极的欧姆接触特性和异质pn结二极管的I-V特性（整流特性），见图3。
实施例三
（1）采用半导体工艺中的清洗方法清洗硅片并用氮气吹干；（2）p-NiO:Ag的制备：采用直径为50mm的NiO:Ag2O陶瓷靶。磁控溅射制备的NiO:Ag薄膜。溅射前的腔体本底真空度优于3x10-4Pa，采用的相对氧分压O2/(O2+Ar)=30％。溅射气压为2Pa，溅射功率150W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为40min，衬底温度为300oC。（3）n-TiOx的制备：采用直径为50mm的TiO2陶瓷靶。溅射前的腔体本底真空度优于3x10-4Pa，采用的相对氧分压O2/(O2+Ar)=0％，溅射气压为1Pa，溅射功率100W。在镀膜之前，预溅射5min以去除靶材表面的杂质。镀膜时间均为60min，衬底温度为RT。（4）电极的制备：采用热蒸发方法在NiO:Ag和TiOx表面边缘制作Al电极。（5）测试用Keithley 2612A检测电极的欧姆接触特性和异质pn结二极管的I-V特性（整流特性），见图4。
Claims (2)
1.一种NiO:Ag/TiOx异质pn结二极管，至少包括pn结和欧姆接触电极，其特征在于：所述pn结是由p型NiO:Ag薄膜和n型TiOx薄膜而得到的异质pn结； 采用NiO:Ag2O陶瓷靶和TiO2陶瓷靶，利用磁控溅射工艺在Si衬底上制备NiO:Ag薄膜和TiOx薄膜形成异质pn结； 制备NiO:Ag薄膜，采用氧分压O2/(O2+Ar)=0％-100％，溅射气压为0.5-2Pa，溅射功率为100-200W； 镀膜时间均为20-120min，衬底温度从RT变化至600oC，退火温度从200oC变化至700oC； 制备TiOx薄膜，采用氧分压O2/(O2+Ar)=0％-100％； 溅射气压为0.5-2Pa，溅射功率为50-200W； 镀膜时间均为20-120min，衬底温度从RT变化至600oC； 退火温度从200 oC变化至700oC。
2.权利要求1所述NiO:Ag/TiOx异质pn结二极管的制备方法，其特征在于：采用溅射法或热蒸发法在pn结上制作电极；其中，NiO:Ag和TiOx表面沉积银，镍，铝或金电极。
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