磁控溅射法制备p型透明导电二氧化锡薄膜
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摘要
宽禁带半导体材料(如GaN、ZnO等)是目前半导体材料研究领域的热点之一,在光电器件、高温电子器件、透明电子器件等方面具有重要的应用前景。二氧化锡(SnO_2)是一种宽带隙氧化物半导体(Eg=3.6～4.0eV),具有对可见光透过率高、电阻率低、热稳定性好、化学性能稳定以及成本低等优点,广泛应用于气敏材料、太阳能电池、透明电极材料以及电热材料等领域。但是,目前应用最多的透明导电氧化物(TCO)薄膜(如In_2O_3:Sn、SnO_2:F等)均为n型导电,而p型的TCO薄膜大多在研究阶段。性能优越的p型TCO薄膜的制备是制备透明pn结的必需,如果成功将对透明电子元器件的制造产生深远的意义。
本论文综合介绍了各种制备SnO_2薄膜的工艺方法、SnO_2薄膜的特性及其应用,SnO_2薄膜的p型掺杂机理,并分析了在相对低的温度下获得性能良好的p型TCO薄膜的途径。本文实验中采用不同的元素对SnO_2进行p型掺杂,并通过不同的工艺参数来制备p型的SnO_2薄膜的性能。通过直流磁控溅射合金靶沉积合金膜(掺杂金属与Sn原子比均为0.2),然后在空气中热氧化得到p型的SnO_2薄膜的方法,分别对SnO_2薄膜进行了掺In、掺Ga试验,成功地获得了p型的SnO_2:In和SnO_2:Ga透明导电薄膜。实验发现,600℃～700℃温度范围内热氧化得到的SnO_2:In薄膜,在可见光范围的平均透过率可以达到80%以上,空穴浓度最高可以达到9.61×10~(18)cm~(-3)。但用同样方法制备的p型的SnO_2:Ga薄膜的电学性能比SnO_2:In薄膜的差。表明对磁控溅射法制备p型SnO_2薄膜时,掺In比掺Ga更有效。实验还通过反应溅射法沉积了SnO_2:In薄膜,发现其电学性能远不及先沉积合金膜,然后热氧化法制备的SnO_2:In薄膜。
本论文还通过磁控溅射多靶沉积法制备了掺Cu的SnO_2薄膜。但实验结果发现铜没有进入Sn的替代位成为双重受主,却以铜的氧化物的形式存在。因此没有实现预期的p型掺杂,但在较低的热氧化温度下,薄膜呈现出弱p型导电特性,这可能是薄膜中存在少量的p型导电的Cu_2O所致。另外,掺Cu量的增加或热氧化温度的升高均会导致掺Cu的SnO_2薄膜的晶体结构从正交结构转变为四方结构。
Wide band-gap semiconductor materials are a kind of hottest semiconductor materials in recent years, such as GaN, ZnO, etc. Tin dioxide (SnO_2) is a kind of wide band gap semiconductor material with bandgap E_g~3.6-4.0 eV. Due to its high optical transparency, low resistivity, thermal and chemical stabilities, and low cost of the source materials, SnC>2 has been widely used in many applications such as gas sensors, solar cells, transparent electrodes, electric heating devices, and etc. However, almost all the transparent conductive oxide (TCO) films (e.g., In_2O_3∶Sn, SnO_2∶F) are n-type conducting, and the p-type TCO films are mostly in research to fabricate transparent pn junctions which are necceary for transparent electronic devices.In this thesis, the preparation technology, property, application and p-type doping mechanism of SnO_2 were introduced. P-type transparent SnO_2 thin films were successfully fabricated by two-step method: alloy films deposited by DC magnetron sputtering (doped with In, Ga/Sn=0.2, respectively), and then thermally oxidized in the air at high temperature. In-doped SnO_2 with transmittance over 80% in the visible region and hole concentration as high as 9.61×10~(18)cm~(-3) were obtained after oxidized between 600 ℃ and 700 ℃, which are superior to Ga-doped SnO_2 films fabricated by the exactly same process. It shows that indium doping is more effective than Ga doping for p-type doping in SnO_2. In addition, SnO_2:In films were prepared by reactive DC magnetron sputtering under different parameters, but the electrical properties of the films are inferior to the films fabricated by the two-step method mentioned above. Cu-doped SnO_2 thin films were also tested to realize p-type conduction, but the results showed that Cu did not substitute Sn to behave as a bi-acceptor as expected, only weak p-type conductance of the film was observed after thermal oxidation, which was possibly due to the existence of some Cu_2O phase in the films. However, the crystallinity of SnO_2 thin films was improved and phase transformation was found.
本论文综合介绍了各种制备SnO_2薄膜的工艺方法、SnO_2薄膜的特性及其应用,SnO_2薄膜的p型掺杂机理,并分析了在相对低的温度下获得性能良好的p型TCO薄膜的途径。本文实验中采用不同的元素对SnO_2进行p型掺杂,并通过不同的工艺参数来制备p型的SnO_2薄膜的性能。通过直流磁控溅射合金靶沉积合金膜(掺杂金属与Sn原子比均为0.2),然后在空气中热氧化得到p型的SnO_2薄膜的方法,分别对SnO_2薄膜进行了掺In、掺Ga试验,成功地获得了p型的SnO_2:In和SnO_2:Ga透明导电薄膜。实验发现,600℃～700℃温度范围内热氧化得到的SnO_2:In薄膜,在可见光范围的平均透过率可以达到80%以上,空穴浓度最高可以达到9.61×10~(18)cm~(-3)。但用同样方法制备的p型的SnO_2:Ga薄膜的电学性能比SnO_2:In薄膜的差。表明对磁控溅射法制备p型SnO_2薄膜时,掺In比掺Ga更有效。实验还通过反应溅射法沉积了SnO_2:In薄膜,发现其电学性能远不及先沉积合金膜,然后热氧化法制备的SnO_2:In薄膜。
本论文还通过磁控溅射多靶沉积法制备了掺Cu的SnO_2薄膜。但实验结果发现铜没有进入Sn的替代位成为双重受主,却以铜的氧化物的形式存在。因此没有实现预期的p型掺杂,但在较低的热氧化温度下,薄膜呈现出弱p型导电特性,这可能是薄膜中存在少量的p型导电的Cu_2O所致。另外,掺Cu量的增加或热氧化温度的升高均会导致掺Cu的SnO_2薄膜的晶体结构从正交结构转变为四方结构。
Wide band-gap semiconductor materials are a kind of hottest semiconductor materials in recent years, such as GaN, ZnO, etc. Tin dioxide (SnO_2) is a kind of wide band gap semiconductor material with bandgap E_g~3.6-4.0 eV. Due to its high optical transparency, low resistivity, thermal and chemical stabilities, and low cost of the source materials, SnC>2 has been widely used in many applications such as gas sensors, solar cells, transparent electrodes, electric heating devices, and etc. However, almost all the transparent conductive oxide (TCO) films (e.g., In_2O_3∶Sn, SnO_2∶F) are n-type conducting, and the p-type TCO films are mostly in research to fabricate transparent pn junctions which are necceary for transparent electronic devices.In this thesis, the preparation technology, property, application and p-type doping mechanism of SnO_2 were introduced. P-type transparent SnO_2 thin films were successfully fabricated by two-step method: alloy films deposited by DC magnetron sputtering (doped with In, Ga/Sn=0.2, respectively), and then thermally oxidized in the air at high temperature. In-doped SnO_2 with transmittance over 80% in the visible region and hole concentration as high as 9.61×10~(18)cm~(-3) were obtained after oxidized between 600 ℃ and 700 ℃, which are superior to Ga-doped SnO_2 films fabricated by the exactly same process. It shows that indium doping is more effective than Ga doping for p-type doping in SnO_2. In addition, SnO_2:In films were prepared by reactive DC magnetron sputtering under different parameters, but the electrical properties of the films are inferior to the films fabricated by the two-step method mentioned above. Cu-doped SnO_2 thin films were also tested to realize p-type conduction, but the results showed that Cu did not substitute Sn to behave as a bi-acceptor as expected, only weak p-type conductance of the film was observed after thermal oxidation, which was possibly due to the existence of some Cu_2O phase in the films. However, the crystallinity of SnO_2 thin films was improved and phase transformation was found.
引文
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