High-Mobility Bismuth-based Transparent p-Type Oxide from High-Throughput Material Screening
High-Mobility Bismuth-based Transparent p-Type Oxide from High-Throughput Material Screening
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DOI：
10.1021/acs.chemmater.5b03794
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发表时间：
2016-01-12
影响因子：
8.6
通讯作者：
Suntivich, Jin
中科院分区：
文献类型：
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作者：
Bhatia, Amit;Hautier, Geoffroy;Suntivich, Jin
许多能源和透明电子应用的成功实施，从透明导体、1透明互补晶体管、2、3高功率电子、4到光伏和太阳能燃料系统、5−7取决于具有良好载流子迁移率和可见透明度的半导体的发现。透明的n型氧化物，如氧化锌、In−Sn−O、In−Ga−Zn−O和其他8−11具有很高的电子迁移率，已经在许多器件中使用。然而，这与p型氧化物形成了鲜明的对比，p型氧化物的性能还没有达到n型氧化物的水平。这种限制通常被认为是氧(O)2p态在价带中局域化的结果。12、13在这一认识的推动下，Hosono和他的同事们假设O2p态的离域是解锁高空穴迁移率的一种策略，有效地降低了空穴的有效质量。他们提出了一种实现这一目标的方法，即通过加入能级与O_2p紧密匹配的高度电负性阳离子来增加金属−的氧杂化。14这一概念导致了作为高性能宽带隙p型材料的含铜氧化物12、15和含氧硫化物16−20的发现。对于可见透明的p型氧化物，这些铜体系的结果被认为是空穴迁移率的基准(∼1−10 cm~2/(V·S))。尽管如此，与可见透明的n型氧化物(>；100cm2/(V·S))相比，这些值是中等的。8，9，21我们注意到Cu2O可以在n型氧化物水平上表现出空穴迁移率。然而，Cu2O在可见光波长下是不透明的。因此，对于透明电子和宽带隙晶体管的应用来说，发现一种具有高空穴迁移率和宽带隙的新型半导体氧化物是至关重要的一步。为了寻找更好的p型化合物，研究人员研究了空间上更广泛的S轨道化学，以更有效地离域O2p态。24−27锡氧化物SnO(Sn2+：[KR]4d105s2)是最有前途的p型S轨道氧化物候选者之一。然而，SnO仍然受到低空穴迁移率(<；5cm2/(V·S))、各向异性输运和低平均透过率(75−80%)的限制。25，26，28−30虽然最近的报道表明，金属β-Sn的加入可以极大地提高空穴迁移率(∼20cm2/(V·S))，31但制备高稳定性的SnO仍然是一个挑战。Bi3+([Xe]4f14 5d10 6s2)化合物为S轨道的利用提供了另一条途径。27然而，到目前为止，所研究的铋基氧化物中的Bi6S态太低，无法进行有效的O-2p杂化。26为了利用Bi3+中的S轨道化学，必须找到一种结构和化学，使Bi态处于合适的能量位置，以支持Bi6s−O2p杂化，同时保持可见的透明度。我们最近报道了使用带隙和价带曲率作为参数，从二元和三元氧化物数据库中筛选高优值系数的p型氧化物。在这里，我们报道了一种具有强金属−氧S−p杂化和可见透明度的S轨道铋系候选者的实验实现。我们的鉴定是我们将高通量计算筛选方法应用于四元氧化物空间的直接结果。我们介绍了它的合成，光学和电学表征，并提供了材料的可见透明度和空穴迁移率的初步演示，以展示这种p型透明氧化物化合物的前景。鉴定…
Successful implementations of many energy and transparent electronic applications, ranging from transparent conductors, 1 transparent complementary transistors, 2, 3 highpower electronics, 4 to photovoltaics and solar fuel systems, 5− 7 hinge on the discovery of a semiconductor with good carrier mobility and visible transparency. Transparent, n-type oxides such as ZnO, In− Sn− O, In− Ga− Zn− O, and others 8− 11 have high electron mobility and are already in use in many devices. However, this stands in contrast to the p-type oxides, where the performances have not yet reached the same level as the n-type. This limitation is generally postulated to be as a result of the localization of the oxygen (O) 2p state in the valence band. 12, 13 Driven by this realization, Hosono and co-workers have postulated the delocalization of the O 2p state as a strategy to unlock the high hole mobility, effectively decreasing the hole effective mass. They proposed an approach to accomplish this goal by incorporating highly electronegative cations with energy levels closely matched to the O 2p to increase the metal− oxygen hybridization. 14 This concept has led to the discovery of Cu-containing oxides 12, 15 and oxysulfides 16− 20 as high-performance wide-band gap, p-type materials. For visible-transparent, p-type oxides, the results from these Cu-systems are considered a hole mobility benchmark (∼ 1− 10 cm2/(V· s)). Still, these values are modest when compared to the performances of the visible-transparent, n-type oxides (> 100 cm2/(V· s)). 8, 9, 21 We note that Cu2O can exhibit the hole mobility on the level of the n-type oxides. 22, 23 However, Cu2O is not transparent in the visible wavelength. For applications in transparent electronics and wide band gap transistors, the discovery of a new semiconducting oxide with high hole mobility and wide band gap is therefore an essential step forward. In an effort to find superior p-type compounds, researchers have investigated the more spatially extended s-orbital chemistry to more efficiently delocalize the O 2p state. 24− 27 Tin monoxide, SnO (Sn2+:[Kr] 4d10 5s2), has shown to be one of the most promising p-type s-orbital oxide candidates. However, SnO is still limited by the low hole mobility (< 5 cm2/(V· s)), an anisotropic transport, and a low average transmission (75− 80%). 25, 26, 28− 30 Although recent report has shown the incorporation of metallic β-Sn can vastly improve the hole mobility (∼ 20 cm2/(V· s)), 31 preparing SnO with high stability is still a challenge. Bi3+([Xe] 4f14 5d10 6s2) compounds offers an alternative path to the s-orbital utilization. 27 However, the Bi 6s states in the studied Bi-based oxides thus far are too low for effective O 2p hybridization. 26 To take advantage of the s-orbital chemistry in Bi3+, it is essential to find a structure and chemistry that has the Bi state at a suitable energy position to support the Bi 6s− O 2p hybridization while retaining visible transparency. We have recently reported the use of band gap and valence band curvatures as parameters for screening for high figure-of-merit p-type oxides from the binary and ternary oxide databases. 13 Herein, we report the experimental realization of an s-orbital bismuth-based candidate with strong metal− oxygen s− p hybridization and visible transparency. Our identification is a direct result of our application of the highthroughput computational screening methodology to the quaternary oxide space. We present its synthesis, optical and electrical characterization and provide a preliminary demonstration of the material’s visible transparency and hole mobility to demonstrate the promising qualities of this p-type transparent oxide compound.To identify …