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Digenite (Cu9S5): Layered p-Type Semiconductor Grown by Reactive Annealing of Copper
Chemistry of Materials ( IF 7.2 ) Pub Date : 2018-03-12 00:00:00 , DOI: 10.1021/acs.chemmater.8b00191 Anat Itzhak 1 , Eti Teblum 1 , Olga Girshevitz 2 , Sivan Okashy 1 , Yury Turkulets 3 , Luba Burlaka 2 , Gili Cohen-Taguri 2 , Efrat Shawat Avraham 1 , Malachi Noked 1 , Ilan Shalish 3 , Gilbert Daniel Nessim 1
Chemistry of Materials ( IF 7.2 ) Pub Date : 2018-03-12 00:00:00 , DOI: 10.1021/acs.chemmater.8b00191 Anat Itzhak 1 , Eti Teblum 1 , Olga Girshevitz 2 , Sivan Okashy 1 , Yury Turkulets 3 , Luba Burlaka 2 , Gili Cohen-Taguri 2 , Efrat Shawat Avraham 1 , Malachi Noked 1 , Ilan Shalish 3 , Gilbert Daniel Nessim 1
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Most of the recently discovered layered materials such as MoS2 or MoSe2 are n-type, while few materials, such as phosphorene, which suffers from rapid oxidation, are p-type. To form devices such as p–n junctions and heterojunctions, new p-type mono-/few-layers are needed. Here, we report a one-step synthesis of layered, crystalline, p-type copper sulfide by thermal annealing of a standard copper foil in an inert environment using chemical vapor deposition (CVD). Optical spectroscopies (photoluminescence and absorption) show definite correlating features around 2.5 eV. Surface photovoltage spectroscopy shows a photovoltage reduction around the same energy range, which would be expected from a bandgap of a p-type material, and p-type conductivity was also observed using a thermoelectric probe. TEM, XRD, and AFM showed that the synthesized material is layered and has a unique stoichiometry of Cu9S5. Using sonication and dropcasting, we succeeded to isolate few-layers and monolayers. We observed good bulk electrical conductivity and characterized the electrical conductivity of few-layer copper sulfide flakes using peak force tunneling atomic force microscopy (PF-TUNA). We observed an increase in conductivity for increasing number of layers. Given its conductivity and layered morphology, we tested the synthesized Cu9S5 as an electrode for a Li-ion battery. The proposed bottom-up synthesis, which is simple and scalable, allows synthesizing bulk quantities of the p-type layered Cu9S5 which can then be exfoliated (top-down) to deposit monolayer flakes on substrates. Combined with the progress achieved in the preparation of n-type layered materials, this p-type Cu9S5 opens the door to the fabrication of 2D p–n heterojunctions.
中文翻译：
Digenite（Cu 9 S 5）：通过铜的反应退火生长的层状p型半导体
最近发现的大多数分层材料，例如MoS 2或MoSe 2p型是n型，而受快速氧化的磷等材料则很少。为了形成诸如PN结和异质结之类的器件，需要新的P型单层/少量层。在这里，我们报告了通过在惰性环境中使用化学气相沉积（CVD）对标准铜箔进行热退火，一步法合成层状结晶p型硫化铜的方法。光学光谱学（光致发光和吸收）在2.5 eV附近显示出明确的相关特征。表面光电压光谱显示在相同能量范围内的光电压降低，这是从p型材料的带隙可以预期的，并且还使用热电探针观察到p型电导率。TEM，XRD和AFM表明合成的材料呈层状并具有独特的Cu化学计量9 S 5。使用超声和压铸法，我们成功地分离了几层和单层。我们观察到良好的整体电导率，并使用峰力隧穿原子力显微镜（PF-TUNA）表征了几层硫化铜薄片的电导率。我们观察到电导率随着层数的增加而增加。鉴于其导电性和层状形态，我们测试了合成的Cu 9 S 5作为锂离子电池的电极。所提出的自下而上的合成方法简单且可扩展，可以合成大量p型层状Cu 9 S 5然后可以将其剥落（自上而下）以在基材上沉积单层薄片。结合在制备n型层状材料方面取得的进展，这种p型Cu 9 S 5为2D p–n异质结的制造打开了大门。
更新日期：2018-03-12
中文翻译：
Digenite（Cu 9 S 5）：通过铜的反应退火生长的层状p型半导体
最近发现的大多数分层材料，例如MoS 2或MoSe 2p型是n型，而受快速氧化的磷等材料则很少。为了形成诸如PN结和异质结之类的器件，需要新的P型单层/少量层。在这里，我们报告了通过在惰性环境中使用化学气相沉积（CVD）对标准铜箔进行热退火，一步法合成层状结晶p型硫化铜的方法。光学光谱学（光致发光和吸收）在2.5 eV附近显示出明确的相关特征。表面光电压光谱显示在相同能量范围内的光电压降低，这是从p型材料的带隙可以预期的，并且还使用热电探针观察到p型电导率。TEM，XRD和AFM表明合成的材料呈层状并具有独特的Cu化学计量9 S 5。使用超声和压铸法，我们成功地分离了几层和单层。我们观察到良好的整体电导率，并使用峰力隧穿原子力显微镜（PF-TUNA）表征了几层硫化铜薄片的电导率。我们观察到电导率随着层数的增加而增加。鉴于其导电性和层状形态，我们测试了合成的Cu 9 S 5作为锂离子电池的电极。所提出的自下而上的合成方法简单且可扩展，可以合成大量p型层状Cu 9 S 5然后可以将其剥落（自上而下）以在基材上沉积单层薄片。结合在制备n型层状材料方面取得的进展，这种p型Cu 9 S 5为2D p–n异质结的制造打开了大门。
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