An in situ phosphorus source for the synthesis of Cu 3 P and the subsequent conversion to Cu 3 PS 4 nanoparticle cluster
- PDF / 535,729 Bytes
- 7 Pages / 584.957 x 782.986 pts Page_size
- 66 Downloads / 130 Views
Wei-Chang Yang School of Materials Engineering, Purdue University, West Lafayette, Indiana 47907, USA
Robert B. Balow Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA
Yunjie Wang and Bryce C. Walker School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, USA
Eric A. Stachb) Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, USA
Rakesh Agrawala) School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, USA (Received 7 August 2015; accepted 8 October 2015)
The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I–V–VI chalcogenides including copper phosphide (Cu3P) and copper thiophosphate (Cu3PS4). Herein, we report a one-pot, solutionbased synthesis of Cu3P nanocrystals utilizing an in situ phosphorus source: phosphorus pentasulfide (P2S5) in trioctylphosphine. By injecting this phosphorus source into a copper solution in oleylamine, uniform and size controlled Cu3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cu3P nanocrystals with decomposing thiourea forms nanoscale Cu3PS4 particles having p-type conductivity and an effective optical band gap of 2.36 eV. The synthesized Cu3PS4 produces a cathodic photocurrent during photoelectrochemical measurements, demonstrating its application as a light-absorbing material. Our process creates opportunities to explore other solution-based metal-phosphorus systems and their subsequent sulfurization for earth abundant, alternative energy materials.
I. INTRODUCTION
Contributing Editor: Gary L. Messing a) Address all correspondence to this author. e-mail: [email protected] b) This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs. org/jmr-editor-manuscripts/ DOI: 10.1557/jmr.2015.333
solution-based methods that utilize the decomposition of trioctylphosphine (TOP).10–13 Here, we report the synthesis of size tunable Cu3P nanocrystals by the reaction of copper nanocrystals with a novel solutionbased phosphorus source: P2S5 in TOP. A hot injection technique was utilized at temperatures between 200 and 300 °C to produce nearly uniform Cu3P nanocrystals. Extending from Cu3P, copper thiophosphate (Cu3PS4) and copper selenophosphate (Cu3PSe4) have recently been reported as having favorable electronic properties for applications as alternative, earth abundant solar absorption materials.14–16 These ternary chalcogenides have similar crystal structures to CdTe, Cu(In,Ga)Se2, and Cu2ZnSnSe4, as well as Cu3AsS4, and it is thus logical to pursue the development of simple and inexpensive syntheses of I–V–VI semiconductors for earth abundant and nontoxic next generation solar devices.17 To date, repo
Data Loading...
