Formation and Characterization of Ge1–x–ySixSny/Ge Heterojunction Structures for Photovoltaic Cell Application
Authors: Nakatsuka Osamu , Asaba Shunsuke , Kurosawa Masashi , Sakashita Mitsuo , Taoka Noriyuki , Zaima Shigeaki 
Published: July 2021

Group-IV alloy semiconductor materials are much attractive for photovoltaic application, as those realizes multijunction photovoltaic with multi-heterostructure like group-III-V compound semiconductors [1]. In addition, group-IV alloy materials are expected to be familiar to Si integrated electronics. Ge1–x–ySixSny is one of candidate materials suitable for multijunction photovoltaic, since ternary alloy semiconductor provides energy band design independent on the lattice constant. The energy band gap of Ge1–x–ySixSny can be controlled from 0.66 eV to 1.0 eV with the epitaxial layer whose lattice is matching to Ge substrate.
We previously reported the epitaxial growth of Ge1–x–ySixSny layers and also investigated the crystalline and electronic properties of them [2, 3]. However, the junction properties of Ge1–x–ySixSny/Ge heterostructure have not been well understood and it is necessary to clarify the crystalline and electronic properties of group-IV ternary alloy hetero junctions. In this study, we examined the crystal growth of pseudomorphic epitaxial layers of Ge1–x–ySixSny ternary alloy on Ge(001) substrates to form heterojunction structure for photovoltaic application. We also investigated the electronic and optoelectronic properties of these Ge1–x–ySixSny/n-Ge heterojunction diodes.
Substrate used was n-type Ge(001) wafer. After chemical cleaning of substrate, a 200 nm-thick undoped Ge1–x–ySixSny layer was grown at 150–350 °C on substrate using molecular beam epitaxy system in ultrahigh vacuum chamber. Ge and Sn were deposited using Knudsen cells and Si was done using electron gun evaporation. Then, we prepared a mesa-shaped structure with wet etching. A 300 nm-thick SiO2 layer was deposited with coating of spin-on-glass and annealing at 450 °C. Finally, an Al electrode was prepared on contact holes to form heterojunction diode structure.
We confirmed the crystalline structure of epitaxial layers with X-ray diffraction reciprocal space mapping. A Ge1–x–ySixSny layer with a high Sn content of 12% can be prepared with lattice matching epitaxy on Ge at a low temperature below 250 °C. It is also found that the small misfit between Ge1–x–ySixSny and Ge effectively impacts on the high crystalline quality and high thermal stability of substitutional Sn atoms in Ge matrix.
Absorption spectroscopy and current-voltage characteristics of undoped Ge1–x–ySixSny/n-Ge heterojunction diodes were also performed. We observed good rectifying property of the diodes meaning that the majority carrier of these undoped Ge1–x–ySixSny ternary alloy layers is hole unintentionally generated due to defects. We also found the extension of the energy band gap of Ge1–x–ySixSny layer with Si and Sn contents. Photovoltaic property of Ge1–x–ySixSny/Ge heterojunction diodes were also measured. We can see the increasing of the open circuit voltage, Voc from 0.08 to 0.12 V for undoped Ge/n-Ge to undoped Ge0.54Si0.36Sn0.10/Ge heterojunction photovoltaic cell structure, which indicates the enhancement of Voc with increasing the energy bandgap of epitaxial layer. We also achieved the improvement of Voc by 0.14 V with 500 °C-annealing in hydrogen (H2) ambient, which suggests the annihilation or termination of point defect in the heterojunction structure.
In conclusions, heterojunction structure with Ge1–x–ySixSny ternary alloy semiconductor layer provides the energy band engineering for photovoltaic applications. Understanding and controlling the defect properties in epitaxial growth and heterojunction formation should be key factors for the enhancement of performance of group-IV multijunction photovoltaic.

References

[1] S. Asaba et al., in Ext. Abstra. of Int. Conf. on Solid State Devices and Materials (SSDM2013), pp. 1172-1173, Fukuoka, Japan, Sept. 2013.
[2] T. Asano et al., Solid State Electronics 110, 49 (2015).
[3] T. Yamaha et al., Appl. Phys. Lett. 108, 061909 (2016).