Understanding and Control of Bipolar Doping in Copper Nitride

TL;DR

This study investigates the mechanisms behind bipolar doping in copper nitride (Cu3N), demonstrating control over conduction types through growth temperature and elucidating defect formation processes using experimental and theoretical methods.

Contribution

The paper provides a comprehensive understanding of bipolar doping in Cu3N by combining experimental measurements with defect theory, introducing a kinetic defect formation model for metastable semiconductors.

Findings

Demonstrated both n-type and p-type Cu3N via temperature-controlled growth.

Identified V_Cu and Cu_i defects as key to p-type and n-type doping, respectively.

Proposed a kinetic defect formation mechanism supported by experiments.

Abstract

Semiconductor materials that can be doped both n-type and p-type are desirable for diode-based applications and transistor technology. Copper nitride (Cu3N) is a metastable semiconductor with a solar-relevant bandgap that has been reported to exhibit bipolar doping behavior. However, deeper understanding and better control of the mechanism behind this behavior in Cu3N is currently lacking in the literature. In this work, we use combinatorial growth with a temperature gradient to demonstrate both conduction types of phase-pure, sputter-deposited Cu3N thin films. Room temperature Hall effect and Seebeck effect measurements show n-type Cu3N with 10^17 electrons/cm^3 for low growth temperature (~35 degrees C) and p-type with 10^15-10^16 holes/cm^3 for elevated growth temperatures (50-120 degrees C). Mobility for both types of Cu3N was ~0.1-1 cm^2/Vs. Additionally, temperature- dependent Hall effect measurements indicate that ionized defects are an important scattering mechanism in p-type films. By combining X-ray absorption spectroscopy and first-principles defect theory, we determined that V_Cu defects form preferentially in p-type Cu3N while Cu_i defects form preferentially in n-type Cu3N. Based on these theoretical and experimental results, we propose a kinetic defect formation mechanism for bipolar doping in Cu3N, that is also supported by positron annihilation experiments. Overall, the results of this work highlight the importance of kinetic processes in the defect physics of metastable materials, and provide a framework that can be applied when considering the properties of such materials in general.