Su-Huai Wei

Classification of Lattice Defects in the Kesterite Cu2ZnSnS4 and Cu2ZnSnSe4 Earth‐Abundant Solar Cell Absorbers

The kesterite-structured semiconductors Cu2ZnSnS4 and Cu2ZnSnSe4 are drawing considerable attention recently as the active layers in earth-abundant low-cost thin-film solar cells. The additional number of elements in these quaternary compounds, relative to binary and ternary semiconductors, results in increased flexibility in the material properties. Conversely, a large variety of intrinsic lattice defects can also be formed, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. Experimental identification of these defects is currently limited due to poor sample quality. Here recent theoretical research on defect formation and ionization in kesterite materials is reviewed based on new systematic calculations, and compared with the better studied chalcopyrite materials CuGaSe2 and CuInSe2 . Four features are revealed and highlighted: (i) the strong phase-competition between the kesterites and the coexisting secondary compounds; (ii) the intrinsic p-type conductivity determined by the high population of acceptor CuZn antisites and Cu vacancies, and their dependence on the Cu/(Zn+Sn) and Zn/Sn ratio; (iii) the role of charge-compensated defect clusters such as [2CuZn +SnZn ], [VCu +ZnCu ] and [ZnSn +2ZnCu ] and their contribution to non-stoichiometry; (iv) the electron-trapping effect of the abundant [2CuZn +SnZn ] clusters, especially in Cu2ZnSnS4. The calculated properties explain the experimental observation that Cu poor and Zn rich conditions (Cu/(Zn+Sn) ≈ 0.8 and Zn/Sn ≈ 1.2) result in the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu2ZnSn(S,Se)4 cells when the S composition is high.

Crystal and Electronic Band Structure of Cu2ZnSnX4 (X = S and Se) Photovoltaic Absorbers: First-Principles Insights

The structural and electronic properties of Cu2ZnSnS4 and Cu2ZnSnSe4 are studied using first-principles calculations. We find that the low energy crystal structure obeys the octet rule and is the kesterite (KS) structure. However, the stannite or partially disordered KS structures can also exist in synthesized samples due to the small energy cost. We find that the dependence of the band structure on the (Cu,Zn) cation ordering is weak and predict that the band gap of Cu2ZnSnSe4 should be on the order of 1.0 eV and not 1.5 eV as was reported in previous absorption measurements.

Calculated natural band offsets of all II–VI and III–V semiconductors: Chemical trends and the role of cation d orbitals

Using first-principles all-electron band structure method, we have systematically calculated the natural band offsets ΔEv between all II–VI and separately between III–V semiconductor compounds. Fundamental regularities are uncovered: for common-cation systems ΔEv decreases when the cation atomic number increases, while for common-anion systems ΔEv decreases when the anion atomic number increases. We find that coupling between anion p and cation d states plays a decisive role in determining the absolute position of the valence band maximum and thus the observed chemical trends.

Halide perovskite materials for solar cells: a theoretical review

Halide perovskites have recently emerged as promising materials for low-cost, high-efficiency solar cells. The efficiency of perovskite-based solar cells has increased rapidly, from 3.8% in 2009 to 19.3% in 2014, by using the all-solid-state thin-film architecture and engineering cell structures with mixed-halide perovskites. The emergence of perovskite solar cells revolutionized the field not only because of their rapidly increased efficiency, but also flexibility in material growth and architecture. The superior performance of the perovskite solar cells suggested that perovskite materials possess intrinsically unique properties. In this review, we summarize recent theoretical investigations into the structural, electrical, and optical properties of halide perovskite materials in relation to their applications in solar cells. We also discuss some current challenges of using perovskites in solar cells, along with possible theoretical solutions.

Effects of Ga addition to CuInSe2 on its electronic, structural, and defect properties

Using a first-principles band structure method we have theoretically studied the effects of Ga additions on the electronic and structural properties of CuInSe2. We find that (i) with increasing xGa, the valence band maximum of CuIn1−xGaxSe2 (CIGS) decreases slightly, while the conduction band minimum (and the band gap) of CIGS increases significantly, (ii) the acceptor formation energies are similar in both CuInSe2 (CIS) and CuGaSe2 (CGS), but the donor formation energy is larger in CGS than in CIS, (iii) the acceptor transition levels are shallower in CGS than in CIS, but the GaCu donor level in CGS is much deeper than the InCu donor level in CIS, and (iv) the stability domain of the chalcopyrite phase increases with respect to ordered defect compounds. Our results are compared with available experimental observations.

Defect physics of the kesterite thin-film solar cell absorber Cu2ZnSnS4

Cu2ZnSnS4 is one of the most promising quaternary absorber materials for thin-film solar cells. Examination of the thermodynamic stability of this quaternary compound reveals that the stable chemical potential region for the formation of stoichiometric compound is small. Under these conditions, the dominant defect will be p-type CuZn antisite, which has an acceptor level deeper than the Cu vacancy. The dominant self-compensated defect pair in this quaternary compound is [CuZn−+ZnCu+]0, which leads to the formation of various polytype structures of Cu2ZnSnS4. We propose that to maximize the solar cell performance, growth of Cu2ZnSnS4 under Cu-poor/Zn-rich conditions will be optimal, if the precipitation of ZnS can be avoided by kinetic barriers.

A phenomenological model for systematization and prediction of doping limits in II–VI and I–III–VI2 compounds

Semiconductors differ widely in their ability to be doped. As their band gap increases, it is usually possible to dope them either n or p type, but not both. This asymmetry is documented here, and explained phenomenologically in terms of the “doping pinning rule.”

Band offsets and optical bowings of chalcopyrites and Zn‐based II‐VI alloys

Using first‐principles band‐structure theory we have systematically calculated the (i) alloy bowing coefficients, (ii) alloy mixing enthalpies, and (iii) interfacial valence‐ and conduction‐band offsets for three mixed‐anion (CuInX2, X=S, Se, Te) and three mixed‐cation (CuMSe2, M=Al, Ga, In) chalcopyrite systems. The random chalcopyrite alloys are represented by special quasirandom structures (SQS). The calculated bowing coefficients are in good agreement with the most recent experimental data for stoichiometric alloys. Results for the mixing enthalpies and the band offsets are provided as predictions to be tested experimentally. Comparing our calculated bowing and band offsets for the mixed‐anion chalcopyrite alloys with those of the corresponding Zn chalcogenide alloys (ZnX, X=S, Se, Te), we find that the larger p−d coupling in chalcopyrite alloys reduces their band offsets and optical bowing. Bowing parameters for ordered, Zn‐based II‐VI alloys in the CuAu, CuPt, and chalcopyrite structures are present...

First-principles calculation of band offsets, optical bowings, and defects in CdS, CdSe, CdTe, and their alloys

Using first principles band structure theory we have calculated (i) the alloy bowing coefficients, (ii) the alloy mixing enthalpies, and (iii) the interfacial valence band offsets for three Cd-based (CdS, CdSe, CdTe) compounds. We have also calculated defect formation energies and defect transition energy levels of Cd vacancy VCd and CuCd substitutional defect in CdS and CdTe, as well as the isovalent defect TeS in CdS. The calculated results are compared with available experimental data.

Effects of Na on the electrical and structural properties of CuInSe2

We found theoretically that Na has three effects on CuInSe2: (1) If available in stoichiometric quantities, Na will replace Cu, forming a more stable NaInSe2 compound having a larger band gap (higher open-circuit voltage) and a (112)tetra morphology. The ensuing alloy NaxCu1−xInSe2 has, however, a positive mixing enthalpy, so NaInSe2 will phase separate, forming precipitates. (2) When available in small quantities, Na will form defect on Cu site and In site. Na on Cu site does not create electric levels in the band gap, while Na on In site creates acceptor levels that are shallower than CuIn. The formation energy of Na(InCu) is very exothermic, therefore, the major effect of Na is the elimination of the InCu defects and the resulting increase of the effective hole densities. The quenching of InCu as well as VCu by Na reduces the stability of the (2VCu−+InCu2+), thus suppressing the formation of the “Ordered Defect Compounds.” (3) Na on the surface of CuInSe2 is known to catalyze the dissociation of O2 int...