We have grown device-grade Cu(In,Ga)Se2 (CIGS) thin films using a RF-cracked Se-radical beam source. A unique combination of film properties: smooth surface, large grain size and high photovoltaic performance are shown. A competitive energy conversion efficiency of 17 % has been demonstrated from a solar cell fabricated using a CIGS absorber grown with a Se-radical source. In addition to the unique combination of film properties and high photovoltaic performance, a significant improvement in the use of Se source material in comparison with the conventional Se-evaporative sources has been demonstrated.

Dependence of band alignments at interfaces between CdS by chemical bath deposition and Cu(In1-xGax)Se2 by conventional 3-stage co-evaporation on Ga substitution ratio x from 0.2 to 1.0 has been systematically studied by means of photoemission spectroscopy (PES) and inverse photoemission spectroscopy (IPES). For the specimens of the In-rich CIGS, conduction band minimum (CBM) by CIGS was lower than that of CdS. Conduction band offset of them was positive about +0.3 ~ +0.4 eV. Almost flat conduction band alignment was realized at x = 0.4 ~ 0.5. On the other hand, at the interfaces over the Ga-rich CIGS, CBM of CIGS was higher than that of CdS, and CBO became negative. The present study reveals that the decrease of CBO with a rise of x presents over the wide rage of x, which results in the sign change of CBO around 0.4 ~ 0.45. In the Ga-rich interfaces, the minimum of band gap energy, which corresponded to energy spacing between CBM of CdS and valence band maximum of CIGS, was almost identical against the change of band gap energy of CIGS. Additionally, local accumulation of oxygen related impurities was observed at the Ga-rich samples, which might cause the local rise of band edges in central region of the interface.

In-situ characterization of composition, electronic structure and their depth profiles of surface of Cu(In1-xGax)Se2 (CIGS) film grown by three stage co-evaporation has been carried out by means of photoemission and inverse photoemission spectroscopy (PES/IPES), for the purpose of investigating the formation mechanism of the CIGS-side wide band-gap region adjacent to CBD-CdS/CIGS interface in cell structure. Sample-transportation in vacuum below 1 x 10-8 Torr yielded almost contamination-free feature of the CIGS surface. The as-transferred surface of Cu0.93(In0.65Ga0.35)Se2 grown at the identical condition for the high performance solar cell exhibited seriously Cu and Ga deficient composition. Chemical formula of this region was inbetween Cu : (In+Ga): Se = 1 : 3 : 5 and 1 : 5 : 8. In-situ UPS/IPES measurements CIGS showed that the as-grown surface region of the CIGS already had expanded band gap energy up to 1.4 eV and n-type character. A gradual decrease of band energy and a rise of valence band maximum as a function of depth from the original surface were observed. These results have revealed that the surface of CIGS by the three stage method already has the wide band gap, which might originate in so-called Cu-vacancy ordered phase.

For understanding the origin of the improvements of properties in the CIGS-based cells, of which the CIGS absorber has been fabricated by H2O-introduced co-evaporation [CIGS-H2O], band alignment at the interfaces between chemical bath deposited CdS and CIGS-H2O with Ga substitution ratio ~ 40 % has been studied by photoemission and inverse photoemission spectroscopy. The CdS layer over the CIGS-H2O showed an identical electronic structure with that of CdS on the conventionally grown CIGS; band gap energy of 2.3 ~ 2.4 and a location of conduction band minimum (CBM) and valence band maximum (VBM) relative to Fermi level were + 0.75 eV and -1.6 ~ -1.7 eV, respectively. In the interface region, decreases of CBM and a rise of VBM were observed. Total amount of the decrease of CBM over the interface was 0.2 ~ 0.3 eV. XPS measurements of the core-level signals over the interface showed a small upward bend bending of 0.1 ~ 0.2 eV. Consequently, the conduction band offset (CBO) and valence bad offset (VBO) at the CBD-interface over the CIGS-H2O (Ga~40%) are about +0.1, and 0.9 ~ 1.1 eV, respectively. This positive CBO is contrast with a slightly negative CBO at the interface between CBD-CdS/conventionally grown CIGS with Ga ~ 40 % measured previously. These results indicate that the H2O introduction is effective to extend the upper limit of the Ga substitution ratio where the Type-I conduction band alignment is maintained. The observed band alignments are consistent with the rise of Voc and efficiency in the CIGS-H2O based cells.

The reasons why the open circuit voltage (Voc) of high-x CuIn1-xGaxSe2 (CIGS)/ZnO solar cells remain low are discussed. Here it is shown that the Voc ceiling can be interpreted simply on the basis of a model that the valence-band energy (Ev) of CIGS is almost immovable irrespective of x. When the conduction-band energy (Ec) of ZnO is lower than that of high-x CIGS (DEc<0), the built-in potential (Vbi) of a CIGS/ZnO junction is equivalent to the flat-band potential (Vbi) that arises from the separation between the Fermi energies of the two materials. If the Ev (and therefore the Fermi energy) of p-type CIGS is constant with increasing x, the Vbi and Voc that follows the Vbi remain unchanged since the Fermi energy of ZnO is constant. This unchangeable Voc reduces the conversion efficiency of high-x CIGS cells in cooperation with reduced photocurrents due to a larger bandgap. A positive offset, ΔEc>o gives rise to a photoelectrons barrier in the conduction-band that partially cancels Voc, thus the Voc of a low-x CIGS cell is governed by the Ec of CIGS. Based upon this concept, a material selection guideline is given for the windows and transparent electrodes appropriate for high-x CIGS absorbers-based solar cells.

Using EBIC and EDX measurements, CIGS solar cells prepared under several different conditions were observed and characterized. The results of EBIC and EDX measurements suggest that Cd plays an important role in the forming of a buried pn-junction in the CIGS layer via diffusion, and de-emphasize the possibility of the formation of the hetero pn-junction at the CdS/CIGS heterointerface. The correlation of the extent of the space charge region and the observed shift in the pn-junction location with the diffusion of the constituent elements in CIGS was investigated.

We have fabricated CIGS:Fe polycrystalline thin films using a standard three-stage method, and investigated the effects of Fe doping on cell performances. The Ga / (In+Ga) ratio was varied between 0.3 ˜ 1.0 (= CGS), and the Fe concentration was varied between 0.0 ˜ 1.2 mol%. The films were characterized by various means, including the cell performance. Increment of the grain size with higher Fe content was observed. Redshift with higher Fe content was observed in the absorbance spectra. The spectral response of the fabricated solar cells deteriorated with higher Fe content, from the long wavelength side.

MBE growth of ZnO films for optical semiconductor devices was investigated on off-angled c-plane sapphire substrates. Twin crystal RHEED patterns and surface facetting observed with c-plane just-oriented substrates were suppressed by enlarging the offset angles from near-zero to 2.87 degrees. Though no significant changes were seen in optical characteristics, FWHM of XRC narrowed and surface morphology improved with larger offset angles, indicating that the offset angle is also a sensitive factor for ZnO film growth.