| || || || || || || || || || || || |
It was recognized over thirty years ago that the introduction of states in a semiconductor band gap presents an alternative to multijunction designs for improving the power conversion efficiency of solar cells. The intermediate band acts as a “stepping stone,” allowing absorption of photons at three different energy levels, corresponding to the three different band gaps. In particular, low-energy photons are captured that would pass through a conventional solar cell (Fig. 1). Detailed theoretical calculations indicated that a single junction cell with a properly located band of intermediate states could achieve power conversion efficiencies up to 62% - i.e. higher than those for optimized double-junction tandem cells (Fig. 2). Even higher efficiencies of up to 71.7% were predicted for materials with two bands of intermediate states.
Figure 1 A schematic of an intermediate band solar cell
Until very recently, practical realization of semiconductors with this multi-band structure had not been achieved. We have designed and synthesized a new class of semiconductor alloys with an intermediate band within the energy gap. The design of our material is based on the recently introduced band anticrossing (BAC) model of highly mismatched semiconductor alloys (HMAs). Group III-N-V alloys in which group V anions are partially replaced with N or group II-O-VI alloys in which column VI element is replaced with O are the well known examples of the HMAs. The electronic structure of the HMAs is determined by the interaction between localized states associated with N or O atoms and the extended states of the host semiconductor. As a result the conduction band splits into two subbands (E- and E+) with non-parabolic dispersion relations.
In most instances, e.g. N in GaAs or O in CdTe, the localized states are located within the conduction band and consequently a relatively wide lower subband is formed. A narrow band can be formed only if the localized states occur well below the conduction band edge.
Figure 2 Comparison of the maximum power conversion efficiency of an intermediate band solar cell, a single gap solar cell, and a double junction tandem cell. The higher gap values for the tandem cell and the IBSC are indicated on the plot. (after Luque et. al. PRL, 78, 5014(1997))
| || |
In this case the E- subband states are of highly localized character and the E+subband states become more extended. This situation occurs for O in ZnTe, MnTe, MgTe. Figure 3 illustrates the formation of a narrow intermediate band by the incorporation of O into ZnTe. In addition to the O content, Mn alloying can also be used to adjust the energy level positions. Thus, band locations corresponding to those that are optimal for a multiband solar cell can be produced in ZnTeO and ZnMnTeO. With multiple band gaps that fall within the solar energy spectrum, Zn1-xMnxOyTe1-y is well suited for the proposed high efficiency intermediate band solar cells (IBSCs). This new II-VI oxide multi-band semiconductor was synthesized using the combination of oxygen ion implantation and pulsed laser melting. This highly non-equilibrium technique allowed for the synthesis of ZnMnOTe alloys with up to 3% of Te replaced with O atoms. Fig. 4 shows PR spectra from a Zn0.88Mn0.12Te substrate and two Zn0.88Mn0.12Te samples implanted with 3.3% of O followed by PLM with laser energy fluence of 0.15 and 0.3 J/cm2. Two optical transitions occurring at energies distinctly different from the fundamental band gap transition EM (=2.31 eV) of the Zn0.88Mn0.12Te matrix can be clearly observed at ~1.8 and 2.6 eV from the samples after PLM.
Fig. 3. Band anticrossing and formation of an intermediate band in Zn1-yMnyTe1-xOx.
These two optical transitions can be attributed to transitions from the valence band to the two conduction subbands, E+ (~2.6 eV) and E- (~1.8 eV) formed as a result of the hybridization of the localized O states and the extended conduction band states of ZnMnTe.
Our results from optical transitions clearly demonstrate that three types of optical transitions are possible in this band structure; (1) the transitions from the valence band to the E+subband with the absorption edge at EV+=E+(k=0)-EV(k=0)=2.56 eV, (2) transitions from the valence band to E- subband with the edge at EV-=E-(k=0)-EV(k=0)=1.83 eV and (3) the low energy transitions from E- to E+ with the absorption edge atE_+=E+(k=0)-E_(k=0)=0.73 eV. The three absorption edges span much of the solar spectrum, demonstrating that these alloys are good candidates for the multi-band semiconductors envisioned for high efficiency photovoltaic devices.
Detailed balance calculations of the power conversion efficiency for a intermediate band solar cell based on this material is shown in Fig. 5. Even for this non-optimal band gap configuration we calculate a power conversion efficiency of 45%, which is higher than the ideal efficiency of any solar cell based on a single junction in a single-gap semiconductor and is comparable to the efficiency of double-junction cells.
The potential technological importance of the multiband semiconductors raises the question if they can also be realized in group III-Nx-V1-x HMAs as well. In most III-V compounds the localized N level lies above the conduction band edge. An exception is the GaAs1-yPy alloy system in which N-level falls below the conduction band edge for y>0.3. Consequently the anticrossing interaction of the N states with the extended conduction band states in these GaAsP alloys is expected to result in the formation of a narrow band of intermediate states. Recently we have also synthesized GaNxAs1-yPy with y=0 to 0.4 using N+-implantation followed by PLM and RTA techniques. With an implanted N concentration of 2%, the N concentration incorporated in the As sublattice amounts to about 1% and 0.3% for films with y≤0.12 and y>0.12, respectively. GaNxAs1-yPy with y>0.2 clearly shows strong optical transitions corresponding to both the lower (E-) and upper (E+) conduction subbands. GaNxAs1-yPy alloys with y>0.3 have a three band structure making them suitable for testing the theoretical predictions of the highly-efficient intermediate band solar cell concept. Theoretical ideal efficiency for IBSC using the GaN0.02As0.58P0.4 is calculated to be >55%.
Fig. 4. Photomodulated reflectance (PR) spectra obtained from Zn0.88Mn0.12Te samples as-grown and implanted with 3.3% O+followed by PLM with energy fluence of 0.15 and 0.3 J/cm2
| || |
Fig. 5: The calculated power conversion efficiency for a solar cell fabricated from a Zn0.88Mn0.12OxTe1-x alloy as a function of O content. The solid line is an empirical polynomial fit of the calculated data.
First demonstration of a dilute nitride based IBSC
Recently we have demonstrated an operational intermediate band
single junction solar cell using dilute GaNAs HMA. This material has a well defined
intermediate band isolated from the bands of the host material. The key to the successful device performance
was a design of proper layers blocking charge transport in the intermediate
band. The devices were fabricated using
metalorganic chemical vapor deposition (MOCVD) a standard commercial epitaxial
materials synthesis method. The
successful realization of the first intermediate band cell opens a new research
field focused on potential applications of a large variety of highly mismatched
alloys for solar power conversion technologies.
- A. Luque, A. Marti., Phys. Rev. Lett., 78, 5014 (1997).
- K. M. Yu, W. Walukiewicz, J. Wu, W. Shan, and J. W. Beeman, M. A. Scarpulla, O. D. Dubon, and P. Becla, “Diluted II-VI Oxide Semiconductors with Multiple Band Gaps,” Phys. Rev. Lett. 91, 246203 (2003).
- W. Shan, K. M. Yu, W. Walukiewicz, J. Wu, J. W. Beeman, and J.W. Ager III, M.A. Scarpulla, O.D. Dubon, and E. E. Haller, “Effects of Pressure on the Band Structure of Highly Mismatched Zn1-yMnyOxTe1-x Alloy,” Appl. Phys. Lett. 84, 924 (2004).
- K. M. Yu, W. Walukiewicz, J.W. Ager III, D. Bour, R. Farshchi, O. D. Dubon, S. X. Li, I. D. Sharp, and E. E. Haller, “Multiband GaNAsP Quaternary Alloys,” Appl. Phys. Lett. 88, 092110 (2006).
- K. M. Yu, W. Walukiewicz, M. A. Scarpulla, O. D. Dubon, W. Shan, J. Wu, J. W. Beeman, and P. Becla, “Synthesis and Properties of Highly Mismatched II-O-VI Alloys,” invited paper, pres. at E-MRS 2004 SPRING MEETING, Symposium M: Dilute nitride and related mismatched semiconductor alloys, Palais de la Musique et des Congres, Strasbourg, France, May 24-28, 2004. IEE Proceedings-Optoelectronics 151 (5): 452-459, Oct. 2004 (IEE-Inst. Elec. Emg., Michael Faraday House, Six Hills Way, Stevenage, Hertford, SG1 2AY, ENGLAND)
- Nair. López, Lothar. A. Reichertz, K.
M. Yu, Kenneth Campman, and Wladek. Walukiewicz, “Engineering the
Electronic Band Structure for Multiband Solar Cells,” Phys. Rev. Lett. 106, 028701 (2011).