Multi-junction III–V solar cells: current status and future potential

Our recent R&D activities of III–V compound multi-junction (MJ) solar cells are presented. Conversion efficiency of InGaP/InGaAs/Ge has been improved up to 31–32% (AM1.5) as a result of technologies development such as double hetero-wide band-gap tunnel junction, InGaP–Ge hetero-face structure bottom cell, and precise lattice-matching of InGaAs middle cell to Ge substrate by adding indium into the conventional GaAs layer. For concentrator applications, grid structure has been designed in order to reduce the energy loss due to series resistance, and world-record efficiency InGaP/InGaAs/Ge 3-junction concentrator solar cell with an efficiency of 37.4% (AM1.5G, 200-suns) has been fabricated. In addition, we have also demonstrated high-efficiency and large-area (7000 cm²) concentrator InGaP/InGaAs/Ge 3-junction solar cell modules of an outdoor efficiency of 27% as a result of developing high-efficiency InGaP/InGaAs/Ge 3-junction cells, low optical loss Fresnel lens and homogenizers, and designing high thermal conductivity modules.Future prospects are also presented. We have proposed concentrator III–V compound MJ solar cells as the 3rd generation solar cells in addition to 1st generation crystalline Si solar cells and 2nd generation thin-film solar cells. We are now developing low-cost and high output power concentrator MJ solar cell modules with an output power of 400 W/m² for terrestrial applications.     

Organic ultraviolet photovoltaic diodes based on copper phthalocyanine as an electron acceptor

Organic ultraviolet (UV) light-sensitive photovoltaic (PV) diodes, based on 4, 4′, 4″-tris-(2-methylphenyl phenylamino) triphenylamine (m-MTDATA) as an electron donor and copper phthalocyanine (CuPc) as acceptor, have been fabricated. The PV diode exhibits high open-circuit voltage (V_OC) of 1.05 V under illumination of 365 nm UV light with 1.7 mW/cm², although the CuPc was generally used as electron donor in other PV diodes. And the short-circuit current (I_SC) of 54.6 μA/cm², fill factor (FF) of 0.304 and power conversion efficiency (η_e) of 1.03% are respectively achieved. This diode can accurately detect the UV radiation according to photo-generated voltage signal.     

Sensitization effect by porphyrin in polythiophene/perylene dye two-layer solar cells

An enhanced photocurrent was observed for a two-layer cell consisting of a regioregular polythiophene (PTh) blended with metal-free porphyrin (H₂tpp) and a perylene tetracarboxylic derivative (PV), compared to a PTh (without H₂tpp)/PV two-layer cell. This is because photoexcited H₂tpp molecules efficiently transfer holes to PTh molecules and then produced electrons in H₂tpp molecules rapidly transfer to PV molecules at the mixed solid/PV interface. In the two-layer photocell with the mixed solid, H₂tpp behaves as a sensitizer, PTh and PV solids as carrier transport layers, and the mixed solid/PV interface as a charge separation site. Power conversion efficiency attained to η=2.9% for the PTh (with H₂tpp)/PV two-layer cell under monochromatic light with 6 μW cm⁻² intensity.     

Fabrication and characterization of 4-tricyanovinyl-N,N-diethylaniline/p-silicon hybrid organic–inorganic solar cells

Hybrid organic–inorganic solar cell was fabricated by thin film of 4-tricyanovinyl-N,N-diethylaniline deposited on p-Si substrates. The capacitance–voltage characteristics indicated that the junction is of abrupt nature. The dark forward current density-voltage characteristics indicated a tunneling conduction at relatively low voltages followed by a space-charge-limited-conduction mechanism at relatively high voltages. Under illumination, the cell exhibits photovoltaic characteristics with an open-circuit voltage of 0.70 V, a short-circuit current density of 9.15 mA cm⁻², and a power conversion efficiency of 3.10%. The effect of γ-rays irradiation (100 kGy absorbed dose) on the characteristics of the cell was also investigated. The fill factor and the power conversion efficiency decrease by 20.9% and 39% of the original value, respectively.     

Dye-sensitized solar cell based on Rose Bengal dye and nanocrystalline TiO2

Dye-sensitized solar cell is fabricated using Rose Bengal dye (RB) for sensitization of nanocrystalline TiO₂ and that imparts extension in spectral response towards visible region by modifying the semiconductor surface. Further, the photoresponse of the cell was evaluated by analyzing its J–V and impedance characteristics under illumination with metal halide light source of 400 W with an incident light of 73 mW/cm². Various photovoltaic parameters like J_sc, V_oc, FF were evaluated and found to be 3.22 mA, 890 mV, 0.53, respectively, resulting conversion efficiency (η) of 2.09%. Impedance analysis of the cell was carried out to investigate the internal resistance of the cell by recording Cole–Cole plots in between real and imaginary impedance in dark and with illumination under variable biasing, i.e. from 0 to 3 V.     

Photovoltaic cells based on cadmium sulphide–phthalocyanine heterojunction

Hybrid photovoltaic (PV) cells based on cadmium sulphide (CdS) single crystal and phthalocyanine (Pc) films have been developed and their PV performance was measured. Five different Pcs have been selected as candidates for the PV cell, PcCu, PcMn, PcZn, PcMg, and PcVO. It was found that all the chosen Pcs are capable of forming a hybrid heterojunction with the CdS surface, and that illumination results in charge separation at the interface. However, the performance of the In/CdS/Pc/Au device was dependent on the Pc used. PV cells with PcMg and PcZn showed the best results. An unoptimized cell with the PcZn film showed an open-circuit voltage V_oc=0.595 V, a short-circuit current density J_sc=1.88 μA/cm², a fill factor FF=0.265, and a power conversion efficiency PCE=3.0×10⁻⁴% under the AM1.5 conditions.     

Super high-efficiency multi-junction and concentrator solar cells

III–V compound multi-junction (MJ) (tandem) solar cells have the potential for achieving high conversion efficiencies of over 50% and are promising for space and terrestrial applications.We have proposed AlInP–InGaP double hetero (DH) structure top cell, wide-band gap InGaP DH structure tunnel junction for sub cell interconnection, and lattice-matched InGaAs middle cell. In 2004, we have successfully fabricated world-record efficiency concentrator InGaP/InGaAs/Ge 3-junction solar cells with an efficiency of 37.4% at 200-suns AM1.5 as a result of widening top cell band gap, current matching of sub cells, precise lattice matching of sub cell materials, proposal of InGaP–Ge heteroface bottom cell, and introduction of DH-structure tunnel junction. In addition, we have realized high-efficiency concentrator InGaP/InGaAs/Ge 3-junction solar cell modules (with area of 7000 cm²) with an out-door efficiency of 27% as a result of developing high-efficiency InGaP/InGaAs/Ge 3-junction cells, low optical loss Fresnel lens and homogenizers, and designing low thermal conductivity modules.Future prospects are also presented. We have proposed concentrator III–V compound MJ solar cells as the 3rd-generation solar cells in addition to 1st-generation crystalline Si solar cells and 2nd-generation thin-film solar cells. We are now challenging to develop low-cost and high output power concentrator MJ solar cell modules with an output power of 400 W/m² for terrestrial applications and high-efficiency, light-weight and low-cost MJ solar cells for space applications.     

Method for analyzing series resistance and diode quality factors from field data Part II: Applications to crystalline silicon

The method described in a prior journal publication [1] is applied to the determination of module series resistance and diode quality factors for several crystalline silicon (c-Si) technology photovoltaic (PV) modules. This method makes use of the functional dependence of the slope of the current–voltage (I–V) characteristics at open circuit (R_oc) against the reciprocal of the short-circuit current density (J_sc), from multiple I–V curves taken under variable illumination. It is shown that calculations of the series resistance for six modules yield values in the range 1.0–1.6 Ω-cm², expressed in unit-cell area terms. The derived values for the series resistance (R_s) determined from the data are investigated for their effect on the module fill factor (FF) values and their dependence at higher light intensity levels. The diode quality factors also derived from the same data are shown to be somewhat larger than those obtained from the more canonical method — slope of the fit of the open-circuit voltage (V_oc) versus logarithm of J_sc. The differences between the two methods are explored within a two-diode model for c-Si. Deriving average values of diode quality factors for series-connected cells using either method is shown to exhibit problematic issues.     

Annual output estimation of concentrator photovoltaic systems using high-efficiency InGaP/InGaAs/Ge triple-junction solar cells based on experimental solar cell's characteristics and field-test meteorological data

The temperature dependences of the electrical characteristics of InGaP/InGaAs/Ge triple-junction solar cells under concentration were evaluated. For these solar cells, conversion efficiency (η) decreased with increasing temperature, and increased with increasing concentration ratio owing to an increase in open-circuit voltage. The decrease in η with increasing temperature decreases with increasing concentration ratio. Moreover, the annual output of a concentrator system with a high-efficiency triple-junction cell was estimated utilizing the experimental solar cell's characteristics obtained in this study and field-test meteorological data collected for 1 year at the Nara Institute of Science and Technology, and compared with that of a nonconcentration flat-plate system.     

The effect of temperature on the charge transport and transient absorption properties of K27 sensitized DSSC

The charge transport and transient absorption properties of K27 dye-sensitized solar cell have been investigated. The current–voltage (I–V) characteristics of the solar cell were analyzed by the thermionic emission theory. The ideality factor, barrier height and series resistance values of the solar cell were determined. The ideality factor higher than unity indicated the presence of non-ideal behavior in current–voltage characteristics at lower voltages. At the higher voltages, the charge transport mechanism for the solar cell is controlled by a space-charge limited current (SCLC) with an exponential distribution of traps. The built potential values are determined from capacitance–voltage plot and were found to be 0.14 and 0.58 V, respectively. The transient absorption data of K27 DSSC device suggest that the fast and slow phases are taking place. While the fast phase corresponds to regeneration of the dye cation by the iodide redox couple, the slow phase corresponds to the decay of long-lived I₂⁻/ TiO₂ electron absorption. The best conversion efficiency for K27 DSSC was found to be 0.317% under 100 mW/cm² (FF=0.584, V_oc=480 mV, I_sc=1.131 mA). The photocurrent results indicate that the photogeneration of charge carriers is a monophotonic process.     

Current–voltage characteristics of electrovoltaic and electrophotovoltaic cells

Electrovoltaic (EV) effect provides a way of generating voltage across an unbiased junction under dark. Electrovoltaic (EV) cell in its simplest form is a device based on n⁺–p–n⁺ (or p⁺–n–p⁺) like structure in which if one p–n junction is subjected to an external forward bias, then, a voltage is developed across the other p–n junction such that the n-side gets a negative polarity with respect to the p-side. Connecting to a load across one of the n⁺–p junctions a bipolar transistor can be operated as a three-terminal EV cell. A new device henceforth known as electrophotovoltaic (EPV) cell wherein EV and PV effects could be expected to work cooperatively was also realized. It is based on a structure which is a combination of n⁺–p–n⁺ EV and n⁺–p–p⁺ photovoltaic (PV) cell structures having a common n⁺–p junction and is able to operate in EV, PV and EPV modes. We have developed one-dimensional physical models of EV and EPV cells and have applied them to explain the observed I–V characteristics of an n–p–n silicon bipolar transistor 2N3055 in EV mode and the EPV cell in EV, PV and EPV modes. While the photovoltaic efficiency η_PV decreases slowly with d/L, where d is the thickness and L is the diffusion length of minority carriers in the base region, the electrovoltaic efficiency η_EV has a strong dependence on d/L and decreases sharply with increase in d/L. Transistor 2N3055 with d/L=0.7 demonstrated η_EV>60%, whereas, our EPV cell with d/L>2.7 had η_EV<3%. However, in the EPV cell, the PV and the EV effects were indeed found to work cooperatively and the output power was enhanced in the EPV mode over the PV mode value although the efficiency η_EPV was less than 4.5%. To achieve substantially high values of efficiencies in EV and EPV modes the EPV cell should be designed to have d/L1.     

Photovoltaic properties of close-space sublimated CdTe solar cells

CdS/CdTe solar cells were fabricated by close-space sublimation with a screen-printed Te-rich CdTe source and their photovoltaic properties were investigated by varying the substrate temperature, cell area, and thicknesses of CdTe and ITO layers. The resistivity of CdTe layers employed in this study was 3×10⁴ Ω cm. The optimum substrate temperature and thickness for CdTe deposition were 600°C and 5 μm, respectively. The CdTe bulk resistance degraded the cell performance above 6 μm. As the cell area increased the V_oc remained almost constant, while the J_sc and FF were strongly degraded because of the increase of the lateral resistance of the ITO layer. The optimum thickness of the ITO layer in this study was 300–450 nm. In this experiment we obtained an efficiency of 9.4% in the 0.5 cm² cells. The series resistance of the cell should be further reduced to increase the fill factor and improve the efficiency.     

The effects of temperature and light concentration on the GaInP/GaAs multijunction solar cell’s performance

Monolithic Ga_0.49In_0.51P/GaAs cascade solar cells with a p⁺/n⁺ GaAs tunnel junction were grown by MOCVD technique. The variation of the photovoltage, photocurrent, fill factor, efficiency, I–V characteristics and spectral response under different temperatures (25–75 °C), and light intensity values (1–40 sun), were investigated experimentally.The open-circuit voltage of the multijunction cell decreases with the temperature increase at a rate of 5.5 mV/°C. The efficiency of the cascade structure under investigation was increased with an increase in the light concentration up to a point where the series resistance and the tunnel junction effects become significant.     

Photoelectrochemical studies of chemically deposited nanocrystalline p-type HgS thin films

Nanocrystalline mercury sulfide (HgS) thin films were deposited by chemical bath deposition (CBD) method onto the glass and fluorine doped tin oxide (FTO) coated glass substrate from an aqueous alkaline bath (pH  8) at room temperature (300 K). Mercuric acetate and thiourea were used as Hg²⁺ and S²⁻ ion sources, respectively. The photoelectrochemical (PEC) studies of HgS films were carried out, and the nanocrystalline films were found to be photoactive in polyiodide solution. The PEC cell configuration was p-HgS/0.1 M (KOH–KI–I₂)/C. From the current–voltage (I–V) characteristics, it is concluded that the HgS films are of p-type electrical conductivity. The photovoltaic output characteristics were used to calculate the fill factor (ff) and solar conversion efficiency (η). The low value of η may be due to the high value of series resistance (R_s) and interface states in the cell, which are responsible for the recombination mechanism.     

The effect of fullerene doping on photoelectric conversion using titanyl phthalocyanine and a perylene pigment

The effect of fullerene (C₆₀) doping on photoelectric conversion using titanyl phthalocyanine (TiOPc) and a perylene pigment, N, N′-dimethyl-3,4 : 9,10-perylenebis(dicarboximide) (MPCI), was investigated. A new three-layer cell, ITO/MPCI/C₆₀-doped TiOPc/TiOPc/Au, exhibited a higher quantum yield for charge-carrier photogeneration than a two-layer cell without the C₆₀-doped TiOPc layer, ITO/MPCI/TiOPc/Au, upon irradiation with monochromatic light which TiOPc mainly absorbs. The three-layer cell showed a high conversion efficiency of 0.63% for incident white light at an intensity of ca. 100 mW cm⁻².     

Formation of porous silicon for large-area silicon solar cells: A new method

Luminescent porous silicon (PS) was prepared for the first time using a spraying set-up, which can diffuse in a homogeneous manner HF solutions, on textured or untextured (1 0 0) oriented monocrystalline silicon substrate. This new method allows us to apply PS onto the front-side surface of silicon solar cells, by supplying very fine HF drops. The front side of N⁺/P monocrystalline silicon solar cells may be treated for long periods without altering the front grid metallic contact. The monocrystalline silicon solar cells (N⁺/P, 78.5 cm²) which has undergone the HF-spraying were made with a very simple and low-cost method, allowing front-side Al contamination. A poor but expected 7.5% conversion efficiency was obtained under AM1 illumination. It was shown that under optimised HF concentration, HF-spraying time and flow HF-spraying rate, Al contamination favours the formation of a thin and homogeneous hydrogen-rich PS layer. It was found that under optimised HF-spraying conditions, the hydrogen-rich PS layer decreases the surface reflectivity up to 3% (i.e., increase light absorption), improves the short circuit current (I_sc), and the fill factor (FF) (i.e., decreases the series resistance), allowing to reach a 12.5% conversion efficiency. The dramatic improvement of the latter is discussed throughout the influence of HF concentration and spraying time on the I–V characteristics and on solar cells parameters. Despite the fact that the thin surfae PS layer acts as a good anti-reflection coating (ARC), it improves the spectral response of the cells, especially in the blue-side of the solar spectrum, where absorption becomes greater, owing to surface band gap widening and conversion of a part of UV and blue light into longer wavelengths (that are more suitable for conversion in a Si cell) throughout quantum confinement into the PS layer.     

Changes in the temperature coefficients of the characteristics of amorphous silicon solar cells subjected to light degradation and recovery

Measuring changes in temperature coefficients is an effective way to estimate the performance of a solar cell. We investigated changes in the temperature coefficients of the I–V characteristics of amorphous silicon (a-Si) solar cells subjected to light degradation and recovery. There is a good correlation between change in the temperature coefficient (Ψ) and the degradation/recovery state of a cell’s conversion efficiency (η). This relationship can be expressed by Ψ_η=−0.0052Δη−0.45. Therefore, the temperature coefficient corresponding to the degradation/recovery state can be estimated.     

Properties of an n-C:P/p-Si carbon-based photovoltaic cell grown by radio frequency plasma-enhanced chemical vapor deposition at room temperature

The phosphorus-doped amorphous carbon (n-C:P) films were grown by radiofrequency (RF) power-assisted plasma-enhanced chemical vapor deposition (PECVD) at room temperature using a solid phosphorus target. The influence of phosphorus doping on the material properties of n-C:P based on the results of simultaneous characterization are reported. Moreover, solar cell properties such as series resistance, short-circuit current density, open-circuit current voltage, fill factor and conversion efficiency along with the spectral response are reported for the fabricated carbon-based n-C:P/p-Si heterojunction solar cells by standard measurement technique. The cells’ performances have been given in the dark I–V rectifying curve and I–V working curve under illumination when exposed to AM 1.5 illumination condition (100 mW/cm², 25 °C). The maximum open-circuit voltage (V_oc) and short-circuit current density (J_sc) for the cells are observed to be approximately 236 V and 7.34 mA/cm², respectively, for the n-C:P/p-Si cell grown at a lower RF power of 100 W. The highest energy conversion efficiency (η) and fill factor (FF) were found to be approximately 0.84% and 49%, respectively. We have observed that the rectifying nature of the heterojunction structures is due to the nature of n-C:P films.     

Light-induced changes in the solar cell parameters and temperature coefficient of n-C/p-Si heterojunction solar cell

Amorphous carbon (a-C) is a potential material for the development of low-cost and high-efficiency solar cell. We report the study of the influence of light soaking up to 100 h on n-C/p-Si heterojunction solar cell. It is observed that the deterioration in the fill factor and the efficiency are significantly smaller as compared to that observed in a-Si:H solar cell. Variations in the temperature coefficients of the I–V characteristics subjected to light degradation and recovery has also been investigated. A good correlation between change in the temperature coefficient and the degradation/recovery state of cell's conversion efficiency has been observed.     

Photoelectrochemical investigations on electrochemically deposited CdSe and Fe-doped CdSe thin films

Thin films of CdSe and Fe-doped CdSe (Fe:CdSe) were deposited onto stainless steel substrates by electrodeposition technique. The photoelectrochemical investigations have been carried out using the cell configurations CdSe/1 M (Na₂S–S–NaOH)/C and Fe:CdSe/1 M (Na₂S–S–NaOH)/C for studying the current–voltage (I–V) characteristics in dark and under illumination, photovoltaic output, spectral response, photovoltaic rise and decay characteristics. The studies reveal that films are n-type conductivity. The junction quality factor in light (n_l), series and shunt resistance (R_s and R_sh), fill factor (FF) and efficiency (η) for the cell have been estimated. After Fe doping, efficiency and FF of PEC solar cell is found to be improved from 0.34% and 31.12 to 1.80% and 35.78, respectively.