Optimization of picosecond laser structuring for the monolithic serial interconnection of CIS solar cells

We report on the optimization of selective picosecond laser structuring for the monolithic serial interconnection of (Cu(In,Ga)(S,Se)₂) CIS thin film solar cells. We introduce a quantitative value to compare the energy efficiency of the different investigated laser processes, the specific ablation energy, which indicates the required energy to remove a certain volume of the specific material. We have examined the structuring efficiencies for induced laser ablation processes for a modification of the beam profile (elliptical and flat‐top beam shaping) and for the application of different laser wavelengths (1064 and 532 nm). Application of induced laser processes (often referred as “lift‐off”) decreases the specific ablation energy dramatically by nearly one order of magnitude. Modifications of the beam profile such as elliptical and flat‐top beam shaping are nearly halving the energy per ablated volume relative to a circular beam. The application of a laser wavelength 532 nm decreases the specific ablation energy compared with 1064 nm significantly for processes involving the CIS layer. We finally demonstrate that with a picosecond laser power of only 2 W, the molybdenum back contact (P1, glass side) and the ZnO front contact (P3, ZnO on CIS) can be structured with a process speed of up to 4 m/s. About 2 µm thick CIS layer (P2) is structured by standard direct laser ablation at higher energy densities with 200 mm/s. Copyright © 2012 John Wiley & Sons, Ltd.     

Achievement of 17.9% efficiency in 30 × 30 cm2 Cu(In,Ga)(Se,S)2 solar cell sub‐module by sulfurization after selenization with Cd‐free buffer

We have achieved 17.9% efficiency in a 30 × 30 cm² Cu(In,Ga)(Se,S)₂ solar cell sub‐module prepared by selenization and sulfurization processes with a Cd‐free buffer. The development of an absorber layer, transparent conducting oxide window layer, and module design was the key focus. This permitted 1.8% higher efficiency than our last experimental result. The quantity and the injection time of the sodium were controlled, resulting in higher open circuit voltage (V_oc) and short circuit current (J_sc). In order to increase J_sc, we changed the thickness of the window layer. Boron‐doped zinc oxide was optimized for higher transmittance without reducing the fill factor. The uniformity of each layer was improved, and patterns were optimized for each module. Therefore, V_oc, J_sc, and FF could be theoretically improved on the reported results of, respectively, 20 mV, 2 mA/cm², and 1.4%. The module's efficiency was measured at the Korea Test Laboratory to compare with the data obtained in‐house. Various analyses were performed, including secondary ion mass spectroscopy, photoluminescence, quantum efficiency, solar simulator, and UV–vis spectrometry, to measure the cell's depth profile, carrier lifetime, external quantum efficiency, module efficiency, and transmittance, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Interconnection of busbar‐free back contacted solar cells by laser welding

We are presenting the module integration of busbar‐free back‐junction back‐contact (BJBC) solar cells. Our proof‐of‐concept module has a fill factor of 80.5% and a conversion efficiency on the designated area of 22.1% prior to lamination. A pulsed laser welds the Al metallization of the solar cells to an Al foil carried by a transparent substrate. The weld spots electrically contact each individual finger to the Al foil, which serves as interconnect between different cells. We produce a proof‐of‐concept module using busbar‐free cell strips of 25 × 125 mm². These are obtained by laser‐dicing of a 125 × 125 mm² BJBC solar cell. The fill factor of this module is increased by 3.5% absolute compared with the initial cell before laser‐dicing. This is achieved mainly by omitting the busbars and reduction of the finger length. The improvement of the module fill factor results in an increase in the module performance of 0.9% absolute before lamination in comparison with the efficiency of the initial 125 × 125 mm² BJBC solar cell. Hence, this interconnection scheme enables the transfer of high cell efficiencies to the module. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of voltage sweep direction on the performance evaluation of P3HT : PCBM solar cells

Investigations on the effect of direction of voltage sweeps, on the current density–voltage (J–V) characteristics in polymer bulk‐heterojunction solar cells, based on the blend of poly(3‐hexylthiophene) (P3HT) and phenyl [6,6] C₆₁ butyric acid methyl ester (PCBM), are reported with time. On the freshly prepared device, the direction of the voltage sweep did not have any effect; however, as the device started degrading, the change in direction of the voltage sweep resulted into different characteristics. Analysis beyond complete degradation, when all the photovoltaic parameters reduced to zero, revealed some interesting results. The J–V characteristics, measured with voltage sweep from −ve to +ve voltage, both in the dark and under illumination, were observed to pass through the second quadrant. On the other hand, with the change in the direction of voltage sweep, viz. from +ve to −ve voltage, the characteristics both in the dark and under illumination passed through the fourth quadrant. These results have been explained on the basis of polarization of the degraded active layer due to applied external voltage. This is an important effect and is observed to depend on the applied voltages during performance evaluation and becomes more prominent with time. This effect puts a question mark on the correctness of the method for calculation of the parameters of a degraded device. Studies on degradation of P3HT : PCBM solar cells showed that both the short circuit current density (J_sc) and the power conversion efficiency (η) decay exponentially, whereas the open circuit voltage (V_oc) decays almost linearly with time. Copyright © 2012 John Wiley & Sons, Ltd.     

Numerical simulations of rear point‐contacted solar cells on 2.2 Ωcm p‐type c‐Si substrates

Rear surface of high‐efficiency crystalline silicon solar cells is based on a combination of dielectric passivation and point‐like contacts. In this work, we develop a 3D model for these devices based on 2.2 Ωcm p‐type crystalline silicon substrates. We validate the model by comparison with experimental results allowing us to determine an optimum design for the rear pattern. Additionally, the 3D model results are compared with the ones deduced from a simpler and widely used 1D model. Although the maximum efficiency predicted by both models is approximately the same, large deviations are observed in open‐circuit voltage and fill factor. 1D simulations overestimate open‐circuit voltage because Dember and electrochemical potential drops are not taken into account. On the contrary, fill factor is underestimated because of higher ohmic losses along the base when 1D analytical model is used. These deviations are larger for relatively low‐doped substrates, as the ones used in the experimental samples reported hereby, and poor passivated contacts. As a result, 1D models could mislead to too short optimum rear contact spacing. Copyright © 2013 John Wiley & Sons, Ltd.     

Non‐destructive optical analysis of band gap profile,crystalline phase,and grain size for Cu(In,Ga)Se2 solar cells deposited by 1‐stage, 2‐stage,and 3‐stage co‐evaporation

Cu(In,Ga)Se₂ (CIGS) thin films co‐evaporated by 1‐stage, 2‐stage, and 3‐stage processes have been studied by spectroscopic ellipsometry (SE). The disappearance of a Cu_2‐xSe optical signature, detected by real time SE during multistage CIGS, has enabled precise endpoint control. Band gap energies determined by SE as depth averages show little process variation for fixed [Ga]/([In] + [Ga]) atomic ratio, whereas their broadening parameters decrease with increasing number of stages, identifying successive grain size enhancements. Refined SE analysis has revealed band gap profiling only for 3‐stage CIGS. Solar cells incorporating these absorbers have yielded increased efficiencies in correlation with phase control, grain size, and band gap profiling. Copyright © 2013 John Wiley & Sons, Ltd.     

Efficiency (>15%) for thin‐film epitaxial silicon solar cells on 70 cm2 area offspec silicon substrate using porous silicon segmented mirrors

We report on the beneficial use of embedded segmented porous silicon broad‐band optical reflectors for thin‐film epitaxial silicon solar cells. These reflectors are formed by gradual increase of the spatial period between the layer segments, allowing for an enhanced absorption of low energy photons in the epitaxial layer. By combining these reflectors with well‐established solar cell processing by photolithography, a conversion efficiency of 15·2% was reached on 73 cm² area, highly doped offspec multicrystalline silicon substrates. The corresponding photogenerated current densities (J_sc) were well above 31 mA/cm² for an active layer of only 20 µm. Copyright © 2010 John Wiley & Sons, Ltd.     

The effect of Mo back contact ageing on Cu(In,Ga)Se2 thin‐film solar cells

In this work, we investigate the effect of ageing Mo‐coated substrates in a dry and N₂ flooded cabinet. The influence was studied by preparing Cu(In,Ga)Se₂ solar cells and by comparing the electrical performance with devices where the Mo layer was not aged. The measurements used for this study were current–voltage (J‐V), external quantum efficiency (EQE), secondary ion mass spectroscopy (SIMS) and capacitance–voltage (C‐V). It was concluded that devices prepared with the aged Mo layer have, in average, an increase of 0.8% in efficiency compared with devices that had a fresh Mo layer. Devices with aged Mo exhibited a nominal increase of 12.5 mV of open circuit voltage, a decrease of 1.1 mA/cm⁻² of short circuit current and a fill factor increase of 2.4%. Heat treatment of fresh Mo layers in oxygen atmosphere was also studied as an alternative to ageing and was shown to provide a similar effect to the aged device's performance. Copyright © 2013 John Wiley & Sons, Ltd.     

>16% thin‐film epitaxial silicon solar cells on 70‐cm2 area with 30‐µm active layer,porous silicon back reflector,and Cu‐based top‐contact metallization

We demonstrate the use of a copper‐based metallization scheme for the specific application of thin‐film epitaxial silicon wafer equivalent (EpiWE) solar cells with rear chemical vapor deposition emitter and conventional POCl₃ emitter. Thin‐film epitaxial silicon wafer equivalent cells are consisting of high‐quality epitaxial active layer of only 30 µm, beneath which a highly reflective porous silicon multilayer stack is embedded. By combining Cu‐plating metallization and narrow finger lines with an epitaxial cell architecture including the porous silicon reflector, a J_sc exceeding 32 mA/cm² was achieved. We report on reproducible cell efficiencies of >16% on >70‐cm² cells with rear epitaxial chemical vapor deposition emitters and Cu contacts. Copyright © 2011 John Wiley & Sons, Ltd.     

CuIn1−xGaxSe2‐based thin‐film solar cells by the selenization of sequentially evaporated metallic layers

Polycrystalline CuIn_1−xGa_xSe₂ (CIGS) thin films were deposited by the non‐vacuum, near‐atmospheric‐pressure selenization of stacked metallic precursor layers. A study was carried out to investigate the influence of significant factors of the absorber on the solar cells performance. An efficiency enhancement was obtained for Cu/(In+Ga) atomic ratios between 0·93 and 0·95. The slope of the observed energy bandgap grading showed a strong influence on the V_OC and the short circuit current density J_SC. An increase of the Ga content in the active region of the absorber was achieved by the introduction of a thin Ga layer on the Mo back contact. This led to an improvement of efficiency and V_OC. Furthermore, an enhanced carrier collection was detected by quantum efficiency measurements when the absorber layer thickness was slightly decreased. Conversion efficiencies close to 10% have been obtained for these devices. Copyright © 2005 John Wiley & Sons, Ltd.     

Impacts of surface sulfurization on Cu(In1−x,Gax)Se2 thin‐film solar cells

In this work, the impacts of surface sulfurization of high‐quality Cu(In_1−x,Ga_x)Se₂ (CIGS) thin films deposited by three‐stage process on the film properties and the cell performance were investigated. The CIGS thin films were sulfurized at 550 °C for 30 min using H₂S gas. The X‐ray photoelectron spectroscopy analysis revealed that sulfur atoms diffused into the CIGS surface layer and that the valence band minimum was lowered by the film sulfurization. The open circuit voltage (V_oc) drastically increased from 0.590 to 0.674 V as a result of the sulfurization process. Temperature‐dependent current–voltage and capacitance–frequency measurements also revealed that interface recombination was drastically decreased by the lowering of the defect's activation energy level at the vicinity of the buffer/CIGS interface after the sulfurization. Copyright © 2014 John Wiley & Sons, Ltd.     

A comparison between thin film solar cells made from co‐evaporated CuIn1‐xGaxSe2 using a one‐stage process versus a three‐stage process

Until this day, the most efficient Cu(In,Ga)Se₂ thin film solar cells have been prepared using a rather complex growth process often referred to as three‐stage or multistage. This family of processes is mainly characterized by a first step deposited with only In, Ga and Se flux to form a first layer. Cu is added in a second step until the film becomes slightly Cu‐rich, where‐after the film is converted to its final Cu‐poor composition by a third stage, again with no or very little addition of Cu. In this paper, a comparison between solar cells prepared with the three‐stage process and a one‐stage/in‐line process with the same composition, thickness, and solar cell stack is made. The one‐stage process is easier to be used in an industrial scale and do not have Cu‐rich transitions. The samples were analyzed using glow discharge optical emission spectroscopy, scanning electron microscopy, X‐ray diffraction, current–voltage‐temperature, capacitance‐voltage, external quantum efficiency, transmission/reflection, and photoluminescence. It was concluded that in spite of differences in the texturing, morphology and Ga gradient, the electrical performance of the two types of samples is quite similar as demonstrated by the similar J–V behavior, quantum spectral response, and the estimated recombination losses. Copyright © 2014 John Wiley & Sons, Ltd.     

Impact of compositional grading and overall Cu deficiency on the near‐infrared response in Cu(In,Ga)Se2 solar cells

Highly efficient thin film solar cells based on co‐evaporated Cu(In,Ga)Se₂ (CIGS) absorbers are typically grown with a [Ga]/([Ga] + [In]) (GGI) gradient across the thickness and a Cu‐poor composition. Upon increasing the Cu content towards the CIGS stoichiometry, lower defect density is expected, which should lead to increased absorption in the near‐infrared (NIR), diffusion length and carrier collection. Further, optimization of the GGI grading is expected to increase the NIR response. In this contribution [Cu]/([In] + [Ga]) (CGI) values are increased by shortening the deposition stage after the first stoichiometric point. In order to obtain comparable Ga contents at the interface for proper band alignment, the front GGI gradings were actively modified. With a relative CGI increase of 7%, we observe an increased photocurrent, originating from an improved NIR external quantum efficiency response. By characterizing the modified absorber properties by reflection‐transmission spectroscopy, we attribute the observed behavior to changes in the optical properties rather than to improved carrier collection. Cu‐dependent modifications of the NIR‐absorption coefficients are likely to be responsible for the variations in the optical properties, which is supported by device simulations. Adequate re‐adjustments of the co‐evaporation process and of the alkali‐fluorides post‐deposition treatments allow maintaining V_oc and FF values, yielding an overall increase of efficiency as compared to a reference baseline. © 2016 The Authors. Progress in Photovoltaics : Research and Applications published by John Wiley & Sons Ltd.     

High‐speed atmospheric atomic layer deposition of ultra thin amorphous TiO2 blocking layers at 100 °C for inverted bulk heterojunction solar cells

Ultrafast, spatial atmospheric atomic layer deposition, which does not involve vacuum steps and is compatible with roll‐to‐roll processing, is used to grow high quality TiO₂ blocking layers for organic solar cells. Dense, uniform thin TiO₂ films are grown at temperatures as low as 100 °C in only 37 s (~20 nm/min growth rate). Incorporation of these films in P3HT‐PCBM‐based solar cells shows performances comparable with cells made using TiO₂ films deposited with much longer processing times and/or higher temperatures. Copyright © 2013 John Wiley & Sons, Ltd.     

Improvement of the cell performance in the ZnS/Cu(In,Ga)Se2 solar cells by the sputter deposition of a bilayer ZnO : Al film

ZnS is a candidate to replace CdS as the buffer layer in Cu(In,Ga)Se₂ (CIGS) solar cells for Cd‐free commercial product. However, the resistance of ZnS is too large, and the photoconductivity is too small. Therefore, the thickness of the ZnS should be as thin as possible. However, a CIGS solar cell with a very thin ZnS buffer layer is vulnerable to the sputtering power of the ZnO : Al window layer deposition because of plasma damage. To improve the efficiency of CIGS solar cells with a chemical‐bath‐deposited ZnS buffer layer, the effect of the plasma damage by the sputter deposition of the ZnO : Al window layer should be understood. We have found that the efficiency of a CIGS solar cell consistently decreases with an increase in the sputtering power for the ZnO : Al window layer deposition onto the ZnS buffer layer because of plasma damage. To protect the ZnS/CIGS interface, a bilayer ZnO : Al film was developed. It consists of a 50‐nm‐thick ZnO : Al plasma protection layer deposited at a sputtering power of 50 W and a 100‐nm‐thick ZnO : Al conducting layer deposited at a sputtering power of 200 W. The introduction of a 50‐nm‐thick ZnO : Al layer deposited at 50 W prevented plasma damage by sputtering, resulting in a high open‐circuit voltage, a large fill factor, and shunt resistance. The ZnS/CIGS solar cell with the bilayer ZnO : Al film yielded a cell efficiency of 14.68%. Therefore, the application of bilayer ZnO : Al film to the window layer is suitable for CIGS solar cells with a ZnS buffer layer. Copyright © 2012 John Wiley & Sons, Ltd.     

ZnO layers deposited by the ion layer gas reaction on Cu(In,Ga)(S,Se)2 thin film solar cell absorbers—impact of ‘damp‐heat’ conditions on the layer properties

Cu(In,Ga)(S,Se)₂ (‘CIGSSe’) based solar cells with a ZnO window extension layer (WEL) deposited by the ion layer gas reaction (ILGAR) reach competitive efficiencies compared to corresponding references with CdS buffer and lead to a simplified device structure. The WEL replaces not only the CdS buffer, but also the undoped part of the usually applied rf‐sputtered ZnO window bi‐layer. The long‐term stability of CIGSSe‐based solar modules is currently under investigation. In order to pass the respective stability tests, which include exposure to ‘damp‐heat’ (DH) conditions (85% relative humidity at 85(C) to accelerate possible aging effects, a good intrinsic material stability is required. In Reference¹ it was revealed, that ILGAR‐ZnO contains a certain amount of meta‐stable hydroxide, which can be directly tuned by the ILGAR process parameters (number of process cycles and process temperature). In order to determine the ILGAR process parameters, which result in intrinsically stable WELs, ILGAR‐ZnO/CIGSSe test structures were investigated by means of scanning electron microscopy (SEM) and x‐ray photoelectron spectroscopy (XPS) before and after a DH‐test. It was found that, induced by the DH‐conditions, a continuous dehydration of the WELs together with a disintegration of the ILGAR‐ZnO layers takes place. This supports an earlier suggested mechanism of a DH‐induced degradation by a release of water at the most critical location in a solar cell, at the heterointerface between window and absorber. By a systematic variation of the ILGAR process parameters it was possible to reduce the hydroxide content in the ILGAR‐ZnO layers resulting in intrinsically more stable samples. Copyright © 2006 John Wiley & Sons, Ltd.     

A comparative study of Cd‐ and Zn‐compound buffer layers on Cu(In1−x,Gax)(Sy,Se1−y)2 thin film solar cells

This paper reports a comparative study of Cu(In,Ga)(S,Se)₂ (CIGSSe) thin‐film solar cells with CBD‐CdS, CBD‐ZnS(O,OH) and ALD‐Zn(O,S) buffer layers. Each buffer layer was deposited on CIGSSe absorber layers which were prepared by sulfurization after selenization (SAS) process by Solar Frontier K. K. Cell efficiencies of CBD‐CdS/CIGSSe, CBD‐ZnS(O,OH)/CIGSSe and ALD‐Zn(O,S)/CIGSSe solar cells exceeded 18%, for a cell area of 0.5 cm². The solar cells underwent a heat‐light soaking (HLS) post‐treatment at 170 °C under one‐sun illumination in the air; among the three condtions, the ALD‐Zn(O,S)/CIGSSe solar cells showed the highest cell efficiency of 19.78% with the highest open‐circuit voltage of 0.718 V. Admittance spectroscopy measurements showed a shift of the N₁ defect's energy position toward shallower energy positions for ALD‐Zn(O,S)/CIGSSe solar cells after HLS post‐treatment, which is in good agreement with their higher open‐circuit voltage and smaller interface recombination than that of CBD‐ZnS(O,OH)/CIGSSe solar cells. Copyright © 2015 John Wiley & Sons, Ltd.     

The effect of Zn1‐xMgxO buffer layer deposition temperature on Cu(In,Ga)Se2 solar cells: A study of the buffer/absorber interface

The effect of atomic layer deposition temperature of Zn_1‐xMg_xO buffer layers for Cu(In,Ga)Se₂ (CIGS) based solar cell devices is evaluated. The Zn_1‐xMg_xO films are grown using diethyl zinc, bis‐cyclopentadienyl magnesium and water as precursors in a temperature range of 105 to 180°C. High efficiency devices are produced in the region from 105 up to 135°C. At a Zn_1‐xMg_xO deposition temperature of 120°C, a maximum cell efficiency of 15·5% is reached by using a Zn_1‐xMg_xO layer with an x‐value of 0·2 and a thickness of 140 nm. A significant drop in cell efficiency due to large losses in open circuit voltage and fill factor is observed for devices grown at temperatures above 150°C. No differences in chemical composition, structure and morphology of the samples are observed, except for the samples prepared at 105 and 120°C that show elemental selenium present at the buffer/absorber interface. The selenium at the interface does not lead to major degradation of the solar cell device efficiency. Instead, a decrease in Zn_1‐xMg_xO resistivity by more than one order of magnitude at growth temperatures above 150°C may explain the degradation in solar cell performance. From energy filtered transmission electron microscopy, the width of the CIGS/Zn_1‐xMg_xO chemical interface is found to be thinner than 10 nm without any areas of depletion for Cu, Se, Zn and O. Copyright © 2008 John Wiley & Sons, Ltd.