Developments of High-Efficiency Flexible Cu（In,Ga）Se2 Thin Film Solar Cells on a Polyimide Sheet by Sodium Incorporation

We present the fabrication of flexible Cu（In,Ga）Se2 （CIGS） solar cells on a polyimide （PI） sheet with and without Na incorporation. A sodium element is incorporated into the CIGS absorber by using a NaF precursor after Mo back contact deposition. X-ray diffraction patterns show that the （112） preferred orientation of the as-grown GIGS films is decreased by Na incorporation. The secondary phase of （Inx,Gal-x）zSe3 is observed for the CIGS films with Na. There is no significant difference in the grain size with and without Na incorporation from surface and cross-sectional SEM images. Additionally, the increase of carrier concentration and decrease of resistivity of CIGS absorber are induced by Na doping. Finally, the flexible CIGS solar cells on PI sheets with efficiency close to 11%, containing Na, are achieved. The improvement of cell efficiency can be attributed to the modified electrical properties of the CIGS film by Na incorporation.     

Cu（In,Ga）Se2 Thin Films on Flexible Polyimide Sheet： Structural and Electrical Properties versus Composition

The structural and electrical properties of Cu（In,Ga）Se2 （CIGS） films grown on polyimide （PI） sheet using the three-stage co-evaporation process are investigated by x-ray diffraction spectra （XRD）, scanning electron microscopy （SEM）, Raman spectra, and Hall effect measurements, respectively. The results show that the properties of CIGS films on PI sheet are strongly dependent on the compositional ratio of Cu/（In＋Oa） （Cu/Ⅲ）. In contrast to the non-stoichiometric CIGS films, stoichiometric CIGS films show better structural and electrical properties, such as a relatively larger grain size, lower resistivity and higher carrier concentration. The flexible CIGS solar cells on PI sheet with the conversion efficiencies of 9.7% and 6.6% are demonstrated for the CIGS absorber layer with Cu/Ⅲ of 0.96 and 0.76, respectively （active area, 0.20cm^2）. The cell efficiency for Cu-poor CIGS films is limited by a relatively lower open circuit voltage and fill factor.     

Flexible Cu（In,Ga）Se2 Thin-Film Solar Cells on Polyimide Substrate by Low-Temperature Deposition Process

The electrical and structural properties of polycrystalline Cu（In, Ga）Se2 films grown on polyimide （PI） substrates below 400℃ via one-stage and three-stage co-evaporation process have been investigated by x-ray diffraction spectra （XRD）, scanning electron microscopy （SEM） and Hall effect measurement. As shown by XRD spectra, the stoichiometric CIGS films obtained by one-stage process exhibit the characteristic diffraction peaks of the （In0.68Ga0.32）2Se3 and Cu（In0.7Ga0.3）2Se. It is also found that the film structures indicate more columnar and compact than the three-stage process films from SEM images. The stoichiometric CIGS films obtained by three-stage process exhibit the coexistence of the secondary phase of （In0.68Ga0.32）2Se3, Cu2-xSe and Cu（In0.7Ga0.3）2Se. High net carrier concentration and sheet conductivity are also observed for this kind of film, related to the presence of Cu2-xSe phase. As a result, when the CIGS film growth temperature is below 400℃, the three-stage process is inefficient for solar cells. By using the one-stage co-evaporation process, the flexible CIGS solar cell on a PI substrate with the best conversion efficiency of 6.38% is demonstrated （active area 0.16cm^2）.     

Thickness optimization of Mo films for Cu（InGa）Se2 solar cell applications

Mo thin films are deposited on soda lime glass (SLG) substrates using DC magnetron sputtering. The Mo film thicknesses are varied from 0.08 μm to 1.5 μm to gain a better understanding of the growth process of the film. The residual stresses and the structural properties of these films are investigated, with attention paid particularly to the film thickness dependence of these properties. Residual stress decreases and yields a typical tensile-to-compressive stress transition with the increase of film thickness at the first stages of film growth. The stress tends to be stable with the further increase of film thickness. Using the Mo film with an optimum thickness of 1 μm as the back contact, the Cu(InGa)Se2 solar cell can reach a conversion efficiency of 13.15%.     

Low contact resistivity between Ni/Au and p-GaN through thin heavily Mg-doped p-GaN and p-InGaN compound contact layer

Thin heavily Mg-doped In Ga N and Ga N compound contact layer is used to form Ni/Au Ohmic contact to p-Ga N.The growth conditions of the compound contact layer and its effect on the performance of Ni/Au Ohmic contact to p-Ga N are investigated. It is confirmed that the specific contact resistivity can be lowered nearly two orders by optimizing the growth conditions of compound contact layer. When the flow rate ratio between Mg and Ga gas sources of p++-In Ga N layer is 10.6% and the thickness of p++-In Ga N layer is 3 nm, the lowest specific contact resistivity of 3.98×10-5?·cm2is achieved. In addition, the experimental results indicate that the specific contact resistivity can be further lowered to1.07×10-7?·cm2by optimizing the alloying annealing temperature to 520℃ .     

The influence of electronic transport across interface junction between Si substrate and the root of ZnO micro-prism on field emission performance

ZnO micro-prisms are prepared on the p-type and n-type Si substrates, separately. The $I$--$V$ curves analysed by AFM show that the interface junctions between the ZnO micro-prisms and the p-type substrate and between the ZnO micro-prisms and the n-type Si substrate exhibit p--n junction behaviour and ohmic contact behaviour, respectively. The formation of the p--n heterojunction and ohmic contact is ascribed to the intrinsic n-type conduction of ZnO material. Better field emission performance (lower onset voltage and larger emission current) is observed from an individual ZnO micro-prism grown on the n-type Si substrate. It is suggested that the n-Si/n-ZnO interfacial ohmic contact benefits the electron emission; while the p-Si/n-ZnO interface heterojunction deteriorates the electron emission.     

Refractive index inhomogeneity of LaF3 film at deep ultraviolet wavelength

It is well known that the optical property of an optical thin film can be influenced by even small inho- mogeneity of refractive index （RI）. In order to investigate the RI inhomogeneity of LaF3 single layer in deep ultraviolet （DUV） range, single-layer LaF3 samples deposited on fused silica and CaF2 substrates are prepared by resistive heating evaporation at different deposition temperatures. The reflectance and transmittance spectra of LaF3 film samples are measured with a spectrophotometer, and used to calculate the RI inhomogeneity. The experimental results show that no RI inhomogeneity of LaF3 film is observed when deposited on CaF2 substrate, while negative RI inhomogeneity is presented when deposited on fused silica substrate. The level of inhomogeneity is affected by the substrate temperature, which decreases with the increasing substrate temperature from 250 to 400 ℃.     

Model for increased efficiency of CIGS solar cells by a stepped distribution of carrier density and Ga in the absorber layer

In this paper, several structures for multilayer Cu(In1-xGax) Se2 (CIGS) thin film solar cells are proposed to achieve high conversion efficiency. All of the modeling and simulations were based on the actual data of experimentally produced CIGS cells reported in the literature. In standard CIGS cells with a single absorber layer, the effects of acceptor density and Ga content on device performance were studied, and then optimized for maximum conversion efficiency. The same procedure was performed for cells with two and three sectioned CIGS absorber layers in which Cu and/or Ga contents were varied within each consecutive section. This produces an internal additional electric field within the absorber layer, which resulted in an increase in carrier collection for longer wavelength photons, and hence, improvement in the conversion efficiency of the cell. An increase of approximately 3% in efficiency is predicted for cells with two layer absorbers. For multilayer cells in which Cu and Ga distribution were stepped simultaneously, the improvement could be approximately 3.5%. This improvement is due to; enhanced carrier collection for longer-wavelength photons, and reduced recombination at the heterojunction and back regions of the cell. These results are confirmed by the physics of the cells.     

Effect of Trimethyl Aluminium Surface Pretreatment on Atomic Layer Deposition Al2O3 Ultra-Thin Film on Si Substrate

Ultra-thin Al2O3 dielectric films have been deposited on Si substrates by using trimethyl aluminium （TMA） and water as precursors in an atomic layer deposition （ALD） system. Growth of the interracial layer between ultra-thin Al2O3 and the Si substrate is effectively suppressed by a long-time TMA surface pretreatment of the Si substrate prior to A1203 atomic layer deposition. High resolution transmission electron microscopy （TEM） images show that the thickness of the interracial layer is reduced to be 0.5nm for the sample with TMA pretreatment lasting 3600s. The x-ray photoelectron spectroscopy results indicate that the A1203 film deposited on the TMApretreated Si surface exhibits very good thermal stability. However, a hysteresis of about 50mV is observed in the C- V curve of the samples with the TMA pretreatment.     

Fabrication of pillar-array superhydrophobic silicon surface and thermodynamic analysis on the wetting state transition

Textured silicon （Si） substrates decorated with regular microscale square pillar arrays of nearly the same side length, height, but different intervals are fabricated by inductively coupled plasma, and then silanized by self-assembly octadecyl- trichlorosilane （OTS） film. The systematic water contact angle （CA） measurements and micro/nanoscale hierarchical rough structure models are used to analyze the wetting behaviors of original and silanized textured Si substrates each as a function of pillar interval-to-width ratio. On the original textured Si substrate with hydrophilic pillars, the water droplet possesses a larger apparent CAs （〉 90~） and contact angle hysteresis （CAH）, induced by the hierarchical roughness of microscale pil- lar arrays and nanoscale pit-like roughness. However, the silanized textured substrate shows superhydrophobicity induced by the low free energy OTS overcoat and the hierarchical roughness of microscale pillar arrays, and nanoscale island-like roughness. The largest apparent CA on the superhydrophobic surface is 169.8~. In addition, the wetting transition of a gently deposited water droplet is observed on the original textured substrate with pillar interval-to-width ratio increasing. Furthermore, the wetting state transition is analyzed by thermodynamic approach with the consideration of the CAH effect. The results indicate that the wetting state changed from a Cassie state to a pseudo-Wenzel during the transition.     

Influence of deposition pressure and power on characteristics of RF-Sputtered Mo films and investigation of sodium diffusion in the films

Mo films deposited by DC sputtering are widely used as back contact in CIGS and CZTS based thin film solar cells. However, there have been only a few studies on the deposition of Mo films by RF sputtering method. In this context, Mo films on SLG substrates were prepared as a function of deposition pressure and power by using RF magnetron sputtering method to contribute to this shortcoming. Mo films were deposited at 250 °C substrate temperature by using 20, 15, 10 mTorr Ar pressures at 120 W RF power and 10 mTorr Ar pressure at 100 W RF power. Structural, morphological and reflectivity properties of RF-sputtered Mo films were clarified by XRD, AFM, FE-SEM and UV–Vis measurements. In addition, due to sodium incorporation from SLG substrate to the absorber layer through Mo back contact layer is so essential in terms of improving the conversion efficiency values of CIGS and CZTS thin film solar cell devices, the effects of Na diffusion in the films were analyzed with SIMS depth profile. The electrical properties of the films such as mobility, carrier density and resistivity were determined by Hall Effect measurements. It was found that Mo films prepared at 120 W, 10 mtorr and 250 °C substrate temperature and then annealed at 500 °C for 30 min, had resistivity as low as 10⁻⁵ Ω cm, as well as higher amount of Na incorporation than other films.     

Adjusting the sodium diffusion into CuInGaSe2 absorbers by preheating of Mo/SLG substrates

We propose a very simple method to adjust the supply of Na from a Mo/soda-lime glass (SLG) substrate into the overgrown CuInGaSe₂(CIGS) layer. Mo/SLG substrates for CIGS solar cells were heated in vacuum (=preheated) before use. Na composition in the finished CIGS films were measured by electron probe microanalysis, in association with the preheating temperature and thickness of the Mo layers. The Na concentration at the surface of the CIGS layers decreased with higher preheating temperature, while the cell performance improved.     

ps-laser scribing of CIGS films at different wavelengths

Continuous growth of the thin-film electronics market stimulates the development of versatile technologies for large-scale patterning of thin-film materials on rigid and flexible substrates, and laser technologies are a promising method to accomplish the scribing processes. Lasers with picosecond pulse duration were applied in scribing of complex multilayered CuIn _x Ga_(1−x)Se₂ (CIGS) solar cells deposited on a polyimide substrate. The ablative properties of the films were examined as a function of the wavelength of laser radiation, pulse energy, and the irradiation dose. The selective removal of ITO and CIGS layers was achieved with 355 nm irradiation without any significant damage to the underlying layers in the ITO/CIGS/Mo/PI solar cell system. The 355 nm wavelength was also found to be favorable for scribing of absorber layer in a ZnO/CIGS/Mo/PI solar cell system. 266 nm radiation significantly modified the film structure due to high absorption. Extensive melt formation in the CIGS layer was found when 532 nm radiation was applied, though the trenches were smooth and crack-free.     

Hydrogen concentration in chalcopyrite thin-film solar cells

A survey of the hydrogen concentration distribution in the various layers of chalcopyrite solar cells is presented. Depth profiles were measured by the nuclear reaction analysis method for the glass substrate, Mo back contact, Cu(In,Ga)S₂ or Cu(In,Ga)Se₂ absorber, CdS buffer, and ZnO window layer. We find that hydrogen is present in all layers in concentrations exceeding the solubility of hydrogen in the corresponding crystalline bulk materials. This indicates that the deposition process and the polycrystallinity of the layers favor the uptake of hydrogen. The measured concentrations range from some 10¹⁸ H/cm³ in the absorber up to some 10²¹ H/cm³ in the CdS buffer layer. Effects of annealing at elevated temperatures are reported.     

Molybdenum thin film deposited by in-line DC magnetron sputtering as a back contact for Cu(In,Ga)Se2 solar cells

In this paper, we reported the effect of the power and the working pressure on the molybdenum (Mo) films deposited using an in-line direct current (DC) magnetron sputtering system. The electrical and the structural properties of Mo film were improved by increasing DC power from 1 to 3 kW. On the other side, the resistivity of the Mo films became higher with the increasing working pressure. However, the adhesion property was improved when the working pressure was higher. In this work, in order to obtain an optimal Mo film as a back metal contact of Cu(In,Ga)Se₂ (CIGS) solar cells, a bilayer Mo film was formed through the different film structures depending on the working pressure. The first layer was formed at a high pressure of 12 mTorr for a better adhesion and the second layer was formed at a low pressure of 3 mTorr for a lower resistivity.     

High-Temperature Characteristics of Ti/Al/Ni/Au Ohmic Contacts to n-GaN

We present the high-temperature characteristics of Ti/Al/Ni/Au（15 nm/220 nm/40 nm/50 nm） multiplayer contacts to n-type GaN （Nd = 3.7 × 10^17 cm^-3, Nd = 3.0 × 10^18 cm^-3）. The contact resistivity increases with the measurement temperature. Furthermore, the increasing tendency is related to doping concentration. The higher the doped, the slower the contact resistivity with decreasing measurement temperature. Ti/Al/Ni/Au ohmic contact to heavy doping n-GaN takes on better high temperature reliability. According to the analyses of XRD and AES for the n-GaN/Ti/Al/Ni/Au, the Au atoms permeate through the Ni layer which is not thick enough into the AI layer even the Ti layer.     

A comparative study of solution based CIGS thin film growth on different glass substrates

CuIn_xGa_1−xSe_yS_2−y (CIGS) thin films were synthesized on glass substrates by a paste coating of Cu, In, and Ga precursor solution with a three-step heat treatment process: oxidation, sulfurization, and selenization. In particular, morphological changes of CIGS films for each heat treatment step were investigated with respect to the kinds of glass substrates: bare, Mo-coated, and F-doped SnO₂ (FTO) soda-lime glasses. Very high quality CIGS film with large grains and low degree of porosity was obtained on the bare glass substrate. Similar morphology of CIGS film was also acquired on the Mo-coated glass except the formation of an undesired Mo oxide interfacial layer due to the partial oxidation of Mo layer during the first heat treatment under ambient conditions. On the other hand, CIGS film with much smaller grains and higher degree of porosity was gained when FTO glass was used as a substrate, resulting in slight solar to electricity conversion behavior (0.20%). Higher power conversion efficiency (1.32%) was attained by the device with the CIGS film grown on Mo-coated glass in spite of the presence of a Mo oxide impurity layer.     

Potential‐induced optimization of ultra‐thin rear surface passivated CIGS solar cells

Ultra‐thin Cu(In,Ga)Se₂ (CIGS) solar cells with an Al₂O₃ rear surface passivation layer between the rear contact and absorber layer frequently show a “roll‐over” effect in the J–V curve, lowering the open circuit voltage (V_OC), short circuit current (J_SC) and fill factor (FF), similar to what is observed for Na‐deficient devices. Since Al₂O₃ is a well‐known barrier for Na, this behaviour can indeed be interpreted as due to lack of Na in the CIGS absorber layer. In this work, applying an electric field between the backside of the soda lime glass (SLG) substrate and the SLG/rear‐contact interface is investi‐gated as potential treatment for such Na‐deficient rear surface passivated CIGS solar cells. First, an electrical field of +50 V is applied at 85 °C, which increases the Na concentration in the CIGS absorber layer and the CdS buffer layer as measured by glow discharge optical emission spectroscopy (GDOES). Subsequently, the field polarity is reversed and part of the previously added Na is removed. This way, the J –V curve roll‐over related to Na deficiency disappears and the V_OC (+25 mV), J_SC(+2.3 mA/cm²) and FF (+13.5% absolute) of the rear surface passivated CIGS solar cells are optimized. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)