CuIn(S,Se)2thin film solar cells from nanocrystal inks: Effect of nanocrystal precursors

CuIn(S,Se)₂ thin film solar cells are fabricated by selenizing CuInS₂ nanocrystals synthesized using a variety of copper and indium precursors. Specifically, copper and indium acetates, acetylacetonates, iodides, chlorides and nitrates are investigated to determine the effect of precursors on electronic properties and device performance. Nanocrystal synthesis with each of these precursors can be optimized to yield similar nanocrystal composition, size and structure. In addition, dense chalcopyrite CuIn(S,Se)₂ thin films with micron sized grains at the surface are formed upon selenization regardless of precursor type. Surprisingly, solar cells fabricated from each nanocrystal ink have roughly the same carrier concentrations of 10¹⁶ to 10¹⁷ cm^− 3 in the absorber layer and achieve active area efficiencies of approximately 5%.     

Preparation of CuInSe2 thin films through metal organic chemical vapor deposition method by using di-μ-methylselenobis(dimethylindium) and bis(ethylisobutyrylacetato) copper(II) precursors

Highly polycrystalline copper indium diselenide (CuInSe₂) thin films on molybdenum substrate were successfully grown at 330 °C through two-stage metal organic chemical vapor deposition (MOCVD) method by using two precursors at relatively mild conditions. First, phase pure InSe thin film was prepared on molybdenum substrate by using a single-source precursor, di-μ-methylselenobis(dimethylindium). Second, on this InSe/Mo film, bis(ethylisobutyrylacetato) copper(II) designated as Cu(eiac)₂ was treated by MOCVD to produce CuInSe₂ films. The thickness and stoichiometry of the product films were found to be easily controlled in this method by adjusting the process conditions. Also, there were no appreciable amounts of carbon and oxygen impurities in the prepared copper indium diselenide films.     

Direct synthesis of CuIn(Sex, S1 − x)2 films from elemental In, Cu, Se, S particle precursor films and its dependence on energy

CuIn(Se_x, S_1 − x)₂ films were prepared by means of non-vacuum, instantaneous, direct synthesis from elemental In, Cu, Se and S particle precursor films by passing an electrical current with precise control through the metal substrate. For a constant reaction period of 1 s, unreacted elemental particles remained in the films for powers below 1 kV A, whereas the reaction to CuIn(Se_x, S_1 − x)₂ (x = 1) appeared to be complete at higher power. Chalcopyrite structure was observed in the range from 1.08 kV A to 1.24 kV A, the sphalerite structure appeared over 1.35 kV A. X-ray diffraction shows single (112) peaks of CuIn(Se_x, S_1 − x)₂ and the peak position agreed with the nominal composition of the precursors.     

Single step deposition method for nearly stoichiometric CuInSe2 thin films

This paper reports the production of high quality copper indium diselenide thin films using pulsed DC magnetron sputtering from a powder target. As-grown thin films consisted of pin-hole free, densely packed grains. X-ray diffraction showed that films were highly orientated in the (112) and/or (204)/(220) direction with no secondary phases present. The most surprising and exciting outcome of this study was that the as-grown films were of near stoichiometric composition, almost independent of the composition of the starting material. No additional steps or substrate heating were necessary to incorporate selenium and create single phase CuInSe₂. Electrical properties obtained by hot point probe and four point probe gave values of low resistivity and showed that the films were all p-type. The physical and structural properties of these films were analyzed using X-ray diffraction, scanning electron microscopy and atomic force microscopy. Resistivity measurements were carried out using the four point probe and hot probe methods. The single step deposition process can cut down the cost of the complex multi step processes involved in the traditional vacuum based deposition techniques.     

Interfacial chemistry control in thin film solar cells based on electrodeposited CuIn(S,Se)2

In this work, we present a study on CuIn(S,Se)₂ absorbers prepared by electrodeposition followed by rapid thermal annealing promising to lower manufacturing cost. However the annealed material contains copper sulpho-selenide of Cu(S_y,Se_1 − y) type which is harmful for the electrical properties of photovoltaic devices. These phases are removed by a cyanide etching. Because of an intrinsic variability of absorber fabrication process, the presented survey is based on statistic approach. We highlighted the influence of a cyanide treatment on surface and bulk compositions. The surface composition follows a distribution according to a Cu(S,Se)-CuIn(S,Se)₂ system and the bulk composition agrees with Cu(S,Se)₂-CuIn₃(S,Se)₅ system. Moreover, surface composition can be modified by adjusting the cyanide concentrations of etching solution without any changes in the bulk one. It ensues that Cu(S,Se) is not only present on the surface but also in the bulk of samples.     

Effects of different selenization conditions on the device parameters of CuIn(Se,S)2 solar cells

Parameter extraction can be used as a tool to determine the optimum chalcogenization condition of the absorber layer in manufacturing thin film solar cells. In this paper, CuIn(Se_1 − y,S_y)₂ solar cells fabricated at different selenization conditions using a two-step process were characterized. Device and performance parameters of the solar cells were determined from the current density-voltage (J-V) characteristics of the devices. The J-V curves were analyzed using the two-diode solar cell model. Devices selenized for 40-60 min exhibit relatively low series and shunt resistances, low fill factor and conversion efficiency. Better performance was observed for solar cells with absorber layer selenized for 10 to 20 min.     

Electrodeposition of CuInSe2 absorber layers from pH buffered and non-buffered sulfate-based solutions

CuInSe₂ (CIS) thin films were deposited on Mo/glass substrates by one-step electrodeposition from aqueous baths containing CuSO₄, In₂(SO₄)₃ and SeO₂ with Li₂SO₄ electrolyte. The quality of the electrodeposited films depended on the presence of pH buffer in the bath. CIS films deposited from non-pH buffered baths showed pronounced (112) orientation, while films exhibiting more random orientation were obtained from pH buffered baths. Denser, smoother samples were obtained from non-pH buffered baths, though with no difference in film composition. As-deposited films exhibit low crystallinity and require recrystallization by annealing in H₂Se. Best devices, ∼ 9%, were obtained with CuInSe₂ films deposited from non-pH buffered baths.     

Electrodeposition based synthesis of S-rich CuIn(S,Se)2 layers for photovoltaic applications: Raman scattering analysis of electrodeposited CuInSe2 precursors

Single step electrodeposition (ED) of Se-rich CuInSe₂ precursors, followed by RTP annealing under sulphurising conditions leading to S-rich CuIn(S,Se)₂ films, constitutes a promising technology for low cost high efficiency solar cells. In this work, a Raman scattering (RS) analysis of Se rich precursors grown under ED conditions leading to different chemical compositions is reported. RS has allowed identification of the main secondary phases in these layers with elemental Se, Cu-Se binary and ordered vacancy compound (OVC) phases. The experimental data show a strong dependence of the spectral contributions related to Se and Cu-Se with the layer molecularity, and the formation of these phases is mainly determined by the content of excess Se in the layers. The correlation of these data with the characteristics of the solar cells fabricated with these precursors, shows the strong impact of the presence of the Cu-Se phase on the performance of the final devices. These results point out the key role played by this binary phase on the formation of secondary phases after the sulphurising step.     

Instantaneous preparation of CuInSe2 films from elemental In, Cu, Se particles precursor films in a non-vacuum process

CuInSe₂ (CIS) films are successfully prepared by means of non-vacuum, instantaneous, direct synthesis from elemental In, Cu, Se particles precursor films without prior synthesis of CIS nanoparticle precursors and without selenization with H₂Se or Se vapor. Our precursor films were prepared on metal substrates by spraying the solvent with added elemental In, Cu, and Se particles. Precursor films were instantaneously sintered using a spot welding machine. When the electric power was fixed to 0.6 kVA, elemental In, Cu, or Se peaks were not observed and only peaks of CIS are observed by X-ray diffraction (XRD) on the film sintered for 7/8 s. We can observe XRD peaks indicative of the chalcopyrite-type structure, such as (101), (103) and (211) diffraction peaks. We conclude that the synthesized CIS crystals have chalcopyrite-type structure with high crystallinity.     

Direct liquid injection metal-organic chemical vapor deposition of HfO2 thin films using Hf(dimethylaminoethoxide)4

Hf(OCH₂CH₂NMe₂)₄, [Hf(dmae)₄] (dmae=dimethylaminoethoxide) was synthesized and used as a chemical vapor deposition precursor for depositing Hf oxide (HfO₂). Hf(dmae)₄ is a liquid at room temperature and has a moderate vapor pressure (4.5 Torr at 80 °C). It was found that HfO₂ film could be deposited as low as 150 °C with carbon level not detected by X-ray photoelectron spectroscopy. As deposited film was amorphous but when the deposition temperature was raised to 400 °C, X-ray diffraction pattern showed that the film was polycrystalline with weak peak of monoclinic (020). Scanning electron microscope analysis indicated that the grain size was not significantly changed with the increase of the annealing temperature. Capacitance–voltage measurement showed that with the increase of annealing temperature, the effective dielectric constant was increased, but above 900 °C, the effective dielectric constant was decreased due to the formation of interface oxide. For 500 Å thin film, the dielectric constant of HfO₂ film annealed at 800 °C was 20.1 and the current–voltage measurements showed that the leakage current density of the HfO₂ thin film annealed at 800 °C was 2.2×10⁻⁶ A/cm² at 5 V.     

Key role of Cu-Se binary phases in electrodeposited CuInSe2 precursors on final distribution of Cu-S phases in CuIn(S,Se)2 absorbers

Using micro-Raman spectroscopy, we demonstrate that the formation of the CuS binary phase in CISEL™ cells absorbers is highly determined by the presence of a Cu-Se binary phase in the precursors and depends on the Cu/In ratio. A selective sulphurization mechanism of the Cu-Se phase is proposed as the origin of CuS platelets. For low Cu/In ratio both binaries are associated to the surface and do not affect the device performance. Conversely, when the binary phase in the precursor is present close to the back contact (for high Cu/In ratio), the CuS binary phase is also formed at this region after sulphurization. Strongly associated to this Cu-rich binary phase, a spinel-type phase is also observed in the sulphurized samples. This phase has n-type conductivity, which has a strong impact on the characteristics of the solar cells. The relationship between the presence of these phases and the electrical properties of the final devices is described, showing that the reduction of the V_oc and the increase of the R_s are related to the formation of a back diode by the spinel-type layer, as consequence of an undesirable n-p-n structure.     

Low-temperature deposition of crystallized TiO2 thin films

Crystallized TiO₂ thin films were deposited on a non-heated substrate by two methods: oxygen-ion-assisted reactive evaporation (ORE) and high-rate reactive sputtering (HRS) using two sputtering sources. When the films were deposited on an unheated glass substrate, amorphous films were initially grown on the substrate in case of both deposition methods, although an increase in oxygen-ion energy above 600 eV led to a growth of a crystallized layer on the amorphous films in the case of ORE. When the films were deposited by HRS on a crystallized TiO₂ seed layer, homo-epitaxial growth was observed, and crystallized TiO₂ films with an excellent hydrophilic property were obtained on unheated substrate. In contrast, when the films were deposited by ORE, amorphous films were initially grown on the crystallized TiO₂ seed layer in a similar manner to the deposition of films on a glass substrate, and homo-epitaxial growth was not observed. These results suggest that the large kinetic energy of titanium atoms arriving at the substrate during HRS is a key factor in promoting epitaxial growth of the TiO₂ film at low temperature.     

Deposition of Sm2O3 doped CeO2 thin films from Ce(DPM)4 and Sm(DPM)3 (DPM=2,2,6,6-tetramethyl-3,5-heptanedionato) by aerosol-assisted metal–organic chemical vapor deposition

Samarium-doped ceria (SDC) thin films were prepared from Sm(DPM)₃ (DPM = 2,2,6,6-tetramethyl-3,5-heptanedionato) and Ce(DPM)₄ using the aerosol-assisted metal–organic chemical vapor deposition method. -Al₂O₃ and NiO-YSZ (YSZ = Y₂O₃-stabilized ZrO₂) disks were chosen as substrates in order to investigate the difference in the growth process on the two substrates. Single cubic structure could be obtained on either -Al₂O₃ or NiO-YSZ substrates at deposition temperatures above 450 °C; the similar structure between YSZ and SDC results in matching growth compared with the deposition on -Al₂O₃ substrate. A typical columnar structure could be obtained at 650 °C on -Al₂O₃ substrate and a more uniform surface was produced on NiO-YSZ substrate at 500 °C. The composition of SDC film deposited at 450 °C is close to that of precursor solution (Sm : Ce = 1 : 4), higher or lower deposition temperature will both lead to sharp deviation from this elemental ratio. The different thermal properties of Sm(DPM)₃ and Ce(DPM)₄ may be the key reason for the variation in composition with the increase of deposition temperature.     

Electrical properties of chemically prepared nonstoichiometric CuIn(S,Se)2 thin films

Polycrystalline thin films of copper indium sulphoselenide [CuIn(S,Se)₂] were deposited on glass substrate by chemical bath deposition technique. The deposition parameters such as pH, temperature and time were optimized. A set of films having different elemental compositions was prepared by varying Cu/In ratio from 1·87–12·15. The films were characterized by X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDAX). The chemical composition of the CuIn(S,Se)₂ was found to be nonstoichiometric. The d.c. conductivities of the films were studied below and near room temperature. The thermo-electric power of the films was also measured and type of semiconductivity was ascertained.     

Comparison between SiO2 films deposited by atomic layer deposition with SiH2[N(CH3)2]2 and SiH[N(CH3)2]3 precursors

Thin SiO₂ layers were deposited by atomic layer deposition (ALD) using either Bis-dimethylamino-silane (BDMAS: SiH₂(N(CH₃)₂)₂) or Tris-dimethylamino-silane (TDMAS: SiH(N(CH₃)₂)₃) precursors. The purpose of this study is to evaluate these precursors for their suitability for ALD of hafnium (Hf)-silicate gate dielectrics. The advantages of these precursors are that the melting points and vapor pressures are moderate. The thickness of SiO₂ deposited using ALD process is controlled by the number of growth cycles and the growth rate was different for each precursor, that for BDMAS being 1.5 times that for TDMAS at the same reactor pressure. The carbon impurity in the SiO₂ film deposited using BDMAS was about half an order of magnitude less than that using for TDMAS. Furthermore, the carbon impurity was reduced to about the detection limit of secondary ion mass spectrometry after high temperature annealing at 1000 °C during 5 s.     

Microstructure developments of F-doped SiO2 thin films prepared by liquid phase deposition

This study presents a systematic investigation of the microstructure dependence of liquid phase deposition (LPD) of SiO₂ films on solution parameters and deposition temperature. The corresponding deposition rate and film roughness were also evaluated under various deposition conditions. Smooth and sufficiently dense SiO₂ films, which are the prerequisite for reliable low-k dielectric applications, were deposited on both silicon and fluorine-doped tin oxide coated glass substrates from supersaturated hydrofluorosilicic acid (H₂SiF₆) solution with the addition of boric acid (H₃BO₃). It is shown that H₂SiF₆ acid controls the surface morphology and grain structure through surface reaction while H₃BO₃ acid prompts bulk precipitation in solution. For the 208-nm thick SiO₂ film, the breakdown field exceeded 1.9 MV/cm and the leakage current density was on the order of 10^− 9 A/cm² at 4 V, indicating excellent insulating properties of LPD SiO₂ films. The strong presence of Si-O-Si and some Si-F with little Si-OH bond as shown in FT-IR spectra indicate that the LPD SiO₂ films have mostly a silica network with some fluorine (F) content. F-doping was self-incorporated into the silica films from the H₂SiF₆ solution during deposition process.     

Chemically deposited lead sulfide and bismuth sulfide thin films and Bi2S3/PbS solar cells

Solar cells with a short-circuit current density (J_sc) of 6 mA/cm², an open circuit voltage (V_oc) of 280 mV and a conversion efficiency of 0.5% under a 1000 W/m² solar radiation were prepared by sequential chemical deposition of Bi₂S₂ (160 nm) and PbS (400 nm) thin films. The optical band gap (E_g) of Bi₂S₃ (160 nm) decreased from 1.67 to 1.61 eV upon heating the as-deposited film at 250 °C in air for 15 min to make it crystalline, but also reduced its thickness to 100 nm. Photoconductivity of this film is 0.003 (Ω cm)^− 1. The E_g of PbS film (200 nm) deposited at 25 °C (24 h) is 0.57 eV, and is 0.49 eV for the film deposited at 40 °C. The electrical conductivity of the latter is 0.48 (Ω cm)^− 1. The photo-generated current density for a Bi₂S₃(100 nm)/PbS(300 nm) absorber stack is above 40 mA/cm² under AM 1.5 G (1000 W/m²) solar radiation. However, the optical losses in the cell structure reduces the J_sc. Spectral sensitivity of the external quantum efficiency of the cell establishes the contribution of Bi₂S₃ and PbS to J_sc. The energy level diagram of the cell structure suggests a built-in potential of 470 mV for the present case. Six series-connected cells gave the V_oc of 1.4 V and J_sc of 5 mA/cm².     

Nickel diffusion in polycrystalline CuInSe2 thin films with a <112> fiber texture

Nickel diffusion in CuInSe₂ thin films was studied in the temperature range 430-520 °C. Thin films of copper indium diselenide (CuInSe₂) were prepared by selenization of CuInSe₂-Cu-In multilayered structure on glass substrate. A thin film of Nickel was deposited and annealed at different temperatures. Surface morphologies of the Ni diffused and undiffused CuInSe2 films were investigated using scanning electron microscope. The alteration of Nickel concentration in the CuInSe₂ thin film was measured by Energy Dispersive X-Ray Fluorescence (EDXRF) technique. These measurements were fitted to a complementary error function solution and the diffusion coefficients at four different temperatures were evaluated. The diffusion coefficients of Ni in CuInSe₂ films were estimated from concentration profiles at temperatures 430-520 °C as D = 1.86 × 10^− 7(cm²s^− 1)exp[− 0.68(eV)/kT].     

Hydrothermal growth of double-layer TiO2 nanostructure film for quantum dot sensitized solar cells

A double-layer (DL) film with a TiO₂ nanosheet-layer on a layer of TiO₂ nanorod-array, was synthesized on a transparent conductive fluorine-doped tin oxide substrate by a two-step hydrothermal method. Starting from the precursors of NaSeSO₃, CdSO₄ and the complex of N(CH₂COOK)₃, CdSe quantum dots (QDs) were grown on the DL-TiO₂ substrate by chemical bath deposition method. The samples were characterized by X-ray diffraction, Scanning electron microscopy, Energy dispersion spectroscopy, and their optical scattering property was measured by light reflection spectrometry. Some CdSe QDs sensitized DL-TiO₂ films serve as the photoanodes, were assembled into solar cell devices and their photovoltaic performance were also characterized. The short circuit current and open-circuit voltage of the solar cells range from 0.75 to 4.05 mA/cm² and 0.20 − 0.42 V under the illumination of one sun (AM1.5, 100 mW/cm²), respectively. The photocurrent density of the DL-TiO₂ film is five times higher than that of a bare TiO₂ nanorod array photoelectrode cell.