Preparation of CuIn1−xGaxSe2 thin films by sputtering and selenization process

CuIn_1−xGa_xSe₂ polycrystalline thin films were prepared by a two-step method. The metal precursors were deposited either sequentially or simultaneously using Cu–Ga (23 at%) alloy and In targets by DC magnetron sputtering. The Cu–In–Ga alloy precursor was deposited on glass or on Mo/glass substrates at either room temperature or 150°C. These metallic precursors were then selenized with Se pellets in a vacuum furnace. The CuIn_1−xGa_xSe₂ films had a smooth surface morphology and a single chalcopyrite phase.     

CuIn1−xGaxSe2-based photovoltaic cells from electrodeposited and chemical bath deposited precursors

We have fabricated 13.7%- and 7.3%-efficient CuIn_1−xGa_xSe₂ (CIGS)-based devices from electrodeposited and chemical bath deposited precursors. As-deposited precursors are Cu-rich films and polycrystalline (grain size is very small) in nature. Only preliminary data is presented on chemical bath deposited precursors. Additional In, Ga, and Se were added to the precursor films by physical evaporation to adjust the final composition to CuIn_1−xGa_xSe₂. Addition of In and Ga and also selenization at high temperature are very crucial to obtain high efficiency devices. Three devices with Ga/(In+Ga) ratios of 0.16, 0.26, and 0.39 were fabricated from electrodeposited precursors. The device fabricated from the chemical bath deposited precursor had a Ga/(In+Ga) ratio of 0.19. The films/devices have been characterized by inductive-coupled plasma spectrometry, Auger electron spectroscopy, X-ray diffraction, electron-probe microanalysis, current-voltage characteristics, capacitance–voltage, and spectral response. The compositional uniformity of the electrodeposited precursor films both in the vertical and horizontal directions were studied. The electrodeposited device parameters are compared with those of a 17.7% physical vapor deposited device.     

Investigations on electron beam evaporated Cu(In0.85Ga0.15)Se2 thin film solar cells

CIGS bulk with composition of CuIn_0.85Ga_0.15Se₂ was synthesized by direct reaction of elemental copper, indium, gallium and selenium. CIGS thin films were then deposited onto well-cleaned glass substrates using the prepared bulk alloy by electron beam deposition method. The structural properties of the deposited films were studied using X-ray diffraction technique. The as-deposited CIGS films were found to be amorphous. On annealing, the films crystallized with a tetragonal chalcopyrite structure. An intermediate Cu-rich phase precipitated at 200 °C and dissociated at higher annealing temperatures. Average grain size calculated from the XRD spectra indicated that the films had a nano-crystalline structure and was further corroborated by AFM analysis of the sample surface. The chemical constituents present in the deposited CIGS films were identified using energy dispersive X-ray analysis. CIGS based solar cells were then fabricated on molybdenum and ITO coated glass substrates and the efficiencies have been evaluated.     

Photoconductivity of Cu(In, Ga) Se2 films

Polycrystalline CuIn_{1 − x}Ga_xSe₂ (0 ≤ x < 0.3) films (CIGS) were deposited by coevaporating the elements from appropriate sources onto glass substrates (substrate temperature 720 to 820 K). Photoconductivity of the polycrystalline CIGS films with partially depleted grains were studied in the temperature range 130–285 K at various illumination levels (0–100 mW/cm²). The data at low temperature (T < 170 K) were analyzed by the grain boundary trapping model with monovalent trapping states. The grain boundary barrier height in the dark and under illumination were obtained for different x-values of CuIn_1−xGa_xSe₂ films. Addition of Ga in the polycrystalline films resulted in a significant decrease in the barrier height. Variation of the barrier height with incident intensity indicated a complex recombination mechanism to be effective in the CIGS films.     

CuIn1−xGaxSe2-based photovoltaic cells from electrodeposited precursor films

We have developed an electrodeposition bath based on a buffer solution so that the stability of the electrodeposition process is enhanced and no metal oxides or hydroxides precipitate out of solution. The buffer-solution-based bath also deposits more gallium in the precursor films. As-deposited precursors are stoichiometric or slightly Cu-rich CuIn_1−xGa_xSe₂. Only a minimal amount of indium was added to the electrodeposited precursor films by physical vapor deposition to obtain a 9.4%-efficient device.     

Electrodeposition of CuInxGa1−xSe2 thin films

CuIn_xGa_1−xSe₂ (CIGS) polycrystalline thin films with various Ga to In ratios were grown using a new two-step electrodeposition process. This process involves the electrodeposition of a Cu–Ga precursor film onto a molybdenum substrate, followed by the electrodeposition of a Cu–In–Se thin film. The resulting CuGa/CuInSe bilayer is then annealed at 600°C for 60 min in flowing Argon to form a CIGS thin film. The individual precursor films and subsequent CIGS films were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy and Auger electron spectroscopy. The as-deposited precursor films were found to be crystalline with a crystal structure matching that of CuGa₂. The annealed bi-layers were found to have the same basic chalcopyrite structure of CuInSe₂, but with peak shifts due to the Ga incorporation. Energy dispersive spectroscopy results show that the observed shifts correlate to the composition of the films.     

New trends to grow the n-CdZn (S1−xSex)2/p-CuIn(S1−xSex)2 heterojunction thin films for solar cell applications

The n-CdZn(S_1−xSe_x) and p-CuIn(S_1−xSe_x)₂ thin films have been grown by the solution growth technique (SGT) on glass substrates. Also the heterojunction (p–n) based on n-CdZn (S_1−xSe_x)₂ and p-CuIn (S_1−xSe_x)₂ thin films fabricated by same technique. The n-CdZn(S_1−xSe_x)₂ thin film has been used as a window material which reduced the lattice mismatch problem at the junction with CuIn (S_1−xSe_x)₂ thin film as an absorber layer for stable solar cell preparation. Elemental analysis of the n-CdZn (S_1−xSe_x)₂ and p-CuIn(S_1−xSe_x)₂ thin films was confirmed by energy-dispersive analysis of X-ray (EDAX). The structural and optical properties were changed with respect to composition ‘x’ values. The best results of these parameters were obtained at x=0.5 composition. The uniform morphology of each film as well as the continuous smooth thickness deposition onto the glass substrates was confirmed by SEM study. The optical band gaps were determined from transmittance spectra in the range of 350–1000 nm. These values are 1.22 and 2.39 eV for CuIn(S_0.5Se_0.5)₂ and CdZn(S_0.5Se_0.5)₂ thin films, respectively. J–V characteristic was measured for the n-CdZn(S_1−xSe_x)₂/p-CuIn(S_1−xSe_x)₂ heterojunction thin films under light illumination. The device parameters V_oc=474.4 mV, J_sc=13.21 mA/cm², FF=47.8% and η=3.5% under an illumination of 85 mW/cm² on a cell active area of 1 cm² have been calculated for solar cell fabrication. The J–V characteristic of the device under dark condition was also studied and the ideality factor was calculated which is equal to 1.9 for n-CdZn(S_0.5Se_0.5)₂/p-CuIn(S_0.5Se_0.5)₂ heterojunction thin films.     

Optical properties of polycrystalline AgxGa2−xSe2 (0.4x1.6) thin films

Polycrystalline thin films of Ag_xGa_2−xSe₂ (0.4x1.6) were prepared onto cleaned glass substrates by the stacked elemental layer (SEL) deposition technique. All the films were annealed in situ at 300 °C for 15 min. The compositions of the films were measured by energy-dispersive analysis of X-ray (EDAX) method. The structural and optical properties of the films were ascertained by X-ray diffraction (XRD) and UV–VIS–NIR spectrophotometry (photon wavelength ranging from 300 to 2500 nm), respectively. The influence of the composition on the optical properties of the material has been investigated. Microstructural perfection is quite evident from the abrupt descent around specific energy of photons in the transmittance spectra. Stoichiometric or slightly silver-deficient films show optimum electron transition energy and minimum sub-band gap absorption.     

The performance of CuIn1−xGaxSe2-based photovoltaic cells prepared from low-cost precursor films

In this paper we report the 15.4%- and 13.4%-efficient CuIn_1−xGa_xSe₂ (CIGS)-based devices from electrodeposited (ED) and electroless deposited (EL) precursors. The efficiency of the device prepared from electroless precursor film has been improved from 12.4% to 13.4%. The dependence of quantum efficiencies on reverse-bias voltage has been measured for a 15.4%-efficient ED device, 18.8%-efficient physical-vapor-deposited device, and 14.2%-efficient Cd-free device. The purpose of this work is to explore and improve the current collection mechanism.     

Issues on the chalcopyrite/defect-chalcopyrite junction model for high-efficiency Cu(In,Ga)Se2 solar cells

Considering the chalcopyrite/defect-chalcopyrite junction model for Cu(In_1−xGa_x)Se₂-based devices and our previously reported findings for the Cu(In_1−xGa_x)₃Se₅ defect chalcopyrites, we have postulated that uniform high-Ga-content photovoltaic structures (with x > 0.35) do not yield acceptable device performance due to the electrical and structural differences between both types of materials (chalcopyrite and defect-chalcopyrite).In this contribution, the structural properties of the surface region of Ga containing absorber materials have been studied by grazing incidence X-ray diffraction. We find that there are significant differences between surface and bulk. A structural model is proposed for the growth of the chalcopyrite/defect-chalcopyrite junction relative to its Ga content. And we demonstrate that closely lattice matched high-Ga-content structures (x > 0.35) can produce solar cells withv acceptable performances. The high-voltage and low-current electrical outputs from high Ga structures are very desirable in module fabrication because overall resistive losses can be substantially reduced.     

Present status and future prospects of CIGSS thin film solar cells

Efficiencies of CuIn_1−xGa_xSe_2−yS_y (CIGSS) modules are comparable to those of lower end crystalline-Si modules. CIGSS layers are prepared by reactive co-evaporation, selenization/sulfurization of metallic or compound precursors, reactive co-sputtering and non-vacuum techniques. CuIn_1−xGa_xS₂ (CIGS2) layers are prepared by sulfurization of Cu-rich metallic precursors and etching of excess Cu_2−xS. Usually heterojunction partner CdS and transparent-conducting bilayer ZnO/ZnO:Al layers are deposited by chemical bath deposition (CBD) or RF magnetron sputtering. CIGSS solar cell efficiencies have been improved by optimizing Cu, Ga and S proportions and providing a minute amount of Na. This paper reviews preparation and efficiency improvement techniques for CIGSS solar cells.     

Room temperature transport measurements on Bridgman-grown p-type CuIn1−xGaxSe2

Room temperature measurements were made of electrical conductivity (σ), Hall coefficient (R_H) and Seebeck coefficient (α) on filamentary samples of p-type CuInSe₂ and CuIn_1−xGa_xSe₂ with x0.3, cut from vertically grown Bridgman ingots. Analysis of the results was done on a two-carrier basis, due to the higher ratio of electron to hole mobility (b) in these materials compared to elemental semiconductors. This treatment yielded a preferred b-value of 5 and to lower calculated hole concentrations than (R_He)⁻¹ and higher hole mobilities than R_Hσ, based on a one-carrier interpretation. This effect was particularly marked in p-type samples with a hole concentration below 10¹⁷ cm⁻³, where even a few percent of minority electrons can play an important role.     

Impact of substrate roughness on CuInxGa1−xSe2 device properties

In comparison to the traditional use of glass substrates, CuIn_xGa_1−xSe₂ (CIGS) deposited onto metal substrates offers improved device cooling under concentration, economical large-scale roll-to-roll processing, and applicability towards lightweight as well as flexible products. However, unlike glass, metal foils tend to exhibit rough surfaces. This study quantifies the effect of substrate roughness on CIGS device performance. Several substrate types with differing average roughnesses were examined. The frequencies of the surface features contributing to roughness are also examined via several different analytical techniques. Devices were prepared and characterized on steel foils, Mo foil, and glass.     

Properties of CuIn1−xGaxSe2

Polycrystalline bulk samples of CuIn_1−xGa_xSe₂ weregrown with nominal x = 0.15, 0.25 and 0.5. Mobility, conductivity and band gap were measured at room and low temperatures. Mobilities for x = 0.21 were several hundred cm² V⁻¹s⁻¹ at room temperature and for x = 0.15 were 10³ cm² V⁻¹ s⁻¹, all n type. The band gaps were estimated from the spectra of photoelectrochemical cells at room temperature (with 8.5 K photoluminescence estimates shown in brackets), as 1.10 eV (1.14) for x = 0.21, and 1.07 eV (1.093) for x = 0.15. Crystal mechanical properties as regards cracks were not as good as for CuInSe₂, using similar growth techniques.     

Electrical conduction studies of hot wall deposited CdSexTe1−x thin films

CdSe_xTe_1−x thin films of different compositions have been deposited on cleaned glass substrates using the hot wall deposition technique under conditions very close to thermodynamical equilibrium with minimum loss of material. The electrical conductivity of the deposited films has been studied as a function of temperature. All the films showed a transition from phonon-assisted hopping conduction through the impurity band to grain-boundary-limited conduction in the conduction/valence band at temperature around 325 K. The conductivity has been found to vary with composition; it varied from 0.0027 to 0.0198 Ω⁻¹ cm⁻¹ when x changed from 0 to 1. The activation energies of the films of different compositions determined at 225 and 400 K have been observed to lie in the range 0.0031–0.0098 and 0.0285–0.0750 eV, respectively. The Hall-effect studies carried out on the deposited films revealed that the nature of conductivity (p or n-type) was dependent on film composition; films with composition x=0 and 0.15 have been found to be p-type and the ones with composition x=0.4, 0.6, 0.7, 0.85 and 1 have been observed to exhibit n-type conductivity. The carrier concentration has been determined and is of the order of 10¹⁷ cm⁻³. The majority of carrier mobilities of the films have been observed to vary from 0.032 to 0.183 cm² V⁻¹ s⁻¹ depending on film composition. The study of the mobility of the charge carriers with temperature in the range of 300–450 K showed that the mobility increased with power of temperature indicating that the type of scattering mechanism in the studied temperature range is the ionized impurity scattering mechanism.     

Optical and electrical studies on molybdenum sulphoselenide [Mo(S1−xSex)2] thin films prepared by arrested precipitation technique (APT)

Nanocrystalline stoichiometric [Mo(S_1−xSe_x)₂] thin films were deposited by using arrested precipitation technique (APT) developed in our laboratory. The precursors used for this are namely, molybdenum triethanolamine complex, thioacetamide and sodium selenosulphite; and various preparative conditions are finalised at the initial stages of deposition. Formation of [Mo(S_1−xSe_x)₂] semiconducting thin films are confirmed by studying growth mechanism, optical and electrical properties. X-ray diffraction analysis showed that the composites are nanocrystalline being mixed ternary chalcogenides of the general formula [Mo(S_1−xSe_x)₂]. The optical studies revealed that the films are highly absorptive (α×10⁴ cm⁻¹) with a band-to-band direct type of transitions and the energy gap decreased typically from 1.86 eV for pure MoS₂ down to 1.42 eV for MoSe₂. The thermoelectrical power measurement shows negative polarity for the generated voltage across the two ends of semiconductor thin films. This indicate that the [Mo(S_1−xSe_x)₂] thin film samples show n-type conduction.     

Fabrication of CuInSe2 films and solar cells by the sequential evaporation of In2Se3 and Cu2Se binary compounds

Cu₂Se/In_xSe(x≈1) double layers were prepared by sequentially evaporating In₂Se₃ and Cu₂Se binary compounds at room temperature on glass or Mo-coated glass substrates and CuInSe₂ films were formed by annealing them in a Se atmosphere at 550°C in the same vacuum chamber. The In_xSe thickness was fixed at 1 μm and the Cu₂Se thickness was varied from 0.2 to 0.5 μm. The CuInSe₂ films were single phase and the compositions were Cu-rich when the Cu₂Se thickness was above 0.35 μm. And then, a thin CuIn₃Se₅ layer was formed on the top of the CuInSe₂ film by co-evaporating In₂Se₃ and Se at 550°C. When the thickness of CuIn₃Se₅ layer was about 150 nm, the CuInSe₂ cell showed the active area efficiency of 5.4% with V_oc=286 mV, J_sc=36 mA/cm² and FF=0.52. As the CuIn₃Se₅ thickness increased further, the efficiency decreased.     

Growth and characterization of CuInxGa1−xTe2 used for photovoltaic conversion

Bulk and thin films of CuIn_0.75Ga_0.25Te₂ have been grown using respectively the sealed quartz ampoule and the flash evaporation techniques. X-ray diffraction results showed that the semiconductor has the chalcopyrite structure. The gaps of the materials were determined from optical measurements and found to be 0.99 and 1.14 eV, respectively for bulk and annealed films. Photoluminescence data showed a broad emission localised at 1.05 eV.     

Preparation and characterization of CdxZn1−xS thin films by spray pyrolysis technique for photovoltaic applications

Cd_xZn_(1−x)S (x = 0, 0.2, 0.4, 0.6, 0.8, and 1) thin films were deposited by the chemical spray pyrolysis technique using a less used combination of chemicals. Depositions were done at 573 K on cleaned glass substrates. The composition, surface morphology and structural properties of deposited films were studied using EDAX, SEM and X-ray diffraction technique. XRD studies reveal that all the films are crystalline with hexagonal (wurtzite) structure and inclusion of Cd into the structure of ZnS improved the crystallinity of the films. In the entire compositions, the (0 0 2) diffraction peak is prominent which gives lattice matching to the chalcogenide semiconductor such as CuIn_xGa_1−xSe₂ and CuIn (s_1−xSe_x)₂, which are used in photovoltaic devices. The value of lattice constant ‘a’ and ‘c’ have been observed to vary with composition from 0.382 to 0.415 nm and 0.625 to 0.675 nm, respectively. The band gap of the thin films varied from 3.32 to 2.41 eV as composition varied from x = 0.0 to 1.0. It was observed that presence of small amount of cadmium results in marked changes in the optical band gap of ZnS.     

Electrical and photoluminescence properties of evaporated CuIn1−xGaxTe2 thin films

Polycrystalline thin films of CuIn_1−xGa_xTe₂ have been deposited by flash evaporation on Corning glass 7059 substrates at T_s=200°C. Hall and resistivity measurements have been carried out down to 77 K. These films are p-type and the variation of the resistivity may be linked to defects, disorder of the material or grain boundaries. The PL spectra of these films after annealing in argon atmosphere at T_a=450°C have showed a broad band emission between 0.98 and 1.12 eV in which the main peak appears at 1.05 eV (at 4.2 K).