Polycrystalline CdTe Thin Films Research Articles

Absorber texture and the efficiency of polycrystalline thin film CdTe solar cells

A range of microstructural changes occur during the deposition and activation of CdTe based thin film solar cells. In particular, the cadmium chloride (CdCl2) activation treatment results in wholesale recrystallisation which transforms the conversion efficiency of the solar cell. One of the noticeable effects is the change of preferred orientation of the CdTe absorber. Highly orientated [111] texture is observed in as deposited or under-treated CdTe based devices. Optimized activation results in a more randomized texture and the [111] preferred texture component is significantly weakened. In this paper we use Electron Backscatter Diffraction to characterise absorber cross-sections. The focus is on how randomization of the absorber texture reflects device performance. We have had access to a range of CdTe devices using a variety of deposition techniques. We have observed a clear pattern that shows that devices with a highly orientated [111] texture have poor efficiency. Devices with a randomized texture have much higher efficiency. Here we illustrate this empirical correlation using devices deposited by Metal Organic Chemical Vapour Deposition with a range of efficiencies from 13.1 % to 17 %. We have also included the analysis of an absorber from a 18.7 % high efficiency CdSeTe/CdTe device to show that texture is similarly important in these advanced devices. We have been able to quantify the effect of texture by using multiples of uniform density or (MUD) values from the inverse pole figures. MUD figures close to 1 correlate with highest efficiency. Although the random texture of the absorber microstructure is only one of several important process factors, it appears to be a necessary feature for highest efficiency CdTe-based polycrystalline solar cells.

The impact of processing on the optical absorption onset of CdTe thin-films and solar cells

We critically examine how two processing steps commonly applied in the preparation of cadmium telluride (CdTe)-based solar cells, i.e., the cadmium chloride treatment and the subsequent stepwise bromine/methanol wet etching process, impact the structural and optical properties of polycrystalline CdTe thin-films. In particular, drawing upon a conjuncture of photothermal deflection spectroscopy and spectroscopic ellipsometry experimental results, we determine the spectral dependence of the optical absorption coefficient, α(E), over the photon energy range from 1.1 to 2.0 eV for samples of rf sputtered (RFS) and close space sublimation (CSS) CdTe. The impact of these processing steps on shaping the grazing incidence x-ray diffraction pattern is also examined. We extend the analysis to devices through interpretation of the spectral dependence of the external quantum efficiency associated with two cadmium chloride treated CdTe-based solar cells. The cells are comparably prepared with the exception of the absorber, one by RFS and the other by CSS. Through the use of our results for the thin-film CdTe optical functions and a model for the solar cell multilayer structure, we simulate the resultant external quantum efficiency spectrum. Through a critical contrast with the corresponding solar cell acquired experimental results, we glean insights into the carrier trapping and recombination processes that occur within the two types of CdTe absorbers.

Enhanced p-Type Doping in Polycrystalline CdTe Films: Deposition and Activation

An in situ nonequilibrium method to increase hole density in polycrystalline CdTe thin films to 1016 cm−3 using group V substitution on Te is presented. Single-phase CdTe films doped with P, As, and Sb were deposited at 550 °C at 100–200 nm/s onto moving cadmium sulfide/high resistance transparent buffer layer/transparent conductive oxide /glass superstrates by vapor transport deposition in Cd overpressure from high purity compound sources. Doping levels before and after activation were determined by capacitance-voltage analysis of diagnostic devices. Secondary ion mass spectrometry depth profiling confirmed dopant incorporation levels of 1017–1018 atoms/cm3 in as-deposited films. Electronic activation was carried out by post-deposition annealing in Cd or CdCl2 vapor with fast cooling, increasing acceptor concentrations to >1015 cm−3 for P and >1016 cm−3 for As and Sb, compared with mid −1014 cm−3 acceptor levels for undoped CdTe films. The activation methods are compatible with post-deposition processing presently used for high-efficiency CdTe solar cells. For the dopants As and Sb, the acceptor concentration increased by substitutional AsTe and SbTe formation, respectively, which was validated by cathodoluminescence spectroscopy.

Study of thin film poly-crystalline CdTe solar cells presenting high acceptor concentrations achieved by in-situ arsenic doping

Doping of CdTe using Group-V elements (As, P, and Sb) has gained interest in pursuit of increasing the cell voltage of CdTe thin film solar devices. Studies on bulk CdTe crystals have shown that much higher acceptor concentration than the traditional copper treatment is possible with As, P or Sb, enabled by high process temperature and/or rapid thermal quenching under Cd overpressure. We report a comprehensive study on in-situ As doping of poly-crystalline CdTe solar cells by MOCVD, whereby high acceptor densities, approaching 3 × 1016 cm−3 were achieved at low growth temperature of 390 °C. No As segregation could be detected at grain boundaries, even for 1019 As cm−3. A shallow acceptor level (+0.1 eV) due to AsTe substitutional doping and deep-level defects were observed at elevated As concentrations. Devices with variable As doping were analysed. Narrowing of the depletion layer, enhancement of bulk recombination, and reduction in device current and red response, albeit a small near infrared gain due to optical gap reduction, were observed at high concentrations. Device modelling indicated that the properties of the n-type window layer and associated interfacial recombination velocity are highly critical when the absorber doping is relatively high, demonstrating a route for obtaining high cell voltage.

Physical properties of rf-sputtered ZnS and ZnSe thin films used for double-heterojunction ZnS/ZnSe/CdTe photovoltaic structures

Polycrystalline ZnX (X = S, Se) and CdTe thin films were prepared by rf magnetron sputtering and by thermal vacuum evaporation (CdTe films), respectively. The structural properties were studied by X-ray diffraction (XRD), which revealed that ZnX films are polycrystalline with a marked (111) texture. After irradiation with protons crystallite sizes decreased while mechanical strains increased. Thicknesses of ZnX films and surface roughness have been measured by X-ray reflectometry (XRR) with thickness values between 58 nm and up to 163 nm and with surface roughness between 1.7 nm and 2.4 nm. Morphological investigations were made by scanning electron microscopy (SEM), drops - free surfaces with compact and uniform aspect being deposited. Absorption and transmission measurements were carried out for all samples deposited on optical glass substrates. Experimentally determined bandgap energies were between 2.31–2.75 eV for ZnSe layers, respectively, 3.10–3.65 eV for ZnS films. Optical transmissions in VIS-NIR regions are higher than 60% for both ZnSe and ZnS films. Glass/ITO/ZnS/ZnSe/CdTe/Cu:Au structures in superstrate configuration were produced by depositing CdTe absorber layers by thermal vacuum evaporation (TVE). Action spectra of the external quantum energy (EQE) and the current-voltage (I-V) characteristics in AM 1.5 conditions (the density power of the incident light is equal with 100 mW/cm2) corresponding for double-heterojunction ZnS/ZnSe/CdTe photovoltaic structures were investigated before and after irradiations with high energy protons (3 MeV).

Improving gas sensing by CdTe decoration of individual Aerographite microtubes

Novel gas sensors have been realized by decorating clusters of tubular Aerographite with CdTe using magnetron sputtering techniques. Subsequently, individual microtubes were separated and electrically contacted on a SiO2/Si substrate with pre-patterned electrodes. Cathodoluminescence, electron microscopy and electrical characterization prove the successful formation of a polycrystalline CdTe thin film on Aerographite enabling an excellent gas response to ammonia. Furthermore, the dynamical response to ammonia exposure has been investigated, highlighting the quick response and recovery times of the sensor, which is highly beneficial for extremely short on/off cycles. Therefore, this gas sensor reveals a large potential for cheap, highly selective, reliable and low-power gas sensors, which are especially important for hazardous gases such as ammonia.

Impact of In Situ Annealing Time on CdTe Polycrystalline Film and Device Performance

We studied the impact of in situ post-growth annealing process on cadmium telluride (CdTe) polycrystalline thin film in this work. Samples of different annealing times have been characterized by x-ray diffraction (XRD) and a scanning electron microscope (SEM). The optoelectronic properties of CdTe film were deeply studied with light I–V testing, external quantum efficiency (EQE) and photoluminescence (PL)/time-resolved photoluminescence (TRPL) measurements. It is found that the in situ post-growth annealing treatment has a great effect on cadmium sulfide (CdS)/CdTe intermixing as well as interface pinholes. Elementary correlations between annealing time, film and junction morphology, carrier lifetime and device performance were investigated, and the annealing time turns out to be crucial to CdTe device performance. Solar cells with CdTe polycrystalline thin film annealed in situ at 550°C/550°C for 10 min show the best performance. With the help of precisely controlled annealing time, better CdTe film microstructure and morphology can be realized after in situ post-growth annealing.

Thin-film CdTe photovoltaics – The technology for utility scale sustainable energy generation

Photovoltaics is an important energy technology for large scale energy generation. In the past few years cost of photovoltaic module manufacturing and installation as well as electricity generation has substantially decreased while the production volume has seen a steep increase. These changes can be attributed to improvement in solar cell efficiencies as well as better manufacturing practices. There are several photovoltaic technologies available in the market but the two primary technologies commercially manufactured for large scale installations are polycrystalline thin-film CdTe and crystalline silicon. Crystalline Si is the oldest and the most widely installed technology while thin-film CdTe is the technology that has demonstrated the largest growth and lowest LCOE (levelized cost of energy). In this study, commercial modules from both these technologies are installed side by side for an accurate comparison of their performance. The modules for comparison are installed with the same approximate nameplate capacity in three different configurations viz. Roof-top, floating on water and ground. Their performance is monitored and analyzed over a 3 month period. Thin-film CdTe demonstrated substantial advantage under all three conditions over crystalline Si in Thailand's tropical climate which is characterized by high temperatures and humidity throughout the year. Advantage demonstrated by thin-film CdTe is further supported by greater economic, environmental, reliability and life-cycle advantages that are summarized in the later part of the study.

Probing the Correlation of Twin Boundaries and Charge Transport of CdTe Solar Cells Using Electron Backscattering Diffraction and Conductive Atomic Force Microscopy

The effect of grain boundaries (GBs) especially twin boundaries (TBs) on the performance of polycrystalline CdTe thin film (1–2 μm in thickness) solar cells remains largely controversial. Understanding the GB’s microstructure and physical property and their impact on the photovoltaic efficiency is critically important to the optimization of the solar cell performance. In this work, we present a systematic study of GBs in CdTe thin film solar cells of different efficiencies in the range of 1.97–9.68%, aiming to elucidate a quantitative correlation of GBs especially TBs with the solar cell charge transport by integrating several advanced approaches including electron backscattering diffraction, transmission electron microscopy, conductive atomic force microscopy, and scanning Kelvin probe force microscopy. Importantly, we have confirmed {111} Σ3 TBs form in the PLD CdTe solar cells and are beneficial by providing an efficient channel for charge transport. The percentage of {111} Σ3 TBs was found to be corre...

High p-type doping, mobility, and photocarrier lifetime in arsenic-doped CdTe single crystals

Group-V element doping is promising for simultaneously maximizing the hole concentration and minority carrier lifetime in CdTe for thin film solar cells, but there are roadblocks concerning point defects including the possibility of self-compensation by AX metastability. Herein, we report on doping, lifetime, and mobility of CdTe single crystals doped with As between 1016 and 1020 cm−3 grown from the Cd solvent by the travelling heater method. Evidence consistent with AX instability as a major contributor to compensation in samples doped below 1017 cm−3 is presented, while for higher-doped samples, precipitation of a second phase on planar structural defects is also observed and may explain spatial variation in properties such as lifetime. Rapid cooling after crystal growth increases doping efficiency and mobility for times up to 20–30 days at room temperature with the highest efficiencies observed close to 45% and a hole mobility of 70 cm2/Vs at room temperature. A doping limit in the low 1017/cm3 range is observed for samples quenched at 200–300 °C/h. Bulk minority carrier lifetimes exceeding 20 ns are observed for samples doped near 1016 cm−3 relaxed in the dark and for unintentionally doped samples, while a lifetime of nearly 5 ns is observed for 1018 cm−3 As doping. These results help us to establish limits on properties expected for group-V doped CdTe polycrystalline thin films for use in photovoltaics.

Post deposition surface treatments to enhance the quality of polycrystalline CdTe thin films for photovoltaic applications

Cadmium telluride (CdTe) is one of the topmost thin film polycrystalline materials used in the photovoltaics (PV) industry today and post deposition surface treatment has been a major step used in the production process for improving the photovoltaic quality of the CdTe material. In the present study, several post deposition surface treatment processes including CdCl2 treatment were carried out on CdTe material and the properties of the materials were then analyzed with the intension of gaining an understanding of the effect of the post deposition process on the material properties and identifying better post deposition treatment processes that can be used to improve the PV quality of the material. In this study, CdTe thin films were potentiostatically electrodeposited using the typical three electrode electrolytic cell consisted of a saturated calomel reference electrode and a high purity graphite counter electrode. 3CdSO4.8H2O and TeO2 were used as the cadmium and the tellurium precursors respectively and CdTe layers were electrodeposited on fluorine doped tin oxide (FTO) glass substrates and glass/FTO/CdS surfaces at pre-identified growth conditions namely; cathodic deposition potential of 650 mV, pH of 2.3 and temperature of 65 °C. Subsequently, deposited samples were annealed in air with CdCl2 and thereafter, comparable samples of glass/FTO/CdTe and glass/FTO/CdS/CdTe were subjected to surface etching with diluted HCl (DH), Br2-CH3OH (BM), HNO3-H3PO4 (NP), K2Cr2O7-H2SO4 (DS) and K2Cr2O7-CH3OH (DM). Surface treated samples were then characterized for their electrical, optical, elemental, morphological and structural properties using photo-electrochemical cell measurements, optical absorption spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy and X-ray diffraction spectroscopy respectively. The study reveals that, post deposition surface treatments with BM and NP etchings enhance the material qualities of polycrystalline CdTe layers to be used for fabrication of PV devices.

Separating grain-boundary and bulk recombination with time-resolved photoluminescence microscopy

Two-photon excitation (2PE) microscopy allows contactless and non-destructive cross-sectional analysis of grain-boundary (GB) and grain-interior (GI) properties in polycrystalline solar cells, with measurements of doping uniformity, space-charge field distribution, and carrier dynamics in different regions of the device. Using 2PE time-resolved microscopy, we analyzed charge-carrier lifetimes near the GBs and in the GI of polycrystalline thin-film CdTe solar cells doped with As. When the grain radius is larger than the minority-carrier diffusion length, GI lifetimes are interpreted as the bulk lifetimes τB, and GB recombination velocity SGB is extracted by comparing recombination rates in the GI and near GBs. In As-doped CdTe solar cells, we find τB = 1.0–2.4 ns and SGB = (1–4) × 105 cm/s. The results imply the potential to improve solar cell voltage via GB passivation and reduced recombination center concentration in the GI.

How to control the stoichiometry of cadmium telluride thin film for photovoltaic applications

In this study, Bube's growth model for a cadmium telluride (CdTe) polycrystalline thin film was re-examined with a view of avoiding his assumptions that neglect the vapor pressures of Cd and Te2 near the film. We proposed a new thermodynamic growth model based on the fact that there is an experimentally verified characteristic ratio (α) of equilibrium partial pressures PCd/2PTe2 that depends on the temperature T and CdTe stoichiometry. By writing PCd(0)=2α(0)PTe2(0) and PCd(h)=2α(h)PTe2(h), where α(0) is determined by source stoichiometry, we can solve the equations for α(h) and thereby determine the stoichiometry of the CdTe thin film grown under physical vapor deposition (PVD) conditions. Simulation was performed to predict the stoichiometry of the CdTe thin film as a function of source stoichiometry for various source-film temperature combinations. The results show that for a typical CdTe PVD process with Tsource>Tthin film: (1) stable deposition, without a non-stoichiometric composition shift, can be achieved at congruent-growth stoichiometry; (2) any stoichiometric deviation from the congruent sublimation point becomes more substantial (in the same direction) in the thin film than in the source; and (3) larger ΔT between the source and the thin film results in a more composition shift.

Control of Cu doping and CdTe/Te interface modification for CdTe solar cells

Copper doping in polycrystalline CdTe thin films and optimal band alignment at the CdTe/back-contact interface are critical for obtaining high performance devices. A CuCl2 solution treatment was used in this work to enhance the p-doping of CdTe. The carrier density of CdTe was increased from 4.72 × 1013 to 1.11 × 1014cm−3 and the open circuit voltage of the device was obviously improved more than ~50mV from 728 to 783mV. In order to further improve device performance, Te/Cu bilayer using rapid thermal processing was implemented to reduce barrier at the back contact. The short time-high temperature process efficiently activated the Te/Cu bilayer back contact and precisely controlled the Cu diffusion. The proper dose of Cu diffusion can further increase the p-doping of CdTe (~2.22 × 1014cm−3), resulting in the apparent increase in response from the CdS spectral region. The chemical reaction occurred between Te and Cu after rapid thermal processing treatments causing the formation of the CuxTe phases, which can form a barrier in the conduction band to reflect electrons and reduce recombination at the back contact. With the increase of the temperature, the open circuit voltage of the device increased. However, the device with excessive Cu contacted at higher temperature showed the reduction in response in the long-wavelength region and decrease in fill factor due to the formation of much more Cu-related recombination states. Finally, open circuit voltage of > 820mV, and fill factor of > 72% for CdTe solar cells with an area of 0.24cm2 were achieved.

Effect of Gallium Doping on the Characteristic Properties of Polycrystalline Cadmium Telluride Thin Film

Ga-doped CdTe polycrystalline thin films were successfully electrodeposited on glass/fluorine doped tin oxide substrates from aqueous electrolytes containing cadmium nitrate (Cd(NO3)2·4H2O) and tellurium oxide (TeO2). The effects of different Ga-doping concentrations on the CdTe:Ga coupled with different post-growth treatments were studied by analysing the structural, optical, morphological and electronic properties of the deposited layers using x-ray diffraction (XRD), ultraviolet–visible spectrophotometry, scanning electron microscopy, photoelectrochemical cell measurement and direct-current conductivity test respectively. XRD results show diminishing (111)C CdTe peak above 20 ppm Ga-doping and the appearance of (301)M GaTe diffraction above 50 ppm Ga-doping indicating the formation of two phases; CdTe and GaTe. Although, reductions in the absorption edge slopes were observed above 20 ppm Ga-doping for the as-deposited CdTe:Ga layer, no obvious influence on the energy gap of CdTe films with Ga-doping were detected. Morphologically, reductions in grain size were observed at 50 ppm Ga-doping and above with high pinhole density within the layer. For the as-deposited CdTe:Ga layers, conduction type change from n- to p- were observed at 50 ppm, while the n-type conductivity were retained after post-growth treatment. Highest conductivity was observed at 20 ppm Ga-doping of CdTe. These results are systematically reported in this paper.

Ion-damage-free planarization or shallow angle sectioning of solar cells for mapping grain orientation and nanoscale photovoltaic properties

Ion beam milling is the most common modern method for preparing specific features for microscopic analysis, even though concomitant ion implantation and amorphization remain persistent challenges, particularly as they often modify materials properties of interest. Atomic force microscopy (AFM), on the other hand, can mechanically mill specific nanoscale regions in plan-view without chemical or high energy ion damage, due to its resolution, directionality, and fine load control. As an example, AFM-nanomilling (AFM-NM) is implemented for top-down planarization of polycrystalline CdTe thin film solar cells, with a resulting decrease in the root mean square (RMS) roughness by an order of magnitude, even better than for a low incidence FIB polished surface. Subsequent AFM-based property maps reveal a substantially stronger contrast, in this case of the short-circuit current or open circuit voltage during light exposure. Electron back scattering diffraction (EBSD) imaging also becomes possible upon AFM-NM, enabling direct correlations between the local materials properties and the polycrystalline microstructure. Smooth shallow-angle cross-sections are demonstrated as well, based on targeted oblique milling. As expected, this reveals a gradual decrease in the average short-circuit current and maximum power as the underlying CdS and electrode layers are approached, but a relatively consistent open-circuit voltage through the diminishing thickness of the CdTe absorber. AFM-based nanomilling is therefore a powerful tool for material characterization, uniquely providing ion-damage free, selective area, planar smoothing or low-angle sectioning of specimens while preserving their functionality. This enables novel, co-located advanced AFM measurements, EBSD analysis, and investigations by related techniques that are otherwise hindered by surface morphology or surface damage.

The study of oxygen concentration in the CdTe thin film prepared by vapor transport deposition for CdTe photovoltaic devices

Polycrystalline CdTe thin films for CdTe solar cell devices are grown using vapor transport deposition (VTD) which is one of promising techniques to prepare CdTe thin film for high efficiency CdTe solar cells. However, few works report the study of the CdTe thin film growth by VTD so far. In this paper, the oxygen concentration is altered to be O2-free, 10, 20, 30, 40 and 50%. The morphology and crystallinity of as-deposited CdTe films are studied by X-ray diffraction and scanning electron microscopy. And the electrical properties for CdTe photovoltaic devices is investigated by current–voltage (J–V), capacitance voltage (C–V), and time-resolved photoluminescence spectroscopy (TRPL) measurements. The results show that a small amount of oxygen in the process has a positive impact on CdTe thin film quality because the oxygen incorporation could effectively change the grain size and make grain orientation more pronounced. The carrier concentration increases from 2.3 × 1013 to 7.5 × 1013 cm−3 when the oxygen concentration increases from 0 to 10%. The result of carrier lifetime also shows a positive correlation with oxygen concentration. A series of devices performance reveal the optimal technological conditions is under 10% oxygen partial pressure. The best small-area CdTe thin film solar cell is obtained with the conversion efficiency of 12.65% without back contact layer.

Swift heavy ion irradiation induced nanograin formation in CdTe thin films

Swift Heavy Ion (SHI) irradiation is a unique technique for nanograin formation through grain fragmentation. Contrary to the generally reported SHI irradiation induced grain growth on CdTe thin films, we report fragmentation leading to nanograin formation. Thermally evaporated polycrystalline CdTe thin films were irradiated with 100MeV 197Au, 107Ag and 58Ni ions beams up to a fluence of 5×1012ions/cm2. Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM) were carried out for surface analysis before and after irradiation. SEM micrographs indicate that the larger grains in the as-deposited films were fragmented into smaller grains due to irradiation. The extent of fragmentation was found to increase with increasing electronic energy loss (Se). AFM pictures also supported the irradiation induced fragmentation. Structural characterization was done using X-ray Diffraction (XRD) technique. The ion induced strain and dislocation density were calculated from the XRD data. Both the strain and dislocation density were found to increase with increasing Se. The observed grain fragmentation is explained on the basis of a combined effect of strain induced disintegration of grains after the Coulomb explosion, and an ‘incomplete’ re-crystallization of the molten thermal spikes. Moreover, the optical band gap Eg (1.5eV for as-deposited film), determined from UV–vis spectroscopy, increased with Se, and possibly because of ion induced strain and defect annealing.

Thin film CdTe based neutron detectors with high thermal neutron efficiency and gamma rejection for security applications

Solid-state neutron detectors offer an alternative to 3He based detectors, but suffer from limited neutron efficiencies that make their use in security applications impractical. Solid-state neutron detectors based on single crystal silicon also have relatively high gamma-ray efficiencies that lead to false positives. Thin film polycrystalline CdTe based detectors require less complex processing with significantly lower gamma-ray efficiencies. Advanced geometries can also be implemented to achieve high thermal neutron efficiencies competitive with silicon based technology. This study evaluates these strategies by simulation and experimentation and demonstrates an approach to achieve >10% intrinsic efficiency with <10−6 gamma-ray efficiency.

Variation of optical, structural, electrical and compositional properties of thermally evaporated CdTe thin films due to substrate temperature

Alteration of substrate temperature of thermally evaporated CdTe thin films can cause changes to the film structure and composition, affecting its optical, electrical as well as morphological properties. In this respect, polycrystalline CdTe thin films were deposited using thermal evaporation technique under different substrate temperatures from 125 to 300 °C. The optical, structural, compositional, morphological and electrical properties were studied using UV–visible spectroscopy, GIXRD, EDX, SEM and van der Pauw method, respectively. Optical measurements revealed that the band gap of the films slightly increase with increasing substrate temperature. Structurally, the lattice parameter and the crystallite size of the CdTe films deposited under a substrate temperature of 200 °C was found to be considerably higher than the rest of the substrate temperatures investigated. Texture coefficient indicate that the (111) plane becomes preferable as the substrate temperature is elevated to 300 °C. The lowest electrical resistivity was also found for samples deposited under a substrate temperature of 200 °C. Furthermore, EDX results reveals the composition of CdTe film considerably vary with respect to the substrate temperature at which the film was fabricated.