Processing options for CdTe thin film solar cells

Processing options for addressing critical issues associated with the fabrication of thin film CdTe solar cells are presented, including window and buffer layer processing, post-deposition treatment, and formation of stable low resistance contacts. The paper contains fundamental data, engineering relationships and device results. Chemical surface deposited CdS and Cd_1−xZn_xS films are employed as the n-type heteropartner window layers. Maintaining junction quality with ultra-thin window layers is facilitated by use of a high resistance oxide buffer layer, such as SnO₂, In₂O₃ or Ga₂O₃, between the heteropartner and the transparent conductive oxide. Thermal annealing of the CdTe/CdS heterostructure in the presence of CdCl₂ and O₂ shifts the chemical equilibrium on the surface of the absorber layer, which influences the bulk electrical properties. Aspects of back contacting CdTe/CdS devices, including etching, Cu application, contact annealing, back contact chemistry and secondary contacts, are discussed. Two commonly employed etches used to produce a Te-rich layer, nitric acid/phosphoric acid mixtures and Br₂/methanol are compared, including the nature and stability of the final treated CdTe surface. The diagnostic abilities of the surface sensitive VASE and GIXRD techniques are highlighted. Various methods of Cu delivery are discussed with consideration to; reaction with Te, processing simplicity, processing time and possible industrial scale-up. Some aspects of back contact stability are presented, including discussion of apparent robust back contacts, which contain a thick Te component.     

Electro-optical characterization and modeling of thin film CdS–CdTe heterojunction solar cells

Optoelectronic characteristics of thin film CdTe–CdS solar cells fabricated at four different laboratories were measured and analyzed. Current versus voltage measurements revealed that, under one sun illumination, tunneling was the dominant current flow mechanism in all cells. Tunneling was also the dominant current flow mechanism in the dark for all types except P3 which exhibited a generation-recombination type current flow process in the dark. A theoretical model involving bulk traps in CdTe and a charged thin layer (T-layer) near the junction under forward bias and/or illumination was developed. The model is able to explain all significant features in the experimental results obtained from current versus voltage, and capacitance.     

CdTe contacts for CdTe/CdS solar cells: effect of Cu thickness, surface preparation and recontacting on device performance and stability

Device performance of thin film CdTe/CdS solar cells having different methods for fabricating the primary back contact are presented. Wet and dry methods for forming the primary contact (Cu₂Te) were evaluated with Cu layers from 0 to 15 nm. Extensive analysis of J–V curves is presented, including effects of temperature, intensity and accelerated stress. A procedure for recontacting stress-degraded cells allowed separation of contact and junction degradation modes. The junction recombination is shown to be a Shockley–Read–Hall mechanism. Stress increases the recombination current density J₀ by 2–3 orders of magnitude, resulting in a loss in V_oc of 100–200 mV which is not restored with recontacting. Rollover is eliminated by recontacting the device while fill factor is partially restored with recontacting. For devices with a Cu layer, no significant differences in illuminated solar cell performance between the wet and dry process were observed before or after stress, but there were large differences in the dark J–V related to a blocking contact. To first order, unstressed devices without Cu contact layers behave similar to stressed devices with Cu; lower V_oc, higher resistance, and appearance of a blocking contact.     

Recent progress on CdTe/CdS thin film solar cells

The CdTe/CdS thin film solar cell is the most suitable to be fabricated on the form of thin films. The processes used to make all the films, which compose the cell, are quite simple and fast. An efficiency of 16.5% has been reached on laboratory scale and modules of 0.6 × 1.2 m² with efficiency larger than 8% are now fabricated and commercialized. A strong contribution to the development of this type of solar cells has been given by the Parma University group with the discovery of a new ohmic back contact for CdTe which is very stable in respect to any other ohmic contact used for CdTe, and by the development of a new all dry process to make the cell. An efficiency of 15.8% has been recently obtained on a 10⁻⁴ m² soda-lime glass without using any copper or any other metal of the first group of the periodic table of the elements at the back contact.     

CdS/CdTe solar cell using sputtering technique

Cadmium telluride films were deposited from a CdTe target using rf planar magnetron system on CdS/ITO/Glass substrates. The as grown films were polycrystalline and consisted of closepacked array of preferentially oriented single crystal grains. Chemical heat treatment using cadmium chloride was used to form the junction between cadmium sulphide and cadmium telluride layers. It also improves the structure of the sputtered CdTe film and the lifetime of carriers.     

Physical basis for the design of CdS/CdTe thin film solar cells

Solar cells based on polycrystalline semiconductor thin films have great potential for decreasing the cost of photovoltaic energy. However, this kind of solar cells has characteristics very different from those fabricated on crystalline silicon for which the carrier-transport and behavior is clearly known. Instead, for hetero-junction solar cells made on less known polycrystalline materials the design is almost empirical. In this work, several physical aspects related to the behavior of polycrystalline thin film solar cells will be discussed, and some considerations for an adequate design of this kind of solar cells will be made. For example, the recombination at the grain boundaries and its influence on the short circuit current as a function of the crystallite sizes on the active material is considered. Based on this, the appropriate thickness of each layer and their resistivity will be discussed. As an example, these considerations will be applied to CdS/CdTe heterojunction solar cells, taking into account typical properties of CdTe thin films used for solar cells.     

A highly efficient and stable CdTe/CdS thin film solar cell

In this paper we describe the fabrication and characteristics of highly efficient and stable CdTe/CdS thin film solar cells. Our cells are prepared in three subsequent phases. Firstly, we deposit via sputtering, without solution of continuity a layer of CdS on top of the front contact made up of a double layer of ITO/SnO₂ deposited on a soda lime glass substrate. The second phase consists in the treatment of the CdS layer, which is the key factor for the fabrication of a good heterojunction, with CdCl₂ and in the subsequent deposition of the CdTe layer via close space sublimation technique. Finally, the back contact is fabricated via sputtering making use of the Sb₂Te₃ compound which guarantees the cell stability. Under global AM1.5 conditions the open-circuit voltage, short-circuit current and fill factor of our best cell, fabricated without antireflecting coating and normalized to the area of 1 cm², were V_oc=858 mV, J_sc=23 mA/cm² and ff=74%, respectively, corresponding to a total area conversion efficiency of η=14.6%.     

Comparative study of performance of CdTe, CdSe and CdS thin films-based photoelectrochemical solar cells

Polycrystalline films of CdTe and CdSe were electrodeposited onto titanium substrates from acidic baths, and, polycrystalline CdS thin films were prepared by chemical bath deposition method. Due to surface treatment these films show good photoelectrochemical behaviour in a polysulphide electrolyte with high conversion efficiency and stability. The solid-state parameters of annealed films are calculated and compared with those of unannealed film-based cells. Chemical etching is found to improve short-circuit current and fill-factor whereas photoelectrochemical etching technique improves the stability of photo-anode in polysulphide solution. Annealing promotes incipient fusion of small crystallites and thereby reduces the grain boundaries which are known to act as recombination centres for minority carriers and trapping centres for majority carriers. The conversion efficiency and stability are found to improve by chemical etching of the semiconductor layer because chemical etching pins Fermi level of CdTe, CdSe and Cds photoanodes and promotes exchange current density.     

15.1% Highly efficient thin film CdS/CdTe solar cell

High-efficiency CdS/CdTe solar cells with thin CdS film have recently been developed. Semiconductive layers of CdS via the CVD method and of CdTe via the CSS method were deposited on an ITO/#7059 substrate. Cell performance depends primarily on the thickness of CdS film, and the conversion efficiency is highest for a CdS film thickness of around 60 nm. Since the CdS film thickness decreases by about 30% during deposition of the CdTe layer, a thickness of 95 nm is required to obtain a 60 nm-thick CdS film after deposition of a CdTe layer. By observing the CdS film during the CdTe deposition process, a decrease was detected before CdTe layer completely covers the surface of the CdS film. By optimizing the thickness of CdS film, an efficiency of 15.12% for the best cell under AM 1.5 verified at JQA was obtained. This fabrication process has good reproducibility; 92.5% of 1 cm² solar cells fabricated under the same conditions have efficiencies above 14%.     

Recent technical advances in thin-film CdS/CdTe solar cells

CdS/CdTe solar cells have attracted attention recently for their potential as low-cost, high-efficiency solar cells of the future. It is because the CdTe layer (used for photoelectric conversion) has a bandgap energy of 1. 51 eV, which corresponds well to sunlight spectra, and the direct transition type energy band structure enables formation of thinner films.We have already industrialized CdS/CdTe solar cells in mass production stage using a printing-sintering process, as large-area modules for electric power generation(Higuchi , 1993, Omura , 1991), and as cells for indoor applications (primarily in calculators. Suyama , 1986). However, this solar cell has a conversion efficiency of approximately 6%.Recently, there has been considerable research into thin-film CdS/CdTe solar cells which have a thinner CdS film formed by CVD or CBD (Britt , 1993) process, and thus are photosensitive to light with wavelengths of 500 nm or less. At present stage of our art, in solar cells formed by the CSS with a CdTe film on CVD CdS, a conversion efficiency of 15. 05% has been obtained in cells with an area of 1 cm² (verified at JQA).     

Thin film CdS/CdTe solar cells: Research perspectives

Polycrystalline thin film CdTe continues to be a leading material for the development of cost effective and reliable photovoltaics. The two key properties of this material are its band gap (1.5 eV), close to the ideal for photovoltaic conversion efficiency (1.45 eV), and its high optical absorption coefficient. Thin film CdTe solar cells are typically hetero-junctions with CdS being the n-type partner, or window layer. Efficiencies as high as 16.5% have been achieved, but still there is some potential for increasing them.We make an analysis of the typical CdS/CdTe superstrate solar cell, and from it we establish critical issues and different lines of research in order to improve the current efficiencies. We also show that present record efficiencies are very close to the practical efficiency limit for a CdS/CdTe hetero-junction cell.     

15% Efficiency CdS/CdTe thin film solar cells using CdS layers doped with metal organic compounds

For improving the photovoltaic performance of CdS/CdTe thin film solar cells, the CdS window layer is one of the most crucial factors. Here we demonstrate the photovoltaic performances of the low-environmental-load CdS/CdTe solar cell employing the CdS layer doped with various metal organic (MO) compounds, i.e., (CH₃)₂SnCl₂, (C₆H₅)₃GeCl, (CH₃CO₂)₃In, [(C₂H₅)₂NCS₂]₂Zn. Due to the MO doping, the degree of (1 1 1) preferential orientation of CdTe on the CdS layer is improved remarkably, influencing the increases in V_oc and F.F. Being almost independent of the kind of the MO compounds, the short circuit current increases due to increasing optical transmittance of the MO-doped CdS layers. As a result, utilizing MO-doped CdS, we have achieved the conversion efficiency of 15.1%.     

Preparation and properties of CdS/CdTe thin film solar cell produced by periodic pulse electrodeposition technique

CdS/CdTe solar cells have been prepared by periodic pulse electrodepositionmethod. 10.8% efficient cell was made with open circuit voltage (V_oc)≈753mV, short-circuit current (J_sc)≈23.6 mA/cm² and fill factor (FF)≈0.61. Current-voltage-temperature measurments showed the variation of ideality factor (A) from 1.88 at 344 K to 4.49 at 202 K whereas voltage factor (α) was almost constant above 276 K. The junction transport is possibly dominated by a tunneling mechanism. Capacitance measurements gave the value of diffusion potential as 1.2 eV, ionized charged density as 5.9 × 10¹⁵ cm⁻³ and number of interface states (N_IS) as 2.8 × 10¹¹ cm⁻² eV⁻¹ at zero volt bias. Measurements of open circuit voltage (V_oc) with temperature gave the value of barrier height as 1.42 eV.     

Diamond/CdTe: a new inverted heterojunction CdTe thin film solar cell

Recently the concept of the inverted photovoltaic cell has become more attainable as a practical cell. This thin film cell consists of a p–n heterojunction in which the window layer is p-type and the absorber layer is n-type. The feasibility of a new inverted p–n heterojunction p-diamond/n-CdTe solar cell has been demonstrated. The non-optimized solar cell structure grown on semi-transparent p-diamond yielded an open circuit voltage of 0.23 V and a short circuit current of 1.54 mA/cm² when illuminated.     

Influence of CdS window layer on 2-μm thick CdS/CdTe thin film solar cells

Influence of the CdS window layer on the PV performances of 2-μm thick CdS/CdTe solar cells has been studied as a function of the CdS thickness, d_CdS. With a reduction of d_CdS from 114 to 95 nm, J_SC increases due to an increase in blue response. While, at d_CdS<85 nm, the conversion efficiency largely decreases due to a decrease in V_OC and FF. The deterioration of the crystallinity of CdTe due to a decrease in the sulfur composition x of the CdTe_1−xS_x mixed-crystal layer is concluded to be the most possible mechanism for the large decreases in V_OC and FF.     

Characterization of etching procedure in preparation of CdTe solar cells

An etching procedure for forming a low resistance contact to polycrystalline CdTe thin films in CdS/CdTe solar cells was studied. The etching solution used was a mixture of HNO₃, H₃PO₄ and H₂O. X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS) and electric measurements revealed that the etching results in a formation of crystalline tellurium on the film surface, thereby increasing substantially the conductivity of the surface layer. The total process was found to consist of three steps: (i) immediately after an immersion into the etching solution there was a certain induction period with no discernible changes, (ii) a subsequent reaction step during which poorly crystallized elemental tellurium was formed, gaseous byproducts liberated and the surface changed its colour, and (iii) after taking out of the etching solution the tellurium crystallized causing a strong decrease in the sheet resistance. In situ XRD and electric measurements were carried out to follow the third step. The chemical aspects of the three steps as well as their contributions to the reproducibility and control of the overall etching procedure have been considered.     

CdTe/CdS Solar cells on flexible molybdenum substrates

Development of CdTe/CdS solar cells on flexible metallic substrates is highly interesting due to the light weight and flexible nature of the solar modules. We have deposited CdTe films onto flexible molybdenum substrates using close-spaced sublimation technique and the CdTe/CdS junction was developed by depositing a thin layer of CdS onto the CdTe substrate from a chemical bath. The devices were characterized by Current–voltage (I–V) and photocurrent spectroscopy techniques. Prior to the deposition of the transparent conducting layer, the devices were annealed in air at different temperatures and found that the devices annealed at 400°C have better photovoltaic parameters. The efficiency of a typical device under 60 mW cm⁻² illumination was estimated as 3.5%.     

Characterisation of CdCl2 treated electrodeposited CdS/CdTe thin film solar cell

An over 10% efficient electrodeposited CdS/CdTe solar cell has been prepared after CdCl₂ treatment. The open circuit voltage, V_oc, short-circuit current, J_sc and fill factor, FF were 758 mV, 21 mA cm⁻² and 0.65 respectively. The diode factor calculated from current-voltage-temperature measurements changed from 1.54 at 324 K to 2.64 at 146 K. The voltage factor, α ranged from 22.83 at 324 K to 29.46 at 146 K. Data from current-voltage-temperature measurements agrees with the model of Miller and Olsen and indicates that the current transport was a combination of tunneling and interface recombination. Capacitance-voltage-temperature measurements showed that capacitance decreased with increasing frequency and increased with temperature. Capacitance was insensitive to temperature indicating an intrinsic or low-doped depletion layer. The density of interface states was found to be 6.4 × 10¹⁰ cm⁻² eV⁻¹ at 293 K. The carrier concentration of CdTe calculated from Mott-Schottky plot was 1.5 × 10¹⁶ cm⁻³.     

CdTe/CdS solar cells on flexible substrates

The development of CdTe/CdS solar cells on flexible substrates is reviewed in this article. Photovoltaic structures on lightweight and flexible substrates have several advantages over the heavy glass based structures in both terrestrial and space applications. The cells mounted on flexible foil are not fragile, the requirements of the supporting structures are minimum and they can be wrapped onto any suitably oriented or curved structures. The specific power of the solar cells is an important factor in space applications and hence development of photovoltaic devices on light weight substrates is interesting. CdTe is one of the leading candidates for photovoltaic applications due to its optimum band gap for the efficient photo-conversion and robustness for industrial production with a variety of film preparation methods. Flexible solar cells with conversion efficiencies exceeding 11% have been developed on polyimide foils. The development of CdTe devices on metallic substrates is impeded due to the lack of a proper ohmic contact between CdTe and the substrate. The polymer substrate has the advantage that the devices can be prepared in both “superstrate” and “substrate” configurations.     

Stability of CdTe/CdS thin-film solar cells

The recent literature regarding the stability of CdTe/CdS photovoltaic cells (as distinguished from modules) is reviewed. Particular emphasis is given to the role of Cu as a major factor that can limit the stability of these devices. Cu is often added to improve the ohmic contact to p-CdTe and the overall cell photovoltaic performance. This may be due to the formation of a Cu₂Te/CdTe back contact. Excess Cu also enhances the instability of devices when under stress. The Cu, as Cu⁺, from either Cu₂Te or other sources, diffuses via grain boundaries to the CdTe/CdS active junction. Recent experimental data indicate that Cu, Cl and other diffusing species reach (and accumulate at) the CdS layer, which may not be expected on the basis of bulk diffusion. These observations may be factors in cell behavior and degradation, for which new mechanisms are suggested and areas for future study are highlighted. Other possible Cu-related degradation mechanisms, as well as some non-Cu-related issues for cell stability are discussed.