First-principles study on the alkali chalcogenide secondary compounds in Cu(In,Ga)Se_2 and Cu_2ZnSn(S,Se)_4 thin film solar cells

The beneficial effect of the alkali metals such as Na and K on the Cu（In.Ga）Se2 （CIGS） and Cu2ZnSn（S,Se）4 （CZTSSe） solar cells has been extensively investigated in the past two decades, however, in most of the studies the alkali metals were treated as dopants. Several recent studies have showed that the alkali metals may not only act as dopants but also form secondary phases in the absorber layer or on the surfaces of the films. Using the first-principles calculations, we screened out the most probable secondary phases of Na and K in CIGS and CZTSSe, and studied their electronic structures and optical properties. We found that all these alkali chalcogenide compounds have larger band gaps and lower VBM levels than CIGS and CZTSSe, because the existence of strong p-d coupling in CIS and CZTS pushes the valence band maximum （VBM） level up and reduces the band-gaps, while there is no such p-d coupling in these alkali chalcogenides. This band alignment repels the photo-generated holes from the secondary phases and prevents the electron-hole recombination. Moreover, the study on the optical properties of the secondary phases showed that the absorption coefficients of these alkali chalcogenides are much lower than those of CIGS and CZTSSe in the energy range of 0-3.4eV, which means that the alkali chalcogenides may not influence the absorption of solar light. Since the alkali metal dopants can passivate the grain boundaries and increase the hole carrier concentration, and meanwhile their related secondary phases have innocuous effect on the optical absorption and band alignment, we can understand why the alkali metal dopants can improve the CIGS and CZTSSe solar cell performance.

A NEW CONCEPT TOWARD INDUSTRIALIZATION OF Cu-Ⅲ-Ⅳ2 THIN FILM SOLAR CELLS AND SOME PRELIMINARY EXPERIMENT RESULTS

A new concept of full vacuum manufacturing for Cu-III-IV2 thin-film solar cells has been discussed. Cu-III-IV2 thin-film solar cells manufactured using full in- line reactive sputtering will result in lower cost than that of the conventional method with CdS layer fabricated with chemical bath deposition (CBS) method. Us ing reactive sputtering process with organo- metallic gases, the compositions a nd electronic properties of Cu-III-IV2 thin-film can be fine-tuned and precisely controlled. n-type Cu-III-IV2 film and ZnS suffer layer can also be deposited u sing the in-line sputtering instead of using the CdS layer. The environmental po llution problems arising from using CdS can be eliminated and the ultimate goal of full in-line process development can then be realized. Some preliminary exper imental results on a modal solar cell fabricated by the new technique in the new concept have been presented.

Analysis of the p^+/p window layer of thin film solar cells by simulation

The application of a p~＋/p configuration in the window layer of hydrogenated amorphous silicon thin film solar cells is simulated and analyzed utilizing an AMPS-ID program.The differences between p~＋-p-i-n configuration solar cells and p-i-n configuration solar cells are pointed out.The effects of dopant concentration, thickness of p~＋-layer,contact barrier height and defect density on solar cells are analyzed.Our results indicate that solar cells with a p~＋-p-i-n configuration have a better performance.The open circuit voltage and short circuit current were improved by increasing the dopant concentration of the p~＋ layer and lowering the front contact barrier height.The defect density at the p/i interface which exceeds two orders of magnitude in the intrinsic layer will deteriorate the cell property.

Research on the optimum hydrogenated silicon thin films for application in solar cells

Hydrogenated silicon （Si：H） thin films for application in solar ceils were deposited by using very high frequency plasma enhanced chemical vapour deposition （VHF PECVD） at a substrate temperature of about 170 ℃, The electrical, structural, and optical properties of the films were investigated. The deposited films were then applied as i-layers for p-i-n single junction solar cells. The current-voltage （I - V） characteristics of the cells were measured before and after the light soaking. The results suggest that the films deposited near the transition region have an optimum properties for application in solar cells. The cell with an i-layer prepared near the transition region shows the best stable performance.

Absorption enhancement in thin film a-Si solar cells with double-sided SiO_2 particle layers

Light absorption enhancement is very important for improving the power conversion efficiency of a thin film a-Si solar cell. In this paper, a thin-film a-Si solar cell model with double-sided SiO2 particle layers is designed, and then the underlying mechanism of absorption enhancement is investigated by finite difference time domain（FDTD） simulation;finally the feasible experimental scheme for preparing the SiO2 particle layer is discussed. It is found that the top and bottom SiO2 particle layers play an important role in anti-reflection and light trapping, respectively. The light absorption of the cell with double-sided SiO2 layers greatly increases in a wavelength range of 300 nm-800 nm, and the ultimate efficiency increases more than 22% compared with that of the flat device. The cell model with double-sided SiO2 particle layers reported here can be used in varieties of thin film solar cells to further improve their performances.

Synthesis of the CuInSe_2 thin film for solar cells using the electrodeposition technique and Taguchi method

The Taguchi method was used to obtain the optimum electrodeposition parameters for the synthesis of the CuInSe2 thin film for solar cells. The parameters consist of annealing temperature, current density, CuCl2 concentration, FeCl3 concentration, H2SeO3 concentration, TEA amount, pH value, and deposition time. The experiments were carried out according to an L18（2^13^7） table An X-ray diffractometer （XRD） and a scanning electron microscope （SEM） were respectively used to analyze the phases and observe the microstructure and the grain size of the CuInSe2 film before and after annealing treatment. The results showed that the CuInSe2 phase was deposited with a preferred plane （112） parallel to the substrate surface. The optimum parameters are as follows： current density, 7 mA/cm^2; CuCl2 concentration, 10 mM; FeCl3 concentration, 50 mM; H2SeO3 concentration, 15 mM; TEA amount, 0 mL; pH value, 1.65; deposition time, 10 min; and annealing temperature, 500℃.

Enhanced optical absorption by Ag nanoparticles in a thin film Si solar cell

Thin film solar cells have the potential to significantly reduce the cost of photovoltaics. Light trapping is crucial to such a thin film silicon solar cell because of a low absorption coefficient due to its indirect band gap. In this paper, we investigate the suitability of surface plasmon resonance Ag nanoparticles for enhancing optical absorption in the thin film solar cell. For evaluating the transmittance capability of Ag nanoparticles and the conventional antireflection film, an enhanced transmittance factor is introduced. We find that under the solar spectrum AM1.5, the transmittance of Ag nanoparticles with radius over 160 nm is equivalent to that of conventional textured antireflection film, and its effect is better than that of the planar antireflection film. The influence of the surrounding medium is also discussed.

In-situ growth of a CdS window layer by vacuum thermal evaporation for CIGS thin film solar cell applications

Highly crystalline and transparent CdS films are grown by utilizing the vacuum thermal evaporation （VTE） method. The structural, surface morphological, and optical properties of the films are studied and compared with those prepared by chemical bath deposition （CBD）. It is found that the films deposited at a high substrate temperature （200 ℃） have a preferential orientation along （002） which is consistent with CBD-grown films. Absorption spectra reveal that the films are highly transparent and the optical band gap values are found to be in a range of 2.44 eV-2.56 eV. Culnl_xGaxSe2 （CIGS） solar cells with in-situ VTE-grown CdS films exhibit higher values of Voc together with smaller values of Jsc than those from CBD. Eventually the conversion efficiency and fill factor become slightly better than those from the CBD method. Our work suggests that the in-situ thermal evaporation method can be a competitive alternative to the CBD method, particularly in the physical- and vacuum-based CIGS technology.

Effect of emitter layer doping concentration on the performance of a silicon thin film heterojunction solar cell

A novel type of n/i/i/p heterojunction solar cell with a-Si：H（15 nm）/a-Si：H（10 nm）/epitaxial c-Si（47 p.m）/epitaxial c-Si（3 um） structure is fabricated by using the layer transfer technique, and the emitter layer is deposited by hot wire chemical vapour deposition. The effect of the doping concentration of the emitter layer Sd （Sd=PH3/（PH3 ＋SiH4＋H2）） on the performance of the solar cell is studied by means of current density-voltage and external quantum efficiency. The results show that the conversion efficiency of the solar cell first increases to a maximum value and then decreases with Sd increasing from 0.1% to 0.4%. The best performance of the solar cell is obtained at Sd = 0.2% with an open circuit voltage of 534 mV, a short circuit current density of 23.35 mA/cm2, a fill factor of 63.3%, and a conversion efficiency of 7.9%.

Surface defect ordered Cu_(2)ZnSn(S,Se)_(4) solar cells with efficiency over 12% via manipulating local substitution

The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.

Path towards high-efficient kesterite solar cells

Kesterite structure semiconductor Cu2ZnSn（S,Se）4 is one of the most promising candidate as a light absorber material to overtake the next generation of thin film solar cells, owing to its low cost, non-toxic, and earth abundant source materials. The Sbockley-Queisser limit of the single junction Cu2ZnSn（S,Se）4 solar cell is over 30%, signifying a large potential of this family of solar cells. In the past years, with the development of synthesis techniques, Cu2ZnSn（S,Se）4 solar cells have attracted considerable atten- tion and the power conversion efficiency of Cu2ZnSn（S,Se）4 solar cell has experienced a rapid progress. Presently, the certified champion efficiency of CZTSSe solar cells has reached to 12.6%, which is far below the efficiency of Cu（ln,Ga）Se2 solar cell. In this review, the developments of Cu2ZnSn（S,Se）4 solar cells in recent years are briefly reviewed. Then the fundamental understanding of Cu2ZnSn（S,Se）4 solar cells is introduced, including materials and device structure, as well as the band alignment of hetero-junction and their impacts on device performance. After that, we mainly review the progress and achievements in the preparation processes, through vacuum and non-vacuum based processes. Finally, we outline the challenges and perspectives of this promising solar cell.

High Performance for Cu(In,Ga)Se2 Quaternary System-Based Solar Cells with Alternative Buffer Layers

In this study, the authors investigated the performance of different buffer layers through the electrical parameters such as Jsc, Voc, QE and η of the quaternary system Cu(In,Ga)Se2 solar cells. The performance of Cu(In,Ga)Se2solar cells has been modeled and numerically simulated by using the SCAPS- 1D device simulation tool. The cells with a ZnSe, Zn(O,S) and (Zn,Mg)O buffer layers were compared with the reference CdS buffer layer. The investigation of ZnSe, Zn(O, S) and (Zn,Mg)O-based cells to substitute the traditional CdS in the future shows that the ZnSe-buffer layer is a potential material to replace CdS, which revealed the best efficiency of 20.76%, the other electrical parameters are: JSC = 34.6 mA/cm2, VOC = 0.76 V and FF = 79.6%. The losses as a function of the temperature are estimated at 0.1%/K, among all kinds of buffer layers studied. We have also shown that the use of a high band-gap buffer layer is necessary to obtain a better short-circuit current density JSC. From our results, we note that the chalcogenide solar cells with Zn-based alternative buffer layer have almost the same stability thatthe traditional CdS buffer layer solar cells have.

Improving the Performance of PbS Quantum Dot Solar Cells by Optimizing ZnO Window Layer

Comparing with hot researches in absorber layer,window layer has attracted less attention in PbS quantum dot solar cells(QD SCs). Actually, the window layer plays a key role in exciton separation, charge drifting, and so on.Herein, ZnO window layer was systematically investigated for its roles in QD SCs performance. The physical mechanism of improved performance was also explored. It was found that the optimized ZnO films with appropriate thickness and doping concentration can balance the optical and electrical properties, and its energy band align well with the absorber layer for efficient charge extraction. Further characterizations demonstrated that the window layer optimization can help to reduce the surface defects, improve the heterojunction quality, as well as extend the depletion width. Compared with the control devices, the optimized devices have obtained an efficiency of 6.7% with an enhanced V_(oc) of 18%, J_(sc) of 21%, FF of 10%, and power conversion efficiency of 58%. The present work suggests a useful strategy to improve the device performance by optimizing the window layer besides the absorber layer.

Theoretical study on the kesterite solar cells based on Cu_2ZnSn(S,Se)_4 and related photovoltaic semiconductors

The kesterite thin film solar cells based on the quaternary Cu2ZnSnS4 and Cu2ZnSnSe4 and their alloys Cu2ZnSn（S,Se）4 have been considered as environment-friendly and non-toxic alternatives to the currently commercialized CdTe and Cu（In,Ga）Se2 thin film solar cells. From the theoretical point of view, we will review how the group I2-II-IV-VI4 quaternary compound semiconductors are derived from the binary CdTe and the ternary CuInSe2 or CuGaSe2 through the cation mutation, and how the crystal structure and electronic band structure evolve as the component elements change. The increased structural and chemical freedom in these quaternary semiconductors opens up new possibility for the tailoring of material properties and design of new light-absorber semiconductors. However, the increased freedom also makes the development of high-efficiency solar cells more challenging because much more intrinsic point defects, secondary phases, surfaces, and grain-boundaries can exist in the thin films and influence the photovoltaic performance in a way different from that in the conventional CdTe and Cu（In,Ga）Se2 solar cells. The experimental characterization of the properties of defects, secondary phase, and grain-boundaries is currently not very efficient and direct, especially for these quaternary compounds. First-principles calculations have been successfully used in the past decade for studying these properties. Here we will review the theoretical progress in the study of the mixed-cation and mixed-anion alloys of the group I2-II-IV- VI4 semiconductors, defects, alkaline dopants, and grain boundaries, which provided very important information for the optimization of the kesterite solar cell performance.

Highly efficient solution-processed CZTSSe solar cells based on a convenient sodium-incorporated post-treatment method

In CZTSSe solar cells,a simple sodium-incorporation post-treatment method toward solution-processed Cu2Zn Sn S4precursor films is presented in this work.An ultrathin NaCl film is deposited on Cu2Zn Sn S4precursor films by spin-coating NaCl solution.In subsequent selenization process,the introduction of Na Cl is found to be benefacial for the formation of Cu2-xSe,which can further facilitate the element transportation,leading to dense and smooth CZTSSe films with large grains and less impurity Cu2Sn(S,Se)3phase.SIMS depth profiles confirm the gradient distribution of the sodium element in Na-doped absorbers.Photoluminescence spectra show that the introduction of appropriate sodium into the absorber can inhibit the band tail states.As high as 11.18% of power conversion efficiency(PCE)is achieved for the device treated with 5 mg mL^-1 NaCl solution,and an average efficiency of Na-doped devices is 10.71%,13%higher than that of the control groups(9.45%).Besides,the depletion width and the charge recombination lifetime can also have regular variation with sodium treatment.This work offers an easy modification method for high-quality Na-doped CZTSSe films and high-performance devices,in the meantime,it can also help to further understand the effects of sodium in CZTSSe solar cells.

Effect of concentration of cadmium sulfate solution on structural,optical and electric properties of Cd_(1-x)Zn_(x)S thin films

Cd_(1-x)Zn_(x)S thin films were deposited by chemical bath deposition(CBD)on the glass substrate to study the influence of cadmium sulfate concentration on the structural characteristics of the thin film.The SEM results show that the thin film surfaces under the cadmium sulfate concentration of 0.005 M exhibit better compactness and uniformity.The distribution diagrams of thin film elements illustrate the film growth rate changes on the trend of the increase,decrease,and increase with the increase of cadmium sulfate concentration.XRD studies exhibit the crystal structure of the film is the hexagonal phase,and there are obvious diffraction peaks and better crystallinity when the concentration is 0.005 M.Spectrophotometer test results demonstrate that the relationship between zinc content x and optical band gap value E_(g) can be expressed by the equation E_(g)(x)=0.59x^(2)+0.69x+2.43.Increasing the zinc content can increase the optical band gap,and the absorbance of the thin film can be improved by decreasing the cadmium sulfate concentration,however,all of them have good transmittance.At a concentration of 0.005 M,the thin film has good absorbance in the 300-800 nm range,80%transmittance,and band gap value of 3.24 eV,which is suitable for use as a buffer layer for solar cells.

Lithium-assisted synergistic engineering of charge transport both in GBs and GI for Ag-substituted Cu2ZnSn(S,Se)4 solar cells

Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still hindered by the fairly low electrical conductivity due to the significant decrease of acceptors amount.In this work, a versatile Li–Ag co-doping strategy is demonstrated to mitigate the poor electrical conductivity arising from Ag through direct incorporating Li via postdeposition treatment(PDT) on top of the Ag-substituted CZTSSe absorber. Depth characterizations demonstrate that Li incorporation increases ptype carrier concentration, improves the carrier collection within the bulk, reduces the defects energy level as well as inverts the electric field polarity at grain boundaries(GBs) for Ag-substituted CZTSSe system. Benefiting from this lithium-assisted complex engineering of electrical performance both in grain interior(GI) and GBs, the power conversion efficiency(PCE) is finally increased from 9.21% to 10.29%. This systematic study represents an effective way to overcome the challenges encountered in Ag substitution,and these findings support a new aspect that the synergistic effects of double cation dopant will further pave the way for the development of high efficiency kesterite PV technology.

Recent advances of flexible perovskite solar cells

In few years only, the efficiency record of perovskite solar cells（PSCs） has raised quickly from 3.8% to over 22%. This emerging photovoltaic technology has primarily shown its great potential of industrialization. Flexible PSCs are thought to be one of the most priority options for mass production, related to the intrinsic advantage of perovskite thin films which could be deposited by facile solution processes at low temperature. Flexible PSCs have at least four advantages in comparison to the rigid counterpart：（1） it can generate higher power output at lighter weight,（2） it is easily portable,（3） it can be easily attached to architectures or textiles with diverse shapes, and（4） it is compatible with roll-to-roll fabrication in a large scale. In this review, we have summarized recent development of the key materials and technologies applied in flexible PSCs. The key materials including flexible substrates, transparent and conductive electrodes, and interfacial materials; some key technologies about roll-to-roll manufacture, encapsulation technology have been overviewed. Finally, a prospect on possible application directions of flexible PSCs has been discussed.

Deposition Methods and Properties of Polycrystalline CdS Thin Films

CdS thin film was used as a suitable window layer for CdS/Cd Te solar cell, and the properties of CdS thin films deposited by pulsed laser deposition（PLD）, chemical bath deposition（CBD） and magnetron sputtering（MS） were reported. The experimental results show that the transmittances of PLD-Cd S thin films are about 85% and the band gaps are about 2.38-2.42 e V. SEM results show that the surface of PLD-Cd S thin film is much more compact and uniform. PLD is more suitable to prepare the Cd S thin films than CBD and MS. Based on the thorough study, by using totally PLD technique, the FTO/PLD-Cd S（150 nm）/CSS-Cd Te solar cell（0.0707 cm^2） can be prepared with an efficiency of 10.475%.

Effects of deposition pressure and plasma power on the growth and properties of boron-doped microcrystalline silicon films

Using diborane as doping gas, p-doped μc-Si：H layers are deposited by using the plasma enhanced chemical vapour deposition （PECVD） technology. The effects of deposition pressure and plasma power on the growth and the properties of μc-Si：H layers are investigated. The results show that the deposition rate, the electrical and the structural properties are all strongly dependent on deposition pressure and plasma power. Boron-doped μc-Si：H films with a dark conductivity as high as 1.42 Ω^-1·cm^-1 and a crystallinity of above 50% are obtained. With this p-layer, μc-Si：H solar cells are fabricated. In addition, the mechanism for the effects of deposition pressure and plasma power on the growth and the properties of boron-doped μc-Si：H layers is discussed.