不同方法及衬底类型对CdS多晶薄膜性能的影响

采用化学水浴法和磁控溅射法分别在AZO、FTO、ITO透明导电玻璃衬底上制备了CdS薄膜,利用扫描电镜、XRD以及透射光谱等测试手段,研究了两种制备方法对不同衬底生长CdS薄膜形貌、结构和光学性能的影响.研究结果表明,不同方法制备的CdS薄膜表面形貌均依赖于衬底的类型,水浴法制备的CdS薄膜晶粒度较大,表面相对粗糙.不同方法制备的CdS薄膜均为立方相和六角相的混相结构,溅射法制备的多晶薄膜衍射峰清晰、尖锐,结晶性较好.水浴法制备的CdS薄膜透过率整体低于溅射法,但在短波处优势明显.     

Secondary phase formation in Zn‐rich Cu2ZnSnSe4‐based solar cells annealed in low pressure and temperature conditions

Zn‐rich Cu₂ZnSnSe₄ (CZTSe) films were prepared by a two‐step process consisting in the DC‐magnetron sputtering deposition of a metallic stack precursor followed by a reactive anneal under a Se + Sn containing atmosphere. Precursor composition and annealing temperature were varied in order to analyze their effects on the morphological, structural, and optoelectronic properties of the films and solar cell devices. Raman scattering measurements show the presence of ZnSe as the main secondary phase in the films, as well as the presence of SnSe at the back absorber region of the films processed with lower Zn‐excess values and annealing temperatures. The ZnSe phase is found to accumulate more towards the surface of the absorber in samples with lower Zn‐excess and lower temperature annealing, while increasing Zn‐excess and annealing temperature promote its aggregation towards the back absorber region of the devices. These measurements indicate a strong dependence of these process variables in secondary phase formation and accumulation. In a preliminary optimization of both the composition and reactive annealing process, a solar cell with 4.8% efficiency has been fabricated, and potential mechanisms limiting device efficiency in these devices are discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Simultaneous Improvement of Charge Generation and Extraction in Colloidal Quantum Dot Photovoltaics Through Optical Management

Inverted structure heterojunction colloidal quantum dot (CQD) photovoltaic devices with an improved performance are developed using single‐step coated CQD active layers with a thickness of ≈60 nm. This improved performance is achieved by managing the device architecture to simultaneously enhance charge generation and extraction by raising optical absorption within the depletion region. The devices are composed of an ITO/PEDOT:PSS/PbS‐CQD/ZnO/Al structure, in which the p–n heterojunction is placed at the rear (i.e., opposite to the side of illumination) of the devices (denoted as R‐Cell). Sufficient optical generation is achieved at very low CQD layer thicknesses of 45–60 nm because of the constructive interference caused by the insertion of ZnO between the CQD and the Al electrode. The power conversion efficiency (PCE) of R‐Cells containing a thin CQD layers (≈60 nm) is much higher (≈6%) than that of conventional devices containing CQD layers with a thickness of ≈300 nm (PCE ≈4.5%). This optical management strategy provides a general guide to obtain the optimal trade‐off between generation and extraction in planar p–n junction solar cells. In terms of device engineering, all the layers in our R‐Cells are fabricated using single coating, which can lead to compatibility with high‐throughput processes.     

Electro‐Optics of Colloidal Quantum Dot Solids for Thin‐Film Solar Cells

The electro‐optics of thin‐film stacks within photovoltaic devices plays a critical role for the exciton and charge generation and therefore the photovoltaic performance. The complex refractive indexes of each layer in heterojunction colloidal quantum dot (CQD) solar cells are measured and the optical electric field is simulated using the transfer matrix formalism. The exciton generation rate and the photocurrent density as a function of the quantum dot solid thickness are calculated and the results from the simulations are found to agree well with the experimentally determined results. It can therefore be concluded that a quantum dot solid may be modeled with this approach, which is of general interest for this type of materials. Optimization of the CQD solar cell is performed by using the optical simulations and a maximum solar energy conversion efficiency of 6.5% is reached for a CQD solid thickness of 300 nm.     

太阳电池中CdS多晶薄膜的微结构及性能

采用化学水浴法制备了CdS多晶薄膜，通过XRD，AFM，XPS和光学透过率谱等测试手段研究了CdS多晶薄膜生长过程中的结构和性能.结果表明，随着沉积的进行，薄膜更加均匀、致密，与衬底粘附力增强，其光学能隙逐渐增大，薄膜由无定形结构向六方(002)方向优化生长，同时出现了Cd(OH)2相.在此基础上，通过建立薄膜的生长机制与性能的联系，沉积出优质CdS多晶薄膜，获得了转化效率为13.38%的CdS/CdTe小面积电池.     

Unveiling the Nanoparticle‐Seeded Catalytic Nucleation Kinetics of Perovskite Solar Cells by Time‐Resolved GIXS

Recently, a new seeding growth approach for perovskite thin films is reported to significantly enhance the device performance of perovskite solar cells. This work unveils the intermediate structures and the corresponding growth kinetics during conversion to perovskite crystal thin films assisted by seeding PbS nanocrystals (NCs), using time‐resolved grazing‐incidence X‐ray scattering. Through analyses of time‐resolved crystal formation kinetics obtained from synchrotron X‐rays with a fast subsecond probing time resolution, an important “catalytic” role of the seed‐like PbS NCs is clearly elucidated. The perovskite precursor‐capped PbS NCs are found to not only accelerate the nucleation of a highly oriented intermediate phase, but also catalyze the conversion of the intermediate phase into perovskite crystals with a reduced activation energy E_a = 47 (±5) kJ mol^?1, compared to 145 (±38) kJ mol^?1 for the pristine perovskite thin film. The reduced E_a is attributed to a designated crystal lattice alignment of the perovskite nanocrystals with perovskite cubic crystals; the pivotal heterointerface alignment of the perovskite crystals coordinated by the Pb NCs leads to an improved film surface morphology with less pinholes and enhanced crystal texture and thermal stability. These together contribute to the significantly improved photovoltaic performance of the corresponding devices.     

Ambient Layer‐by‐Layer ZnO Assembly for Highly Efficient Polymer Bulk Heterojunction Solar Cells

The use of metal oxide interlayers in polymer solar cells has great potential because metal oxides are abundant, thermally stable, and can be used in flexible devices. Here, a layer‐by‐layer (LbL) protocol is reported as a facile, room‐temperature, solution‐processed method to prepare electron transport layers from commercial ZnO nanoparticles and polyacrylic acid (PAA) with a controlled and tunable porous structure, which provides large interfacial contacts with the active layer. Applying the LbL approach to bulk heterojunction polymer solar cells with an optimized ZnO layer thickness of ≈25 nm yields solar cell power‐conversion efficiencies (PCEs) of ≈6%, exceeding the efficiency of amorphous ZnO interlayers formed by conventional sputtering methods. Interestingly, annealing the ZnO/PAA interlayers in nitrogen and air environments in the range of 60–300 °C reduces the device PCEs by almost 20% to 50%, indicating the importance of conformational changes inherent to the PAA polymer in the LbL‐deposited films to solar cell performance. This protocol suggests a new fabrication method for solution‐processed polymer solar cell devices that does not require postprocessing thermal annealing treatments and that is applicable to flexible devices printed on plastic substrates.     

Graphene Doping Improved Device Performance of ZnMgO/PbS Colloidal Quantum Dot Photovoltaics

Lead sulfide (PbS) colloidal quantum dots (CQDs) solar cells possess the advantages of absorption into the infrared, solution processing, and multiple exciton generation, making them very competitive as a low‐cost photovoltaic alternative. Employing an n‐i‐p ZnO/tetrabutylammonium (TBAI)–PbS/ethanedithiol (EDT)–PbS device configuration, the present study reports a 9.0% photovoltaic device through ZnMgO electrode engineering and graphene doping. Sol–gel‐derived Zn_0.9Mg_0.1O buffer layer shows better transparency and higher conduction band maximum than ZnO, and incorporation of graphene and chlorinated graphene oxide into the TBAI–PbS and EDT–PbS layer respectively boosts carrier collection, leading to device with significantly enhanced open circuit voltage and short‐circuit current density. It is believed that incorporation of graphene into PbS CQD film as proposed here, and more generally nanosheets of other materials, would potentially open a simple and powerful avenue to overcome the carrier transport bottleneck of CQD optoelectronic device, thus pushing device performance to a new level.     

太阳电池中CdS薄膜的制备及其性能的研究

分别采用化学池沉积(CBD)和真空蒸发法,在三种衬底(玻片、ITO玻片、SnO2玻片)上沉积CdS薄膜,并利用扫描电镜(SEM)、透射光谱、X射线衍射(XRD)等方法对沉积膜进行了测试分析,同时阐述了两种不同方法下CdS膜的生长沉积机制。     

Optimization of vapor post‐deposition processing for evaporated CdS/CdTe solar cells

The effects of thermal annealing in conjunction with CdCl₂ vapor heat treatment on the properties of CdTe/CdS thin films and devices deposited by physical vapor deposition are reported. Results are compared for three treatment variations: high‐temperature anneal only, high‐temperature anneal followed by CdCl₂ vapor heat treatment and CdCl₂ vapor heat treatment only. X‐ray diffraction, transmission electron microscopy and scanning electron microscopy show improved crystallographic properties of the CdTe film and reduced CdS/CdTe interdiffusion when a high‐temperature anneal is used prior to CdCl₂ treatment. The CdTe/CdS solar cells fabricated using an anneal at 550°C in argon prior to the CdCl₂ vapor heat treatment exhibited improved electrical characteristics compared to cells fabricated with no anneal step, yielding an open‐circuit voltage exceeding 850 mV. Copyright © 1999 John Wiley & Sons, Ltd.     

CIGS Thin Films for Cd-Free Solar Cells by One-Step Sputtering Process

Cu(In_1?x Ga _x )Se₂ (CIGS) thin films were deposited by a one-step radio frequency (RF) magnetron sputtering process using a quaternary CIGS target. The influence of substrate temperature on the composition, structure, and optical properties of the CIGS films was investigated. All the CIGS films exhibited the chalcopyrite structure with a preferential orientation along the (112) direction. The CIGS film deposited at 623 K showed significant improvement in film crystallinity and surface morphology compared to films deposited at 523 and 573 K. To simplify the manufacturing procedure of solar cells and avoid the use of the toxic element Cd, the properties of ZnS films prepared by RF sputtering were also investigated. The results revealed that the sputtered ZnS film exhibits good lattice matching with the sputtered CIGS film with significantly lower optical absorption loss. Finally, all-sputtered Cd-free CIGS-based heterojunction solar cells with the structure SLG/Mo/CIGS/ZnS/AZO/Al grids were fabricated without post-selenization. Furthermore, the results demonstrated the feasibility of using a full sputtering process for the fabrication of Cd-free CIGS-based solar cell.     

SHORT COMMUNICATION: Thin‐film free‐standing monocrystalline si solar cells with heterojunction emitter

We propose a novel approach to thin‐film silicon solar cells, namely the freestanding monocrystalline silicon layer transfer process with heterojunction emitter (FMS‐HJ). High crystallographic quality mono‐Si films were deposited on freestanding porous silicon (PS) films by chemical vapor deposition (CVD). These free‐standing mono‐Si (FMS) films were processed into solar cells by creating a‐a‐Si/c‐Si heterojunction. In our preliminary experiments a thin‐film FMS‐HJ solar cell with 9.6% efficiency was realized in a 20‐μμm‐thin active layer. Copyright © 2005 John Wiley & Sons, Ltd.     

Deposition and doping of CdS/CdTe thin film solar cells

1% oxygen is incorporated into both CdS and CdTe layers through RF sputtering of CdS/CdTe thin film solar cells. The optical and electrical parameters of the oxygenated and O₂-free devices are compared after CdCl₂ treatment and annealing in ambient Ar and/or air. The effects of ambient annealing on the electrical and optical properties of the films are investigated using current-voltage characterization, field emission scanning electron microscopy, X-ray diffraction, and optical transmission spectroscopy. The 1% oxygen content can slightly increase the grain size while the crystallinity does not change. Annealing in ambient Ar can increase the transmission rate of the oxygenated devices.     

Polymer/Nanocrystal Hybrid Solar Cells: Influence of Molecular Precursor Design on Film Nanomorphology,Charge Generation and Device Performance

In this work, molecular tuning of metal xanthate precursors is shown to have a marked effect on the heterojunction morphology of hybrid poly(3‐hexylthiophene‐2,5‐diyl) (P3HT)/CdS blends and, as a result, the photochemical processes and overall performance of in situ fabricated hybrid solar cells. A series of cadmium xanthate complexes is synthesized for use as in situ precursors to cadmium sulfide nanoparticles in hybrid P3HT/CdS solar cells. The formation of CdS domains is studied by simultaneous GIWAXS (grazing incidence wide‐angle X‐ray scattering) and GISAXS (grazing incidence small‐angle X‐ray scattering), revealing knowledge about crystal growth and the formation of different morphologies observed using TEM (transmission electron microscopy). These measurements show that there is a strong relationship between precursor structure and heterojunction nanomorphology. A combination of TAS (transient absorption spectroscopy) and photovoltaic device performance measurements is used to show the intricate balance required between charge photogeneration and percolated domains in order to effectively extract charges to maximize device power conversion efficiencies. This study presents a strong case for xanthate complexes as a useful route to designing optimal heterojunction morphologies for use in the emerging field of hybrid organic/inorganic solar cells, due to the fact that the nanomorphology can be tuned via careful design of these precursor materials.     

The Zn(S,O,OH)/ZnMgO buffer in thin‐film Cu(In,Ga)(Se,S)2‐based solar cells part II: Magnetron sputtering of the ZnMgO buffer layer for in‐line co‐evaporated Cu(In,Ga)Se2 solar cells

A ZnS/Zn_1‐xMg_xO buffer combination was developed to replace the CdS/i‐ZnO layers in in‐line co‐evaporated Cu(In,Ga)Se₂(CIGS)‐based solar cells. The ZnS was deposited by the chemical bath deposition (CBD) technique and the Zn_1‐xMg_xO layer by RF magnetron sputtering from ceramic targets. The [Mg]/([Mg] + [Zn]) ratio in the target was varied between x = 0·0 and 0·4. The composition, the crystal structure, and the optical properties of the resulting layers were analyzed. Small laboratory cells and 10 × 10 cm² modules were realized with high reproducibility and enhanced stability. The transmission is improved in the wavelength region between 330 and 550 nm for the ZnS/Zn_1‐xMg_xO layers. Therefore, a large gain in the short‐circuit current density up to 12% was obtained, which resulted in higher conversion efficiencies up to 9% relative as compared to cells with the CdS/i‐ZnO buffer system. Peak efficiencies of 18% with small laboratory cells and 15·2% with 10 × 10 cm² mini‐modules were demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.     

CdTe-HgCdTe叠层太阳电池CdS窗口层透射光谱性能研究

CdS窗口层光谱透射率的提高对CdTe-HgCdTe叠层太阳电池有效利用入射太阳光并增大电池的短路电流密度有重要的影响。通过研究化学水浴法、近空间升华法和磁控溅射法制备的CdS薄膜在CdCl2退火前后的光谱平均透过率和短路电流密度损失表明:在光谱区520~820 nm,化学水浴法制备的CdS薄膜在退火前后具有最高的光谱平均透过率,对应的CdTe顶电池有最小的短路电流密度损失;在光谱区820~1150和520~1150 nm,磁控溅射法制备的CdS薄膜在退火前后均具有最高的光谱平均透过率,对应的HgCdTe底电池和CdTe-HgCdTe叠层太阳电池有最小的短路电流密度损失。在光谱区520~820、820~1150和520~1150 nm,CdCl2退火可以显著增大CdS薄膜的光谱平均透过率,降低对应CdTe顶电池、HgCdTe底电池和CdTe-HgCdTe叠层电池的短路电流密度损失。     

Flexible CdTe solar cells on polymer films

Lightweight and flexible CdTe/CdS solar cells on polyimide films have been developed in a ‘superstrate configuration’ where the light is absorbed in CdTe after passing through the polyimide substrate. The average optical transmission of the approximately 10‐μm‐thin spin‐coated polyimide substrate layer is more than ∼75% for wavelengths above 550 nm. RF magnetron sputtering was used to grow transparent conducting ZnO:Al layers on polyimide films. CdTe/CdS layers were grown by evaporation of compounds, and a CdCl₂ annealing treatment was applied for the recrystallization and junction activation. Solar cells of 8·6% efficiency with V_oc = 763 mV, I_sc = 20·3 mA/cm² and FF = 55·7% were obtained. Copyright © 2001 John Wiley & Sons, Ltd.     

X-ray imaging camera tube using sputter-deposited CdTe/CdSheterojunction

CdTe heterojunction devices have been fabricated for the first time by an RF sputter deposition method for application to X-ray imaging sensors. The electrical resistivities of sputter-deposited polycrystalline CdS and CdTe films are greater than 10⁶ Ω-cm and 10⁹ Ω-cm, respectively. The fabricated CdS/CdTe heterojunction sensor shows a good diode characteristic and a high sensitivity to X-ray radiation. An X-ray imaging camera tube consisting of CdS/CdTe heterojunction photoconductive target shows three times larger responsivity to X-rays than the conventional PbO X-ray tube. The dark current density of the device is observed to be lower than 10 nA/cm² at 20 V target voltage at room temperature     

PbS and CdS Quantum Dot‐Sensitized Solid‐State Solar Cells: “Old Concepts,New Results”

Lead sulfide (PbS) and cadmium sulfide (CdS) quantum dots (QDs) are prepared over mesoporous TiO₂ films by a successive ionic layer adsorption and reaction (SILAR) process. These QDs are exploited as a sensitizer in solid‐state solar cells with 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) as a hole conductor. High‐resolution transmission electron microscopy (TEM) images reveal that PbS QDs of around 3 nm in size are distributed homogeneously over the TiO₂ surface and are well separated from each other if prepared under common SILAR deposition conditions. The pore size of the TiO₂ films and the deposition medium are found to be very critical in determining the overall performance of the solid‐state QD cells. By incorporating promising inorganic QDs (PbS) and an organic hole conductor spiro‐OMeTAD into the solid‐state cells, it is possible to attain an efficiency of over 1% for PbS‐sensitized solid‐state cells after some optimizations. The optimized deposition cycle of the SILAR process for PbS QDs has also been confirmed by transient spectroscopic studies on the hole generation of spiro‐OMeTAD. In addition, it is established that the PbS QD layer plays a role in mediating the interfacial recombination between the spiro‐OMeTAD⁺ cation and the TiO₂ conduction band electron, and that the lifetime of these species can change by around 2 orders of magnitude by varying the number of SILAR cycles used. When a near infrared (NIR)‐absorbing zinc carboxyphthalocyanine dye (TT1) is added on top of the PbS‐sensitized electrode to obtain a panchromatic response, two signals from each component are observed, which results in an improved efficiency. In particular, when a CdS‐sensitized electrode is first prepared, and then co‐sensitized with a squarine dye (SQ1), the resulting color change is clearly an addition of each component and the overall efficiencies are also added in a more synergistic way than those in PbS/TT1‐modified cells because of favorable charge‐transfer energetics.     

Cu2ZnSnS4 photovoltaic cell with improved efficiency fabricated by high‐temperature annealing after CdS buffer‐layer deposition

To improve the photovoltaic properties of Cu₂ZnSnS₄ (CZTS) cells, we investigated the effect of both the thickness of the deposited CdS layers and the post‐annealing temperature following CdS deposition on the photovoltaic properties of CZTS cells using a two‐layer CZTS structure. By depositing a thin CdS layer (40 nm) followed by high temperature annealing (603 K), we observed a remarkable increase in the short‐circuit current density because of the enhancement of the external quantum efficiency in the wavelength range of 400–800 nm. The best CZTS cell exhibited a conversion efficiency of 9.4% in the active area (9.1% in the designated area). In addition, we also fabricated a CZTS cell with open‐circuit voltage of 0.80 V by appropriately tuning the composition of the CZTS layers. Copyright © 2016 John Wiley & Sons, Ltd.