Surface passivation of phosphorus‐diffused n+‐type emitters by plasma‐assisted atomic‐layer deposited Al2O3

In recent years Al₂O₃ has received tremendous interest in the photovoltaic community for the application as surface passivation layer for crystalline silicon. Especially p‐type c‐Si surfaces are very effectively passivated by Al₂O₃, including p‐type emitters, due to the high fixed negative charge in the Al₂O₃ film. In this Letter we show that Al₂O₃ prepared by plasma‐assisted atomic layer deposition (ALD) can actually provide a good level of surface passivation for highly doped n‐type emitters in the range of 10–100 Ω/sq with implied‐V_oc values up to 680 mV. For n‐type emitters in the range of 100–200 Ω/sq the implied‐V_oc drops to a value of 600 mV for a 200 Ω/sq emitter, indicating a decreased level of surface passivation. For even lighter doped n‐type surfaces the passivation quality increases again to implied‐V_oc values well above 700 mV. Hence, the results presented here indicate that within a certain doping range, highly doped n‐ and p‐type surfaces can be passivated simultaneously by Al₂O₃. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

ITO: Zr bi-layers deposited by reactive O2 and Ar plasma with high work function for silicon heterojunction solar cells

We report the influence of reactive oxygen (O₂) and argon (Ar) plasma based ITO:Zr bi-layers for silicon heterojunction (SHJ) solar cells. The purpose of reactive O₂ sputtered ITO:Zr was to improve the Hall mobility and work function while the Ar based ITO:Zr films play an important role to maintain good electrical characteristics. The thickness of reactive O₂ based ITO:Zr films was fixed at 15 nm while Ar based films was varied from 65 to 125 nm, respectively. ITO:Zr bi-layers with the thickness of 15/105 nm deposited by O₂ and Ar plasma, respectively, showed lowest resistivity of 2.358 × 10⁻⁴ Ω cm and high Hall mobility of 39.3 cm²/V · s. All ITO:Zr bi-layers showed an average transmittance of above 80% in the visible wavelength (380–800 nm) region. Work function of ITO:Zr bi-layers was calculated from the X-ray photoelectron spectroscopic (XPS) data. The ITO:Zr work function was enhanced from 5.3 eV to 5.16 eV with the variation of ITO:Zr bi-layers from 15/65 to 15/125 nm, respectively. Front barrier height in SHJ solar cells can be modified by using TCO films with high work function. The SHJ solar cells were fabricated by employing the ITO:Zr bi-layer as front anti-reflection coating. The SHJ solar cells fabricated on ITO:Zr bi-layer with the thickness of 15/105 nm showed the best photo-voltage parameters as; V_oc = 739 mV, J_sc = 39.12 mA/cm², FF = 75.97%, η = 21.96%.     

Theoretical simulation of photovoltaic response of graphene-on-semiconductors

Using the fundamental models for voltage and current, we report on the photovoltaic behavior of graphene-on-semiconductor-based devices. The graphene-n-Si and graphene-n-GaAs systems are studied for open-circuit voltage (V _OC) and short-circuit current density (J _SC) under low- and high-level injection conditions. The effects of semiconductor doping density and surface recombination velocity on the V _OC of both systems are investigated. The V _OC for graphene-n-Si under low- and high-level injection conditions are found to be 0.353 V and 0.451 V, respectively, whereas the V _OC for graphene-n-GaAs under low- and high-level injection conditions are 0.441 V and 0.471 V, respectively. The J _SC for graphene-n-Si under low- and high-level injection conditions are calculated as 3 mAcm^?2 and 4.78 mAcm^?2, respectively, whereas the J _SC for graphene-n-GaAs under low- and high-level injection conditions are 5.2 mAcm^?2 and 6.68 mAcm^?2, respectively. These results are in good agreement with the reported experimental work.     

High‐performance a‐Si1–xOx:H/c‐Si heterojunction solar cells realized by the a‐Si:H/a‐Si1–xOx:H stack buffer layer

We used amorphous silicon oxide (a‐Si_1–xO_x:H) and microcrystalline silicon oxide (µc‐Si_1–xO_x:H) as buffer layer and p‐type emitter layer, respectively, in n‐type silicon hetero‐junction (SHJ) solar cells. We proposed to insert a thin (2 nm) intrinsic amorphous silicon (a‐Si:H) thin film between the thin (2.5 nm) a‐Si_1–xO_x:H buffer layer and the p‐layer to form a stack buffer layer of a‐Si:H/a‐Si_1–xO_x:H. As a result, a high open‐circuit voltage (V_OC) and a high fill factor (FF) were obtained at the same time. Finally, a high efficiency of 19.0% (J_SC = 33.46 mA/cm², V_OC = 738 mV, FF = 77.0%) was achieved on a 100 μm thick polished wafer using the stack buffer layer.

     

2,7-Carbazole and thieno[3,4-c]pyrrole-4,6-dione based copolymers with deep highest occupied molecular orbital for photovoltaic cells

Three kinds of donor–acceptor (D–A) type photovoltaic polymers were synthesized based on 2,7-carbazole and thieno[3,4-c]pyrrole-4,6-dione (TPD). The conjugation of weakly electron (e)-donating 2,7-carbazole and strongly e-accepting TPD moieties yielded a deep highest occupied molecular orbital (HOMO) and its energy level was fine-controlled to be −5.72, −5.67 and −5.57 eV through the incorporation of thiophene (T), thieno[3,2-b]thiophene (TT) and bithiophene (BT) as a π-bridge. Polymer:[6,6]-phenyl-C₇₁ butyric acid methyl ester (PC₇₁BM) based bulk heterojunction solar cells exhibited a high open-circuit voltage (V_OC) in the range, 0.86–0.94 V, suggesting good agreement with the measured HOMO levels. Despite the high V_OC, the thiophene (or thienothiophene)-containing PCTTPD (or PCTTTPD) showed poor power conversion efficiency (PCE, 1.14 and 1.25%) because of the very low short-circuit current density (J_SC). The voltage-dependent photocurrent and photoluminescence quenching measurements suggested that hole transfer from PC₇₁BM to polymer depends strongly on the HOMO level of the polymer. The PCTTPD and PCTTTPD devices suffered from electron–hole recombination at the polymer/PC₇₁BM interfaces because of the insufficient energy offset between the HOMOs of the polymer and PC₇₁BM. The PCBTTPD:PC₇₁BM device showed the best PCE of 3.42% with a V_OC and J_SC of 0.86 V and 7.79 mA cm⁻², respectively. These results show that photovoltaic polymers should be designed carefully to have a deep HOMO level for a high V_OC and sufficient energy offset for ensuring efficient hole transfer from PC₇₁BM to the polymer.     

Annealing effect on the structural and optical properties of a Cd1−xZnxS thin film for photovoltaic applications

Herein is a report of a study on a Cd_1−xZn_xS thin film grown on an ITO substrate using a chemical bath deposition technique. The as-deposited films were annealed in air at 400 °C for 30 min. The composition, surface morphology and structural properties of the as-deposited and annealed Cd_1−xZn_xS thin films were studied using EDX, SEM and X-ray diffraction techniques. The annealed films have been observed to possess a crystalline nature with a hexagonal structure. The optical absorption spectra were recorded within the range of 350-800 nm. The band gap of the as-deposited thin films varied from 2.46 to 2.62 eV, whereas in the annealed film these varied from 2.42 to 2.59 eV. The decreased band gap of the films after annealing was due to the improved crystalline nature of the material.     

Detailed analysis of ultrathin fluorescent red dye interlayer for organic photovoltaic cells

The influence of an ultrathin 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) fluorescent dye layer at donor/acceptor heterojunction on the performance of small-molecule organic photovoltaic (OPV) cell is studied. The structure of OPV cell is of indium-tin oxide (ITO)/copper phthalocyanine (CuPc)/DCJTB/fullerene (C₆₀)/bathophenanthroline (Bphen)/Ag. The results show that open circuit voltage (V_OC) increases to 0.57 V as the film thickness of DCJTB layer increases from 0.2 to 2.0 nm. By using an equivalent circuit model, the enhancement of V_OC is found to be attributed to the reduced reverse saturation current density (J_S) which is due to the lower highest occupied molecular orbital (HOMO) level in DCJTB than that in CuPc. Also, the short circuit current density (J_SC) is affected when the DCJTB layer becomes thicker, resulting from the high series resistance R_SA due to the low charge carrier mobility of fluorescent red dye.     

Novel fabrication route for carbon-free and dense CuInSe2 (CIS) thin films via a non-vacuum process for solar cell application

Carbon-free CuInSe₂ (CIS) thin film with a dense microstructure has been prepared using a novel non-vacuum based fabrication route. Cu_xS_y and In₂Se₃ binary nanoparticles, approximately 10 nm in size, were synthesized by a low temperature colloidal process. The precursor film was deposited using the coating ink formulated with the binary nanoparticles and pyridine, and then annealed in the rapid thermal annealing (RTA) chamber at 540 °C for 15 min under selenium (Se) atmosphere. Scanning electron micrographs, X-ray diffraction patterns and Raman spectra showed a phase pure carbon-free and dense CIS thin film was prepared in this method. A solar cell device fabricated using this CIS thin film showed the following photovoltaic characteristics: V_OC = 350 mV, J_SC = 24.72 mA cm⁻², FF = 38.73% and η = 3.36% under standard AM 1.5 condition.     

Post-fabrication annealing effects on the performance of P3HT:PCBM solar cells with/without ZnO nanoparticles

In this study, P3HT:PCBM organic photovoltaic (OPV) devices, with or without ZnO nanoparticles buffer layer between the photoactive layer (P3HT:PCBM) and the cathode (Al top electrode), were fabricated. The devices were annealed at 145 °C either before or after depositing the top electrode. The objective of this study was to investigate the effects of the ZnO buffer layer and pre-/post-fabrication annealing on the general performance of these devices. The short-circuit current density (J_SC), open-circuit voltage (V_OC) and the external quantum efficiency (EQE) of the OPV devices were improved by the insertion of the ZnO layer and post-fabrication annealing. The post-fabrication annealed devices, with or without the ZnO layer, exhibited higher values of J_SC, V_OC and EQE than those of similar devices annealed before depositing the Al metal. This can be attributed to, among other things, improved charge transport across the interface between the photoactive layer and the Al top electrode as a result of post-annealing induced modification of the interface morphology.     

Investigation of Cu2ZnSnS4 solar cell buffer layer fabricated via spray pyrolysis

Copper zinc tin sulfide solar cells were fabricated by using spray pyrolysis from a window layer to an absorber layer. ZnS and In₂S₃ buffer layers were deposited on the TiO₂ layer, and the photovoltaic characteristics were investigated. The ZnS buffer demonstrated a poor photovoltaic performance because of its poor surface coverage and micro-cracks at fluorine-doped tin oxide/TiO₂ layers. The In₂S₃ buffer layer sprayed at low temperature (<360 °C) showed a large difference between photo and dark currents beyond the open-circuit voltage (V_OC). When the spraying temperature exceeded 390 °C, the devices showed high dark leakage currents at reverse biases because of the high conductivity of the buffer layer, resulting in decreased V_OC and short-circuit current density (J_SC). The optimum temperature for spraying In₂S₃ is 360 °C, and the best performing device showed 410 mV, 30.4 mA/cm², 35.3%, and 4.4% of V_OC, J_SC, fill factor, and efficiency, respectively.     

前端接触势垒高度对非晶硅和微晶硅异质结太阳电池的影响

运用AMPS-1D（Analysis of Microelectronic and Photonic Structures） 程序系统分析了前端接触（铟锡氧化物）的势垒分别对非晶硅和微晶硅太阳电池性能的影响,比较了两种影响的差异并分析了具体原因. 研究表明：与微晶硅相比,非晶硅受铟锡氧化物功函数Φ_ITO的影响更加显著. 随着Φ_ITO的增加非晶硅的各项物理性能（如太阳电池效率、填充因子等）得到明显改善,而微晶硅的各项参数虽然也随Φ_ITO增加而改变,但更容易趋于饱和. 模拟结果显示,在实际的太阳电池装备过程中可根据前端电极的性能来选择合适的p型硅材料. 关键词： 铟锡氧化物 非晶硅 微晶硅 计算机模拟     

Incorporation of a liquid crystal to enhance the luminescence properties of Langmuir–Blodgett films of OC1OC6-PPV

The control of molecular architecture provided by the Langmuir–Blodgett (LB) method allows one to obtain enhanced luminescence properties in polymer films, which can be exploited in polymer light emitting diodes (PLEDs). In this study, we show that incorporating a liquid crystal (LC) (PCH302/304) into poly-(2-methoxy-5-hexyloxy-p-phenylene-vinylene) (OC₁OC₆-PPV) in LB films leads to a 4-fold increase in photoluminescence and 2-fold increase in electroluminescence for (ITO/OC₁OC₆-PPV(LC5%)/Al) devices for emission at 585 nm, with the current vs. voltage (I vs. V) characteristics exhibiting a typical behavior of rectifying diode. The enhanced luminescence was attributed to an efficient separation of emitting OC₁OC₆-PPV units induced by the LC in the LB film, which were less ordered than LB films from neat OC₁OC₆-PPV.     

Ultraviolet photoelectron spectroscopy investigation of interface formation in an indium-tin oxide/fluorocarbon/organic semiconductor contact

It has been demonstrated that hole-injection in organic light-emitting devices (OLEDs) can be enhanced by inserting a UV-illuminated fluorocarbon (CF_x) layer between indium-tin oxide (ITO) and organic hole-transporting layer (HTL). In this work, the process of interface formation and electronic properties of the ITO/CF_x/HTL interface were investigated with ultraviolet photoelectron spectroscopy. It was found that UV-illuminated fluorocarbon layer decreases the hole-injection barrier from ITO to α-napthylphenylbiphenyl diamine (NPB). Energy level diagrams deduced from the ultraviolet photoelectron spectroscopy (UPS) spectra show that the hole-injection barrier in ITO/UV-treated CF_x/NPB is the smallest (0.46 eV), compared to that in the ITO/untreated CF_x/NPB (0.60 eV) and the standard ITO/NPB interface (0.68 eV). The improved current density-voltage (I-V) characteristics in the UV-treated CF_x-coated ITO contact are consistent with its smallest barrier height.     

Two-layer hybrid anti-reflection film prepared on the plastic substrates

Two-layer hybrid anti-reflection (AR) and anti-static (AS) films are formed on the flexible substrates such as polyethylene terephthalate and triacetyl cellulose. The AR layer is composed of two layers; indium-tin oxide (ITO) and thermo-curable fluorinated alkoxy silane compounds (JN7) made by DC magnetron roll sputtering and direct wet coating method, respectively. The polymer for an upper layer was used as the low refractive index (n_F=1.35) material, while ITO was chosen as the high refractive index (n_ITO=2.0) material with good electrical conductivity. The AR property (R<0.8%) and the AS and electromagnetic shielding properties (i.e. the electrical conductivity) were almost the same as the conventional transparent multi-layer AR system.     

Application of crystalline silicon surface oxidation to silicon heterojunction solar cells

We study the effect of ultra-thin oxide (SiO_x) layers inserted at the interfaces of silicon heterojunction (SHJ) solar cells on their open-circuit voltage (V_OC). The SiO_x layers can be easily formed by dipping c-Si into oxidant such as hydrogen peroxide (H₂O₂) and nitric acid (HNO₃). We confirm the prevention of the undesirable epitaxial growth of Si layers during the deposition of a-Si films by the insertion of the ultra-thin SiO_x layers. The formation of the SiO_x layers by H₂O₂ leads to better effective minority carrier lifetime (τ_eff) and V_OC than the case of using HNO₃. c-Si with the ultra-thin SiO_x layers formed by H₂O₂ dipping, prior to deposition of a-Si passivation layers, can have high implied V_OC of up to ∼0.714 V.     

Low-temperature synthesis of conducting boron-doped nanocrystalline silicon oxide thin films as the window layer of solar cells

Low-temperature synthesis of highly transparent conducting B-doped (p-type) nc-SiO_X:H films has been pursued by 13.56 MHz plasma-CVD, using a combination of SiH₄, CO₂ and B₂H₆, diluted by H₂ and He. Higher substrate temperature (T_S) encourages nanocrystallization in B-doped nc-SiO_X:H network by reducing bonded H-content, while bonded O-content also reduces simultaneously. At optimized T_S = 150 °C, p–nc-SiO_X:H film having an optical band gap ~1.98 eV, high conductivity ~0.18 S cm⁻¹, has been obtained via dopant-induced escalation of the electrically active carriers at a deposition rate ~5.3 nm/min. The p–nc-SiO_X:H film appears as a promising window layer for the top sub-cell of multi-junction silicon solar cells. A single-junction nc-Si:H based p-i-n solar cell of efficiency (η) ~7.14% with a current-density (J_SC) ~14.18 mA/cm², reasonable fill-factor (FF) ~66.2% and open-circuit voltage (V_OC) ~0.7606 V has been fabricated, using the optimum p-type nc-SiO_X:H as the window layer deposited at T_S = 150 °C.     

Synthesis of SnS thin films via galvanostatic electrodeposition and fabrication of CdS/SnS heterostructure for photovoltaic applications

In this work SnS thin films were electrochemically deposited on ITO coated glass substrate by galvanostatic electrodeposition at different pH of the plating bath. The working electrode used in these studies was low cost high purity graphite rod. The as-deposited films were found to be smooth, pinhole free and well adherent to the substrate with no powdery deposition. EDX measurements revealed that all the SnS films were non-stoichiometric in nature with variation from Sn-excess to S-excess compositions. XRD pattern showed that all the SnS thin films had orthorhombic polycrystalline structure. The direct bandgaps of all the films were found to be in the range 1.54-1.58 eV. ITO/SnS/In structure exhibited linear current-voltage characteristics, establishing the ohmic nature of both ITO/SnS and SnS/In junctions. Furthermore, SnS layer was grown on CdS film using electrodeposition technique. The heterostructure ITO/CdS/SnS/In was characterized under dark and illuminated conditions. From forward biased I-V characteristics several junction parameters like barrier height, diode ideality factor and series resistance of the heterostructure were extracted using Cheung model.     

Surface photovoltage and XPS studies of electronic structure in defective nickel oxide powders

Surface photovoltage measurements of polycrystalline powder samples of nickel oxide have revealed differences in band bending (V_s) related to the defect concentrations of the oxide. The powders prepared at 700°C and 1450°C in air consist of small single crystals with low concentrations ( <10⁹ cm⁻²) of extended defects, but considerably different nickel vacancy concentrations. The defective NiO (700°C) gave V_s = 760 mV and the equilibrated NiO (1450°C) V_s = 230 mV under UV illumination, possibly due to Fermi level pinning of the Ni 3d⁸ band near V′_Ni and V″_Ni, respectively. These results are consistent with values of V_s (i.e. 630 and 240 mV, respectively) for these two samples obtained previously from XPS measurements of the dependence of surface charging on temperature. A visible transition at ≈ 2.5 eV, giving Δφ = 135 mV, is also found in the equilibrated NiO (1450°C) sample but not in the defective NiO (700°C) sample. The results are discussed in relation to other work on the electronic band structure and surface states of nickel oxide.     

Effects of Ga contents on properties of CIGS thin films and solar cells fabricated by co-evaporation technique

This study examined the effects of Ga content in the CIGS absorber layer on the properties of the corresponding thin films and solar cells fabricated using a co-evaporation technique. The grain size of CIGS films decreased with increasing Ga content presumably because Ga diffusion during the 2nd stage of the co-evaporation process is more difficult than In diffusion. The main XRD peaks showed a noticeable shift to higher diffraction angles with increasing Ga content, which was attributed to Ga atoms substituting for In atoms in the chalcopyrite structure. Band gap energy and the net carrier concentration of CIGS films increased with Ga/(In + Ga) ratios. Regarding the solar cell parameters, the short circuit current density (J_SC) decreased linearly with Ga/(In + Ga) ratios due to the lack of absorption in the long-wavelength portion of the spectrum, while the open circuit voltage (V_OC) increase with those. However, V_OC values at high Ga/(In + Ga) regions (>0.35) was far below than those extrapolated from the low Ga contents regions, finally resulting in an optimum Ga/(In + Ga) ratio of 0.28 where the solar cell showed the highest efficiency of 15.56% with V_OC, J_SC and FF of 0.625 V, 35.03 mA cm⁻² and 0.71, respectively.     

Potential‐induced optimization of ultra‐thin rear surface passivated CIGS solar cells

Ultra‐thin Cu(In,Ga)Se₂ (CIGS) solar cells with an Al₂O₃ rear surface passivation layer between the rear contact and absorber layer frequently show a “roll‐over” effect in the J–V curve, lowering the open circuit voltage (V_OC), short circuit current (J_SC) and fill factor (FF), similar to what is observed for Na‐deficient devices. Since Al₂O₃ is a well‐known barrier for Na, this behaviour can indeed be interpreted as due to lack of Na in the CIGS absorber layer. In this work, applying an electric field between the backside of the soda lime glass (SLG) substrate and the SLG/rear‐contact interface is investi‐gated as potential treatment for such Na‐deficient rear surface passivated CIGS solar cells. First, an electrical field of +50 V is applied at 85 °C, which increases the Na concentration in the CIGS absorber layer and the CdS buffer layer as measured by glow discharge optical emission spectroscopy (GDOES). Subsequently, the field polarity is reversed and part of the previously added Na is removed. This way, the J –V curve roll‐over related to Na deficiency disappears and the V_OC (+25 mV), J_SC(+2.3 mA/cm²) and FF (+13.5% absolute) of the rear surface passivated CIGS solar cells are optimized. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)