Bridging the Buried Interface with Piperazine Dihydriodide Layer for High Performance Inverted Solar Cells.

Given that it is closely related to perovskite crystallization and interfacial trap densities, buried interfacial engineering is crucial for creating effective and stable perovskite solar cells. Compared with the in-depth studies on the defect at the top perovskite interface, exploring the defect of the buried side of perovskite film is relatively complicated and scanty owing to the non-exposed feature. Herein, the degradation process is probed from the buried side of perovskite films with continuous illumination and its effects on morphology and photoelectronic characteristics with a facile lift-off method. Additionally, a buffer layer of Piperazine Dihydriodide (PDI2 ) is inserted into the imbedded bottom interface. The PDI2 buffer layer is able to lubricate the mismatched thermal expansion between perovskite and substrate, resulting in the release of lattice strain and thus a void-free buried interface. With the PDI2 buffer layer, the degradation originates from the growing voids and increasing non-radiative recombination at the imbedded bottom interfaces are suppressed effectively, leading to prolonged operation lifetime of the perovskite solar cells. As a result, the power conversion efficiency of an optimized p-i-n inverted photovoltaic device reaches 23.47% (with certified 23.42%) and the unencapsulated devices maintain 90.27% of initial efficiency after 800 h continuous light soaking.

Improved fill factor in inverted planar perovskite solar cells with zirconium acetate as the hole-and-ion-blocking layer.

Planar perovskite solar cells (PSCs) have gained great interest due to their low-temperature solution preparation and simple process. In inverted planar PSCs, an additional buffer layer is usually needed on the top of the PCBM electron-transport layer (ETL) to enhance the device performance. In this work, we used a new buffer layer, zirconium acetate (Zr(Ac)4). The inclusion of the Zr(Ac)4 buffer layer leads to the increase of FF from ∼68% to ∼79% and PCE from ∼14% to ∼17% in the planar PSCs. The UPS measurement indicates that the Zr(Ac)4 layer has a low HOMO level of -8.2 eV, indicating that the buffer layer can act as a hole-blocking layer. Surface morphology and surface chemistry investigations reveal that the elements I, MA and Pb can diffuse across the PCBM ETL, damaging the device performance. The covering Zr(Ac)4 molecules fill in the pinholes of the PCBM layer and effectively block the ions/molecules of the perovskite from diffusion across the ETL. The resulting more robust PCBM/Zr(Ac)4 ETL leads to weaker ionic charge accumulation and lower diode leakage current. The double role of hole-and-ion blocking of the Zr(Ac)4 layer explains the improved FF and PCE in the PSCs.

Correction: Improved fill factor in inverted planar perovskite solar cells with zirconium acetate as the hole-and-ion-blocking layer.

Correction for 'Improved fill factor in inverted planar perovskite solar cells with zirconium acetate as the hole-and-ion-blocking layer' by Xuewen Zhang et al., Phys. Chem. Chem. Phys., 2018, 20, 7395-7400.

Electron transporting organic materials with an exceptional large scale homeotropic molecular orientation.

An electron transporting anthraquinone derivative demonstrated a stable large-scale homeotropic alignment on an open substrate surface, which substantially improved its charge carrier mobility. The electron mobility (µ(E)) increased by two orders of magnitude from 3.2 × 10(-4) cm(2) V(-1) s(-1) for the film without alignment to 1.2 × 10(-2) cm(2) V(-1) s(-1) for the homeotropically aligned film. A distinct enhancement in the UV absorption spectra of the films around the short wavelength range was observed to be associated with the molecular alignments. These alignments are less sensitive to the substrate under test. The anchoring force of the columnar stacks appears to be related to the nature of the material associated with the strong interaction between the molecules and substrate interface.

Raman and Visible-Near Infrared Spectra of Cu(InGa)Se2 Films.

Cu(InxGa1-x)Se2(CIGS) precursor films were prepared on ITO glass with potentiostatic electrodeposition. High quality CIGS films were obtained by selenization of the precursor films at high temperature in tubular furnace full of argon gas. X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-Vis-NIR spectroscopy were used to characterize the structure, morphology, composition and Vis-NIR absorption of CIGS films, respectively. XRD results show the selenized CIGS films have a preferential orientation (112) with average crystallite of 24.7 nm. Raman spectroscopy reveals that the CIGS films are pure quaternaryphases with chalcopyrite structure, and without binary or ternary phases in the films. Vis-NIR measurements determine that the bandgap of CIGS increases with the increase of Ga concentration in the film. When the Ga concentration is 5.41%, its bandgap is about 1.11 eV, and the calculated ratio of Ga to (Ga+In) is 16.3%, which is less than the ratio of Ga to (Ga+In), 21.4%, measured by SEM. This indicates that crystallinity of CIGS filmsneeds to be further improved. All the measurements demonstratethat optimum ITO/CIGS has a promising application in bifacial solar cells. In this paper, we provide a newmethodtoelectrodeposit low cost CIGS precursor films and a new method forselenization ofthe precursor films at high temperature. As a result, theuniform and compact CIGS films with good adhesion on ITO are successfully fabricated by these methods. The above characterization show that we have obtained CIGS films with high crystallinity, near stoichiometry, few impurity phases and superior light absorption. Electrodeposition, like magnetron sputtering, is very suitable for large-scale industrial production. The research work in this paper is therefore important and considerable to massive production of electrodeposition of CIGS films.

Raman and Visible-Near Infrared Spectra of Cu(InGa)Se2 Films.

Cu(InxGa1-x)Se2(CIGS) precursor films were prepared on ITO glass with potentiostatic electrodeposition. High quality CIGS films were obtained by selenization of the precursor films at high temperature in tubular furnace full of argon gas. X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-Vis-NIR spectroscopy were used to characterize the structure, morphology, composition and Vis-NIR absorption of CIGS films, respectively. XRD results show the selenized CIGS films have a preferential orientation (112) with average crystallite of 24.7 nm. Raman spectroscopy reveals that the CIGS films are pure quaternaryphases with chalcopyrite structure, and without binary or ternary phases in the films. Vis-NIR measurements determine that the bandgap of CIGS increases with the increase of Ga concentration in the film. When the Ga concentration is 5.41%, its bandgap is about 1.11 eV, and the calculated ratio of Ga to (Ga+In) is 16.3%, which is less than the ratio of Ga to (Ga+In), 21.4%, measured by SEM. This indicates that crystallinity of CIGS filmsneeds to be further improved. All the measurements demonstratethat optimum ITO/CIGS has a promising application in bifacial solar cells. In this paper, we provide a newmethodtoelectrodeposit low cost CIGS precursor films and a new method forselenization ofthe precursor films at high temperature. As a result, theuniform and compact CIGS films with good adhesion on ITO are successfully fabricated by these methods. The above characterization show that we have obtained CIGS films with high crystallinity, near stoichiometry, few impurity phases and superior light absorption. Electrodeposition, like magnetron sputtering, is very suitable for large-scale industrial production. The research work in this paper is therefore important and considerable to massive production of electrodeposition of CIGS films.

Dynamic interface charge governing the current-voltage hysteresis in perovskite solar cells.

The accumulation of mobile ions causes space charge at interfaces in perovskite solar cells. There is a slow dynamic process of ion redistribution when the bias is changed. The interface charge affects band bending and thus the photocurrent of the solar cells. Consequently the dynamic process of the interface charge governs the current-voltage hysteresis. Very low interface charge density leads to hysteresis-free devices.

In situ observation of thermal-driven structural transitions of a ß-NaYF4 single nanoparticle aided with correlative cathodoluminescence electron microscopy.

NaYF4 systems have been widely studied as up-conversion host matrices, and their phase transitions are flexible and worth investigating in great detail. Herein, the evolution of morphology and crystal structure of a Eu3+-doped ß-NaYF4 single nanoparticle heated in an air atmosphere was investigated using in situ transmission electron microscopy (TEM). The annealing process revealed that the hexagonal ß-NaYF4 phase undergoes sequential transformations into high-temperature cubic phases at both 350 °C and 500 °C. The emission characteristics of Eu3+ in the single nanoparticle after heating treatment were also analyzed using Correlative Cathodoluminescence Electron Microscopy (CCLEM). The results of CCLEM suggest a gradual decrease followed by a subsequent increase in structural symmetry. A comprehensive spectroscopic and structural analysis encapsulates the entire transformation process as NaYF4 → YOF → Y2O3. In situ energy dispersive spectroscopy analyses (EDS) support this reaction process. The aforementioned technique yields correlative lattice-resolved TEM images and nanoscale spectroscopic information, which can be employed to assess the structure-function relationships on the nanoscale.

Rinsing Intermediate Phase Strategy for Modulating Perovskite Crystal Growth and Fabricating Highly Efficient and Stable Inverted Solar Cells.

During the fabrication of metal halide perovskite films, polycrystal growth and maturation are largely influenced by high-temperature annealing. However, this process would cause crystals to expand or contract at various depths in the film, leading to microscopic structural deformation and further altering the optoelectronic properties of the perovskite film. Herein, we propose an additional rinsing intermediate phase (RIP) strategy that involves precovering the perovskite film surface with a mixed organic layer prior to high-temperature annealing. The lattice distortion of the microscopic structure brought on by the driving force of the heat field is greatly reduced as a result of the modulation for the upper surface of the intermediate phase film by the rinse layer. This strategy can prepare films with high crystallinity, minor residual stresses, fewer defects, and overall film uniformity. As a result, the modified inverted perovskite solar cell (PSC) achieves a certified power conversion (PCE) of 22.76%. Meanwhile, since the rinse layer is involved in the entire crystal formation process, ion migration and buildup in the device are prevented between the interface. Consequently, the devices still retain 90% of their initial PCE, demonstrating enhanced operational stability after 500 h of operation. This method of modulating the intermediate perovskite state offers an investigation into improving the traditional method of making thin films, which is anticipated to hasten the commercialization of perovskite photovoltaics.

[Ideal white organic light emitting devices based on doped PFO].

In the present paper, the electroluminescence emission from a doped polymer layer was studied. The blue fluorene PFO was used as the host material and MEH-PPV as the dopant. The spectral characteristics and color stability of the emission on CIE chromaticity diagram were investigated. With the doping ratio of 2.5 Wt%, the device shows turn-on voltage of 3 V, and color coordinates of (0.33, 0.33) at 11 V. The color coordinates of the device was stable with changing voltage in a large range, and located in the ideal white area in the range of 5-20 V voltage.

[Comparative study on thin films of cadmium sulfide prepared by chemical bath deposition and radio frequency magnetron sputtering].

Thin films of cadmium sulfide (CdS) were prepared with ammonium chloride, cadmium chloride, potassium hydroxide and thiourea by chemical bath deposition (CBD). For comparison, CdS films were also deposited by radio frequency (RF) magnetron sputtering, using CdS and argon as a target and reactive gas, respectively. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ultraviolet-visible spectroscopy. The results show that the CdS films prepared by the above two methods have (002) orientation, the CdS films deposited by RF magnetron sputtering are more compact and much smoother than those prepared by CBD, and have lager crystalline size of about 20-30 nm. The CdS films prepared by CBD have smaller crystalline size and more defects. The properties of CdS thin films prepared by RF magnetron sputtering are totally superior to those of CdS films by CBD, but the optical transmittance of CdS thin films at short wavelength is an exception. The energy gap of CdS films prepared by the two methods are all in the range of 2.3-2.5 eV.

Electronic and Optical Properties of van der Waals Heterostructures Based on Two-Dimensional Perovskite (PEA)2PbI4 and Black Phosphorus.

Combining two-dimensional (2D) perovskites with other 2D materials to form a van der Waals (vdW) heterostructure has emerged as an intriguing way of designing electronic and optoelectronic devices. The structural, electronic, and optical properties of the 2D (PEA)2PbI4/black phosphorus (BP) [PEA:(C4H9NH3)+] vdW heterostructure have been investigated using first-principles calculations. We found that the (PEA)2PbI4/BP heterostructure shows a high stability at room temperature. It is demonstrated that the (PEA)2PbI4/BP heterostructure exhibits a type-I band arrangement with high carrier mobility. Moreover, the band gap and band offset of (PEA)2PbI4/BP can be effectively modulated by an external electric field, and a transition from semiconductor to metal is observed. The band edges of (PEA)2PbI4 and BP in the (PEA)2PbI4/BP heterostructure, which show significant changes with the external electric field, provide further support. Furthermore, the BP layers can enhance the light absorption of the (PEA)2PbI4/BP heterostructures. Our results indicate that the 2D perovskite and BP vdW heterostructures are competitive candidates for the application of low-dimensional photovoltaic and optoelectronic devices.

Optimization of a SnO2-Based Electron Transport Layer Using Zirconium Acetylacetonate for Efficient and Stable Perovskite Solar Cells.

SnO2 is a promising material for use as an electron transfer layer (ETL) in perovskite photovoltaic devices due to its suitable energy level alignment with the perovskite, high electron mobility, excellent optical transmission, and low-temperature processability. The development of high-quality SnO2 ETLs with a large coverage and that are pinhole-free is crucial to enhancing the performance and stability of the perovskite solar cells (PSCs). In this work, zirconium acetylacetonate (ZrAcac) was introduced to form a double-layered ETL, in which an ideal cascade energy level alignment is obtained. The surface of the resulting ZrAcac/SnO2 (Zr-SnO2) layer is compact and smooth and had a high coverage of SnO2, which enhances the electron extractability, improves ion blocking, and reduces the charge accumulation at the interface. As a result, the fill factor (FF, 80.99%), power conversion efficiency (PCE, 22.44%), and stability of the Zr-SnO2 device have been significantly improved compared to PSCs with only a SnO2 ETL. In addition, the PCE of the Zr-SnO2 device is maintained at more than 80% of the initial efficiency after 500 h of continuous illumination.

Exploring reversible quenching of fluorescence from a pyrazolo[3,4-b]quinoline derivative by protonation.

Pyrazolo[3,4-b]quinoline derivatives are reported to be highly efficient organic fluorescent materials suitable for applications in light-emitting devices. Although their fluorescence remains stable in organic solvents or in aqueous solution even in the presence of H(2)O, halide salts (LiCl), alkali (NaOH) and weak acid (acetic acid), it suffers an efficient quenching process in the presence of protic acid (HCl) in aqueous or ethanolic solution. This quenching process is accompanied by a change in the UV spectrum, but it is reversible and can be fully recovered. Both steady-state and transient fluorescence spectra of 1-phenyl-3,4-dimethyl-1H-pyrazolo-[3,4-b]quinoline (PAQ5) during quenching are measured and analyzed. It is found that a combined dynamic and static quenching mechanism is responsible for the quenching processes. The ground-state proton-transfer complex [PAQ5H(+)] is responsible for static quenching. It changes linearly with proton concentration [H(+)] with a bimolecular association constant K(S)=1.95 M(-1) controlled by the equilibrium dissociation of HCl in ethanol. A dynamic quenching constant K(D)=22.4 M(-1) is obtained by fitting to the Stern-Volmer equation, with a bimolecular dynamic quenching rate constant k(d)=1.03x10(9) s(-1) M(-1) under ambient conditions. A change in electron distribution is simulated and explains the experiment results.

High-Performance Photovoltaic Materials Based on the Superlattice Structures of Organic-Inorganic Halide Perovskite and Superhalogen Hybrid Perovskite.

The use of superlattice structures is an attractive strategy for expanding the family of perovskites and obtaining excellent optoelectronic materials. Mixing of cations and partial replacement of halogens by superhalogens are advantageous for improving the stability and optoelectronic properties of hybrid perovskites. Herein, the superlattice structures of the (CsPbI3)n/MAPbI2BF4, (FAPbI3)n/MAPbI2BF4, (MAPbI3)n/CsPbI2BF4, and (FAPbI3)n/CsPbI2BF4 hybrid perovskites were investigated using first-principles density functional theory calculations. The results show that these superlattice structures have tunable direct band gaps and small effective electron and hole masses. Additionally, the charge densities for the valence band maximum and conduction band minimum states are located in different regions of the superlattices. Suggesting that these structures are type-II superlattices that show greatly reduced electron-hole recombination rates. Excellent optical absorption properties for all of perovskite superlattices and the calculated power conversion efficiency of 22.77% for the single-junction solar cells based on the (FAPbI3)3/MAPbI2BF4 and (FAPbI3)3/CsPbI2BF4 perovskites were obtained.

Secondary Grain Growth in Organic-Inorganic Perovskite Films with Ethylamine Hydrochloride Additives for Highly Efficient Solar Cells.

The grain boundaries of perovskite polycrystalline are regarded as a defect region that not only provides carrier recombination sites but also introduces device degradation pathways. Efforts to enlarging the grain size of a perovskite film and reducing its grain boundary are crucial for highly efficient and stable perovskite solar cells (PSCs). Some effective methods that facilitate grain growth are postdeposition thermal annealing and solvent vapor annealing. However, a detailed understanding of grain growth mechanisms in perovskite films is lacking. In this study, perovskite films were prepared by adding ethylamine hydrochloride (EACl) to the precursor solution. This additive strategy promotes a new grain growth mode, secondary grain growth, in perovskite films. Secondary grain growth leads to much larger grains with a high crystallographic orientation. These excellent properties lead to reduced grain boundaries and the densities of boundary defects. The improved film quality results in a prolonged charge-carrier lifetime and a significantly enhanced power conversion efficiency (PCE). Compared with the 18.42% PCE of the control device, the PCE of the device with EACl additives reaches 21.07%.

Electronic and optical absorption properties of organic-inorganic perovskites as influenced by different long-chain diamine molecules: first-principles calculations.

Organic-inorganic perovskites have demonstrated significant promise as photovoltaic materials due to their excellent photoelectric properties. However, monoamino three-dimensional (3D) perovskites, such as CH3NH3PbI3 (MAPbI3) and NH2CHNH2PbI3 (FAPbI3) exhibit low thermal and chemical stability, leading to low device durability. As such, we sought to address this problem by evaluating the performance of five diamino-3D perovskites with different molecule chain lengths, including NH3(CH2)2NH3PbI4 (EDAPbI4), NH3(CH2)3NH3PbI4 (DPAPbI4), NH3(CH2)4NH3PbI4 (BDAPbI4), NH3(CH2)5NH3PbI4 (PDAPbI4), and NH3(CH2)6NH3PbI4 (HDAPbI4), as well as one monoamino-2D perovskite, (CH3(CH2)3NH3)2PbI4 (BA2PbI4) using first-principles calculations. We analyzed the geometries, formation energies, electronic structures, and optical absorption properties of each of these materials. We determined the composition of the conduction and valence bands and analyzed the charge transfer between the inorganic layer and organic molecules. The transport characteristics of the electrons in the different directions were analyzed by calculating the effective mass in different directions. Based on these results, BDAPbI4 was predicted to exhibit the best photovoltaic performance, as well as demonstrating a light effective mass of the electrons and holes, a reduced bandgap, and a large optical absorption, compared to the other perovskites assessed in this study.

[Investigation on electroluminescence of MEH-PPV/ZnSe nanocomposite device].

ZnSe nanocrystals were synthesized in aqueous solution by using mercapto-acetate acid as stabilizer. Products were characterized by X-ray diffraction patterns (XRD) and X-ray photoelectron spectra (XPS). A surfactant was used to transfer the nanocrystals from the aqueous solution to organic solvent, so that ZnSe and MEH-PPV could be mixed sufficiently and were used as an emitting layer in a multilayered electroluminescence device: Glass/ITO/MEH-PPV : ZnSe /BCP/Alq3/LiF/Al. A comparison between absorption spectra and photoluminescence spectra of ZnSe nanocrystals and MEH-PPV thin film exhibits an effective energy transfer from ZnSe nanocrystals to MEH-PPV, which is one reason for the existing difference between photoluminescence spectrum and electroluminescence spectrum of MEH-PPV : ZnSe nanocomposite film. The recombination mechanism of the nanocomposite film under photoexcitation and electric injection was discussed respectively. The authors investigated the photo- and electroluminescence properties of the device, and found that the EL intensity of ZnSe nanocrystals increased with the applied voltages. The I-V characteristic of this device is similar to that of a classic diode.

[Investigation on performance enhancement of bulk heterojunction organic solar cells].

Four organic solar cells with the different structures were fabricated. The structures are Device1 ITO/LiF/PEDOT: PSS/MEH-PPV/C60/Al, Device 2 ITO/PEDOT : PSS/MEH-PPV/C60/Al, Device 3 ITO/LiF/PEDOT : PSS/MEH-PPV : C60/C60/Al and Device 4 ITO/PEDOT : PSS/MEH-PPV : C60/C60/Al. Then we compared the current-voltage (I-V) characteristics of these devices and found that the insertion of a thin LiF layer between the ITO electrode and the PEDOT : PSS layer resulted in much improved device performance. The short-circuit current density (J(sc)) and fill factor (FF) of Device 1 were enhanced by 74% and 31%, respectively as compared to those of Device 2. The short-circuit current density (J(sc)) of Device 3 is about 1.4 times as large as that of Device 4. The increased solar cell performance mostly can be attributed to the fact that the hole transport to the anode can be effectively suppressed by a thin LiF layer, and the thin LiF layer between the ITO electrode and the PEDOT: PSS layer can form better interface properties. Hence, such change in structure of solar cells improves the performance of the organic solar cells effectively.

[A new measurement method of time-resolved spectrum].

A new method for measuring time-resolved spectrum (TRS) is brought forward. Programming with assemble language controlled the micro-control-processor (AT89C51), and a kind of peripheral circuit constituted the drive circuit, which drived the stepping motor to run the monochromator. So the light of different kinds of expected wavelength could be obtained. The optical signal was transformed to electrical signal by optical-to-electrical transform with the help of photomultiplier tube (Hamamatsu 1P28). The electrical signal of spectrum data was transmitted to the oscillograph. Connecting the two serial interfaces of RS232 between the oscillograph and computer, the electrical signal of spectrum data could be transmitted to computer for programming to draw the attenuation curve and time-resolved spectrum (TRS) of the swatch. The method for measuring time-resolved spectrum (TRS) features parallel measurement in time scale but serial measurement in wavelength scale. Time-resolved spectrum (TRS) and integrated emission spectrum of Tb3+ in swatch Tb(o-BBA)3 phen were measured using this method. Compared with the real time-resolved spectrum (TRS). It was validated to be feasible, credible and convenient. The 3D spectra of fluorescence intensity-wavelength-time, and the integrated spectrum of the swatch Tb(o-BBA)3 phen are given.