Organic Photovoltaic Cells with Improved Performance Using Bathophenanthroline as a Buffer Layer

采用Bphen作为缓冲层,研究Bphen处在电子受体材料C₆₀和阴极Ag之间对有机薄膜光伏电池(OPV)性能的影响．通过引入2.5nm厚的Bphen,在100 mW/cm²光照下,CuPc/C₆₀结构的器件效率从0.87%提高到2.25%． 对光生电流-电压的分析表明,Bphen缓冲层可以有效的提高电子从C₆₀层向Ag阴极的传输能力和平衡器件中载流子的传输能力．系统研究了Bphen厚度对OPV器件性能的影响,发现随着Bphen厚度的增加,电导率的降低是限制器件性能的主要原因．此外,采用紫外-可见光分光光度计测试了器件的吸收光谱,发现Bphen缓冲层可以增强CuPc/C₆₀的光吸收能力．     

Stable organic solar cells employing MoO3-doped copper phthalocyanine as buffer layer

A stable organic solar cell with structure of ITO/buffer/donor/acceptor/cathode is presented. A thin layer (5 nm) of MoO₃-doped CuPc is adopted as the buffer in CuPc/C₆₀ organic heterojunction photovoltaic (PV) solar cells, resulting in two times longer lifetime. The surface morphology of buffer layer plays a decisive role in improving the stability.     

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.     

Photocurrent analysis of organic photovoltaic cells based on CuPc/C60 with Alq3 as a buffer layer

The performance of an organic photovoltaic(OPV) cell based on copper phthalocyanine CuPc/C60 with a tris(8-hydroxyquinolinato) aluminum(Alq3) buffer layer has been investigated.It was found that the power conversion efficiency of the device was 1.51% under illumination with an intensity of 100 mW/cm2,which was limited by a squareroot dependence of the photocurrent on voltage.The photocurrent-optical power density characteristics showed that the OPV cell had a significant space-charge limited photocurrent with a varied saturation voltage and a three quarters power dependence on optical power density.Also,the absorption spectrum was measured by a spectrophotometer,and the results showed that the additional Alq3 layer has a minor effect on photocurrent generation.     

The electronic structure of GaP (110) and Cu-Phthalocyanine overlayers studied by ellipsometry

Ellipsometric spectroscopy in the spectral range 1.4 eV<<4 eV is used to study cleaved GaP (110) surfaces after adsorption of hydrogen and oxygen and after deposition of Cu-Phthalocyanine (CuPc) molecules. The adsorption of gases and of CuPc induces band bending changes which are derived from changes of the optical constants in the space charge layer due to an electric field effect. For the clean surface, furthermore, information is obtained about electronic surface states. CuPc overlayers with thicknesses below one monolayer exhibit an optical absorption which suggests a chemisorption interaction through the macrocyclic-system of the Pc-molecules.     

4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺掺杂MoOx作为空穴传输层对有机太阳电池性能的影响

通过采用4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺 (m-MTDATA)掺入MoO_x作为器件的空穴传输层来提高酞菁铜(CuPc)/C₆₀小分子 有机太阳电池的效率. 采用真空蒸镀的方法制备了一系列器件, 其中结构为铟锡氧化物 (ITO)/m-MTDATA:MoO_x(3:1)(30 nm)/CuPc(20 nm)/C₆₀(40 nm)/4,7-二苯 基-1,10-菲罗啉 (Bphen)(8 nm)/LiF(0.8 nm)/Al(100 nm)的器件, 在AM1.5 (100 mW/cm²)模拟太阳光的照射条件下, 开路电压V_oc=0.40 V, 短路电流J_sc=6.59 mA/cm², 填充因子为0.55, 光电转换效率达1.46%, 比没有空穴传输层的器件ITO/CuPc(20 nm)/C₆₀(40 nm)/Bphen(8 nm)/LiF(0.8 nm)/Al(100 nm) 光电转换效率提高了38%. 研究表明, 加入m-MTDATA:MoO_x(3:1)(30 nm)空穴传输层减小了有机层和ITO电极之间的接触电阻, 从而减小了整个器件的串联电阻, 提高了器件的光电转换效率.     

Orientation-dependent ionization potential of CuPc and energy level alignment at C60/CuPc interface

The electronic structure evolution of interfaces of fullerene (C₆₀) with copper phthalocyanine (CuPc) on highly oriented pyrolytic graphite (HOPG) and on native silicon oxide has been investigated with ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. The LUMO edge of C₆₀ was found to be pinned at the interface with CuPc on SiO₂. A substantial difference in the electron affinity of CuPc on the two substrates was observed as the orientation of CuPc is lying flat on HOPG and standing up on SiO₂. The ionization potential and electron affinity of C₆₀ were not affected by the orientation of CuPc due to the spherical symmetry of C₆₀ molecules. We observed band bending in C₆₀ on the standing-up orientation of CuPc molecules, while the energy levels of C₆₀ on the flat-lying orientation of CuPc molecules were observed to be flat. The observation points to a dependence of photoexcited charge transfer on the relative molecular orientation at the interface.     

有机光伏器件的激子阻挡层的工作机制(英文)

研究了有机光伏器件的激子阻挡层(EBL)的工作机制,对于像bathocuproine(BCP)和bathophenanthroline(Bphen)这样的电子阻挡层,主要利用的是他们的强的电子传输能力。而像copper phthalocyanine(CuPc)作为电子阻挡层则可利用它大的空穴传输能力和较低的HOMO能级。我们还发现当CuPc厚度为10～30nm时,CuPc表现出比BCP和Bphen高的EB特性。文中还较为详细地叙述了CuPc作为电子阻挡层的运行机制。     

Photovoltaic properties of a heterojunction based on copper phthalocyanine films on the surface of polycrystalline cadmium sulfide

The photovoltaic effect has been detected and studied in thin-film structures based on thermally deposited 200-nm-thick copper phthalocyanine (CuPc) films on the surface of polycrystalline CdS. The structures under study demonstrate the linear current-voltage characteristics at external electric fields to 3.5 × 10⁴ V/cm. Two components of the photovoltage of different signs have been revealed when the sample is illuminated in the wavelength range from 350 to 700 nm. The first component has the positive sign on the CuPc film side and is observed when using the radiation with a wavelength lesser than 500 nm, i.e., in conditions of predominant absorption of the radiation in the CdS layer. The second component has the negative sign on the CuPc film side and is observed when using the radiation with a wavelength in the range from 500 to 570 nm, corresponding to the spectral region of the absorption edge of the CuPc films. The dependences of the photovoltage on the radiation intensity studied in the range from 5 × 10¹² to 10¹⁴ photons cm^?2 s^?1 are different in the cases of the two detected components. Mechanisms of generation of the photovoltage components associated with a change in the band bending during photogeneration of charge carriers in the region of space charge in CdS and a change in conditions of the charge transfer in the interfacial CuPc/CdS region during the radiation absorption in the CuPc film have been proposed.     

Low-temperature scanning tunneling microscopy and near-edge X-ray absorption fine structure investigation of epitaxial growth of F<Subscript>16</Subscript>CuPc thin films on graphite

Low-temperature scanning tunneling microscopy (LT-STM) and near-edge X-ray absorption fine structure (NEXAFS) measurements are used to study the epitaxial growth and molecular orientation of organic thin films of copper hexadecafluorophthalocyanine (F₁₆CuPc) on highly oriented pyrolytic graphite (HOPG). Our results show that F₁₆CuPc molecules lie flat on HOPG up to 5 nm thickness, stabilized by interfacial and interlayer π–π interactions. LT-STM experiments reveal the coexistence of two different in-plane orientations of the F₁₆CuPc monolayer on HOPG. On the second layer of F₁₆CuPc on HOPG, however, all F₁₆CuPc molecules possess the same in-plane orientation.     

Fluorescence investigations of pure and mixed evaporated dye layers

Fluorescence spectroscopy is used to investigate energy transfer processes in evaporated layers consisting of several different dyes. In this study films ofN,N-dimethylperylene-3,49,10-bis-dicarboximide (methylperylene pigment, MPP), coevaporated with copper phthalocyanine (CuPc) at varying ratios, and double layers of MPP and CuPc with different thicknesses are investigated. It is shown that energy transfer from MPP to CuPc occurs in both mixed and double layers. The energy transfer leads to a strong quenching of the MPP fluorescence and sensitized CuPc emission in the NIR region. The concentration dependence of the fluorescence quenching in mixed layers can be described by a Stern-Volmer plot. A simple model based on exciton diffusion between MPP molecules toward active quenching centers is used to determine the diffusion length.     

Effects of rubrene mixing on the electronic structures of donor/acceptor interface in organic photovoltaic device

Rubrene mixing has been shown to be an effect mean for enhancing both the open circuit voltage (Voc) and the short-circuit current (Jsc) of copper-phthalocyanine (CuPc)/fullerene (C₆₀) based solar cell. While the increase in Jsc can be readily explained by the additional rubrene absorption and the introduction of a bulk heterojunction; causes for Voc increase are still not clear. The energy offset between the highest occupied molecular orbital (HOMO) level of donor and the lowest unoccupied molecular orbital (LUMO) level of acceptor (HOMO_D-LUMO_A) at the CuPc/C₆₀ interface was found to increase substantially upon rubrene mixing in either side of the interface. As the HOMO_D-LUMO_A is generally considered to limit the Voc, its increase agrees well with the device results. Energy level bending and associated built-in electric fields were also observed and their possible implications to device performance are discussed.     

Electronic properties of the organic semiconductor hetero-interface CuPc/C60

We present a study of the electronic properties of the interface between the well-established molecular organic semiconductor copper phthalocyanine (CuPc) and the fullerite C₆₀ using photoelectron spectroscopy and the Kelvin-probe (KP) method. Upon deposition of CuPc on C₆₀, we found interfacial shifts of the vacuum level indicating the formation of a dipole layer, while band bending is found to be negligible. The interface dipole of 0.5 eV measured with KP is close to the difference between the work functions of bulk CuPc and C₆₀. No evidence for a chemical interaction at the interface is concluded from the absence of additional features in the core-level spectra at the earliest stages of deposition. The energy-level alignment diagram at the CuPc/C₆₀ interface is derived.     

Natural hybrid organic–inorganic photovoltaic devices

Natural hybrid organic–inorganic photovoltaic devices based on TiO₂ have been realized. Chlorophyll A (from anacystis nidulans algae), chlorophyll B (from spinach), carmic acid (from insect Coccus cacti L.), synthetic trans-β-carotene, natural fresh picked Morus nigra, and their mixtures have been used as an organic photo active layer to fabricate photovoltaic prototypes. In order to reduce the charge’s interfacial recombination, different thicknesses (5–45 nm) of Si layers, subsequently oxidized in air, were inserted between the TiO₂ and chlorophyll B. Scanning electron microscopy of TiO₂ and Si/TiO₂ systems shows the coexistence at least of four classes of nanoparticles of 60, 100, 150 and 250 nm in size. Auger electron spectroscopy of the Si L_2,3V V transition demonstrates the presence of silica and SiO_x suboxides. Photocurrent measurements versus radiation wavelength in the range 300–800 nm exhibit different peaks according to the absorption spectra of the organic molecules.All realized photovoltaic devices are suitable for solar light electric energy conversion. Those made of a blend of all organic molecules achieved higher current and voltage output. The Si/TiO₂-based devices containing chlorophyll B exhibited an enhanced photocurrent response with respect to those with TiO₂ only.     

薄膜生长速率对有机光伏器件性能的影响

采用真空热蒸发镀膜的方法制备了酞菁铜(CuPc)和富勒烯(C60)构成的平面异质结结构光伏器件,并初步研究了CuPc薄膜生长速率对器件光伏性能的影响,我们发现以较大薄膜生长速率制备的器件表现出较大的短路电流和能量转换效率。X射线衍射和原子力显微镜观察的结果表明生长速率较大的CuPc薄膜结晶相含量较少,薄膜结构较均匀、致密、平整,这可能使得CuPc薄膜激子扩散和载流子迁移特性得到提高,也可能改善其与C60受主薄膜和ITO阳极的接触,并有利于载流子的分离和收集,从而表现出较好的光伏特性。     

Organic solar cells with very high fill factor and voltage using tetrapropyl‐tetraphenyl‐diindenoperylene as green donor

We present 2,3,10,11‐tetrapropyl‐1,4,9,12‐tetraphenyl‐diindeno[1,2,3‐cd:1′,2′,3′‐lm]perylene (P4‐Ph4‐DIP) as new green donor for small molecule organic solar cells (SMOSC). P4‐Ph4‐DIP absorbs in the green spectral range of 490–580 nm and thus is a decisive building block towards broad coverage of the sun spectrum. SMOSC with P4‐Ph4‐DIP as donor and C₆₀ as blue‐absorbing acceptor display very high fill factors FF > 76% and open circuit voltages of 0.99 V, reaching η = 1.92% for 12 nm P4‐Ph4‐DIP. Current voltage and external quantum efficiency spectra suggest that an exciton diffusion length E_D < 20 nm is the main limiting factor. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrochemically intercalated MxC60 thin films in a solid state cell (M = Li,K): Optical and photoelectrochemical characterization

Solid-state electrochemical cells have been prepared with C₆₀ vacuum-evaporated thin films, a Li- or K-source counter electrode and a polymer PEO-LiClO₄ (PEO-KClO₄) electrolyte. The electrochemical intercalation in C₆₀ of Li⁺ (or K⁺) ions has been performed under constant current conditions up to a formal stoichiometry of the fulleride film equal to Li₁₂C₆₀ (K₅C₆₀). A complete charge-transfer pocess from the intercalated alkali to the alkali-metal compound has been assumed. Several quasi-equilibrium potential plateaux were observed during intercalation, that we associate with the coexistence of phases with different intercalant concentration. The electrochemical intercalation process is irreversible to a large extent. Optical and photoelectrochemical spectroscopy of the fulleride films was done in-situ at different moments of the intercalation reaction by illuminating the film electrodes through the transparent and conducting glass substrates. The photo electrochemical spectral response agrees well with the optical absorption spectra, both indicating a bandgap of 2.2 eV. The photoelectrochemical response shows a minimum forx = 3 (in the K_xC₆₀ compound) and a maximum atx = 4 (in both K_xC₆₀ andLi_xC₆₀ compounds), in agreement with previous conductivity results. NIR diffuse reflectance spectra of the solid-state cell show absorption bands in the fulleride films at a wavelength of 1100 nm. A band-energy diagram has been proposed for the M_xC₆₀/PEO-MClO₄/M electrochemical cell.On leave from Instituto de Fisica, Facultad de Ingenleria, C.C. 30, 11000 Montevideo, Uruguay     

Optical absorption studies of copper phthalocyanine thin films

The optical absorption of thermally evaporated copper phthalocyanine (CuPc) was studied in the UV-VIS-NIR region. The absorption spectra recorded in the UV-VIS region show two well-defined absorption bands of the phthalocyanine molecules, namely, the Soret (B) and the Q-band . The Q-band shows its characteristic splitting (Davydov splitting) of the main absorption peak in the metal phthalocyanine correlates with the relative tendencies of the metal to out-of-plane bonding. Some of the important spectral characteristics such as the molar extinction coefficient (ε_molar), the oscillator strength (f), the electric dipole strength (q²) and absorption half-bandwidth (Δλ) of the principle optical transitions were evaluated. The analysis of the spectral behavior of the absorption coefficient α in the absorption region revealed two indirect allowed transitions with corresponding energies 2.95±0.03 and 1.55±0.02 eV.The spectra of the infrared absorption allow characterization of vibration modes for the powder, as-deposited material and thin films of CuPc annealed at 423 K for two hours. Discussion of the obtained results and their comparison with the previous published data are also given.     

Photoelectric characteristics of photodetectors based on a GaAs/CuPc heterojunction

A study is made of the volt-ampere, volt-farad, and spectral characteristics of photodetectors based on an n-GaAs/p-CuPc heterojunction. When exposed to white light (E=600 W/m²) through Ag, the elements Cu/GaAs/CuPc/Ag have the following characteristics: U_xx=0.6 V; I_sc=30.2 A/m², FF=0.49. Based on this data and with allowance for the transmission factor (τ=7%), η=18%. Quantum efficiency is 0.5 el./phot. in the UV-region at λ₁ = 300 nm, while α₂ = 0.85 el./phot. in the visible region at λ₂ = 800 nm. The limiting sensitivity of the photodetector is 10⁻¹¹ W. The following was determined from the volt-farad and spectral characteristics: C_b=8.6·10⁻⁴ F/m²; barrier width w₁=16nm in CuPc and w₂=34 nm in CaAs; exciton diffusion length L₁=2.5 nm and L₂=7.5 nm, respectively. The photodetectors undergo almost no degradation. The values of U_xx and I_sc remain constant with multiple exposures to UV-light of 140 W/m² intensity over 6 h at constant temperature. The sensitivity region of the photodetectors is from 200 to 1000 nm. It is found that an anisotropic heterojunction in the form of two series-connected Schottky barriers is created at the boundary between n-GaAs and oxygen-doped p-CuPc in the presence of charged surface states at the interface. Vologda Polytechnic Institute. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 41–45, July, 1996.     

Effect of chlorine-containing bleaching agents on diffuse reflection of light by cellulose pulp

We have studied diffuse reflectance in the spectral range λ = 380–760 nm of sulfate cellulose pulp with initial hardness G = 30–70 after it was treated with a chlorine-containing bleaching agent with active chlorine concentration C = 0%–10% for different time intervals. We determined the general behavior and basic features of the concentration and time dependences of the brightness B and the diffuse reflectance spectral ratio (R ₄₃₇/R ₆₅₀)⋅100% at λ = 457 nm and 650 nm. Based on the data obtained, we propose an optimal algorithm for using optical spectral technologies for metered addition of chlorine-containing bleaching agents.