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.     

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.     

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.     

Electronic non-equilibrium conditions at C60–pentacene heterostructures

The electronic structure of vacuum-sublimed layered organic heterostructures of pentacene (PEN) and fullerene (C₆₀) on conducting polymer substrates was investigated using ultraviolet photoelectron spectroscopy (UPS). The conditions at the PEN/C₆₀interface changed from thermodynamic non-equilibrium (i.e. the onset of the PEN highest occupied molecular orbital above the substrate Fermi-energy) for thin PEN coverages on C₆₀ to thermodynamic equilibrium for thicker PEN coverages (i.e. Fermi-level pinning of PEN). This finding is attributed to a coverage-dependent pinhole connection of PEN through the C₆₀ layer with the substrate. The experiments demonstrate the importance of organic thin film morphology for UPS measurements to assess the energy level alignment at organic/organic heterointerfaces.     

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.     

Analysis of hybrid donor layer in organic solar cells based on SubPc and rubrene

In this paper, photovoltaic characteristics of ITO/PEDOT:PSS/SubPc:Rubrene (mixed ratio R by weight)/C₆₀/Bphen/Ag organic solar cells (OSCs) are analyzed in detail. The intrinsic properties of a SubPc:rubrene doped layer on device performance were discussed based on theoretical analysis of the experimental OSCs. The ratio R was 0, 0.25, 0.5, and 0.75,1, respectively. The results showed that when R was 0.75 performing the best, which owned the highest short circuit current (J _sc ) 6.61 mA/cm² and highest power conversion efficiency (PCE) 2.44%, the FF was 41% and the open circuit current (V _oc ) was 0.905 V. The suitable HOMO level, absorption capacity, carrier transport ability and exciton diffusion length (L _D ) of organic material are very important for the performance of the device.     

Energy level alignment between C60 and Al using ultraviolet photoelectron spectroscopy

The energy level alignment between C₆₀ and Al has been investigated by using ultraviolet photoelectron spectroscopy. To obtain the interfacial electronic structure between C₆₀ and Al, C₆₀ was deposited on a clean Al substrate in a stepwise manner. The valence-band spectra were measured immediately after each step of C₆₀ deposition without breaking the vacuum. The measured onset of the highest occupied molecular orbital energy level was located at 1.59 eV from the Fermi level of Al. The vacuum level was shifted 0.68 eV toward lower binding energy with additional C₆₀ layers. The observed vacuum level shift means that the interface dipole exists at the interface between C₆₀ and Al. The barrier height of electron injection from Al to C₆₀ is 0.11 eV, which is smaller value than that of hole injection.     

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．     

Charge-transfer at silver/phthalocyanines interfaces

Valence band photoemission spectroscopy (VB-PES) and inverse photoemission spectroscopy (IPES) were employed to determine the occupied and unoccupied density of states upon silver deposition onto layers of two phthalocyanines (H₂Pc and CuPc). The two different Pc molecules give rise to very distinct behaviour already during the initial stage of silver deposition. While in the CuPc case no shift occurs in the energy levels, the H₂Pc highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are shifting simultaneously by 0.3 eV, i.e., the HOMO shifts away from the Fermi level while LUMO shifts towards the Fermi level. As the silver quantity increases the HOMO levels of both Pcs are shifting towards the Fermi level. When the Fermi level is resolved in the VB spectra, the characteristic features of H₂Pc and CuPc are smeared out to some extent. Shifts in HOMO and LUMO energy positions as well as changes in line shapes are discussed in terms of charge-transfer and chemical reactions at the interfaces.     

使用不同阴极缓冲层提升性能的反型有机太阳能电池

使用含Al_q3、Bphen、BCP、HATNA和Cs₂CO₃作为阴极缓冲层,制备了基于SubPc和C₆₀的反型平面异质结有机太阳能电池. 比较了有机阴极缓冲层的最低未占有分子轨道和电子迁移率对有机太阳能电池性能的影响. 结果显示,Al_q3、Bphen和HATNA能够大幅度提升器件的性能. 使用退火过后的HATNA作为阴极缓冲层获得了最高的效率,比没有阴极缓冲层的器件提升了7倍. 另外,使用空间电荷限制电流理论进行仿真的结果表明,通过加入HATNA作阴极缓冲层,反型有机太阳能电池结构中处于有机/电极界面处的肖特基势垒降低了27%.     

Mechanical and electronic properties of endofullerene Ne@C60 studied via structure distortions

Elastic, strength, electronic properties and vibrational spectra of Ne@C₆₀ (I _h) in its ground electronic state (X ¹A_g) were investigated with density functional theory at B3PW91/6-31G level via structure distortions. The elastic properties were obtained from the potential energy curves (PECs) in all of the five independent distortional directions of the molecule with symmetries of 1. D _5d, 2. D _3d, 3. D _2h, 4. C _2h(1) and 5. C _2h(2). PECs were examined where the structure of Ne@C₆₀ was destroyed. The necessary energies to destroy the structure were thus obtained, which illuminated the stability of Ne@C₆₀. PECs were found to be anisotropic and were accurately fitted to polynomials. Elongations in the direction of D _5d and compression in D _2h encountered potential energy surface cross-linkages, which might be considered as a single electron pump for further application in the design of single electron devices. Time-dependent B3PW91/6-31G analysis predicted significant electronic spectra changes associated with structure distortions. Similarities and differences of the properties were compared with those in C₆₀ and He@C₆₀.     

New evaluation of fullerene molecules on Si(111)-(7 × 7) reconstructed structure using non-contact scanning non-linear dielectric microscopy

Fullerene (C₆₀) molecules on an Si(111)-(7 × 7) surface have been investigated using non-contact scanning non-linear dielectric microscopy (NC-SNDM) under an ultra-high vacuum. The topography, the interface between the C₆₀ molecule and Si adatoms, and the internal structure of the C₆₀ molecules were successfully investigated. For ～ 0 ML and ～ 0.4 ML coverage, both phase reversal sites and sites without phase reversal could be observed in the first order phase (θ1) image. On the other hand, for 1 ML coverage, phase reversal could not be identified. These results indicate that charge transfer only occurred from Si adatoms to C₆₀ molecules at three-fold symmetric sites on the Si(111)-(7 × 7) surface, and the electric dipole moment is reflected in the electronic state of the C₆₀ molecules. The internal structure of C₆₀ molecules was clearly observed in topography by the second order amplitude (A₂) feedback signal for 1 ML coverage, reflecting the LDOS originating from the t_1u orbital.     

New spectroscopic results on acetylene dimers and trimers

Spectra of acetylene dimers and trimers containing one or more C₂D₂ monomer are studied in the ν₃ fundamental band region of C₂D₂ (≈2440?cm^?1) using a tuneable infrared diode laser to probe a pulsed supersonic slit jet expansion. Four new subbands are observed in the perpendicular band of (C₂D₂)₂, and this enables the first direct determination of the A rotational constant for an acetylene dimer. The value found for A is significantly larger than the previous indirect value based on microwave spectra. The dimer parallel band is observed and found to be highly perturbed, and observations are extended for the mixed dimer C₂D₂ – C₂H₂. The trimers (C₂D₂)₃, (C₂D₂)₂ – C₂H₂, and C₂D₂ – (C₂H₂)₂ are observed spectroscopically for the first time. Establishment of a precise band origin is difficult for (C₂D₂)₃ because of the inherent nature of the spectrum, but this is possible for two out of three of the bands of the mixed trimers.     

Fullerene-C60 and crown ether doped on C60 sensors for high sensitive detection of alkali and alkaline earth cations

Fullerenes are effective acceptor components with high electron affinity for charge transfer. The significant influences of chemical adsorption of the cations on the electrical sensitivity of pristine C₆₀ and 15-(C₂H₄O)₅/C₆₀ nanocages could be the basis of new generation of electronic sensor design. The density functional theory calculation for alkali and alkaline earth cations detection by pristine C₆₀ and 15-(C₂H₄O)₅/C₆₀ nanocages are considered at B3LYP level of theory with 6–31 G(d) basis set. The quantum theory of atoms in molecules analysis have been performed to understand the nature of intermolecular interactions between the cations and nanocages. Also, the natural bond orbital analysis have been performed to assess the intermolecular interactions in detail. Furthermore, the frontier molecular orbital, energy gap, work function, electronegativity, number of transferred electron (∆N), dipole moment as well as the related chemical hardness and softness are investigated and calculated in this study. The results show that the adsorption of cations (M=Na⁺, K⁺, Mg²⁺ and Ca²⁺) are exothermic and the binding energy in pristine C₆₀ nanocage and 15-(C₂H₄O)₅/C₆₀ increases with respect to the cations charge. The results also denote a decrease in the energy gap and an increase in the electrical conductivity upon the adsorption process. In order to validate the obtained results, the density of state calculations are employed and presented in the end as well.     

Rubrene作电子传输层的异质结有机太阳能电池

以Rubrene为电子传输层(ETL),制备了结构为ITO/MoO3(5nm)/Rubrene(50nm)/C60(45nm)/Rubrene(0,3,5.5,9.5nm)/Al(130nm)的有机太阳能电池.与没有ETL的器件相比,含5.5nmRubrene的电池的开路电压、填充因子、功率转换效率分别从0.68V,0.488,0.315%增加到0.86V,0.574,0.490%.实验结果分析表明:热的Al原子直接沉积在C60上,破坏了C60层,形成高功函数的C60/Al阴极,弱化内建电场,降低电池性能;当插入ETL后,C60层得到保护,热的Al原子沉积破坏了Rubrene层,形成了缺陷态能级,提高电池的内建电场,促进了电子的传输.进一步的单电子电池实验表明,缺陷态能级低于C60的最低未占据分子轨道.     

Evolution of excess electron binding motifs under both internal‐push (from exo C–F bonds) and external‐push (from endo C–F bonds) electron effects in endohedral metallofullerenes with endo C–F bonds

How does the endo C–F bond influence the excess electron binding motif? For lithium‐doped endohedral perfluorofullerenes with endo C–F bonds, under both internal‐push (from exo C–F bonds) and external‐push (from endo C–F bonds) electron effects, the singly occupied molecular orbital electron cloud of the sphere‐like Li···F₈@C₆₀F₅₂ (D₂) is partially dispersed within the σ_p–s antibonding orbital of endo C–F bonds and the space between C^δ+–F_endo^δ– double electric layers, which makes Li···F₈@C₆₀F₅₂ have partial excess electron (electride characteristics) and partial lithium salt characteristics, while in the tube‐like Li···F₂@C₆₀F₅₈ (C_s), as the Li is changing from approaching F to keeping away from F and to approaching another one, the singly occupied molecular orbital electron cloud is mainly dispersed from within the p orbital of the short endo C–F bond to within the middle of the two F atoms and again to within the p orbital of the short endo C–F bond, which indicates an evolution from lithium salt characteristic to excess electron characteristic, and again to lithium salt characteristic. Copyright © 2012 John Wiley & Sons, Ltd.     

High-performance n-channel organic thin-film transistors based on the dual effects of heterojunction and surface modification

This paper presents two n-channel organic heterojunction transistors with modified insulator by using hexadecafluorophthalocyaninatocopper (F₁₆CuPc)/copper phthalocyanine (CuPc) and F₁₆CuPc/pentacene as the active layers. Compared with a single-layer device, it reports that an improved field-effect mobility and a 6-fold higher drain current are observed. The highest mobility of 0.081~cm²/(V.s) was obtained from F₁₆CuPc/CuPc heterojunction devices. This result is attributed to the dual effects of the organic heterojunction and interface modification. Furthermore, for two heterojunction devices, the performance of the F₁₆CuPc/CuPc-based transistor is better than that of F₁₆CuPc/pentacene. This is attributed to the morphologic match of two organic components.     

Dipoles and band alignment for benzene/Au(111) and C<Subscript>60</Subscript>/Au(111) interfaces

A local orbital DFT-approach combined with a “scissor”-operator is used to obtain the Charge Neutrality Level and the screening parameter in the benzene/Au(111) and C₆₀/Au(111) interfaces. The “pillow” dipole and interface Fermi level are also calculated. The total dipole induced across the interface is compared with the experimental evidences: while the agreement for C₆₀/Au(111) is excellent, for benzene/Au(111), some discrepancies appear that are discussed in the light of other models.     

C72,La2@C72几何结构和电子性质的计算研究

采用密度泛涵理论(density functional theory, DFT)中的广义梯度近似(generally gradient approximation, GGA)对富勒烯C₇₂和内掺金属La富勒烯La₂@C₇₂三种同分异构体的几何结构和电子结构进行研究.发现在C₇₂的三种同分异构体中，满足独立五边形规则(isolated-pentagon-rule，IPR)的C₇₂(D_{6d< 关键词： 72}')" href="#">C₇₂ 2@C₇₂')" href="#">La₂@C₇₂ 密度泛涵理论 几何结构 电子结构