Tunable Dopants with Intrinsic Counterion Separation Reveal the Effects of Electron Affinity on Dopant Intercalation and Free Carrier Production in Sequentially Doped Conjugated Polymer Films

Carrier mobility in doped conjugated polymers is limited by Coulomb interactions with dopant counterions. This complicates studying the effect of the dopant's oxidation potential on carrier generation because different dopants have different Coulomb interactions with polarons on the polymer backbone. Here, dodecaborane (DDB)‐based dopants are used, which electrostatically shield counterions from carriers and have tunable redox potentials at constant size and shape. DDB dopants produce mobile carriers due to spatial separation of the counterion, and those with greater energetic offsets produce more carriers. Neutron reflectometry indicates that dopant infiltration into conjugated polymer films is redox‐potential‐driven. Remarkably, X‐ray scattering shows that despite their large 2‐nm size, DDBs intercalate into the crystalline polymer lamellae like small molecules, indicating that this is the preferred location for dopants of any size. These findings elucidate why doping conjugated polymers usually produces integer, rather than partial charge transfer: dopant counterions effectively intercalate into the lamellae, far from the polarons on the polymer backbone. Finally, it is shown that the IR spectrum provides a simple way to determine polaron mobility. Overall, higher oxidation potentials lead to higher doping efficiencies, with values reaching 100% for driving forces sufficient to dope poorly crystalline regions of the film.     

The Effects of Crystallinity on Charge Transport and the Structure of Sequentially Processed F4TCNQ‐Doped Conjugated Polymer Films

The properties of molecularly doped films of conjugated polymers are explored as the crystallinity of the polymer is systematically varied. Solution sequential processing (SqP) was used to introduce 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F₄TCNQ) into poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) while preserving the pristine polymer's degree of crystallinity. X‐ray data suggest that F₄TCNQ anions reside primarily in the amorphous regions of the film as well as in the P3HT lamellae between the side chains, but do not π‐stack within the polymer crystallites. Optical spectroscopy shows that the polaron absorption redshifts with increasing polymer crystallinity and increases in cross section. Theoretical modeling suggests that the polaron spectrum is inhomogeneously broadened by the presence of the anions, which reside on average 6–8 Å from the polymer backbone. Electrical measurements show that the conductivity of P3HT films doped by F₄TCNQ via SqP can be improved by increasing the polymer crystallinity. AC magnetic field Hall measurements show that the increased conductivity results from improved mobility of the carriers with increasing crystallinity, reaching over 0.1 cm² V^?1 s^?1 in the most crystalline P3HT samples. Temperature‐dependent conductivity measurements show that polaron mobility in SqP‐doped P3HT is still dominated by hopping transport, but that more crystalline samples are on the edge of a transition to diffusive transport at room temperature.     

The Effect of Ageing on Exciton Dynamics,Charge Separation,and Recombination in P3HT/PCBM Photovoltaic Blends

A study of how light‐induced degradation influences the fundamental photophysical processes in the active layer of poly(3‐hexylthiophene)/[6,6]‐phenyl C₆₁‐butyric acid methyl ester (P3HT/PCBM) solar cells is presented. Non‐encapsulated samples are systematically aged by exposure to AM 1.5 illumination in the presence of dry air for different periods of time. The extent of degradation is quantified by the relative loss in the absorption maximum of the P3HT, which is varied in the range 0% to 20%. For degraded samples an increasing loss in the number of excitons within the P3HT domains is observed with longer ageing periods. This loss occurs rapidly, within the first 15 ps after photoexcitation. A more pronounced decrease in the population of polarons than excitons is observed, which also occurs on a timescale of a few picoseconds. These observations, complemented by a quantitative analysis of the polaron and exciton population dynamics, unravel two primary loss mechanisms for the performances of aged P3HT/PCBM solar cells. One is an initial ultrafast decrease in the polaron generation, apparently not related to the exciton diffusion to the polymer/fullerene interface; the second, less significant, is a loss in the exciton population within the photoexcited P3HT domains. The steady‐state photoinduced absorption spectra of degraded samples exhibits the appearance of a signal ascribed to triplet excitons, which is absent for non‐degraded samples. This latter observation is interpreted considering the formation of degraded sites where intersystem crossing and triplet exciton formation is more effective. The photovoltaic characteristics of same blends are also studied and discussed by comparing the decrease in the overall power conversion efficiency of solar cells.     

NH3掺杂ZnO薄膜的生长及特性

采用金属有机物化学气相沉积(MOCVD)方法,以NH3作为N元素的掺杂源,在蓝宝石衬底上生长了掺N的ZnO薄膜.利用X射线衍射、X射线光电子能谱、原子力显微镜、霍尔测量及先致荧光光谱等测试技术分析了薄膜的结晶性质、表面形貌、光电性质及掺杂元素N的价键特性.结果表明,NH3 的掺杂会影响ZnO薄膜的结晶特性,薄膜虽然仍是(002) 面择优取向生长,但同时也出现了ZnO的(100)及(101)面生长.在薄膜生长时N元素掺入到ZnO薄膜当中,并形成N-Zn、N-H、N-C键.C、H杂质的存在,使掺N ZnO薄膜表现为高阻,同时也影响了薄膜的光致发光特性.     

Precise Control of Lamellar Thickness in Highly Oriented Regioregular Poly(3‐Hexylthiophene) Thin Films Prepared by High‐Temperature Rubbing: Correlations with Optical Properties and Charge Transport

Precise control of orientation and crystallinity is achieved in regioregular poly(3‐hexylthiophene) (P3HT) thin films by using high‐temperature rubbing, a fast and effective alignment method. Rubbing P3HT films at temperatures T_R ≥ 144 °C generates highly oriented crystalline films with a periodic lamellar morphology with a dichroic ratio reaching 25. The crystallinity and the average crystal size along the chain axis direction, l_c, are determined by high‐resolution transmission electron microscopy and differential scanning calorimetry. The inverse of the lamellar period l scales with the supercooling and can accordingly be controlled by the rubbing temperature T_R. Uniquely, the observed exciton coupling in P3HT crystals is correlated to the length of the average planarized chain segments l_c in the crystals. The high alignment and crystallinity observed for T_R > 200 °C cannot translate to high hole mobilities parallel to the rubbing because of the adverse effect of amorphous zones interrupting charge transport between crystalline lamellae. Although tie chains bridge successive P3HT crystals through amorphous zones, their twisted conformation restrains interlamellar charge transport. The evolution of charge transport anisotropy is correlated to the evolution of the dominant contact plane from mainly face‐on (T_R ≤ 100 °C) to edge‐on (T_R ≥ 170 °C).     

Self‐Assembled Dense Colloidal Cu2Te Nanodisk Networks in P3HT Thin Films with Enhanced Photocurrent

The integration of colloidal nanocrystals with polymers adds optoelectronic functionalities to flexible and mechanically robust organic films. In particular, self‐assembled structures of nanocrystals in polymers can act as functional components enhancing, for instance, transport or optical properties of the hybrid material. This study presents Cu₂Te hexagonal nanodisks that assemble into ribbons with a face‐to‐face configuration in poly(3‐hexylthiophene‐2,5‐diyl) through a controlled solvent evaporation process. The ribbons form weaving patterns that create 3D networks fully embedded in the thin polymer film at high nanodisk concentration. The photoresponse of these composite films measured in a layered vertical geometry demonstrates increased photocurrent with increasing nanocrystal loading. This study attributes this behavior to the presence of networks of Cu₂Te nanodisks that form a bulk heterojunction with the semiconducting polymer, which improves exciton dissociation and the overall photoelectric response.     

Effect of SWNT Defects on the Electron Transfer Properties in P3HT/SWNT Hybrid Materials

Poly(3‐hexylthiophene) (P3HT) hybrids with single‐walled carbon nanotubes (SWNTs) were prepared using a series of SWNTs with various defect contents on their surfaces. The hybrids were synthesized by exploiting the π–π interaction between P3HT and the SWNTs, resulting in efficient dispersion of the carbon nanotubes in the P3HT solution. UV‐visible and photoluminescence (PL) spectra showed that the carbon nanotubes quench the PL of P3HT in the hybrids, indicating that electron transfer occurs from photo‐excited P3HT to the SWNTs. This electron transfer from P3HT to carbon nanotubes was disrupted by the presence of defects on the SWNT surfaces. However, the PL lifetime of P3HT in the hybrids was found to be the same as that of pure P3HT in solution, indicating the formation of a ground‐state non‐fluorescent complex of P3HT/SWNTs.     

Temperature‐Resolved Local and Macroscopic Charge Carrier Transport in Thin P3HT Layers

Previous investigations of the field‐effect mobility in poly(3‐hexylthiophene) (P3HT) layers revealed a strong dependence on molecular weight (MW), which was shown to be closely related to layer morphology. Here, charge carrier mobilities of two P3HT MW fractions (medium‐MW: M_n = 7 200 g mol^?1; high‐MW: M_n = 27 000 g mol^?1) are probed as a function of temperature at a local and a macroscopic length scale, using pulse‐radiolysis time‐resolved microwave conductivity (PR‐TRMC) and organic field‐effect transistor measurements, respectively. In contrast to the macroscopic transport properties, the local intra‐grain mobility depends only weakly on MW (being in the order of 10^?2 cm² V^?1 s^?1) and being thermally activated below the melting temperature for both fractions. The striking differences of charge transport at both length scales are related to the heterogeneity of the layer morphology. The quantitative analysis of temperature‐dependent UV/Vis absorption spectra according to a model of F. C. Spano reveals that a substantial amount of disordered material is present in these P3HT layers. Moreover, the analysis predicts that aggregates in medium‐MW P3HT undergo a “pre‐melting” significantly below the actual melting temperature. The results suggest that macroscopic charge transport in samples of short‐chain P3HT is strongly inhibited by the presence of disordered domains, while in high‐MW P3HT the low‐mobility disordered zones are bridged via inter‐crystalline molecular connections.     

Mapping of Domain Orientation and Molecular Order in Polycrystalline Semiconducting Polymer Films with Soft X‐Ray Microscopy

We utilize scanning transmission X‐ray microscopy (STXM) to study the domain structure of polycrystalline films of the semiconducting polymer poly(9,9’‐dioctylfluorene‐co‐benzothiadiazole) (F8BT). By taking several images at different orientations of the film with respect to the polarization of the X‐ray beam, we are able to compute quantitative maps of molecular alignment/order and molecular orientation, including both the backbone direction and phenyl ring plane orientation, as well as the in‐plane and out‐of‐plane components. We show that polycrystalline F8BT films consist of well‐ordered micron‐sized domains with the transition from one domain orientation to another characterized either by a smooth transition of orientation or by ～ 200 nm wide disordered domain boundaries. The morphology of the disordered domain boundaries resemble the electroluminescence patterns observed previously in F8BT light‐emitting field‐effect transistors suggesting that charge trapping at these disordered domain boundaries facilitates charge recombination in ambipolar operation. A relatively narrow distribution of local average tilt angles is observed that correlates with film structure, with the ordered domains in general showing a higher tilt angle than the disordered domain boundaries. We also use secondary electron detection to image the surface domain structure of polycrystalline F8BT films and demonstrate that the polycrystalline structure extends to the film/air interface. Finally, we calculate ideal NEXAFS spectra corresponding to a perfect F8BT crystal oriented with the 1s – π^* transition dipole moment parallel and perpendicular to the electric field vector of a perfectly linearly polarized X‐ray beam.     

基于ZnO纳米线阵列和P3HT的混合光电二极管特性

为了发展低成本、大面积和高性能光电二极管,采用简单的化学浴沉积方法,在氧化铟锡(I TO) 玻璃基底上生长良好取向的ZnO纳米线阵列(ZNWA),然后在生长的ZNWA上旋涂规整的聚3-己 基噻吩(P3HT)层,形成结构为ITO/ZNWA/P3HT/Ag的光电二极管。系统研究了此光电二极管在 暗态和在太阳模拟器的光照下的电流-电压 (I-V)特性。实验结果表明,器件在暗态和光照下都表现出良好 的二极管特性。暗态下,在偏压±2V处的整流 率为3211, 理想因子为1.8、低开启电压为0.5V和反偏饱和电流为1．13×10－7 A。在20mW/cm²光照下,在偏压±2V处的整流率为39.1、开启电压为0.3V。器件中产生了大量的光生载流子,根据器件的能级结构图和光生载流子的 输运过程对此光电二极管的光响应机理进行了解释。     

Photovoltaics Based on Hybridization of Effective Dye‐Sensitized Titanium Oxide and Hole‐Conductive Polymer P3HT

Here, the fabrication of quasi‐solid‐state TiO₂/dye/poly(3‐hexylthiophene) (P3HT) solar cells is reported, in which the dyes with oleophilic thienyl groups were employed and ionic liquid (IL), 1‐ethyl‐3‐methylimidazolium (EMIm) containing lithium bis(trifluromethanesulfone)amide (Li‐TFSI) and 4‐tert‐butylpyridine (t‐BP) are assembled with dyed TiO₂ surfaces. One of the devices gave a high conversion efficiency of up to 2.70% under 1 sun illumination. The excellent performance is ascribed to successful molecular self‐organization at interface of the dye molecules and P3HT, and to the efficient charge separation and diffusion acquired by introduction of the IL coupled with Li‐TFSI and t‐BP.     

Doping Dependent In‐Plane and Cross‐Plane Thermoelectric Performance of Thin n‐Type Polymer P(NDI2OD‐T2) Films

Thermoelectric generators pose a promising approach in renewable energies as they can convert waste heat into electricity. In order to build high efficiency devices, suitable thermoelectric materials, both n‐ and p‐type, are needed. Here, the n‐type high‐mobility polymer poly[N,N′‐bis(2‐octyldodecyl)naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene) (P(NDI2OD‐T2)) is focused upon. Via solution doping with 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)‐N,N‐diphenylaniline (N‐DPBI), a maximum power factor of (1.84 ± 0.13) µW K^?2 m^?1 is achieved in an in‐plane geometry for 5 wt% dopant concentration. Additionally, UV–vis spectroscopy and grazing‐incidence wide‐angle X‐ray scattering are applied to elucidate the mechanisms of the doping process and to explain the discrepancy in thermoelectric performance depending on the charge carriers being either transported in‐plane or cross‐plane. Morphological changes are found such that the crystallites, built‐up by extended polymer chains interacting via lamellar and π–π stacking, re‐arrange from face‐ to edge‐on orientation upon doping. At high doping concentrations, dopant molecules disturb the crystallinity of the polymer, hindering charge transport and leading to a decreased power factor at high dopant concentrations. These observations explain why an intermediate doping concentration of N‐DPBI leads to an optimized thermoelectric performance of P(NDI2OD‐T2) in an in‐plane geometry as compared to the cross‐plane case.     

Real‐Time Investigation of Crystallization and Phase‐Segregation Dynamics in P3HT:PCBM Solar Cells During Thermal Annealing

Crystallization and phase segregation during thermal annealing lead to the increase of power‐conversion efficiency in poly(3‐hexylthiophene) (P3HT):[6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) bulk‐heterojunction solar cells. An understanding of the length and time scale on which crystallization and phase segregation occur is important to improve control of the nanomorphology. Crystallization is monitored by means of grazing incidence X‐ray diffraction in real time during thermal annealing. Furthermore, the change in film density is monitored by means of ellipsometry and the evolution of carrier mobilities by means of field effect transistors, both during annealing. From the combination of such measurements with those of device performance as a function of annealing time, it is concluded that the evolution of microstructure involves two important time windows: i) A first one of about 5 minutes duration wherein crystallization of the polymer correlates with a major increase of photocurrent; ii) a second window of about 30 minutes during which the aggregation of PCBM continues, accompanied by an increase in the fill factor.     

Rapid and Facile Formation of P3HT Organogels via Spin Coating: Tuning Functional Properties of Organic Electronic Thin Films

Poly(3‐hexyl thiophene) (P3HT) is widely regarded as the benchmark polymer when studying the physics of conjugated polymers used in organic electronic devices. P3HT can self‐assemble via π–π stacking of its backbone, leading to an assembly and growth of P3HT fibrils into 3D percolating organogels. These structures are capable of bridging the electrodes, providing multiple pathways for charge transport throughout the active layer. Here, a novel set of conditions is identified and discussed for P3HT organogel network formation via spin coating by monitoring the spin‐coating process from various solvents. The development of organogel formation is detected by in situ static light scattering, which measures both the thinning rate by reflectance and structural development in the film via off‐specular scattering during film formation. Optical microscopy and thermal annealing experiments provide ex situ confirmation of organogel fabrication. The role of solution characteristics, including solvent boiling point, P3HT solubility, and initial P3HT solution concentration on organogel formation, is examined to correlate these parameters to the rate of film formation, organogel‐onset concentration, and overall network size. The correlation of film properties to the fabrication parameters is also analyzed within the context of the hole mobility and density‐of‐states measured by impedance spectroscopy.     

Systematic Control of Nucleation Density in Poly(3‐Hexylthiophene) Thin Films

While molecular ordering via crystallization is responsible for many of the impressive optoelectronic properties of thin‐film semiconducting polymer devices, crystalline morphology and its crucial influence on performance remains poorly controlled and is usually studied as a passive result of the conditions imposed by film deposition parameters. A method for systematic control over crystalline morphology in conjugated polymer thin films by very precise control of nucleation density and crystal growth conditions is presented. A precast poly(3‐hexylthiophene) film is first swollen into a solution‐like state in well‐defined vapor pressures of a good solvent, while the physical state of the polymer chains is monitored using in situ UV–vis spectroscopy and ellipsometry. Nucleation density is selected by a controlled deswelling of the film or by a self‐seeding approach using undissolved crystalline aggregates that remain in the swollen film. Nucleation densities ranging successively over many orders of magnitude are achieved, extending into the regime of spherulitic domains 10 to 100 μm in diameter, a length scale highly relevant for typical probes of macroscopic charge transport such as field‐effect transistors. This method is presented as a tool for future systematic study of the structure‐function relation in semicrystalline semiconducting polymers in a broad range of applications.     

Energetics of Donor‐Doping,Metal Vacancies,and Oxygen‐Loss in A‐Site Rare‐Earth‐Doped BaTiO3

The energetics of La‐doping in BaTiO₃ are reported for both (electronic) donor‐doping with the creation of Ti³⁺ cations and ionic doping with the creation of Ti vacancies. The experiments (for samples prepared in air) and simulations demonstrate that ionic doping is the preferred mechanism for all concentrations of La‐doping. The apparent disagreement with electrical conduction of these ionic doped samples is explained by subsequent oxygen‐loss, which leads to the creation of Ti³⁺ cations. Simulations show that oxygen‐loss is much more favorable in the ionic‐doped system than undoped BaTiO₃ due to the unique local structure created around the defect site. These findings resolve the so‐called “donor‐doping” anomaly in BaTiO₃ and explain the source of semiconductivity in positive temperature coefficient of resistance (PTCR) BaTiO₃ thermistors.     

The Origin of the High Voltage in DPM12/P3HT Organic Solar Cells

Organic solar cells made using a blend of DPM12 and P3HT are studied. The results show that higher V_oc can be obtained when using DPM12 in comparison to the usual mono‐substituted PCBM electron acceptor. Moreover, better device performances are also registered when the cells are irradiated with sun‐simulated light of 10–50 mW cm^?2 intensity. Electrochemical and time‐resolved spectroscopic measurements are compared for both devices and a 100‐mV shift in the density of states (DOS) is observed for DPM12/P3HT devices with respect to PCBM/P3HT solar cells and slow polaron‐recombination dynamics are found for the DPM12/P3HT devices. These observations can be directly correlated with the observed increase in V_oc, which is in contrast with previous results that correlated the higher V_oc with different ideality factors obtained using dark‐diode measurements. The origin for the shift in the DOS can be correlated to the crystallinity of the blend that is influenced by the properties of the included fullerene.     

High‐Resolution Spectroscopic Mapping of the Chemical Contrast from Nanometer Domains in P3HT:PCBM Organic Blend Films for Solar‐Cell Applications

A high‐resolution near‐field spectroscopic mapping technique is successfully applied to investigate the influence of thermal annealing on the morphology of a poly(3‐hexylthiophene) and [6,6]‐penyl‐C₆₁ butyric acid methyl ester (P3HT:PCBM) blend film. Based on the simultaneously recorded morphological and spectroscopic information, the interplay among the blend film morphology, the local P3HT:PCBM molecular distribution, and the P3HT photoluminescence (PL) quenching efficiency are systematically discussed. The PL and Raman signals of the electron donor (P3HT) and acceptor (PCBM) are probed at an optical resolution of approximately 10 nm, which allows the chemical nature of the different domains to be identified directly. In addition, the local PL quenching efficiency, which is related to the electron transfer from P3HT to PCBM, is quantitatively revealed. From these experimental results, it is proposed that high‐resolution near‐field spectroscopic imaging is capable of mapping the local chemical composition and photophysics of the P3HT:PCBM blends on a scale of a few nanometers.