Morphology Associated Positive Correlation between Carrier Mobility and Carrier Density in Highly Doped Donor–Acceptor Conjugated Polymers

Molecular doping in conjugated polymers (CPs) has recently received intensive attention for its potential to achieve high electrical conductivity in organic thermoelectric materials. In particular, it affects not only the carrier density n but also the carrier mobility µ because high degree of molecular doping changes the morphological properties. Herein, the effect of molecular doping in CP thin films on the pathways and mechanisms of charge transport is investigated, which govern the µ-n relationship. Two representative donor–acceptor type CPs with similar µ but different molecular assembly in an undoped state, that is poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)] (DPPDTT) and indacenodithiophene-co-benzothiadiazole (IDTBT), are prepared. Heavy doping with iron chloride (FeCl₃) induced DPPDTT with highly crystalline edge-on orientation to increase its µ up to 19.6 cm² V⁻¹ s⁻¹, whereas IDTBT with irregular intermolecular stacking showed little change in µ. It is revealed that this different µ-n relationship is highly attributed to the initial molecular ordering of CP films. The charge transport mechanism also becomes significantly different: both coherent and incoherent transports are observed in the doped DPPDTT, whereas incoherent transport is only found in the doped IDTBT. This study suggests guidelines for enhancing charge transport of CPs under doping in terms of structural disorder.     

The effect of introducing Al ions in cationic deposition bath on as-prepared PbS thin film through SILAR deposition method

Undoped and Al doped lead sulfide (PbS) thin films were grown on soda lime glass substrates by Successive Ionic Layer Adsorption and Reaction (SILAR) deposition method. Al content in aqueous cationic solution was varied by adding 0.5–2% of aluminum nitrate in step of 0.5. The characterization of the film was carried out using X-ray diffraction, scanning electron microscopy, and optical and electrical measurement techniques. X-ray diffraction analysis revealed that both the undoped and doped films were polycrystalline and exhibited galena type cubic structure with average crystallite size in the range of 15.5–30.9 nm. The compositional analysis results indicated that Pb, S and Al were present in the samples. Optical studies revealed prominent blue-shift in the absorption edge of as-deposited samples upon doping as compared to that of bulk PbS and this shift was due to a quantum confinement effect. The room temperature conductivity of the PbS thin films was in the range of 1.343×10⁻⁷–1.009×10⁻⁶ (Ω cm)⁻¹for doped samples and 5.172×10⁻⁸ for undoped PbS thin film sample. The optical band gap energy has inverse relation with grain size and electrical conductivity is closely related to structural parameters like grain size, crystallinity and microstrain. The estimated lattice parameter, grain size, optical band gaps and electrical properties were correlated with Al concentration in the cationic solution.     

Charge transport,doping and luminescence in solution-processed,phosphorescent, air-stable tellurophene thin films

Recently synthesized small molecule tellurophenes containing ring-appended pinacolboronate (BPin) side groups possess remarkable guest-free air-stable solid-state phosphorescence, structure-based color-tunability and aggregation induced enhanced emission. The charge transport, doping and luminescence behavior of thin transparent films of a tellurophene with BPin groups positioned at the 2,5-positions (B-Te-6-B) was investigated. Film formation played a critical role in determining the hole mobility and the photoluminescence (PL) lifetime. Drop-coated films showed the strongest crystallinity, the highest PL quantum yields and a hole mobility (μ_p) of 1.1 × 10⁻⁴ cm² V⁻¹ s⁻¹, which places tellurophenes in a select group of high mobility phosphorescent emitters. B-Te-6-B was also found to spontaneously form high aspect-ratio microwires upon drop-casting from supersaturated solutions. Oxidative doping in solution by a N(C₆H₄Br)₃[SbCl₆]/LiNTf₂ reagent combination (Tf = SO₂CF₃) increased conductivity by 2-4 orders of magnitude without inducing a color change in the films, while exposure to iodine vapor induced a dramatic change in color together with a 4-6 order of magnitude change in the conductivity. The optical transparency, facile electrical doping and relatively high hole mobilities of B-Te-6-B in solution processed thin films offer promise for the use of tellurophenes as host-free emissive layers and hole transport layers in organic optoelectronic devices.     

Annealing effects on physical properties of doped CdTe thin films for photovoltaic applications

Polycrystalline Cadmium Telluride (CdTe) thin films were prepared on glass substrates by thermal evaporation at the chamber ambient temperature and then annealed for an hour in vacuum ~1×10⁻⁵ mbar at 400 °C. These annealed thin films were doped with copper (Cu) via ion exchange by immersing these films in Cu (NO₃)₂ solution (1 g/1000 ml) for 20 min. Further these films were again annealed at different temperatures for better diffusion of dopant species. The physical properties of an as doped sample and samples annealed at different temperatures after doping were determined by using energy dispersive x-ray analysis (EDX), x-ray diffraction (XRD), Raman spectroscopy, transmission spectra analysis, photoconductivity response and hot probe for conductivity type. The optical band gap of these thermally evaporated Cu doped CdTe thin films was determined from the transmission spectra and was found to be in the range 1.42–1.75 eV. The direct energy band gap was found annealing temperatures dependent. The absorption coefficient was >10⁴ cm⁻¹ for incident photons having energy greater than the band gap energy. Optical density was observed also dependent on postdoping annealing temperature. All samples were found having p-type conductivity. These films are strong potential candidates for photovoltaic applications like solar cells.     

Dependence of charge carrier mobility of 4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine on doping concentration of tetrafluoro-tetracyano-quinodimethane

Electrical transport of pure and tetrafluoro-tetracyano-quinodimethane doped 4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA) films have been studied at various temperatures and doping concentrations. Pure films show space charge limited conduction with field and temperature dependent mobility. The J-V characteristics of doped m-MTDATA were ohmic at low voltages due to thermally released carriers from dopant states. At higher voltages the current density increases nonlinearly due to field dependent mobility and carrier concentration thereby filling of tail states of HOMO of the host. The conductivity of doped films were analysed using the Unified Gaussian Disorder Model (UGDM). The carrier concentration obtained from the fitting show a non-linear dependence on doping concentration which may be due to a combined effect of thermally activated carrier generation and increased carrier mobility.     

Structural phase transition in pentacene caused by molecular doping and its effect on charge carrier mobility

The structural properties and charge carrier mobility of pentacene doped by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) and 2,2-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (F6-TCNNQ) are studied by X-ray diffraction, scanning electron microscopy, field effect transistor measurements, and space charge limited currents (SCLC). We observe the presence of polycrystalline and amorphous domains within the doped pentacene film grown under co-deposition conditions. The appearance of the amorphous phase is induced by the molecular dopants F4-TCNQ and F6-TCNNQ. A strong drop of crystallite size is obtained at a doping concentration of around 7 and 4 wt.%, respectively. The loss of the polycrystalline structure is correlated to a strong decrease of the charge carrier mobility in pentacene in horizontal and vertical film structures. We discuss typical scenarios of charge transport for polycrystalline and amorphous thin films in order to explain the observed loss of mobility originated by the doping induced structural phase transition. In this way an optimum doping concentration for highest conductivity with acceptable mobility is determined which can help to improve the performance of organic solar cells and organic high-frequency rectification diodes.     

Influence of doping with third group oxides on properties of zinc oxide thin films

The study of modifications in structural, optical and electrical properties of vacuum evaporated zinc oxide thin films on doping with III group oxides namely aluminum oxide, gallium oxide and indium oxide are reported. It was observed that all the films have transmittance ranging from 85 to 95%. The variation in optical properties with dopants is discussed. On doping the film with III group oxides, the conductivity of the films showed an excellent improvement of the order of 10³ Ω^?1 cm^?1. The measurements of activation energy showed that all three oxide doped films have 2 donor levels below the conduction band.     

Degenerately Doped Semi-Crystalline Polymers for High Performance Thermoelectrics

Thermoelectric (TE) energy conversion in conjugated polymers is considered a promising approach for low-energy harvesting and self-powered temperature sensing. To enhance the TE performance, it is necessary to understand the relationship between the Seebeck coefficient (α) and electrical conductivity (σ). Typical doped polymers exhibit α–σ relationship that is distinct from that of inorganic materials due to their large structural and energetic disorder, which prevents them from achieving the maximum TE power factor (PF = α²σ). Here, an ideal α–σ relationship in the Kang–Snyder model following a transport parameter s  = 1 is demonstrated with two degenerately doped semi-crystalline polymers, poly[(4,4′-(bis(hexyldecylsulfanyl)methylene)cyclopenta[2,1-b:3,4-b′]dithiophene)-alt-(benzo[c][1,2,5]thiadiazole)] (PCPDTSBT) and poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBT) using a sequential doping method. The results allow the realization of the PFs reaching theoretic maxima (i.e., 112.01  µ W m⁻¹ K⁻² for PPDT2FBT and 49.80  µ W m⁻¹ K⁻² for PCPDTSBT) and close to metallic behavior in heavily doped films. Additionally, it is shown that the PF maxima appear when the doping state switches from non-degenerate to degenerate. Strategies towards an optimal α–σ relationship enable optimization of the PF and provide an understanding of the charge transport of doped polymers.     

Properties of antimony doped ZnO thin films deposited by spray pyrolysis technique

Antimony (Sb) doped zinc oxide (ZnO) thin films were deposited on the glass substrate at 450°C using spray pyrolysis technique. Effect of Sb doping on surface morphology structural, optical and electrical properties were studied. X-ray diffraction (XRD) analysis showed that both the undoped and doped ZnO thin films are polycrystalline in nature with (101) preferred orientation. SEM analysis showed a change in surface morphology of Sb doped ZnO thin films. Doping results in a marked increase in conductivity without affecting the transmittance of the films. ZnO films prepared with 3 at % Sb shows the lowest resistivity of 0.185 Ohm cm with a Hall mobility of 54.05 cm² V^–1 s^–1, and a hole concentration of 6.25 × 10¹⁷ cm^–3.     

Charge carrier mobility study of a mesogenic thienothiophene derivative in bulk and thin films

A novel mesogenic 2,5-bis-(5-octylthiophene)-thieno[3,2b]thiophene (TT) derivative has been synthesized. The fused-ring thiophene, end-capped with two octylthiophenes, exhibits ordered lamellar mesophases which were characterized by polarizing optical microscopy, differential scanning calorimetry and small-angle X-ray diffraction at various temperatures. The charge transport properties were investigated by time-of-flight technique as a function of temperature. On cooling from isotropic phase, a maximum hole mobility value of 0.07 cm² V⁻¹ s⁻¹ was measured in the highly ordered mesophase of the bulk films. Field-effect transistor experiments on both solution and vacuum deposited thin films have also been performed. The solution-processed films exhibit charge carrier mobilities several orders of magnitude lower than values extracted from bulk time-of-flight curves and from vacuum deposited thin film transistors. This work provides evidence that the melt-processing route is an efficient alternative to commonly used solution-processing for fabrication of charge transporting layers from liquid crystalline semiconductors, with performances comparable to evaporation techniques.     

Polaron Transport and Thermoelectric Behavior in La‐Doped SrTiO3 Thin Films with Elemental Vacancies

The electrodynamic properties of La‐doped SrTiO₃ thin films with controlled elemental vacancies are investigated using optical spectroscopy and thermopower measurement. In particular, a correlation between the polaron formation and thermoelectric properties of the transition metal oxide (TMO) thin films is observed. With decreasing oxygen partial pressure during the film growth (P(O₂)), a systematic lattice expansion is observed along with the increased elemental vacancy and carrier density, experimentally determined using optical spectroscopy. Moreover, an absorption in the mid‐infrared photon energy range is found, which is attributed to the polaron formation in the doped SrTiO₃ system. Thermopower of the La‐doped SrTiO₃ thin films can be largely modulated from –120 to –260 μV K^?1, reflecting an enhanced polaronic mass of ≈3 < m _polron/m < ≈4. The elemental vacancies generated in the TMO films grown at various P(O₂) influences the global polaronic transport, which governs the charge transport behavior, including the thermoelectric properties.     

A theoretical study on the charge transport properties of DNA

The charge transport properties of DNA are studied by the first-principle simulation to discuss the possibility of applying DNA to molecular wire. Both the hopping model and band-like model are introduced. By using hopping model, the theoretical hole mobilities calculated by Marcus theory between the same bases in DNA are 5.6 × 10⁻³, 4.1 × 10⁻², 2.0 × 10⁻² and 1.2 × 10⁻⁴ cm²V⁻¹s⁻¹ for T-T, A-A, C-C and G-G; and the calculated electron mobilities are 5.3 × 10⁻⁸, 1.5 × 10⁻⁴, 8.1 × 10⁻⁷ and 7.5 × 10⁻¹⁰ cm²V⁻¹s⁻¹ for T-T, A-A, C-C and G-G, respectively. And the charge transport for both holes and electrons between different bases exhibits directivity. By using band-like model, we calculated the band width of DNA with double helix structure and bilinear structure to investigate which structure will facilitate to the charge transport. We found that the band width of DNA increased when DNA transforming from the double helix structure to the bilinear structure, which means DNA with the bilinear structure possesses better charge transport properties. This research sheds a light on the molecular design for the molecule serving as the molecular wire.     

Solution Processing Route to Multifunctional Titania Thin Films: Highly Conductive and Photcatalytically Active Nb:TiO2

This paper reports the synthesis of highly conductive niobium doped titanium dioxide (Nb:TiO₂) films from the decomposition of Ti(OEt)₄ with dopant quantities of Nb(OEt)₅ by aerosol‐assisted chemical vapor deposition (AACVD). Doping Nb into the Ti sites results in n‐type conductivity, as determined by Hall effect measurements. The doped films display significantly improved electrical properties compared to pristine TiO₂ films. For 5 at.% Nb in the films, the charge carrier concentration was 2 × 10²¹ cm^?3 with a mobility of 2 cm² V^–1 s^–1 . The corresponding sheet resistance is as low as 6.5 Ω sq^–1 making the films suitable candidates for transparent conducting oxide (TCO) materials. This is, to the best of our knowledge, the lowest reported sheet resistance for Nb:TiO₂ films synthesized by vapour deposition. The doped films are also blue in colour, with the intensity dependent on the Nb concentration in the films. A combination of synchrotron, laboratory and theoretical techniques confirmed niobium doping into the anatase TiO₂ lattice. Computational methods also confirmed experimental results of both delocalized (Ti⁴⁺) and localized polaronic states (Ti³⁺) states. Additionally, the doped films also functioned as photocatalysts. Thus, Nb:TiO₂ combines four functional properties (photocatalysis, electrical conductivity, optical transparency and blue colouration) within the same layer, making it a promising alternative to conventional TCO materials.     

High Thermoelectric Performance of ZnO by Coherent Phonon Scattering and Optimized Charge Transport

ZnO is identified as a potentially attractive n-type oxide thermoelectric material due to its abundance, nontoxicity, and a high degree of stability. However, working with ZnO is challenging due to its high thermal conductivity from its strong ionic bonds and low electrical conductivity due to its low charge concentrations. Here, it is demonstrated that the electrical and thermal transport properties of ZnO can be simultaneously improved via the successful doping of Al and ZnS coating. The ZnS coating in Al-doped ZnO is observed and analyzed through microstructure and spectroscopic studies. The power factor for 1% ZnS-coated Zn_0.98Al_0.02O is increased to ≈0.75 mW m⁻¹ K⁻² at 1073 K, 161% higher than pure ZnO. This enhancement in the power factor can be explained by the aliovalent Al³⁺ doping and modifications in intrinsic defects, leading to an increased carrier concentration. Interestingly, ZnS coating significantly reduces lattice thermal conductivity to ≈2.31 W m⁻¹ K⁻¹ at 1073 K for 2% ZnS-coated Zn_0.98Al_0.02O, a 62% decrease over pure ZnO. This large reduction in lattice thermal conductivity can be elucidated based on coherent phonon scattering via Callaway's model. Overall, the figure of merit, zT, increases to 0.2 in 2% ZnS-coated Zn_0.98Al_0.02O, which is 272% higher than pure ZnO at 1073 K.     

Characterization of solution processed,p-doped films using hole-only devices and organic field-effect transistors

We report a solution processed, p-doped film consisting of the organic materials 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (MTDATA) as the electron donor and 2-(3-(adamantan-1-yl)propyl)-3,5,6-trifluorotetracyanoquinodimethane (F3TCNQ-Adl) as the electron acceptor. UV–vis–NIR absorption spectra identified the presence of a charge transfer complex between the donor and acceptor in the doped films. Field-effect transistors were used to characterize charge transport properties of the films, yielding mobility values. Upon doping, mobility increased and then slightly decreased while carrier concentration increased by two orders of magnitude, which in tandem leads to conductivity increasing from 4 × 10^?10 S/cm when undoped to 2 × 10^?7 S/cm at 30 mol% F3TCNQ-Adl. The hole density was calculated based on mobility values extracted from OFET data and conductivity values extracted from bulk I–V data for the MTDATA: x mol% F3TCNQ-Sdl films. These films were then shown to function as the hole injection/hole transport layer in a phosphorescent blue OLED.     

Effect of doping concentration on the properties of bismuth doped tin sulfide thin films prepared by spray pyrolysis

Bismuth doped tin sulfide (SnS:Bi) thin films were deposited onto glass substrates by the spray pyrolysis technique at the substrate temperature of 350 °C. The effect of doping concentration [Bi/Sn] on their structural, optical and electrical properties was investigated as a function of bismuth doping between 0 and 8 at%. The XRD results showed that the films were polycrystalline SnS with orthorhombic structure and the crystallites in the films were oriented along (111) direction. Atomic force microscopy revealed that the particle size and surface roughness of the films increased due to Bi-doping. Optical analysis exhibited the band gap value of 1.40 eV for SnS:Bi (6 at%) which was lower than the band gap value for 0 at% of Bi (1.60 eV). The film has low resistivity of 4.788×10⁻¹ Ω-cm and higher carrier concentration of 3.625×10¹⁸ cm⁻³ was obtained at a doping ratio of 6 at%.     

Careful Choices in Low Temperature Ceramic Processing and Slow Hydration Kinetics Can Affect Proton Conduction in Ceria

Low-temperature ceramic proton conductors such as ceria are important for applications ranging from sensors and resistive switches to new devices like implantable solid-oxide glucose fuel cells. Spray pyrolysis offers a promising fabrication route for proton-conducting ceria, with direct liquid-to-solid synthesis and control over crystallinity and grain size. To date, there are conflicting reports on ceria's proton conduction mechanism, particularly whether the interior contributes to proton conduction or transport occurs exclusively along a surface water layer. In this work, proton conductivity is observed in sprayed ceria thin films at 125 °C and below. Post-annealed films exhibit higher conductivity than as-deposited films of 3.3 × 10⁻⁵ S cm⁻¹ at 25 °C, which is comparable to previous reports and ascribed to the increase in crystallinity and grain size by post-annealing. This indicates that the interior of ceria in fact contributes to proton conduction. Remarkably slow hydration kinetics of ceria are observed, with time-dependent conductivity equilibrating to 9.53 × 10⁻⁶ S cm⁻¹ after up to 76 h. This implies kinetics may have suppressed proton conduction in previous studies, explaining the strong fluctuations in reports to date. Slow protonation kinetics must be considered when designing functional ceria ceramics, for example, in electrochemical bio-energy conversion, sensing or neuromorphic computing.     

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.     

Modulation Doping Leads to Optimized Thermoelectric Properties in n-Type Bi6Cu2Se4O6 due to Interface Effects

Heterogeneous composites consisting of Bi₆Cu₂Se_3.6Cl_0.4O₆ and Bi₂O₂Se are prepared according to the concept of modulation doping. With prominently increased carrier mobility and almost unchanged effective mass, the electrical transport properties are considerably optimized resulting in a peak power factor ≈1.8 µW cm⁻¹ K⁻² at 873 K, although the carrier concentration is slightly deteriorated. Meanwhile, the lattice thermal conductivity is lowered to ≈0.62 W m⁻¹ K⁻¹ due to the introduction of the second phase. The modified Self-consistent Effective Medium Theory is utilized to explain the deeper mechanism of modulation doping. The enhancement of apparent carrier mobility is derived from the highly active phase interfaces as fast carrier transport channels, while the reduced apparent thermal conductivity is ascribed to the existence of thermal resistance at the phase interfaces. Ultimately, an optimized ZT ≈0.23 is obtained at 873 K in Bi₆Cu₂Se_3.6Cl_0.4O₆ + 13% Bi₂O₂Se. This research demonstrates the effectiveness of modulation doping for optimizing thermoelectric properties once again, and provides the direct microstructure observation and consistent theoretical model calculation to emphasize the role of interface effects in modulation doping, which should be probably applicable to other thermoelectrics.     

CsPbBr3 Nanocrystal Films: Deviations from Bulk Vibrational and Optoelectronic Properties

Metal‐halide perovskites (MHP) are highly promising semiconductors for light‐emitting and photovoltaic applications. The colloidal synthesis of nanocrystals (NCs) is an effective approach for obtaining nearly defect‐free MHP that can be processed into inks for low‐cost, high‐performance device fabrication. However, disentangling the effects of surface ligands, morphology, and boundaries on charge‐carrier transport in thin films fabricated with these high‐quality NCs is inherently difficult. To overcome this fundamental challenge, terahertz (THz) spectroscopy is employed to optically probe the photoconductivity of CsPbBr₃ NC films. The vibrational and optoelectronic properties of the NCs are compared with those of the corresponding bulk polycrystalline perovskite and significant deviations are found. Charge‐carrier mobilities and recombination rates are demonstrated to vary significantly with the NC size. Such dependences derive from the localized nature of charge carriers within NCs, with local mobilities dominating over interparticle transport. It is further shown that the colloidally synthesized NCs have distinct vibrational properties with respect to the bulk perovskite, exhibiting blue‐shifted optical phonon modes with enhanced THz absorption strength that also manifest as strong modulations in the THz photoconductivity spectra. Such fundamental insights into NC versus bulk properties will guide the optimization of nanocrystalline perovskite thin films for optoelectronic applications.