Close-Space Sublimation as a Scalable Method for Perovskite Solar Cells.

Vacuum techniques for perovskite photovoltaics (PV) are promising for their scalability but are rarely studied with techniques readily adaptable for industry. In this work, we study the use of close-space sublimation (CSS) for making perovskite solar cells, a technique that has seen widespread use in industry, including in PV, and benefits from high material-transfer and low working pressures. A pressed pellet of formamidinium iodide (FAI) can be used multiple times as an organic source, without needing replacement. Using CSS at a rough vacuum (10 mbar), efficient cesium formamidinium lead iodide perovskite based solar cells are obtained reaching a maximum photoconversion efficiency (PCE) of 18.7%. They maintain their performance for >650 h when thermally stressed at 85 °C in a nitrogen environment. To explain the initial rise in PCE upon heating, we used drift-diffusion simulations and identified a reduction in bulk trap density as the primary factor.

Sequential vs myeloablative vs reduced intensity conditioning for patients with myelodysplastic syndromes with an excess of blasts at time of allogeneic haematopoietic cell transplantation: a retrospective study by the chronic malignancies working party of the EBMT.

The optimal conditioning for patients with higher risk MDS receiving potentially curative allogeneic haematopoietic stem cell transplant(allo-HCT) remains to be defined. This is particularly the case for patients with excess of blasts at time of allo-HCT. Sequential (Seq) conditioning, whereby chemotherapy is followed rapidly by transplant conditioning, offers an opportunity to decrease disease burden, potentially improving outcomes allo-HCT outcomes. Herein we present the only analysis comparing Seq to myeloablative (MAC) and reduced intensity conditioning (RIC) specifically focussed on MDS patients with excess of blasts at allo-HCT. 303 patients were identified in the EBMT registry, receiving RIC (n = 158), Seq (n = 105), and MAC (n = 40). Median follow-up was 67.2 months and median age at allo-HCT was 59.5 years (IQR 53.5-65.6). For the entire cohort, 3 y overall survival (OS) was 50% (95% CI 45-56%) and relapse free survival (RFS) 45% (95% CI 40-51%). No significant differences in OS (log-rank p = 0.13) and RFS (log-rank p = 0.18) were observed between conditioning protocols. On multivariable analysis, lower performance status, worse IPSS-R cytogenetics, sibling donor (compared to 8/8 MUD) and ≥20% blasts at allo-HCT were associated with worse outcomes. In conclusion, the Seq protocol did little to influence the outcome in this high-risk group of patients, with outcomes mostly determined by baseline disease risk and patient characteristics such as performance status.

A method for identifying the cause of inefficient salt-doping in organic semiconductors.

Doping to enhance the electrical conductivity of organic semiconductors is not without its challenges: The efficacy of this process depends on many factors and it is not always clear how to remedy poor doping. In the case of doping with salts, one of the possible causes of poor doping is a limited yield of integer charge transfer resulting in the presence of both cations and anions in the film. The charge of such ions can severely limit the electrical conductivity, but their presence is not easily determined. Here we introduce a set of simple conductivity measurements to determine whether poor doping in the case where the dopant is a salt is due to limited integer charge transfer. By tracking how the conductivity changes over time when applying a bias voltage for an extended amount of time we can pinpoint whether unwanted ions are present in the film. Firstly, we introduce the principle of this approach by performing numerical simulations that include the movement of ions. We show that the conductivity can increase or decrease depending on the type of ions present in the film. Next, we show that the movement of these dopant ions causes a build-up of space-charge, which makes the current-voltage characteristic non-linear. Next, we illustrate how this approach may be used in practice by doping a fullerene derivative with a series of organic salts. We thus provide a tool to make the optimization of doping more rational.

Vacuum-Deposited Cesium Tin Iodide Thin Films with Tunable Thermoelectric Properties.

Most current thermoelectric materials have important drawbacks, such as toxicity, scarceness, and peak operating temperatures above 300 °C. Herein, we report the thermoelectric properties of different crystalline phases of Sn-based perovskite thin films. The 2D phase, Cs2SnI4, is obtained through vacuum thermal deposition and easily converted into the black ß phase of CsSnI3 (B-ß CsSnI3) by annealing at 150 °C. B-ß CsSnI3 is a p-type semiconductor with a figure of merit (ZT) ranging from 0.021 to 0.033 for temperatures below 100 °C, which makes it a promising candidate to power small electronic devices such as wearable sensors which may be interconnected in the so-called Internet of Things. The B-ß phase is stable in nitrogen, whereas it spontaneously oxidizes to Cs2SnI6 upon exposure to air. Cs2SnI6 shows a negative Seebeck coefficient and an ultralow thermal conductivity. However, the ZT values are 1 order of magnitude lower than for B-ß CsSnI3 due to a considerably lower electrical conductivity.

Representational similarity scores of digits in the sensorimotor cortex are associated with behavioral performance.

Previous studies aimed to unravel a digit-specific somatotopy in the primary sensorimotor (SM1) cortex. However, it remains unknown whether digit somatotopy is associated with motor preparation and/or motor execution during different types of tasks. We adopted multivariate representational similarity analysis to explore digit activation patterns in response to a finger tapping task (FTT). Sixteen healthy young adults underwent magnetic resonance imaging, and additionally performed an out-of-scanner choice reaction time task (CRTT) to assess digit selection performance. During both the FTT and CRTT, force data of all digits were acquired using force transducers. This allowed us to assess execution-related interference (i.e., digit enslavement; obtained from FTT & CRTT), as well as planning-related interference (i.e., digit selection deficit; obtained from CRTT) and determine their correlation with digit representational similarity scores of SM1. Findings revealed that digit enslavement during FTT was associated with contralateral SM1 representational similarity scores. During the CRTT, digit enslavement of both hands was also associated with representational similarity scores of the contralateral SM1. In addition, right hand digit selection performance was associated with representational similarity scores of left S1. In conclusion, we demonstrate a cortical origin of digit enslavement, and uniquely reveal that digit selection is associated with digit representations in primary somatosensory cortex (S1). Significance statement In current systems neuroscience, it is of critical importance to understand the relationship between brain function and behavioral outcome. With the present work, we contribute significantly to this understanding by uniquely assessing how digit representations in the sensorimotor cortex are associated with planning- and execution-related digit interference during a continuous finger tapping and a choice reaction time task. We observe that digit enslavement (i.e., execution-related interference) finds its origin in contralateral digit representations of SM1, and that deficits in digit selection (i.e., planning-related interference) in the right hand during a choice reaction time task are associated with more overlapping digit representations in left S1. This knowledge sheds new light on the functional contribution of the sensorimotor cortex to everyday motor skills.

Backbone-driven host-dopant miscibility modulates molecular doping in NDI conjugated polymers.

Molecular doping is the key to enabling organic electronic devices, however, the design strategies to maximize doping efficiency demands further clarity and comprehension. Previous reports focus on the effect of the side chains, but the role of the backbone is still not well understood. In this study, we synthesize a series of NDI-based copolymers with bithiophene, vinylene, and acetylenic moieties (P1G, P2G, and P3G, respectively), all containing branched triethylene glycol side chains. Using computational and experimental methods, we explore the impact of the conjugated backbone using three key parameters for doping in organic semiconductors: energy levels, microstructure, and miscibility. Our experimental results show that P1G undergoes the most efficient n-type doping owed primarily to its higher dipole moment, and better host-dopant miscibility with N-DMBI. In contrast, P2G and P3G possess more planar backbones than P1G, but the lack of long-range order, and poor host-dopant miscibility limit their doping efficiency. Our data suggest that backbone planarity alone is not enough to maximize the electrical conductivity (σ) of n-type doped organic semiconductors, and that backbone polarity also plays an important role in enhancing σ via host-dopant miscibility. Finally, the thermoelectric properties of doped P1G exhibit a power factor of 0.077 µW m-1 K-2, and ultra-low in-plane thermal conductivity of 0.13 W m-1K-1 at 5 mol% of N-DMBI, which is among the lowest thermal conductivity values reported for n-type doped conjugated polymers.

Molecular Doping Directed by a Neutral Radical.

Molecular doping makes possible tunable electronic properties of organic semiconductors, yet a lack of control of the doping process narrows its scope for advancing organic electronics. Here, we demonstrate that the molecular doping process can be improved by introducing a neutral radical molecule, namely nitroxyl radical (2,2,6,6-teramethylpiperidin-i-yl) oxyl (TEMPO). Fullerene derivatives are used as the host and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazoles (DMBI-H) as the n-type dopant. TEMPO can abstract a hydrogen atom from DMBI-H and transform the latter into a much stronger reducing agent DMBI•, which efficiently dopes the fullerene derivative to yield an electrical conductivity of 4.4 S cm-1. However, without TEMPO, the fullerene derivative is only weakly doped likely by a hydride transfer following by an inefficient electron transfer. This work unambiguously identifies the doping pathway in fullerene derivative/DMBI-H systems in the presence of TEMPO as the transfer of a hydrogen atom accompanied by electron transfer. In the absence of TEMPO, the doping process inevitably leads to the formation of less symmetrical hydrogenated fullerene derivative anions or radicals, which adversely affect the molecular packing. By adding TEMPO we can exclude the formation of such species and, thus, improve charge transport. In addition, a lower temperature is sufficient to meet an efficient doping process in the presence of TEMPO. Thereby, we provide an extra control of the doping process, enabling enhanced thermoelectric performance at a low processing temperature.

Controlling n-Type Molecular Doping via Regiochemistry and Polarity of Pendant Groups on Low Band Gap Donor-Acceptor Copolymers.

We demonstrate the impact of the type and position of pendant groups on the n-doping of low-band gap donor-acceptor (D-A) copolymers. Polar glycol ether groups simultaneously increase the electron affinities of D-A copolymers and improve the host/dopant miscibility compared to nonpolar alkyl groups, improving the doping efficiency by a factor of over 40. The bulk mobility of the doped films increases with the fraction of polar groups, leading to a best conductivity of 0.08 S cm-1 and power factor (PF) of 0.24 µW m-1 K-2 in the doped copolymer with the polar pendant groups on both the D and A moieties. We used spatially resolved absorption spectroscopy to relate commensurate morphological changes to the dispersion of dopants and to the relative local doping efficiency, demonstrating a direct relationship between the morphology of the polymer phase, the solvation of the molecular dopant, and the electrical properties of doped films. Our work offers fundamental new insights into the influence of the physical properties of pendant chains on the molecular doping process, which should be generalizable to any molecularly doped polymer films.

Revealing Charge Carrier Mobility and Defect Densities in Metal Halide Perovskites via Space-Charge-Limited Current Measurements.

Space-charge-limited current (SCLC) measurements have been widely used to study the charge carrier mobility and trap density in semiconductors. However, their applicability to metal halide perovskites is not straightforward, due to the mixed ionic and electronic nature of these materials. Here, we discuss the pitfalls of SCLC for perovskite semiconductors, and especially the effect of mobile ions. We show, using drift-diffusion (DD) simulations, that the ions strongly affect the measurement and that the usual analysis and interpretation of SCLC need to be refined. We highlight that the trap density and mobility cannot be directly quantified using classical methods. We discuss the advantages of pulsed SCLC for obtaining reliable data with minimal influence of the ionic motion. We then show that fitting the pulsed SCLC with DD modeling is a reliable method for extracting mobility, trap, and ion densities simultaneously. As a proof of concept, we obtain a trap density of 1.3 × 1013 cm-3, an ion density of 1.1 × 1013 cm-3, and a mobility of 13 cm2 V-1 s-1 for a MAPbBr3 single crystal.

Trends in allogeneic haematopoietic cell transplantation for myelofibrosis in Europe between 1995 and 2018: a CMWP of EBMT retrospective analysis.

We performed a retrospective assessment of patient- and transplant-specific characteristics and outcomes for 4142 patients undergoing allogeneic haematopoietic cell transplant for myelofibrosis between 1995 and 2018 across 278 centres. Activity increased steadily across the four analysed eras (<2006, 2006-2010, 2011-2014 and 2015-2018). Median recipient age increased over time between the earliest and most recent cohort (49.4 years (range, 20.1-68) versus 59.3 years (range, 18.1-78.1). Increasing number of patients with a Karnofsky performance status <90 underwent transplant over time. Increased utilisation of matched unrelated donors was apparent (<2006, 22.5% versus 2015-18, 45.2%; p < 0.001). Decreased use of myeloablative conditioning, increased use of busulphan-based platforms and anti-thymocyte globulin was evident. Of note, rates of acute (a)GVHD grade II-IV by day +100 decreased over time (p = 0.027) as did rates of chronic (c) GVHD, predominantly extensive cGVHD (<2006, 36% (31-41%) versus 2015-18, 23% (21-25%); p = 0.001). Overall, significant factors associated with worse overall survival and non-relapse mortality (NRM) remained older age, use of donors other than matched sibling, recipient CMV seropositivity and a lower Karnofsky performance status (<90). Multivariable analysis demonstrated improvements in overall survival and reductions in relapse risk over time with stable NRM rates despite increasing numbers of older, less fit patients and use of unrelated donors.

Amphipathic Side Chain of a Conjugated Polymer Optimizes Dopant Location toward Efficient N-Type Organic Thermoelectrics.

There is no molecular strategy for selectively increasing the Seebeck coefficient without reducing the electrical conductivity for organic thermoelectrics. Here, it is reported that the use of amphipathic side chains in an n-type donor-acceptor copolymer can selectively increase the Seebeck coefficient and thus increase the power factor by a factor of ≈5. The amphipathic side chain contains an alkyl chain segment as a spacer between the polymer backbone and an ethylene glycol type chain segment. The use of this alkyl spacer does not only reduce the energetic disorder in the conjugated polymer film but can also properly control the dopant sites away from the backbone, which minimizes the adverse influence of counterions. As confirmed by kinetic Monte Carlo simulations with the host-dopant distance as the only variable, a reduced Coulombic interaction resulting from a larger host-dopant distance contributes to a higher Seebeck coefficient for a given electrical conductivity. Finally, an optimized power factor of 18 µW m-1 K-2 is achieved in the doped polymer film. This work provides a facile molecular strategy for selectively improving the Seebeck coefficient and opens up a new route for optimizing the dopant location toward realizing better n-type polymeric thermoelectrics.

Electrical Conductivity of Doped Organic Semiconductors Limited by Carrier-Carrier Interactions.

High electrical conductivity is a prerequisite for improving the performance of organic semiconductors for various applications and can be achieved through molecular doping. However, often the conductivity is enhanced only up to a certain optimum doping concentration, beyond which it decreases significantly. We combine analytical work and Monte Carlo simulations to demonstrate that carrier-carrier interactions can cause this conductivity decrease and reduce the maximum conductivity by orders of magnitude, possibly in a broad range of materials. Using Monte Carlo simulations, we disentangle the effect of carrier-carrier interactions from carrier-dopant interactions. Coulomb potentials of ionized dopants are shown to decrease the conductivity, but barely influence the trend of conductivity versus doping concentration. We illustrate these findings using a doped fullerene derivative for which we can correctly estimate the carrier density at which the conductivity maximizes. We use grazing-incidence wide-angle X-ray scattering to show that the decrease of the conductivity cannot be explained by changes to the microstructure. We propose the reduction of carrier-carrier interactions as a strategy to unlock higher-conductivity organic semiconductors.

Effects of Fluorination on Fused Ring Electron Acceptor for Active Layer Morphology, Exciton Dissociation, and Charge Recombination in Organic Solar Cells.

Fluorination is one of the effective approaches to alter the organic semiconductor properties that impact the performance of the organic solar cells (OSCs). Positive effects of fluorination are also revealed in the application of fused ring electron acceptors (FREAs). However, in comparison with the efforts allocated to the material designs and power conversion efficiency enhancement, understanding on the excitons and charge carriers' behaviors in high-performing OSCs containing FREAs is limited. Herein, the impact of fluorine substituents on the active layer morphology, and therefore exciton dissociation, charge separation, and charge carriers' recombination processes are examined by fabricating OSCs with PTO2 as the donor and two FREAs, O-IDTT-IC and its fluorinated analogue O-IDTT-4FIC, as the acceptors. With the presence of O-IDTT-4FIC in the devices, it is found that the excitons dissociate more efficiently, and the activation energy required to split the excitons to free charge carriers is much lower; the charge carriers live longer and suffer less extent of trap-assisted recombination; the trap density is 1 order of magnitude lower than that of the nonfluorinated counterpart. Overall, these findings provide information about the complex impacts of FREA fluorination on efficiently performed OSCs.

N-type organic thermoelectrics: demonstration of ZT > 0.3.

The 'phonon-glass electron-crystal' concept has triggered most of the progress that has been achieved in inorganic thermoelectrics in the past two decades. Organic thermoelectric materials, unlike their inorganic counterparts, exhibit molecular diversity, flexible mechanical properties and easy fabrication, and are mostly 'phonon glasses'. However, the thermoelectric performances of these organic materials are largely limited by low molecular order and they are therefore far from being 'electron crystals'. Here, we report a molecularly n-doped fullerene derivative with meticulous design of the side chain that approaches an organic 'PGEC' thermoelectric material. This thermoelectric material exhibits an excellent electrical conductivity of >10 S cm-1 and an ultralow thermal conductivity of <0.1 Wm-1K-1, leading to the best figure of merit ZT = 0.34 (at 120 °C) among all reported single-host n-type organic thermoelectric materials. The key factor to achieving the record performance is to use 'arm-shaped' double-triethylene-glycol-type side chains, which not only offer excellent doping efficiency (~60%) but also induce a disorder-to-order transition upon thermal annealing. This study illustrates the vast potential of organic semiconductors as thermoelectric materials.

Long-range exciton diffusion in molecular non-fullerene acceptors.

The short exciton diffusion length associated with most classical organic semiconductors used in organic photovoltaics (5-20 nm) imposes severe limits on the maximum size of the donor and acceptor domains within the photoactive layer of the cell. Identifying materials that are able to transport excitons over longer distances can help advancing our understanding and lead to solar cells with higher efficiency. Here, we measure the exciton diffusion length in a wide range of nonfullerene acceptor molecules using two different experimental techniques based on photocurrent and ultrafast spectroscopy measurements. The acceptors exhibit balanced ambipolar charge transport and surprisingly long exciton diffusion lengths in the range of 20 to 47 nm. With the aid of quantum-chemical calculations, we are able to rationalize the exciton dynamics and draw basic chemical design rules, particularly on the importance of the end-group substituent on the crystal packing of nonfullerene acceptors.

Can Ferroelectricity Improve Organic Solar Cells?

Blends of semiconducting (SC) and ferroelectric (FE) polymers have been proposed for applications in resistive memories and organic photovoltaics (OPV). For OPV, the rationale is that the local electric field associated with the dipoles in a blend could aid exciton dissociation, thus improving power conversion efficiency. However, FE polymers either require solvents or processing steps that are incompatible with those required for SC polymers. To overcome this limitation, SC (poly(3-hexylthiophene)) and FE (poly(vinylidene fluoride-trifluoroethylene)) components are incorporated into a block copolymer and thus a path to a facile fabrication of smooth thin films from suitably chosen solvents is achieved. In this work, the photophysical properties and device performance of organic solar cells containing the aforementioned block copolymer consisting of poly(vinylidene fluoride-trifluoroethylene): P(VDF-TrFE), poly(3-hexylthiophene): P3HT and the electron acceptor phenyl-C61 -butyric acid methyl ester: [60]PCBM are explored. A decrease in photovoltaic performance is observed in blends of the copolymer with P3HT:[60]PCBM, which is attributed to a less favorable nanomorphology upon addition of the copolymer. The role of lithium fluoride (the cathode modification layer) is also clarified in devices containing the copolymer, and it is demonstrated that ferroelectric compensation prevents the ferroelectricity of the copolymer from improving photovoltaic performance in SC-FE blends.

An international survey on the management of patients receiving CAR T-cell therapy for haematological malignancies on behalf of the Chronic Malignancies Working Party of EBMT.

PURPOSE OF THE STUDY: Two chimeric antigen receptor (CAR) T-cell therapies - Tisagenlecleucel (Kymriah™) and Axicabtagene ciloleucel (Yescarta™) - have been approved for commercial use. In order to inform forthcoming EBMT guidelines on the management of adults and children undergoing autologous CAR T-cell therapy, we undertook a survey of experienced clinicians. METHODS: An online survey with a dual focus on (1) 'real world' patient eligibility criteria and (2) models of care for patient follow-up was sent to experienced physicians. RESULTS: There were 41 respondents (10 countries) and 93% worked in FACT-JACIE-accredited transplant centres. Most felt that a history of malignancy (57%), prior allo-HCT for B-NHL (78%-81%) and prior treatment with anti-CD19/CD3 BiTE antibodies (76%-86%) do not constitute contra-indications to CAR T therapy. Clinicians were divided as to whether CNS involvement represented an exclusion criterion. There was agreement that patients with viral infections (HIV, Hepatitis B or Hepatitis C) are not eligible. There is no common model of care for long-term follow-up. Most respondents believed that patients should attend the hospital two (43%) to three (33%) times weekly during the first month following discharge. A majority (69%) of respondents work in centres where there is an MDT meeting with a specific focus on follow-up following CAR T Therapy. Follow-up care is currently delivered either in HCT or haematology-oncology outpatient clinics. CONCLUSION: The responses reveal wide variation in perceived patient eligibility criteria and highlight the need for consensus guidelines. The findings also illustrate the embryonic nature of current follow-up arrangements.

1,8-diiodooctane acts as a photo-acid in organic solar cells.

The last decade saw myriad new donor polymers, among which benzodithiophene-co-thienothiophene polymers are attractive due to their relatively high power conversion efficiency in bulk heterojunction solar cells. We examine the effect of UV-light on the stability of these polymers. The relationship between the polymer chemical structure and the UV-stability of the cells is explored on the one hand, and on the other hand, the effect of additives on their UV-stability: 1,8-diiodooctane against 1-chloronaphthalene in the cells and 1,8-octanedithiol in solution. For example, PBDTTT-E with 18% efficiency loss is more stable than PBDTTT-ET with 36% loss throughout the exposure. While 1,8-diiodooctane acts as photo-acid and leads to accelerated degradation of the solar cells, 1-chloronaphthalene does not. Acidity is known to be detrimental to the efficiency and stability of organic solar cells. The degradation is initiated upon UV-irradiation by the cleavage of the side chains, resulting in more electron traps and by the formation of iodine, dissolved HI and carbon-centered radicals from 1,8-diiodooctane as revealed by 1H NMR spectrum. The 1,8-octanedithiol spectra do not show such species. Finally, the mechanisms behind the effect of 1,8-diiodooctane are explained, paving the way for the design of new, efficient as well as stable materials and additives.

Photostability of Fullerene and Non-Fullerene Polymer Solar Cells: The Role of the Acceptor.

Recently, the advent of non-fullerene acceptors (NFAs) made it possible for organic solar cells (OSCs) to break the 10% efficiency barrier hardly attained by fullerene acceptors (FAs). In the past five years alone, more than hundreds of NFAs with applications in organic photovoltaics (OPVs) have been synthesized, enabling a notable current record efficiency of above 15%. Hence, there is a shift in interest toward the use of NFAs in OPVs. However, there has been little work on the stability of these new materials in devices. More importantly, there is very little comparative work on the photostability of FA versus NFA solar cells to ascertain the pros and cons of the two systems. Here, we show the photostability of solar cells based on two workhorse acceptors, in both conventional and inverted structures, namely, ITIC (as NFA) and [70]PCBM (as FA), blended with either PBDB-T or PTB7-Th polymer. We found that, irrespective of the polymer, the cell structure, or the initial efficiency, the [70]PCBM devices are more photostable than the ITIC ones. This observation, however, opposes the assumption that NFA solar cells are more photochemically stable. These findings suggest that complementary absorption should not take precedence in the design rules for the synthesis of new molecules and there is still work left to be done to achieve stable and efficient OSCs.

N-Type Organic Thermoelectrics of Donor-Acceptor Copolymers: Improved Power Factor by Molecular Tailoring of the Density of States.

It is demonstrated that the n-type thermoelectric performance of donor-acceptor (D-A) copolymers can be enhanced by a factor of >1000 by tailoring the density of states (DOS). The DOS distribution is tailored by embedding sp2 -nitrogen atoms into the donor moiety of the D-A backbone. Consequently, an electrical conductivity of 1.8 S cm-1 and a power factor of 4.5 µW m-1 K-2 are achieved. Interestingly, an unusual sign switching (from negative to positive) of the Seebeck coefficient of the unmodified D-A copolymer at moderately high dopant loading is observed. A direct measurement of the DOS shows that the DOS distributions become less broad upon modifying the backbone in both pristine and doped states. Additionally, doping-induced charge transfer complexes (CTC) states, which are energetically located below the neutral band, are observed in DOS of the doped unmodified D-A copolymer. It is proposed that charge transport through these CTC states is responsible for the positive Seebeck coefficients in this n-doped system. This is supported by numerical simulation and temperature dependence of Seebeck coefficient. The work provides a unique insight into the fundamental understanding of molecular doping and sheds light on designing efficient n-type OTE materials from a perspective of tailoring the DOS.