透明導電膜を必要としないタンデム型色素増感太陽電池の構造最適化と効率の向上

九州工業大学博士学位論文（要旨）学位記番号：生工博甲第253号 学位授与年月日平成28年3月25

Recent Advancements in Tin Halide Perovskite-Based Solar Cells and Thermoelectric Devices

The excellent optoelectronic properties of tin halide perovskites (Sn-PVKs) have made them a promising candidate for replacing toxic Pb counterparts. Concurrently, their enormous potential in photon harvesting and thermoelectricity applications has attracted increasing attention. The optoelectronic properties of Sn-PVKs are governed by the flexible nature of SnI6 octahedra, and they exhibit extremely low thermal conductivity. Due to these diverse applications, this review first analyzes the structural properties, optoelectronic properties, defect physics, and thermoelectric properties of Sn-PVKs. Then, recent techniques developed to solve limitations with Sn-PVK-based devices to improve their photoelectric and thermoelectric performance are discussed in detail. Finally, the challenges and prospects for further development of Sn-PVK-based devices are discussed

Daratumumab: A drug with transfusion dilemma

Daratumumab (DARA) is an anti-CD38 monoclonal antibody which has promising results in relapsed and refractory multiple myeloma (RRMM). DARA interferes with blood compatibility testing by causing incompatible results while crossmatching by antihuman globulin phase and presenting as a panagglutination picture in the indirect antiglobulin test. Immunohematology workup must be done to rule out allo- or autoantibody and to issue compatible unit to the patient as transfusion support is vital for all these patients and must not be delayed. Here, we present a case report of one such patient who was undergoing treatment with DARA for RRMM and had incompatibility found during crossmatching. Out of the available methods to resolve this problem, we utilized the treatment of red cells with 2-mercaptoethanol at our blood center which was effective, time saving, feasible, and less resource demanding. During the progressive course of disease, our patient required transfusion on a regular basis, and we were able to provide compatible units on each instance utilizing the same technique

Antibody Repertoire and Graft Outcome Following Solid Organ Transplantation

The first real major breakthrough that laid the basis of HLA antibody detection in the field of solid organ transplantation, came with the introduction of the complement dependent cytotoxicity (CDC) test in 1964 by Terasaki and McClelland. Since then, methods for antibody detection have evolved remarkably from conventional cell-based assays to the current advanced solid phase systems on the Luminex platform, with increasing degree of sensitivity and specificity. The latter have been indispensable for more accurate identification of donor specific HLA antibodies in broadly reactive allo antisera, and to guide donor selection and kidney paired exchange programs through virtual crossmatching, in addition to serving as excellent tools for initiating pre-transplant desensitization and post- transplant antibody monitoring. Consensus is evolving on the optimal routine employment of these methods in donor selection strategies along with an understanding of the clinical relevance of antibodies detected by each of them. The immunoassays based on the Luminex platform and flow cytometric beads are however unable to discriminate complement fixing from non-complement fixing HLA antibodies. This is important because the former are considered clinically more pertinent in the peri-transplant period. The C1q assay which is a modification of the solid phase assay based on Luminex single antigen beads, which can be used effectively to monitor high dose IVIG desensitization is essentially a surrogate complement fixing assay, retaining the exquisite sensitivity and specificity of the Luminex platform. Currently, information obtained from these assays is preliminary and much needs to be done to standardize technologies and set a consensus ‘MFI cut off’ for antibody positivity. Besides the overriding influence of anti-HLA antibodies on overall solid organ graft survival, immune response to non-HLA antigens has become a topic of substantial interest in recent years. An ever expanding list of non-HLA antigens has been implicated in graft rejection for various organs, of which the most noted are the Major Histocompatibility Complex class I chain-related molecule A (MICA), Vimentin, Myosin, Angiotensin II type 1 receptor (AT1R), Tubulin and Collagen. MICA is one of the most polymorphic and extensively studied non-HLA antigenic targets especially in renal transplantation. Although there are clear indications of MICA antibodies being associated with adverse graft outcome, to date a definitive consensus on this relationship has not been agreed. Because MICA molecules are not expressed constitutively on immunocompetent cells such as T and B lymphocytes, it is of utmost importance to address the impact of MICA donor specific antibodies (DSA) as compared to those that are non- donor specific (NDSA) on graft outcome. The soluble isoform of MICA molecule (sMICA) that is derived from the proteolytic shedding of membrane bound molecules has the potential to engage the NK-cell activating receptor NKG2D and down-regulate its expression. Consequent to the interaction of NKG2D by sMICA, the receptor ligand complex is endocytosed and degraded and thus suppresses NKG2D mediated lysis of the target by NK cells. Thus interaction between NKG2D and sMICA leads to expansion of immunosuppressive/anergic T cells thereby resulting in suppression of NKG2D mediated host innate immunity. These concept support the possible involvement of an immunosuppressive role for sMICA during allotransplantation as shown recently for heart transplantation. This research topic focuses on the clinical utility of investigating the complete antibody repertoire in solid organ transplantation

Enhancing the Electronic Properties and Stability of High-EfficiencyTin-Lead Mixed Halide Perovskite Solar Cells via DopingEngineering

Overcoming Voc loss to increase the efficiency of perovskite solar cells (PSCs) has been aggressively studied. In this work, we introduce and compare rubidium iodide (RbI) and potassium iodide (KI) alkali metal halides (AMHs) as dopants in a tin–lead (SnPb)-based perovskite system to improve the performance of PSCs by enhancing their Voc. Improvement in terms of surface morphology, crystallinity, charge transfer, and carrier transport in the SnPb perovskites was observed with the addition of AMH dopants. Significant power conversion efficiency improvement has been achieved with the incorporation of either dopant, and the highest efficiency was 21.04% in SnPb mixed halide PSCs when the RbI dopant was employed. In conclusion, we can outline the enhancement strategy that yields a remarkable efficiency of >20% with a smaller Voc loss and improved storage, light, and thermal stability in SnPb PSCs via doping engineering

Lead-free perovskite solar cells using Sb and Bi-based A3B2X9 and A3BX6 crystals with normal and inverse cell structures

Abstract Research of CH3NH3PbI3 perovskite solar cells had significant attention as the candidate of new future energy. Due to the toxicity, however, lead (Pb) free photon harvesting layer should be discovered to replace the present CH3NH3PbI3 perovskite. In place of lead, we have tried antimony (Sb) and bismuth (Bi) with organic and metal monovalent cations (CH3NH3 +, Ag+ and Cu+). Therefore, in this work, lead-free photo-absorber layers of (CH3NH3)3Bi2I9, (CH3NH3)3Sb2I9, (CH3NH3)3SbBiI9, Ag3BiI6, Ag3BiI3(SCN)3 and Cu3BiI6 were processed by solution deposition way to be solar cells. About the structure of solar cells, we have compared the normal (n-i-p: TiO2-perovskite-spiro OMeTAD) and inverted (p-i-n: NiO-perovskite-PCBM) structures. The normal (n-i-p)-structured solar cells performed better conversion efficiencies, basically. But, these environmental friendly photon absorber layers showed the uneven surface morphology with a particular grow pattern depend on the substrate (TiO2 or NiO). We have considered that the unevenness of surface morphology can deteriorate the photovoltaic performance and can hinder future prospect of these lead-free photon harvesting layers. However, we found new interesting finding about the progress of devices by the interface of NiO/Sb3+ and TiO2/Cu3BiI6, which should be addressed in the future study

High-Efficiency Lead-Free Wide Band Gap Perovskite Solar Cells via Guanidinium Bromide Incorporation

Despite lead halide perovskite(top)/silicon(bottom) tandem solar cell achieving >29% efficiency, the toxicity of lead limits the adoption of perovskites in electronic devices. To solve this problem, tin perovskite has been suggested as an alternative candidate to be used as the top cell. However, most of the reports on tin perovskite solar cells are based on narrow band gap materials (band gap: 1.20–1.40 eV), which are not suitable to be used as the tandem top cell. In addition, the efficiency of the previously reported wide band gap lead-free perovskites is not satisfactory, shown to be less than 2.00%. This study explores the fabrication of the wide band gap (1.61 eV) ASnI2Br perovskite solar cells through the optimization of formamidinium and guanidinium content to improve the efficiency from 1.68 to 7.00%. Substituting the A site with larger cation results in a larger crystal size, which translated into higher device stability. Better energy-level alignment within the device significantly enhanced the charge injection and extraction, which translated into higher open-circuit voltage. This work provides proof that tin-halide perovskite solar cells have the potential in the fabrication of lead-free all-perovskite tandem solar cells.This research was supported by JST Mirai Program (JPMJMI17EA) and the Chinese Scholarship Council (CSC202008050034)