In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skel...In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.展开更多
Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is...Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is attributed to the instability of Sn^(2+),which easily oxidizes to Sn^(4+),creating Sn vacancies and increasing the open-circuit voltage loss.In this work,we implemented tin thiocyanate(Sn(SCN)_(2))as an additive for passivating the bulk defects of a germanium-doped tin halide perovskite film.Adding Sn^(2+)and SCN-ions reduces the Sn and iodine vacancies,limiting non-radiative recombination and favoring longer charge-carrier dynamics.Moreover,the addition of Sn(SCN)_(2) induces a higher film crystallinity and preferential orientation of the(l00)planes parallel to the substrate.The passivated devices showed improved photovoltaic parameters with the best open-circuit voltage of 0.716 V and the best efficiency of 12.22%,compared to 0.647 V and 10.2%for the reference device.In addition,the passivated solar cell retains 88.7%of its initial efficiency after 80 min of illumination under 100 mW cm^(-2) and is substantially better than the control device,which reaches 82.6%of its initial power conversion efficiency only after 30 min.This work demonstrates the passivation potential of tin-based additives,which combined with different counterions give a relatively large space of choices for passivation of Sn-based perovskites.展开更多
0.INTRODUCTION.The Jiuwandashan Sn-polymetallic ore cluster,located in the western part of the Jiangnan Orogen and the Nanling Metallogenic Belt,is one of the most significant Precambrian tin ore concentration areas i...0.INTRODUCTION.The Jiuwandashan Sn-polymetallic ore cluster,located in the western part of the Jiangnan Orogen and the Nanling Metallogenic Belt,is one of the most significant Precambrian tin ore concentration areas in South China(Figure 1a;Mao et al.,1987).Recently,this region has garnered considerable research attention due to its intense mafic-felsic magmatic activity and large-scale Sn-polymetallic mineralization(Li et al.,2020;Chen J F et al.,2019;Huang and Wang,2019;Zhang et al.,2019;Chen L et al.,2018;Xiang et al.,2018;Su et al.,2014).A series of medium-to large-scale Sn-polymetallic deposits,including Jiumao,Liuxiu,Yidong,Honggangshan,and Shaping(Figure 1b),have been identified within this region,with proven tin reserves of approximately 200000 t.High-precision dating methods have yielded cassiterite U-Pb ages of ca.830 Ma,pointing to a Neoproterozoic Sn-polymetallic mineralization event in South China(Zhang et al.,2019;Xiang et al.,2018).展开更多
基金supported by Japan Society for the Promotion of Science(JSPS),a Grant-in-Aid for Scientific Research(B)(JP23K23398)(for M.G.)and(JP24K01570)(for K.T.).
文摘In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.
基金support from the Focus Group‘Next Generation Organic Photovoltaics’participating with the Dutch Institute for Fundamental Energy Research(DIFFER)(FOM130)Advanced Materials research program of the Zernike National Research Centre under the Bonus Incentive Scheme(BIS)of the Dutch Ministry for Education,Culture and Science.
文摘Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is attributed to the instability of Sn^(2+),which easily oxidizes to Sn^(4+),creating Sn vacancies and increasing the open-circuit voltage loss.In this work,we implemented tin thiocyanate(Sn(SCN)_(2))as an additive for passivating the bulk defects of a germanium-doped tin halide perovskite film.Adding Sn^(2+)and SCN-ions reduces the Sn and iodine vacancies,limiting non-radiative recombination and favoring longer charge-carrier dynamics.Moreover,the addition of Sn(SCN)_(2) induces a higher film crystallinity and preferential orientation of the(l00)planes parallel to the substrate.The passivated devices showed improved photovoltaic parameters with the best open-circuit voltage of 0.716 V and the best efficiency of 12.22%,compared to 0.647 V and 10.2%for the reference device.In addition,the passivated solar cell retains 88.7%of its initial efficiency after 80 min of illumination under 100 mW cm^(-2) and is substantially better than the control device,which reaches 82.6%of its initial power conversion efficiency only after 30 min.This work demonstrates the passivation potential of tin-based additives,which combined with different counterions give a relatively large space of choices for passivation of Sn-based perovskites.
基金financially supported by the National Natural Science Foundation of China(No.42472117)China Geological Survey(Nos.DD20243431,DD20230342,DD20240064)。
文摘0.INTRODUCTION.The Jiuwandashan Sn-polymetallic ore cluster,located in the western part of the Jiangnan Orogen and the Nanling Metallogenic Belt,is one of the most significant Precambrian tin ore concentration areas in South China(Figure 1a;Mao et al.,1987).Recently,this region has garnered considerable research attention due to its intense mafic-felsic magmatic activity and large-scale Sn-polymetallic mineralization(Li et al.,2020;Chen J F et al.,2019;Huang and Wang,2019;Zhang et al.,2019;Chen L et al.,2018;Xiang et al.,2018;Su et al.,2014).A series of medium-to large-scale Sn-polymetallic deposits,including Jiumao,Liuxiu,Yidong,Honggangshan,and Shaping(Figure 1b),have been identified within this region,with proven tin reserves of approximately 200000 t.High-precision dating methods have yielded cassiterite U-Pb ages of ca.830 Ma,pointing to a Neoproterozoic Sn-polymetallic mineralization event in South China(Zhang et al.,2019;Xiang et al.,2018).
