Improving the performance of arylamine-based hole transporting materials in perovskite solar cells： Extending π-conjugation length or increasing the number of side groups？

In this work, we prepared three simple arylamine-based hole transporting materials from commercially available starting materials. The effect of extending z-conjugation length or increasing the number of side groups compared with reference compound on the photophysical, electrochemical, hole mobility properties and performance in perovskite solar cells were further studied. It is noted that these two kinds of molecular modifications can significantly lower the HOMO level and improve the hole mobility, thus improving the hole injection from valence band of perovskite. On the other hand, the compound with more side groups showed higher hole injection efficiency due to lower HOMO level and higher hole mo- bility compared with the compound with extending π-conjugation length. The perovskite solar cells with the modified molecules as hole transporting materials showed a higher efficiency of 15.40% and 16.95%, respectively, which is better than that of the reference compound （13.18%）. Moreover, the compound with increasing number of side groups based devices showed comparable photovoltaic performance with that of conventional spiro-OMeTAD （16.87%）.

Crystal Chemistry Research of Minerals of Nigerite Group and Its Significance

There is a type of complex oxide mineral, composed of many elements such as Sn, Mg, Fe, Zn, Ti, Mn, Al, etc., in the areas of Anhua, Linwu and Shizhuyuan of Hunan Province. These minerals belong to nigerite, Mg-nigerite (pengzhizhongite), etc.. According to the principle of closest packing, the crystal chemical properties of nigerite (brown), pengzhizhongite (buff), Zn-nigerite (fawn), Fe-nigerite, Mn-nigerite (greenish-black) etc. have been analyzed. Their crystal structures may be characterized by O (the layers of cation octahedral coordinations), T_1 (the mixed layers of cation octahedral coordinations and cation tetrahedral coordinations in same directions), T_2 (the mixed layers of cation octahedral coordinations and cation tetrahedral coordination in different directions). The position of layer-O and layer-T is alternate permutation. The crystal structure of pengzhizhongite (6 H ) may be expressed by …OT_2OT_1OT_1…, taaffeite (8 H ), …OT_2OT_1OT_2OT_1…, and nigerite (24 R ), … OT_1OT_2 OT_2OT_1 …×3 etc.. In their structure, there are not only the crystal structure units of spinel … OT_2 OT_2 … but also the units of nolanite … OT_1 OT_1 …. The research of these minerals has important theoretic and practical significance in the fields of minerals, gemology, material science etc..

Stabilizing Buried Interface via Synergistic Effect of Fluorine and Sulfonyl Functional Groups Toward Efficient and Stable Perovskite Solar Cells

The interfacial defects and energy barrier are main reasons for interfacial nonradiative recombination.In addition,poor perovskite crystallization and incomplete conversion of PbI_(2) to perovskite restrict further enhancement of the photovoltaic performance of the devices using sequential deposition.Herein,a buried interface stabilization strategy that relies on the synergy of fluorine(F)and sulfonyl(S=O)functional groups is proposed.A series of potassium salts containing halide and non-halogen anions are employed to modify SnO_(2)/perovskite buried interface.Multiple chemical bonds including hydrogen bond,coordination bond and ionic bond are realized,which strengthens interfacial contact and defect passivation effect.The chemical interaction between modification molecules and perovskite along with SnO_(2) heightens incessantly as the number of S=O and F augments.The chemical interaction strength between modifiers and perovskite as well as SnO_(2) gradually increases with the increase in the number of S=O and F.The defect passivation effect is positively correlated with the chemical interaction strength.The crystallization kinetics is regulated through the compromise between chemical interaction strength and wettability of substrates.Compared with Cl−,all non-halogen anions perform better in crystallization optimization,energy band regulation and defect passivation.The device with potassium bis(fluorosulfonyl)imide achieves a tempting efficiency of 24.17%.

Self-assembled donor-acceptor hole contacts for inverted perovskite solar cells with an efficiency approaching 22%: The impact of anchoring groups

Self-assembled molecules(SAMs) have shown great potential in replacing bulk charge selective contact layers in high-performance perovskite solar cells(PSCs) due to their low material consumption and simple processing. Herein, we design and synthesize a series of donor-acceptor(D-A) type SAMs(MPA-BTCA, MPA-BT-BA, and MPA-BT-RA, where MPA is 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline;BT is benzo[c][1,2,5]-thiadiazole;CA is 2-cyanoacrylic acid, BA is benzoic acid, RA is rhodanine-3-propionic acid) with distinct anchoring groups, which show dramatically different properties. MPA-BTCA with CA anchoring groups exhibited stronger dipole moments and formed a homogeneous monolayer on the indium tin oxide(ITO) surface by adopting an upstanding self-assembling mode. However, the MPA-BT-RA molecules tend to aggregate severely in solid state due to the sp~3 hybridization of the carbon atom on the RA group, which is not favorable for achieving a long-range ordered self-assembled layer.Consequently, benefiting from high dipole moment, as well as dense and uniform self-assembled film,the device based on MPA-BT-CA yielded a remarkable power conversion efficiency(PCE) of 21.81%.Encouragingly, an impressive PCE approaching 20% can still be obtained for the MPA-BT-CA-based PSCs as the device area is increased to 0.80 cm^(2). Our work sheds light on the design principles for developing hole selecting SAMs, which will pave a way for realizing highly efficient, flexible, and large-area PSCs.

Raman Spectroscopy of Garnet-group Minerals

The Raman spectra of the natural end members of the garnet-group minerals, which include pyrope, almandine and spessarite of Fe-Al garnet series and grossularite, andradite and uvarovite of Ca-Fe garnet series, have been studied. Measured Raman spectra of these minerals are reasonably and qualitatively assigned to the intemal modes, translational and rotatory modes of SiO4 tetrahedra,as well as the translational motion of bivalent cations in the X site. The stretch and rotatory Alg modes for the Fe-Al garnet series show obvious Raman shifts as compared with those for the Ca-Fe garnet series, owing to the cations residing in the X site connected with SiO4 tetrahedra by sharing the two edges. The Raman shifts of all members within either of the series are attributed mainly to the properties of cations in the X site for the Fe-Al garnet series and in the Y site for the Ca-Fe gamet series.

The Photoluminescence Spectra of the Aeschynite Group Minerals

Raman and photoluminescence spectra of the metamict and annealing recrystallization titanoaeschynite-(Nd) and nioboaeschynite-(Ce), found in Baiyunobo mineral deposit in China, were measured and discussed. The peaks or bands in the spectra of the metamic minerals are weak, broad and diffuse, but sharpen notably after heating. The results show that the distortion of the structure and disorder state of the elements exists in the minerals when natural crystalline minerals transformed in-to metamict minerals after a long period of self-irradiation structure damaging. And all bands in the photoluminescence spectra of the aeschynite group mineral stem from emission transitions of Nd3+, when 514.5 nm laser is used as the excitation source.

Study on Visible Photoluminescence and Absorption Spectra of Fergusonite Group Minerals

Visible photoluminescence and absorption spectra of the metamict and annealing-recrystallized fergusonite and brocenite, found in Bayun Obo ore deposit in China, were determined and discussed. The results show that the glow centers of the fergusonite group minerals are Er3+ and Eu3 + when 488.0 and 514.5 nm lasers are used as excitation sources. The luminescence of fergusonites results mainly from Er3+, whereas that of brocenites is produced by Er3+ and Eu3+. The absorption spectra indicate that Nd3 + may be an important sensitizer to the luminescence of Er3 + and Eu3+.

Decorating hole transport material with −CF_(3) groups for highly efficient and stable perovskite solar cells

The hole transport material (HTM) plays an extremely important role to determine the power conversion efficiency (PCE) and the stability of perovskite solar cells (PSCs). Herein, we report an effective strategy to improve the performance of HTMs by introducing −CF_(3) groups via the rational decorative mode. Upon direct attachment or nonconjugated alkoxyl bridging of −CF_(3) groups on the terminal diphenylamines, the resulting molecular HTMs, i.e., 2,7-BCzA4CF_(3) and 2,7-BCzA4OCCF_(3), show distinct properties. Compared with 2,7-BCzA4CF_(3), the nonconjugated alkoxyl bridging −CF_(3) group-based 2,7-BCzA4OCCF_(3) exhibits better thermal stability, hydrophobicity, and a dramatically upgraded hole mobility by 135.7-fold of magnitude to 1.71 × 10^(−4) cm^(2) V^(−1) S^(−1). The PSCs with 2,7-BCzA4OCCF_(3) as HTM exhibit an PCE of up to 20.53% and excellent long-term stability, maintaining 92.57% of their performance for 30 days in air with humidity of 30% without encapsulation. This work provides beneficial guidelines for the design of new HTMs for efficient and stable PSCs.

Orientational Domains at Room Temperature in La_(0.33) Ca_(0.67) MnO_3 Perovskite

Orientational domains at room temperature in orthorhombic perovskite La 0.33 Ca 0.67 MnO 3 were studied by group theory and observed systematically using transmission electron microscopy. There are six orientational variants ( A, A', B,B', C and C' ) in orthorhombic perovskite La 0.33 Ca 0.67 MnO 3. Their orthorhombic b O directions are parallel to the a P, b P and c P directions of the cubic prototypic perovskite, respectively. In each case there are two orientational variants (e.g., A and A' ) with their a O and c O axes interchanged. Among the possible 15 boundaries between these 6 variants there are only two types of domain boundaries: (1) m<100> boundaries C'/C, A'/A, and B'/B. (2) m<110> boundaryies C'/A, C'/A', C'/B, C'/B', C/A, C/A', C/B, C/B', B'/A, B'/A', B/A, and B/A' .

Improved crystallinity and self-healing effects in perovskite solar cells via functional incorporation of polyvinylpyrrolidone

Air moisture is the key issue for perovskites which invades the films and accelerates the damage of devices. Here, polyvinylpyrrolidone(PVP) is introduced to the methylammonium lead iodide(MAPbI_(3)) perovskite precursor to control crystal growth and endow the devices with self-healing ability in a moisture environment. The strong C=O...ΗAΝ hydrogen bonding interactions between PVP and MAPbI_(3) was confirmed by nuclear magnetic resonance measurements. By introducing hydrogen bonding in the MAPbI_(3)-based PSCs, we form a compact perovskite film of excellent electronic quality with a power conversion efficiency(PCE) of up to 20.32%. Furthermore, the O...ΗAΝ hydrogen bonding interactions at the grain boundaries suppress the decomposition of methylammonium cations and improve the recyclable dissolution–recrystallization of perovskite. As a result, the MAPbI_(3)-PVP based cells exhibited striking moisture stability and self-healing behavior, with negligible decay in efficiency after 500 h of operation in high humidity(65% ± 5% relative humidity) and rapid recovering ability after their removal from the humid environment.

Phase Regulation and Defect Passivation Enabled by Phosphoryl Chloride Molecules for Efficient Quasi‑2D Perovskite Light‑Emitting Diodes

Quasi-2D perovskites have attracted tremendous interest for application as lightemission layers in light-emitting diodes(LEDs).However,the heterogeneous n phase and non-uniform distribution still severely limit the further development of quasi-2D perovskite LEDs(Pero-LEDs).Meanwhile,the increased defect density caused by the reduced dimension and grain size induces non-radiative recombination and further deteriorates the device performance.Here,we found that a series of molecules containing phosphoryl chloride functional groups have noticeable enhancement effects on the device performance of quasi-2D Pero-LEDs.Then,we studied the modification mechanism by focusing on the bis(2-oxo-3-oxazolidinyl)phosphinic chloride(BOPCl).It is concluded that the BOPCl can not only regulate the phase distribution by decreasing the crystallization rate but also remain in the grain boundaries and passivate the defects.As a result,the corresponding quasi-2D Pero-LEDs obtained a maximum external quantum efficiency(EQE_(max))of 20.82%and an average EQE(EQE_(ave))of around 20%on the optimal 50 devices,proving excellent reproducibility.Our work provides a new selection of molecular types for regulating the crystallization and passivating the defects of quasi-2D perovskite films.

A bilateral cyano molecule serving as an effective additive enables high-efficiency and stable perovskite solar cells

The existence of defects in perovskite films is a major obstacle that prevents perovskite solar cells (PSCs) from high efficiency and long-term stability. A variety of additives have been introduced into perovskite films for reducing the number of defects. Lewis base-based additive engineering has been considered as an effective way to eliminate defects, especially the defects caused by the uncoordinated Pb^(2+). In this work, for the first time, a bilateral cyano molecule (succinonitrile, SN) which is a commonly used plasticizer in solid electrolyte of solid-state lithium batteries was selected as an additive to modify organic–inorganic hybrid perovskite films in PSCs. SN is featured with two cyano groups (–C≡N) distributing at both terminals of the carbon chain, providing two cross-linking points to interact with perovskites crystals via coordinating with uncoordinated Pb2+ and forming hydrogen bonds with –NH2 groups in perovskite. It was found that the addition of SN into perovskite precursor solution could effectively reduce defects, particularly inhibit the appearance of Pb0 and thus suppress trap-assisted nonradiative charge carrier recombination. As a result, the efficiency of CH_(3)NH_(3)PbI_(3)(Cl) (MAPbI_(3)(Cl))-based PSCs was improved from 18.4% to 20._(3)% with enhanced long-term stability at N2 and humid air atmosphere. This work provides a facile and effective strategy to enhance the PCE and stability of PSCs simultaneously, facilitating the commercialization of PSCs.

Tailoring molecular termination for thermally stable perovskite solar cells

Interfacial engineering has made an outstanding contribution to the development of high-efficiency perovskite solar cells(PSCs).Here,we introduce an effective interface passivation strategy via methoxysilane molecules with different terminal groups.The power conversion efficiency(PCE)has increased from 20.97%to 21.97%after introducing a 3-isocyanatopropyltrimethoxy silane(IPTMS)molecule with carbonyl group,while a trimethoxy[3-(phenylamino)propyl]silane(PAPMS)molecule containing aniline group deteriorates the photovoltaic performance as a consequence of decreased open circuit voltage.The improved performance after IPTMS treatment is ascribed to the suppression of non-radiative recombination and enhancement of carrier transportation.In addition,the devices with carbonyl group modification exhibit outstanding thermal stability,which maintain 90%of its initial PCE after 1500 h exposure.This work provides a guideline for the design of passivation molecules aiming to deliver the efficiency and thermal stability simultaneously.

Bottom-up holistic carrier management strategy induced synergistically by multiple chemical bonds to minimize energy losses for efficient and stable perovskite solar cells

The defects from electron transport layer,perovskite layer and their interface would result in carrier nonradiative recombination losses.Poor buried interfacial contact is detrimental to charge extraction and device stability.Here,we report a bottom-up holistic carrier management strategy induced synergistically by multiple chemical bonds to minimize bulk and interfacial energy losses for high-performance perovskite photovoltaics.4-trifluoromethyl-benzamidine hydrochloride(TBHCl)containing–CF_(3),amidine cation and Cl^(-)is in advance incorporated into SnO_(2)colloid solution to realize bottom-up modification.The synergistic effect of multiple functional groups and multiple-bond-induced chemical interaction are revealed theoretically and experimentally.F and Cl^(-)can passivate oxygen vacancy and/or undercoordinated Sn^(4+)defects by coordinating with Sn^(4+).The F can suppress cation migration and modulate crystallization via hydrogen bond with FA^(+),and can passivate lead defects by coordinating with Pb^(2+).The–NH_(2)–C=NH^(+)_(2)and Cl^(-)can passivate cation and anion vacancy defects through ionic bonds with perovskites,respectively.Through TBHCl modification,the suppression of agglomeration of SnO_(2)nanoparticles,bulk and interfacial defect passivation,and release of tensile strains of perovskite films are demonstrated,which resulted in a PCE enhancement from 21.28%to 23.40%and improved stability.With post-treatment,the efficiency is further improved to 23.63%.

Geochemistry and mineralogy of platinum-group elements(PGE)in chromites from CentralnoyeⅠ,Polar Urals,Russia

The Polar Urals region of northern Russia is well known for large chromium （Cr）-bearing massifs with major chromite orebodies, including the Centralnoye I deposit in the Ray-Iz ultramafic massif of the Ural ophiolite belt. New data on platinum （Pt）-group elements （PGE）, geochemistry and mineralogy of the host dunite shows that the deposit has anomalous iridium （Ir） values. These values indicate the predominance of ruthenium--osmium--iridium （Ru--Os--Ir）-bearing phases among the platinum-group mineral （PGM） assemblage that is typical of mantle-hosted chromite ores. Low Pt values in chromites and increased Pt values in host dunites might reflect the presence of cumulus PGM grains. The most abundant PGM found in the chromite is erlichmanite （up to 15 μm）. Less common are cuproiridsite （up to 5 μm）, irarsite （up to 4--5 μm）, and laurite （up to 4 μm）. The predominant sulfide is heazlewoodite, in intergrowth with Ni--Fe alloys, sporadically with pentlandite, and rarely with pure nickel. Based on the average PGE values and esti- mated Cr-ore resources, the Centralnoye I deposit can be considered as an important resource of PGE.

The Surface Groups and Active Site of Fibrous Mineral Materials

The exposed and transformed groups of fibrous brucite,wollastonite,chrysotile asbestos,sepiolite,palygorskite,clinoptilolite,crocidolite and diatomaceous earth mineral materials are analyzed by IR spectra after acid and alikali etching,strong mechanical and polarity molecular interaction.The results show the active sites concentrate on the ends in stick mineral materials and on the defect or hole edge in pipe mineral materials.The inside active site of mineral materials plays a main role in small molecular substance.The shape of minerals influence their distribution and density of active site.The strong mechanical impulsion and weak chemical force change the active site feature of minerals,the powder process enables minerals exposed more surface group and more combined types.The surface processing with the small polarity molecular or the brand of middle molecular may produce ionation and new coordinate bond,and change the active properties and level of original mineral materials.

Geodynamic significance and genesis of chromitites from the Islahiye ophiolite(Gaziantep,SE Anatolia)as constrained by platinum group element(PGE)compositions and mineral chemistry characteristics

Chromitites associated with intensely altered dunites and harzburgites from fourteen dif ferent localities in the Islahiye ophiolites(SE Anatolia)is reported here for the first time.These chromitites were observed as lenticular and banded bodies with disseminated and massive textures and containing magnesiochromite grains with the following composition:CrO=58.91–59.74 wt%,Al_(2)O_(3)=10.85–11.20 wt%,and TiO=0.09–0.13 wt%.The Mg#[Mg/(Mg+Fe)]values of magnesiochromite from the Islahiye ophiolite range between 0.52 and 0.60 and their Cr#[Cr/(Cr+Al)]values vary from 0.7802 to 0.7844.These contents vary with a constant pattern,coincident with the estimated parental liquids that have originated from the derivative of a single bulk of boninitic magma together with Al,Ti-poor,and Cr-rich initial contents.The chromitites are serpentinised in almost all parts of the study area,and harzburgite and dunite can be observed in different locations.Although the overall composition of platinum group elements(PGE)in most examined chromitites varies between 97 and 191 ppb,three chromitites from the Islahiye region present enrichments in overall PGE(up to 214 ppb).The mineralogical and geochemical features of chromitites from the Islahiye region exhibit a robust similarity to podiform chromitites in the mantle fragment of supra–subduction zone type ophiolitic bodies.The estimated parental magmas of the investigated chromites are consistent with the diff erentiation of arcrelated melts and do not suggest an oceanic spreading centre tectonic environment.The Islahiye chromites are enriched in IPGE(Ir,Os,Ru),with the occasional presence of Ru and Ir and higher Os contents in chromite.Furthermore,we did not find any platinum group minerals(PGM)associated with the serpentine silicate sample matrix,which would have stated a secondary enrichment in PGEs.All chromitites in the investigated region have high Cr and low Ti values,are defined as magnesiochromite and were crystallised from a characteristic boninitic magma.

C≡N-based carbazole-arylamine hole transporting materials for perovskite solar cells: Substitution position matters

Hole transporting materials(HTMs)containing passivating groups for perovskite materials have attracted much attention for efficient and stable perovskite solar cells(PSCs).Among them,C≡N-based molecules have been proved as efficient HTMs.Herein,a series of novel C≡N functionalized carbazole-arylamine derivatives with variable C≡N substitution positions(para,meta,and ortho)on benzene-carbazole skeleton(on the adjacent benzene of carbazole)were synthesized(p-HTM,m-HTM and o-HTM).The experimental results exhibit that the substitution positions of the Ctriple bondN unit on HTMs have minor difference on the HOMO energy level and hydrophobicity.m-HTM has a relatively lower glass transition temperature compared with that of p-HTM and o-HTM.The functional theory calculations show that the C≡N located on meta position exposed very well,and the exposure direction is also the same with the methoxy.Upon applying these molecules as HTMs in PSCs,their device performance is found to sensitively depend on the substitution position of the C≡N unit on the molecule skeleton.The devices using m-HTM and o-HTM exhibit better performance than that of p-HTM.Moreover,m-HTM-based devices exhibit better light-soaking performance and long-term stability,which could be resulted from better interaction with the perovskite according to DFT results.Moreover,we further prepared a HTM with two C≡N units on the symmetrical meta position of molecular skeleton(2m-HTM).Interestingly,2m-HTM-based devices exhibit relatively inferior performance compared with that of the m-HTM,which could be resulted from weak negative electrical character of C≡N unit on 2m-HTM.The results give some new insights for designing ideal HTM for efficient and stable PSCs.

Redetermination of the Depositional Age of the Haerdaban Group in the Northern Margin of the Yili Block,Western Tianshan,NW China:Implications for Regional Tectonics and Pb-Zn Mineralization

The Yili Block in the Western Tianshan orogen is a key area for understanding the early crustal formation and evolution of the Central Asian orogenic belt,due to the widely-distributed Precambrian rocks.Also,it hosts a lot of medium–to large-scale sedimentary exhalative(SEDEX)Pb-Zn deposits that mainly occur in Proterozoic metamorphosed clasticcarbonate rocks.In this study,LA-ICP-MS U-Pb analyses were carried out on detrital zircons in siltstones of the Precambrian Haerdaban Group in the Haerdaban Pb-Zn deposit and magmatic zircons in the diorite dyke that cuts through the strata and orebodies.The maximum depositional age of the siltstones was determined to be about 604 Ma,the diorite having formed at approximately 500 Ma.As such,the Haerdaban Group was most likely formed in the Neoproterozoic Sinian,rather than the previously considered Mesoproterozoic Changchengian.Detrital materials of the Haerdaban Group were mostly derived from the Nanhua–Sinian mafic dykes and granitic rocks around Lake Sayram at the northern margin of the Yili Block.It is proposed that the Yili Block,together with the Kazakhstan and Central Tianshan blocks and the Tarim Craton,might all pertain to the same Rodinia supercontinent,which has great potential for targeting large to super-large SEDEX Pb-Zn deposits.

Structural and Chemical Characteristic of Tourmaline, and Mineralogy of Associated Micas from Tourmaline Bearing Quartzite of KombéII (Bafia Group, Central Africa Fold Belt);Implication on the Metamorphic Conditions

Bafia Group is part of the southernmost portion of the Central African Fold Belt (CAFB) in Cameroon. The geological feature of the group is characterized by the presence of metamorphic rocks in which tourmaline had been recognized among accessory minerals. In the present study, attention is focus on the tourmaline bearing quartzite to the southeast of Kombé II. Structure refinement shows that tourmaline is a Fe-dravite with the formula X(Na0.95[]0.05)Y(Mg2.39Fe0.61)Z(Al5.10Mg0.90)(BO3)3T[Si6O18](OH)3[(O,OH)0.88F0.12]. The Fe-dravite is hosted in a Ca-poor quartzite, which is made up, in addition to quartz and tourmaline, of biotite and muscovite. The structure of the dravites shows a low vacancy at the X site, which militates for a crystallization of the tourmaline at a high temperature > 750℃. This is in agreement with previous work which shows that the metamorphic peak in the associated biotite gneiss reaches 825℃. The R1 value of 1.24% means that the crystal structure of the tourmalines is of high quality. The genetical link between gold mineralization and tourmaline should stimulate exploration interest in the study area.