Designed molecular sources for the synthesis of metal pnictides nanocrystals

设计用于合成金属磷氮化物纳米晶体的分子源

• 批准号: 242778552
• 负责人: Professor Dr. Manfred Scheer
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/242778552?language=en
• 关键词: Designed; molecular; sources; synthesis; metal

Despite promising potentialities in many fields of applications such as microelectronics or photovoltaics, the chemistry of metal pnictides (GaAs, InP etc.) nanocrystals (NCs) is lingering far behind that of metal NCs or of chalcogenides NCs such as oxides or sulfides. This situation is essentially due to the lack of reliable and robust methods to synthesize controlled nano-objects.The objective of our proposal is the development of low-cost solution-based strategies for the synthesis of size, surface, shape and composition controlled NCs of groups 12 to 14 pnictides (more precisely, phosphides and arsenides). The target materials for the NCs will be Zn3P2 for group 12-pnictide, InP, InAs and GaAs for the group 13 pnictides and SiPx, GePx and SnP for the group 14-pnictides. They have been chosen on the basis of both the scientific importance for applications and the synthetic challenges.The originality of our approach relies on the design of high energy precursors to provide a reactivity-based, low-temperature method to overcome the synthetic problems and blocking points reported in the literature for pnictide-based nanomaterials. This work will involve the use of either two matched-reactivity precursors (one precursor for each element) or single source precursors (exhibiting preformed M-E bonds for the formation of MxEy NCs; M = Ga, In, Zn, Si, Ge, Sn; E = P, As), all compounds being specifically designed for NCs synthesis. While multi-source precursors are usually easy to obtain, the synthesis of single-source precursors is a challenging approach in this chemistry. Relevant features of these molecular species are (i) halogen-free (or cleanly removable in the gas or solution phase without interacting with NCs) precursors in order to prevent the NCs from potential halide contamination, (ii) labile substituents to facilitate their removal to produce naked atoms and allow synthesis of NCs at low T, and (iii) easy accessibility in large scale. Our strategy relies on the study of the reactivity of the precursor and of the NCs growth mechanism. The understanding of the chemistry behind these processes will be the basis to overcome the scientific barriers and the limitations currently existing for the target materials. We are aiming in particular, at synthesizing NCs in soft conditions (using organometallic approaches), at low temperature (< 150°C). This will allow (i) the development of safer and cost-effective procedures, (ii) the opportunity to realize in situ mechanistic and kinetics studies and most of all, (iii) the avoidance of uncontrolled side-reactions that occur at high temperature and (iv) a better control of the kinetics (and reproducibility) of every synthesis steps (nucleation, growth, ripening) yielding to controlled nano-objects.The preliminary examination of physical (in particular opto-electronic) properties will be performed to provide a first evaluation of the relevancy of theses NCs for applications.

尽管在微电子或光伏等许多应用领域具有很大的潜力，但金属镍基（GaAs， InP等）纳米晶体（nc）的化学性质远远落后于金属纳米晶体或硫族纳米晶体（如氧化物或硫化物）的化学性质。这种情况主要是由于缺乏可靠和稳健的方法来合成受控纳米物体。我们建议的目标是开发基于低成本溶液的策略，用于合成12至14基团的核苷酸（更准确地说，磷化物和砷化物）的尺寸，表面，形状和组成控制的nc。NCs的靶材料为12-pnictide组的Zn3P2, 13 -pnictide组的InP、InAs和GaAs， 14-pnictides组的SiPx、GePx和SnP。它们的选择是基于应用的科学重要性和合成挑战。我们的方法的独创性依赖于高能前体的设计，提供了一种基于反应性的低温方法，以克服文献中报道的基于颗粒的纳米材料的合成问题和阻塞点。这项工作将涉及使用两个匹配的反应性前驱体（每个元素一个前驱体）或单一来源前驱体（表现出形成MxEy NCs的预形成M-E键；M = Ga, In, Zn, Si, Ge, Sn; E = P, As），所有化合物都是专门为NCs合成而设计的。虽然多源前体通常很容易获得，但单源前体的合成在该化学中是一种具有挑战性的方法。这些分子种类的相关特征是：(i)无卤素（或在气相或溶液相中干净地去除，而不与nc相互作用）前体，以防止nc受到潜在的卤化物污染，（ii）不稳定的取代基，以促进其去除以产生裸原子，并允许在低T下合成nc，以及（iii）易于大规模获取。我们的策略依赖于前体的反应性和nc生长机制的研究。了解这些过程背后的化学原理将是克服目前存在的目标材料的科学障碍和限制的基础。我们的目标是在低温（< 150°C）的软条件下（使用有机金属方法）合成nc。这将允许(i)开发更安全、更具成本效益的程序，（ii）有机会实现原位机制和动力学研究，最重要的是，（iii）避免在高温下发生的不受控制的副反应，（iv）更好地控制每一个合成步骤（成核、生长、成熟）的动力学（和可重复性），从而产生受控的纳米物体。将进行物理（特别是光电）性质的初步检查，以对这些纳米材料的应用相关性进行初步评估。

项目成果

Transition-metal complexes containing parent phosphine or phosphinyl ligands and their use as precursors for phosphide nanoparticles.

• DOI: 10.1021/ic5012082
• 发表时间: 2014-10
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Susanne Bauer;Cornelia Hunger;M. Bodensteiner;Wilfried-Solo Ojo;Arnaud Cros-Gagneux;B. Chaudret;C. Nayral;F. Delpech;M. Scheer

Synthesis of Oxide-Free InP Quantum Dots: Surface Control and H2-Assisted Growth

• DOI: 10.1021/acs.chemmater.7b04069
• 发表时间: 2017-11-28
• 期刊: CHEMISTRY OF MATERIALS
• 影响因子: 8.6
• 作者: Baquero, Edwin A.;Virieux, Heloise;Delpech, Fabien
• 通讯作者: Delpech, Fabien