Chemical Mechanisms of Inorganic Phototropic Growth

无机向光生长的化学机制

• 批准号: 1905963
• 负责人: Nathan Lewis
• 金额: $ 54万
• 依托单位: California Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-07-01 至 2023-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1905963&HistoricalAwards=false
• 关键词: Chemical; Mechanisms; Inorganic; Phototropic; Growth

Part 1: Non-Technical Summary Controlled patterning of materials is important for semiconductor integrated circuit fabrication, 3-D electronics, advanced functional biomaterials, optical materials, and catalyst supports. In this project, jointly supported by the Solid State and Materials Chemistry and Electronic and Photonic Materials Programs in the Division of Materials Research, Professor Nathan S. Lewis of the California Institute of Technology seeks to develop and exploit a fundamental understanding of inorganic phototropic growth. In conventional lithography, materials grow where light is present, whereas in phototropic growth, the materials grow toward the light source. By manipulating the wavelength, intensity, and polarization of the light beams provided by sources as simple as ordinary light bulbs or LEDs, inorganic phototropic growth can spontaneously produce complex, self-organized nanoscale patterns that can be controlled in three dimensions in real time. Such scientific research is foundational to national competitiveness in materials research, information, optical-communications, nanotechnology, and chemical-sensing. To meet the objective of this project, the Lewis Group is exploring the range of materials that exhibit inorganic phototropic growth, examining the generality of the phenomenon by expanding phototropic reactivity to light-induced controlled etching of materials, and using phototropic growth to create materials with unique three-dimensional properties. The experimental work is being integrated with modeling and simulation to develop a mechanistic understanding of inorganic phototropic growth. The research will be integrated with solar energy and materials-discovery outreach programs led by Caltech, specifically the Juice from Juice and Project SEAL hands-on science modules for use at the high-school level throughout the country, with special emphasis on school districts comprising underrepresented groups and diverse student populations. Part 2: Technical SummaryIn this project, Professor Nathan S. Lewis of the California Institute of Technology is examining the mechanisms underlying inorganic phototropic growth, i.e., the production of spontaneous, self-organized mesostructures aligned along the direction of a polarized, incoherent, uniform intensity light beam during electrodeposition of semiconductors. The morphologies are determined by the inherent optical response of the electronic processes within semiconductors stimulated by the tunable properties (e.g. wavelength, polarization, and direction) of the light present during the electrodeposition. The process is adaptive: if the light is moved or otherwise changed, subsequent growth adapts to the changed conditions. To date, this phenomenon has been demonstrated experimentally only for amorphous or polycrystalline chalcogen and chalcogenide materials. This project will investigate whether inorganic phototropic growth can be extended to other materials and how lattice structures and optoelectronic properties influence the mechanisms of inorganic phototropic growth. The work will also investigate how substrate-electrolyte interfaces affect the early-stage development of the ordered nanostructures by studying nucleation of Se-Te alloys on substrates with varied electronic properties. In addition, phototropic growth will be exploited to design and synthesize complex three-dimensionally structured materials with desired functionality, such as chiral metamaterials and plasmonic materials with tailored optoelectronic properties. The experimental observations will be used in conjunction with development of a mechanistic simulation tool that combines full-wave electromagnetic calculations with Monte-Carlo-based mass addition to predict the structures produced by phototropic growth of a variety of semiconductors under arbitrary optical inputs. This project is jointly supported by the Solid State and Materials Chemistry and Electronic and Photonic Materials Programs in the Division of Materials Research.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

第一部分：材料的受控图案化对于半导体集成电路制造、3-D电子学、高级功能生物材料、光学材料和催化剂载体是重要的。 本计画由材料研究部之固态与材料化学及电子与光子材料计画共同赞助，加州理工学院的刘易斯致力于发展和利用对无机光致生长的基本理解。 在常规光刻中，材料在存在光的地方生长，而在向光生长中，材料朝向光源生长。 通过操纵由像普通灯泡或LED一样简单的光源提供的光束的波长、强度和偏振，无机光致生长可以自发地产生复杂的、自组织的纳米级图案，这些图案可以在真实的时间中在三维中被控制。 这种科学研究是国家在材料研究、信息、光通信、纳米技术和化学传感方面竞争力的基础。 为了实现该项目的目标，刘易斯小组正在探索一系列表现出无机光致生长的材料，通过将光致反应性扩展到光诱导材料的受控蚀刻来检查该现象的普遍性，并使用光致生长来创建具有独特三维特性的材料。 实验工作正在与建模和模拟相结合，以发展对无机光致生长的机械理解。 该研究将与加州理工学院领导的太阳能和材料发现外展计划相结合，特别是Juice from Juice和Project SEAL动手科学模块，用于全国高中水平，特别强调学区包括代表性不足的群体和多样化的学生群体。 第二部分：技术总结在本项目中，Nathan S.加州理工学院的刘易斯正在研究无机向光生长的机制，即，在半导体的电沉积过程中，自发的、自组织的介观结构的产生沿着偏振的、非相干的、均匀强度的光束的方向沿着排列。 这些形貌是由电沉积过程中存在的光的可调特性（例如波长、偏振和方向）激发的半导体内的电子过程的固有光学响应决定的。这个过程是自适应的：如果光被移动或以其他方式改变，随后的生长会适应变化的条件。 迄今为止，这种现象仅在非晶或多晶硫属元素和硫属化物材料的实验中得到证实。 本计画将探讨无机光致性成长是否可延伸至其他材料，以及晶格结构与光电性质如何影响无机光致性成长的机制。 这项工作还将研究如何基板电解质界面影响的有序纳米结构的早期阶段的发展，通过研究不同的电子性能的基板上的硒-碲合金的成核。 此外，光致生长将被用来设计和合成具有所需功能的复杂三维结构材料，例如具有定制光电特性的手性超材料和等离子体材料。 实验观察将与机械模拟工具的开发结合使用，该工具将全波电磁计算与基于蒙特-卡罗的质量加成相结合，以预测在任意光输入下各种半导体的向光生长产生的结构。 该项目由材料研究部的固态和材料化学以及电子和光子材料计划共同支持。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Optically tunable mesoscale CdSe morphologies via inorganic phototropic growth

通过无机向光生长实现光学可调介观 CdSe 形貌

• DOI: 10.1039/d0tc02126a
• 发表时间: 2020
• 期刊: Journal of Materials Chemistry C
• 影响因子: 6.4
• 作者: Hamann, Kathryn R.;Carim, Azhar I.;Meier, Madeline C.;Thompson, Jonathan R.;Batara, Nicolas A.;Yermolenko, Ivan S.;Atwater, Harry A.;Lewis, Nathan S.
• 通讯作者: Lewis, Nathan S.

Assessing Effects of Near-Field Synergistic Light Absorption on Ordered Inorganic Phototropic Growth

评估近场协同光吸收对有序无机向光性生长的影响

• DOI: 10.1021/jacs.0c13085
• 发表时间: 2021
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Carim, Azhar I.;Meier, Madeline C.;Kennedy, Kathleen M.;Richter, Matthias H.;Hamann, Kathryn R.;Lewis, Nathan S.
• 通讯作者: Lewis, Nathan S.

Inclination of polarized illumination increases symmetry of structures grown via inorganic phototropism

• DOI: 10.1039/d3mh00839h
• 发表时间: 2023-08-02
• 期刊: MATERIALS HORIZONS
• 影响因子: 13.3
• 作者: Meier，Madeline C.;Lewis，Nathan S.;Carim，Azhar I.
• 通讯作者: Carim，Azhar I.

Preseeded Optical Scatterers as a Template for Enhancing Order in Inorganic Phototropic Growth

预种光学散射体作为增强无机向光性生长秩序的模板

• DOI: 10.1021/acs.jpcc.1c02746
• 发表时间: 2021
• 期刊: The Journal of Physical Chemistry C
• 作者: Simonoff, Ethan;Thompson, Jonathan R.;Meier, Madeline C.;Kennedy, Kathleen M.;Hamann, Kathryn R.;Lewis, Nathan S.
• 通讯作者: Lewis, Nathan S.

Path-Dependent Morphological Evolution of Se–Te Mesostructures Prepared by Inorganic Phototropic Growth

无机向光生长制备的Se-Te介观结构的路径依赖形态演化

• DOI: 10.1021/jacs.0c09798
• 发表时间: 2020
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Hamann, Kathryn R.;Carim, Azhar I.;Meier, Madeline C.;Lewis, Nathan S.
• 通讯作者: Lewis, Nathan S.