Quantum Diamonds at the Beach: Chemical Insights into Silica Growth on Nanoscale Diamond using Multimodal Characterization and Simulation.
Quantum Diamonds at the Beach: Chemical Insights into Silica Growth on Nanoscale Diamond using Multimodal Characterization and Simulation.
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DOI：
10.1021/acsnanoscienceau.3c00033
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发表时间：
2023-12-20
期刊：
影响因子：
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通讯作者：
Wolcott, Abraham
中科院分区：
文献类型：
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作者：
Sandoval, Perla J;Lopez, Karen;Arreola, Andres;Len, Anida;Basravi, Nedah;Yamaguchi, Pomaikaimaikalani;Kawamura, Rina;Stokes, Camron X;Melendrez, Cynthia;Simpson, Davida;Lee, Sang-Jun;Titus, Charles James;Altoe, Virginia;Sainio, Sami;Nordlund, Dennis;Irwin, Kent;Wolcott, Abraham
随着量子计算和量子传感平台的成熟，金刚石等承载量子比特的材料的表面化学是一个重要的探索途径。一般来说，将金刚石和纳米级金刚石（ND）特别是与二氧化硅接合是将室温量子比特集成到具有灵活功能化化学的光子器件、光纤、细胞或组织中的潜在途径。虽然ND核上的二氧化硅生长已成功用于量子传感和生物标记，但引发生长的表面机制尚不清楚。本报告描述了负责金刚石上硅键形成的表面化学，并使用X射线吸收光谱（XAS）探测金刚石表面化学及其电子结构，随着二氧化硅厚度的增加。使用改进的Stöber（Schiller）方法在富含羧酸的ND核上合成2-35 nm厚的SiO2壳。金刚石的形态，表面和电子结构的特点是重叠技术，包括电子显微镜。重要的是，我们发现，SiO2的羧化ND上的生长消除了羧酸的存在，并且碱性乙醇溶液在二氧化硅生长之前将ND表面转化为富含醇的表面。这些数据支持了ND表面上的醇由于在乙醇中被氢氧化铵再羟基化而产生甲硅烷基醚（ND-O-Si-（OH）3）键的机制。首次观察到金刚石电子结构随SiO2厚度的变化，并计算出最大探测深度为14 nm。基于俄歇电子逸出深度的XAS谱使用NIST数据库模拟表面分析电子谱（SESSA）来支持我们的实验结果。此外，过渡边缘传感器产生的共振非弹性X射线散射（RIXS）图增强了XAS提供的化学分析。研究人员使用金刚石或高压高温（HPHT）ND和其他外来材料（例如，用于量子传感应用的碳化硅或氮化硼）可以利用这些结果通过经由表面醇基团形成共价键来设计新的层状或核-壳量子传感器。
Surface chemistry of materials that host quantum bits such as diamond is an important avenue of exploration as quantum computation and quantum sensing platforms mature. Interfacing diamond in general and nanoscale diamond (ND) in particular with silica is a potential route to integrate room temperature quantum bits into photonic devices, fiber optics, cells, or tissues with flexible functionalization chemistry. While silica growth on ND cores has been used successfully for quantum sensing and biolabeling, the surface mechanism to initiate growth was unknown. This report describes the surface chemistry responsible for silica bond formation on diamond and uses X-ray absorption spectroscopy (XAS) to probe the diamond surface chemistry and its electronic structure with increasing silica thickness. A modified Stöber (Cigler) method was used to synthesize 2–35 nm thick shells of SiO2 onto carboxylic acid-rich ND cores. The diamond morphology, surface, and electronic structure were characterized by overlapping techniques including electron microscopy. Importantly, we discovered that SiO2 growth on carboxylated NDs eliminates the presence of carboxylic acids and that basic ethanolic solutions convert the ND surface to an alcohol-rich surface prior to silica growth. The data supports a mechanism that alcohols on the ND surface generate silyl–ether (ND–O–Si–(OH)3) bonds due to rehydroxylation by ammonium hydroxide in ethanol. The suppression of the diamond electronic structure as a function of SiO2 thickness was observed for the first time, and a maximum probing depth of ∼14 nm was calculated. XAS spectra based on the Auger electron escape depth was modeled using the NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to support our experimental results. Additionally, resonant inelastic X-ray scattering (RIXS) maps produced by the transition edge sensor reinforces the chemical analysis provided by XAS. Researchers using diamond or high-pressure high temperature (HPHT) NDs and other exotic materials (e.g., silicon carbide or cubic-boron nitride) for quantum sensing applications may exploit these results to design new layered or core–shell quantum sensors by forming covalent bonds via surface alcohol groups.