The chemical bath deposition (CBD) of ZnO nanowires (NWs) is of high interest, but their formation occurs in a growth medium containing many impurities including carbon, nitrogen, and hydrogen, rendering the accurate determination of predominant crystal defects as highly debated. In addition to the typical interstitial hydrogen in bond-centered sites $\left({\mathrm{H}}_{\mathrm{BC}}\right)$ and zinc vacancy-hydrogen $\left(V_{\mathrm{Zn}}\text{−}n\mathrm{H}\right)$ complexes, we reveal that nitrogen-related defects play a significant role on the physical properties of unintentionally doped ZnO NWs. We show by density functional theory that the $V_{\mathrm{Zn}}\text{−}{\mathrm{N}}_{\mathrm{O}}\text{−}\mathrm{H}$ defect complex acts as a deep acceptor with a relatively low formation energy and exhibits a prominent Raman line at $3078\mathrm{c}{\mathrm{m}}^{\text{–}1}$ along with a red-orange emission energy of ∼1.82 eV in cathodoluminescence spectroscopy. The nature and concentration of the nitrogen- and hydrogen-related defects are found to be tunable using thermal annealing under oxygen atmosphere, but a rather complex, fine evolution including successive formation and dissociation processes is highlighted as a function of annealing temperature. ZnO NWs annealed at the moderate temperature of 300 °C specifically exhibit one of the smallest free charge carrier densities of $5.6\times {10}^{17}\mathrm{c}{\mathrm{m}}^{\text{–}3}$ along with a high mobility of $\sim 60\mathrm{c}{\mathrm{m}}^2/\mathrm{V}\mathrm{s}$ following the analysis of longitudinal optical phonon-plasmon coupling. These findings report a comprehensive diagram showing the complex interplay of each nitrogen- and hydrogen-related defect during thermal annealing and its dependence on annealing temperature. They further reveal that the engineering of the nitrogen- and hydrogen-related defects as the major source of crystal defects in ZnO NWs grown by CBD is capital to precisely control their electronic structure properties governing their electrical and optical properties in any devices.

中文翻译：

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使用热退火工程化ZnO纳米线中与氮和氢有关的缺陷

ZnO纳米线（NWs）的化学浴沉积（CBD）引起了人们的极大兴趣，但是它们的形成发生在含有许多杂质（包括碳，氮和氢）的生长介质中，因此准确测定主要的晶体缺陷已引起人们的广泛争议。除了以键为中心的位置中存在典型的间隙氢以外$（{\mathrm{H}}_{\mathrm{公元前}}）$ 和锌空位氢 $（{\mathrm{伏特}}_{锌}\text{-}ñ\mathrm{H}）$配合物，我们发现与氮有关的缺陷对无意掺杂的ZnO NW的物理性质起着重要作用。我们通过密度泛函理论表明${\mathrm{伏特}}_{锌}\text{-}{\mathrm{ñ}}_{\mathrm{Ø}}\text{-}\mathrm{H}$ 缺陷复合物充当具有相对较低形成能的深受体，并在以下位置表现出突出的拉曼谱线 $3078\mathrm{C}{\mathrm{米}}^{\text{–}\mathrm{1个}}$阴极发光光谱中的橙红色发射能量约为1.82 eV。发现与氮和氢有关的缺陷的性质和浓度在氧气气氛下使用热退火是可调节的，但是作为退火温度的函数，突出了相当复杂，精细的演变，包括连续的形成和解离过程。在300°C的中等温度下退火的ZnO NW特别表现出最小的自由电荷载流子密度之一$5.6\times {10}^{17}\mathrm{C}{\mathrm{米}}^{\text{–}3}$ 以及高机动性 $〜60\mathrm{C}{\mathrm{米}}^{\mathrm{2个}}/\mathrm{伏特}\mathrm{s}$下面分析纵向光学声子-等离子体激元耦合。这些发现报告了一个综合图，显示了在热退火过程中每个与氮和氢有关的缺陷之间的复杂相互作用及其对退火温度的依赖性。他们进一步揭示，与氮和氢有关的缺陷作为CBD生长的ZnO NWs晶体缺陷的主要来源的工程技术对于精确控制其电子结构性质，控制其在任何器件中的电学和光学性质是至关重要的。