Unprecedented dipole alignment in fα-phase nylon-11 nanowires or high-performanceenergy-harvesting applications
Yeon Sik Choi, Sung KyunKim MATERIALSSCIENCE
Science Advances
10 Jun 2020:
https://advances.sciencemag.org/content/6/24/eaay5065
摘要
铁电聚合物中的偶极子排列通常用于电荷控制应用领域。本文通过实验首次在α相尼龙11纳米线中实现了理想有序的偶极子排列。这是一个史无前例的发现,因为通常只有在使用外加电场的铁电聚合物中才能实现偶极子排列,而本文在所制备的“非铁电”α相尼龙-11纳米线中实现了偶极子排列,尼龙-11自30年前提出以来从未真正实现,是一种被忽视已久的多晶型尼龙。本文结果表明α相尼龙-11中的强氢键作用有助于提高分子有序性,从而造成表面电位的强度和热稳定性异常。这一发现对摩擦电能收集领域具有深远的意义,因为表面电位的增强会提高机械能收集性能。因此,本文方法为基于尼龙-11这一不寻常的有序相,实现稳健、高性能的机械能量采集器铺平了道路。
引言
铁电聚合物中的剩余极化是指当外加电场降为零时所保持的极化。通常,铁电聚合物材料,如聚偏氟乙烯(PVDF)及其共聚物,在电极化后表现出非零剩余极化【1,2】。这些材料被广泛应用于各种领域,包括传感器、组织再生材料和能量收集装置【3-6】。特别是,由于随着材料中剩余极化强度的增加,接触面上积累的电荷量(即摩擦电荷)也随之增加,因此铁电材料在基于机械振动的能量收集应用方面(如在摩擦电发电机中)受到了广泛关注【7-11】。然而,根据下一代高性能能量采集器的要求,制备具有强热稳定剩余极化的聚合物一直是一个长期存在的问题【12-14】。
在铁电聚合物中,剩余极化可以通过分子排列(即择优晶体取向)和电极化产生的偶极子排列(即施加高于材料矫顽场的电场)产生。用这种方法得到的剩余极化(Pr(μC cm─2))总是远低于饱和极化,因为一旦电场被移除,强取向的聚合物分子就会松弛成平衡构象。此外,在居里温度(TC)以上,由于发生了结构相变,铁电聚合物容易失去Pr。这些现象表明,铁电聚合物剩余极化强度低、热稳定性差是由其分子结构决定的。具有氢键的聚合物可以潜在克服这些局限,奇数尼龙,特别是尼龙-11,是众所周知的具有氢键的铁电聚合物。因此,通过广泛的氢键作用,尼龙-11可以表现出更好的堆积和更稳定的分子构型。(必须注意的是,即使有氢键,尼龙-11的Pr也不能超过含氟聚合物的Pr,因为其成分和分子结构不同。)此外,尼龙-11具有良好的热稳定性和铁电性能,与PVDF及其共聚物相当【15-18】。然而,在尼龙-11的各种晶体结构中,由于实现极化的唯一方法是通过电极化(注释S1详细说明了尼龙-11的晶体结构),因而铁电性能(包括剩余极化)仅在亚稳δ′相获得,具有相对稀疏的链堆积和随机氢键【14-16】。对于热力学稳定的α相,尽管基于更密集的分子堆积和有序的氢键使其具有优异的热稳定性,但无法通过电极化实现偶极子排列【19,20】。这是因为α相中紧密堆积的氢键将偶极子的旋转抑制到电击穿点,这就是α相被称为“极性”但“非铁电”相的原因【21,22】。
本文发现了α相尼龙11纳米线中异常有序和热稳定的偶极子排列。通过纳米限制效应,即“热辅助纳米模板渗透(TANI)法”,在不需要外加电极化场的情况下,自发获得了具有确定偶极排列的α相尼龙11纳米线。通过分子模拟确定了完全对齐的α相尼龙11的理想 Pr值。为了证明α相纳米线中择优晶体取向的形成,本文使用含有及不含纳米模板载体的纳米线进行了详细的x射线衍射(XRD)分析。基于Kelvin探针力显微镜(KPFM)分析法直接测量了α相纳米线的极高表面电位,其对应单向偶极子排列,表明具有完全对齐偶极子的α相的净极化远大于电极化铁电δ′相。通过对α相尼龙11纳米线热退火前后表面电位和分子结构变化进行研究,证实了其偶极子排列的稳健热稳定性。相应地,在相同机械激励下,基于用TANI法制备的α相尼龙11纳米线的摩擦电能发电机的输出功率密度是铝(Al)基装置的34倍。
结果
理想极化强度
尼龙-11作为一种半结晶聚合物,至少有三种晶体结构,称为三斜(α和α′)、单斜(β)和假六方相(γ, δ和 δ′)【2,23】。其中,只有亚稳态的假六方相,如δ′相,因其稀疏的链堆积和随机氢键作用而显示出铁电性质。如图1(A和D)所示,未极化的δ′相在假六方相晶胞内具有随机取向的尼龙-11链,从而消除了偶极矩【23】。附加机械拉伸和随后的电极化可使链旋转,因此酰胺基指向同一方向,从而产生净偶极矩(图1、B和E)【14-16】。相反,α相可以在三斜单元晶胞中采用排列良好的分子结构,而无需拉伸和/或高压极化(图1、C和F)。这是因为氢键通过范德瓦尔斯相互作用被组织成定义明确的薄片,相邻链的酰胺基沿着链轴大约处于相同的高度【23】。因此,垂直于链轴的偶极矩指向一个方向。然而,必须注意的是,α相的这种单向偶极矩仅限于一个局部结晶区,并且在晶化过程中,这些结晶区的净极化方向随机确定。此外,由于氢键分子旋转到电击穿点的限制,也不可能使α相结构中的每一个偶极子都能对齐排列。结果表明,原始α相(体)样品的净极化远小于电极化δ′相样品的净极化。
图1 尼龙-11的分子结构与链堆积
(A and D)Schematics show packing of nylon-11 monomeric units in unpoled δ′-phasenylon-11 viewed along the c axis and b axis,respectively. All molecules lie in a random orientation. (B and E)The crystal structures and molecular packing of the poled δ′-phase. All theoxygen atoms point to the same direction. (C and F)Crystal structure of α-phase nylon-11. The fully stretched molecules in transconfiguration with sheets of strong hydrogen bonding gives the α-phase arelatively well-ordered crystal structure. The yellow lines indicateintermolecular hydrogen bonding. Gray spheres, carbon atoms; red spheres,oxygen atoms; blue spheres, nitrogen atoms; white spheres, hydrogen atoms.
所以当α体相中的偶极子完全对齐时,极化程度能有多高?为了评估尼龙-11中可能的最大极化,本文通过分子尺度模拟(模拟过程的细节在注释S2中讨论)估计了完全对齐δ′相和α相的“理想”Pr值【24】。在一次近似下,Pr与偶极矩和结晶度成线性关系【12,25】。通过分子模拟,可以通过给原子分配部分原子电荷来测量单个分子的偶极矩。对于最小重复单元,δ′相和α相的单位晶胞偶极矩分别为88 × 10─30和101 × 10─30 C m。在δ′相完全对齐的情况下,假设结晶度约为40%, Pr计算值为3.2 μC cm─2,这与实验测定值(约5.0 μC cm─2) 吻合良好【2】。相比之下,具有相同结晶度的α相的Pr为7.5 μC cm─2,这意味着具有完全对齐偶极子的α相的净极化远大于电极化铁电δ′相的净极化。这是因为在α相中完全拉伸的链状结构和排列整齐的氢键薄片使每个单体的偶极矩最大化【25】。此外,考虑到晶体结构,三斜α相中相邻分子之间的距离远小于假六方相δ′中相邻分子之间的距离【26】。
纳米限诱导的择优晶体取向
为了排列α相尼龙11纳米线中的偶极子,本文开发了TANI方法作为一种有效的纳米限制技术(材料和方法及注释S3中给出了详细实验过程)【27,28】。这是因为,到目前为止,具有热力学稳定α相的尼龙-11纳米线还未通过传统的模板润湿方法得以实现,因为该方法在合成路线方面存在困难【11,29】。图2A显示了阳极氧化铝(AAO)纳米多孔模板的扫描电子显微镜(SEM)图像。上表面和横截面图像表明,其孔径约为200 nm。用TANI方法制备的纳米线的形貌如图2B所示。用弱酸溶解AAO后,检测到宽度(200 nm)和长度(60 μm)均匀的长链状纳米线。这些纳米线的尺寸与模板孔道的尺寸相似。用原子力显微镜(AFM)测量了纳米线的表面形貌。与尼龙-11薄膜相比,纳米线具有无晶界且均匀光滑的表面形貌(图S2和S3)。注意,由于TANI可在非真空和相对低温环境下操作的工艺特点,并且AAO模板内的α相纳米线相对容易处理,因此这种制备方法可大范围应用(注释S4)。
图2 纳米线形态与x射线分析
(A) SEM image of thenanotemplate surface with 200 nm pores. Inset shows the template cross section.(B) SEM image of template-freed nanowires fabricated by the TANI method.(C) Left: XRD patterns of nanowires fabricated by the conventionaltemplate-wetting (black) and the TANI (red) methods. Top right: Changes in theaverage intensities of the XRD peak at 20° and 24.2° as a function of solutionconcentration. Bottom right: Changes in the crystallite sizes perpendicular tothe (200) planes (D(200)) of 5 wt % samples as a function ofprocessing temperature. ■, middle line, and top and bottom boundaries indicatemean, median, and 75 and 25% values, respectively. a.u., arbitrary units. (D)XRD patterns of α-phase nylon-11 film (black) and nanowires (NW) without (red)and within (orange) a nanoporous AAO template. Inset schematics display themorphology of sample and the direction of x-ray beam (θ) with a scatteringvector (q). (E) XRD patterns of calculated (black) andexperimentally observed (red and orange) α-phase nylon-11 nanowires. Calculatedpatterns I and II assumed random orientation of crystals with large (>100nm) and small crystallite sizes (D200) (~25 nm), respectively.Calculated pattern III assumed preferred crystal orientation with actual D200.
用XRD对其晶体结构进行了详细的表征。据报道,α相尼龙11薄膜在2θ = 7.8°、20°和24.2°处出现衍射峰【23】。然而可以发现,通过传统的模板润湿方法制备的纳米线在2θ = 21.6°和22.8°处产生弱峰强度的衍射图(图2C,左,黑色)【29】。结果表明,传统的纳米限制方法无法制备出结晶度较好的α相尼龙11纳米线。相比之下,用本文所提TANI方法制备的纳米线显示出与所报道的α相薄膜相同的峰值位置,其衍射强度远高于传统制备的纳米线(图2C,左,红色)。这意味着TANI方法的溶剂蒸汽–填充封闭加热系统通过抑制溶剂在纳米孔内的蒸发速度,有效地模拟了典型α相薄膜制备技术的缓慢结晶过程。此外,TANI方法可以更精确地控制晶体结构,其中本文可以通过调节溶液浓度和加工温度来控制结晶速率。如图2C(左和右上)所示,随着溶液浓度的降低,2θ = 24.2°处峰值的相对强度逐渐降低,而20°处峰的相对强度保持在误差范围内。这是因为更稀的溶液通过增加聚合物链的自由体积使结晶速度进一步降低。考虑到每一个峰对应于一个特定的晶格平面,由5 wt%溶液得到的只有一个不同峰的衍射图表明,通过TANI方法可以获得更多对齐的分子结构。附加加热也可以控制纳米孔内的聚合物结晶过程。5 wt%样品垂直于(200)平面(D(200))方向的微晶尺寸随加工温度的变化表明,平均D(200)随加工温度的升高而逐渐增大(图2C,右下)。这表明附加加热使链的迁移率增加,这是分子重新定向和排列的驱动力。(必须注意的是, D(200) 图中的误差归因于不同样品之间的偏差。由XRD测量设置和剖面拟合产生的实验误差在2 nm范围内。)这些XRD结果表明,采用TANI工艺可以制备出理想的α相纳米线。
为了证实纳米线的晶体学,本文制备了α相尼龙11薄膜进行比较。图2D显示了α相薄膜(黑色)及用5 wt%溶液在80 ℃加热下通过TANI方法制备的无模板纳米线(红色)的XRD图。α相尼龙-11薄膜在2θ = 20°和24.2°处有两个明显的峰,在7.8°处有一个小峰,分别对应于(200), (210/010)和(001)晶面【23】。在没有AAO模板的纳米线中,还观察到了与α相薄膜相同的峰位,这表明TANI方法可以制备α相尼龙11纳米线。值得注意的是,无模板纳米线的衍射图显示(200)平面的峰更尖锐,其半峰全宽(FWHM)小于α相薄膜,导致纳米线(25 nm)中的D(200) 远大于薄膜(16 nm)中的D(200) 。此外,α相纳米线和薄膜样品的结晶度相似,约为48%(结晶度计算详情见注释S5)。考虑到大多数通过传统的模板润湿工艺制备的纳米线的结晶度比具有相同晶体结构的薄膜差,这些结果表明,TANI方法实际上能够产生比α相薄膜具有更大晶体尺寸的高结晶α相纳米线【30,31】。所开发的尼龙11纳米线的热力学特征也证实了TANI方法是基于纳米限制效应合成纳米线的(注释S6)。利用傅里叶变换红外(IR)光谱测量研究了α相纳米线中的化学键(注释S7)。图S8中,在相同的IR光谱范围内,从α相纳米线观察到在N-H拉伸和酰胺I区都有更高的相对峰值强度。考虑到N-H拉伸(3300 cm─1)和酰胺I(1635 cm─1)能带分别反映了氢键强度的总体分布和氢键的局部有序性,可以推断TANI方法在氢键形成的基础上进一步促进了有序晶体的生长【16,32,33】。
通过对纳米多孔AAO模板内的纳米线进行详细的XRD分析,验证了分子取向的方向(图2D,橙色)。原则上,在反射模式下检测的单晶样品只会产生一组垂直于样品表面具有散射矢量(q)的晶格面。这意味着,如果纳米线具有择优晶体取向,那么垂直排列的纳米线和随机放置的纳米线之间的衍射图的差异将指示晶体取向的方向。如前所述,无模板的α相尼龙11纳米线在2θ = 20°和24.2°处显示两个明显的峰,在7.8°处有一个小峰,分别对应于(200),(210/010)和(001)晶面(图2D,红色)。相比之下,AAO模板内的α相纳米线在2θ(200) = 20°处只有一个明显衍射峰(图2D,橙色)。(001)和(210/010)晶面强度缺乏意味着纳米线实际上是定向的,因此在反射模式几何中这些峰不可见。峰值宽度约为8°的(200)反射上的摇摆曲线也证实了这一观察结果(注释S8)。这些结果表明,TANI法制备的纳米线具有择优晶体取向,其中分子链轴垂直于纳米线的长度方向,与以前的报道一致【34-36】。
分子模拟结果验证了α相纳米线中微晶尺寸(Dp)和择优晶体取向的测定(图2E)。在理想Dp(>100 nm)和随机晶体取向的假设下,在模拟粉末衍射图中,在2θ(210/010) =24.2°处观察到最高峰值,在2θ(200) = 20°处有第二高峰值(图2E,顶部)【37】。然而,引入25 nm的实验测量D200 值改变了24.2° ~ 20°范围内最高峰值的顺序并拓宽了衍射图(图2E,中间)。考虑到非晶区可能在22.2°左右产生宽衍射峰,模拟数据与无模板α相纳米线(红点)的实验数据吻合较好。然而,需要注意的是,其它的峰更宽,这意味着这些方向上的微晶尺寸小于垂直于(200)晶面的微晶尺寸。最后,应用Rietveld-Toraya方程计算的择优晶体取向,得到的衍射图中在2θ(200) = 20°(图2E,底部)处有明显较高且尖锐的峰,与AAO模板(橙色点)内α相纳米线的实验测量衍射图很好地吻合【38,39】。计算结果与实验结果的相对峰值强度和FWHM的一致性证实了α相纳米线中较大晶体确实优先排列,且(200)晶面垂直于纳米线的轴线。
α相纳米线的表面电位
本文认为通过提升材料的净偶极矩强度,可以提高材料的表面电位和产生的表面摩擦电荷【7-11】。此外,尼龙-11的这种净偶极矩主要由偶极子的排列引起,因为当定向极化尼龙-11的偶极子密度接近于零时,Pr值接近于零【40,41】。这表明纳米限制效应产生的择优晶体取向所产生的偶极子排列可以增强表面电位,表面电位的强度与分子取向的程度密切相关【42】。
为了研究α相纳米线的表面电位,利用KPFM进行了详细的分析(KPFM技术和测量程序详细信息见注释S9)。虽然铁电材料的 Pr 是由极化-电场(P-E)滞回曲线观察到的,但由于非铁电材料没有表现出这种滞回特性,因此不能用这种方法测量其净偶极矩。相反,KPFM可以测量材料的表面电位,并且已经证明净偶极矩有助于表面电位的大小【7,43,44】。当比较尼龙11纳米线和未极化薄膜的表面电位时,纳米线显示出比相同晶体结构薄膜更高的值(图3和图S11)。[AAO模板样品内的纳米线顶部表面由纳米线尖端填充;因此,可以忽略AAO模板对表面电位的影响(图S12)。] 与相应的薄膜样品相比,δ′和α相纳米线样品的表面电位分别增加了2倍和30倍。这些结果表明,晶体生长过程中的纳米限制效应有效排列了偶极子,并在纳米线中产生了较强的净偶极矩【45,46】。必须注意的是,α相纳米线的表面电位(576 mV)远高于δ′相纳米线(395 mV)。这与分子模拟的Pr计算结果一致,表明TANI方法通过纳米限制诱导的分子有序化在α相尼龙-11中产生了很强的表面电位。(注意,当比较δ′相和α相薄膜的表面电位时,由于两种薄膜都未极化,因此分子有序性并非表面电位的主要影响因素。因此,应该考虑其它次要因素,如晶体尺寸和表面粗糙度,来近似这些未极化薄膜的表面电位。)
图3 表面电位分析
Plots of the surface potentialof various films and nanowires. Thermal stability of nanowire samples was alsoinvestigated by surface potential measurement before (white bar) and after(orange bar) thermal annealing at 165°C. Inset schematics indicate the way tomeasure the surface potential using KPFM.
热稳定性试验证实了氢键作用对偶极取向变化的显著影响。在165 ℃热退火后,δ′相纳米线的表面电位从395 mV下降到0 mV(图3B,橙色条)。这是因为亚稳δ′相的择优晶体取向因热搅拌而消失【23】。相比之下,α相纳米线即使在高温热退火后,仍能在误差范围内保持较高的表面电位(约570 mV),这表明在退火过程中α相纳米线的偶极子排列可以保持不变。热退火后XRD图的变化进一步证实了α相纳米线分子构型的热稳定性(图S13)。对于δ′相纳米线,对应于(hk0)晶面的21.6°峰值强度在热退火后降低,而在2θ = 20.4°处峰值强度增加(图S13A)。相比之下,165 ℃退火前后α相纳米线的衍射图中的峰位置和强度几乎相同(图S13B)。这意味着α相纳米线内的分子构型具有热稳定性,因此,由于具有强氢键、有序和高度堆积的分子结构,由此在接近熔化温度时,产生的择优晶体取向可以保持不变。
为了验证由更高净偶极矩引起的电荷积累能力的增强,本文测量了机械摩擦前后表面电位的变化。这是因为表面上的累积电荷可以通过与具有不同工作功能的其它材料接触而转移,并且AFM探针在材料表面的摩擦导致了这种效应【43】。特别是由于极化方向、偶极取向程度,以及表面电荷亲和力的变化,铁电聚合物的剩余极化强度会影响摩擦过程中电荷的转移量【8】。本文测量了原始δ′和α相纳米线样品在机械摩擦前后的表面电位(图4)。摩擦后,δ′相纳米线的平均表面电位从510 mV下降至469 mV,表明δ′相纳米线表面的累积电荷(对应于41 mV的表面电位变化)通过AFM探针转移。对于α相纳米线,摩擦后表面电位变化(646 ~ 422 mV)较大,变化值为224 mV。这些结果表明α相纳米线由于其偶极子排列使电荷积累能力最大化。与α相薄膜的比较也证实,电荷转移的增加可归因于纳米线中的偶极子排列,而在薄膜中未出现偶极子排列(图S14)。
图4 摩擦前后(A和C)δ′相和(B和D)α相纳米线表面电位分析
(A and B) AFM topology andsurface potential images before (left) and after (right) rubbing process.Dashed squares, rubbing area. Scale bars, 1 μm. Blue dashed line, the dataacquisition position for plotting. (C and D) Surface potential changes before(black square) and after (red circle) rubbing process.
基于纳米线的能量收集装置
作为实际演示,本文提出了用于能量收集应用的摩擦电发电机。为了获得高水平的能量收集性能,具有供电子倾向的材料必须与具有受电子倾向的材料配对,在合成和有机供电子材料中,尼龙11属于探索较少的一类【11】。在优化TANI法制备的α相尼龙11纳米线的基础上,研制了一种面积为3.14 cm2的接触分离式摩擦电发电机。还制备了Al膜和δ′相纳米线基装置,以比较装置性能(注释S10)。
图5A显示了在先前描述的能量收集装置(0.5 mm)中,在频率为5 Hz、大小为0.7 N的周期性冲击下测量的短路电流密度(JSC)【27】。Al基装置的JSC峰值约为13 mA m−2。由于尼龙具有较好的电荷供体特性和偶极子排列效应, JSC约为 38 mA m−2 的δ′相纳米线摩擦电发电机的装置性能高于Al基装置,这与以前的研究结果一致【11】。α相纳米线基装置具有更高的输出性能,峰值 JSC约为74 mA m−2,可能原因在于具有更高的净偶极矩。在阻抗匹配条件下,α相纳米线、δ′相尼龙-11纳米线和Al基装置的峰值输出功率密度分别为3.38、1.03和0.099 W m−2,负载电阻分别约为5、20和20兆欧(图5B和图S16A)。α相纳米线基摩擦电发电机的输出功率分别是δ′相纳米线和Al基装置的3倍和34倍。α和δ′相纳米线基装置的输出功率比较表明,α相纳米线紧密堆积和排列的分子结构中较高的净偶极矩有助于装置性能的提高,与模型和表面电位分析结果一致(注释S11详细解释了摩擦电荷转移过程)。必须注意的是,考虑到纳米线的特性和能量收集装置的设计,这些能量收集性能不是来自尼龙-11纳米线的压电性,而是来自其摩擦电性(注释S12)。在稳定性方面,α相尼龙11纳米线基摩擦电发电机在整个疲劳试验期间(约540,000次循环)和长期可靠性试验期间(约2周)的输出电流密度变化可以忽略不计,分别表明了α相纳米线中偶极子排列的较高机械稳定性和纳米线基装置的稳健性(图S16D和S17)。必须指出的是,α相纳米线的机械刚度远高于δ′相纳米线,因为α相纳米线中存在具有有序氢键作用的较大微晶【47】。尽管在疲劳试验期间α或δ′相纳米线均未观察到磨损,但这种刚度差异意味着α相纳米线装置更适用于摩擦型装置,包括摩擦电能采集器。
图5 摩擦电发电机性能
(A) Short-circuit outputcurrent densities of triboelectric generators with different combinations ofmaterials: Al (black), δ′-phase nanowire (orange), and α-phase nanowire (red).(B) The power density of the same devices as a function of loadresistance. The power density is calculated by multiplying the current densitysquared with the load resistance.
讨论
本文制作的尼龙-11纳米线呈现出偶极子排列,具有史无前例的净偶极矩强度和热稳定性。通过TANI方法的纳米限制效应,成功制备了具有偶极子排列的α相尼龙11纳米线。通过XRD和IR测试证实了微晶具有较大尺寸且氢键排列得以提升,并用分子模拟解释了衍射数据,揭示了择优晶体取向的机理。基于KPFM测量,通过分析表面电位的变化,研究了净偶极矩的强度和偶极子排列的热稳定性。结果表明,由于α相尼龙-11具有有序的结晶区和较高的分子堆积密度,其净偶极矩远高于极化铁电δ′相。此外,强氢键作用(以前被认为是尼龙-11极化的严重不利因素)实际上有助于增强分子结构的稳定性,从而在接近熔化温度时产生恒定的净偶极矩。将α相尼龙11纳米线用于摩擦电发电机时,其输出功率分别是δ′相纳米线和Al基装置的3倍和34倍。本文为利用纳米材料和纳米制备方法为下一代高性能能量收集应用开发出强健且热稳定的偶极子排列提供了新的视角。
MATERIALS AND METHODS
Materials
Nylon-11 (polyamide-11),[─NH(CH2)10CO─]n, with molecularweights (Mw) of 201.31 g/mol, was purchased fromSigma-Aldrich. Calculated weight percent nylon-11 solutions were prepared informic acid (Sigma-Aldrich, reagent grade ≥95%) at 70°C.
Fabrication of nylon-11nanowires
To prepare the nanowires,25-mm-diameter AAO templates (Anopore, Whatman) with a pore diameter of 200 nmand a thickness of 60 mm were placed on an 800-μl nylon-11 solution droplet. Inthe case of a conventional template-wetting method, the AAO template was placedon the solution and was then left at room temperature for at least 24 hourswith no protective covering (29). As the formic acidnaturally evaporated through the pores, the solution was drawn up through thepores via capillary forces, and the nylon-11 was able to crystallize intonanowires. In the case of the TANI method for the α-phase nanowires, the AAOtemplate was attached to a square glass slide before placing on top of thesolution to limit the exposure of the template’s top surface to the air, thuslimiting the rate of formic acid evaporation. In addition, a lid was placedover the sample to further reduce exposure to the surrounding air and to allowthe local environment to become saturated with formic acid vapor, and thesample was then placed on a hot plate. The δ′-phase nanowires were produced bymaximizing the evaporation speed of the solution (11). The AAO template was placedon top of a drop of 17.5 wt % nylon-11 solution in accordance with theconventional template-wetting method. No additional protective layers wereadded, and the solution was not heated during the crystallization. To controlthe crystallization rate of the solution, assisted gas flow with a speed of ~3m s─1 was introduced upon the AAO template using a portablemini fan placed immediately next to the floating template. The rate of assistedgas was controlled by fan rotation speed and measured by an anemometer. Thewhole fabrication process proceeded under room temperature.
After treatment
For accurate characterization,the thin nylon-11 film that formed underneath the AAO template had to beremoved. To do so, excess material was scraped off using a razor blade. Next,formic acid was warmed on a hot plate to 80°C and swabbed over the templatebottom surface using a cotton bud. Once the thin nylon-11 films had beenremoved, the nanowire-filled template was washed in deionized water and driedat room temperature. To obtain the template-freed nanowires, thenanowire-filled template was immersed in a 40 volume % phosphoric acid solutionfor 4 hours. To achieve the assembled (and template-freed) nanowire film,acid-immersed nanowires should be lifted off by silicon wafer from the surfaceof acid solution. The assembled film was then washed carefully in deionizedwater and dried at room temperature.
Fabrication of nylon-11 films
The α-phase nylon-11 filmswere produced by casting the nylon-11 solution onto the hot plate (~80°C), anda lid was placed over the sample to reduce the crystallization speed.
Fabrication of triboelectricenergy generators
To fabricate the triboelectricenergy generators, a 100-nm-thick Au layer was deposited on the bottom side ofthe nanowires-filled AAO template by using benchtop sputter (k550 Emitech). Asa counterpart material, a 100-μm-thick Teflon film was prepared, and Au wassputtered on the bottom side of the Teflon film. A 24-mm-thick aluminum filmwith the same diameter of 2 cm was also prepared to compare the triboelectricgenerator performance with the nanowire-based devices. The mechanical input wasgenerated using a vibrational impacting system, where a permanent magneticshaker (LDS Systems V100) was connected to an amplifier (LDS Systems PA25E-CE)driven by a signal generator (Thurlby Thandar TG1304) to generate vibrationmotion of the impacting arm based on a programmed signal in the signalgenerator. The impacting arm underwent periodic oscillations at frequency f (27). Energy-harvesting data inthe form of output voltages and currents were collected by two different dataacquisition modules: multimeter (Keithley 2002) for voltage and picoammeter(Keithley 6487) for current measurement. A top-down schematic of thistriboelectric generator system, including the actuating and data-collectingconfiguration, is shown in fig. S15.
Characterization
Three-dimensional molecularimages of nylon-11 were rendered using BIOVIA Materials Studio (DassaultSystèmes BIOVIA). The morphology of the nanowires was investigated usingfield-emission scanning electron microscopy (FEI Nova NanoSEM) and AFM (BrukerMultiMode) with an antimony n-doped Si (tip radius, <35 nm; resonancefrequency, 150 kHz). Detailed crystal structural characterization was carriedout by an XRD machine (Bruker D8) with Cu Kα radiation (λ = 0.15418 nm). Thesample was placed on a highly p-doped silicon substrate during theXRD measurement. The size of corresponding crystals (Dp) wascalculated from the diffraction peaks using Scherrer equation (48): Dp =(K × λ)/(B cos θ), where K is the Scherrerconstant, B is the FWHM of diffraction peak (in radians), andθ is the diffraction peak position (angle). To help optimize the process, theXRD data from more than 90 samples were measured to assess changes in Dp andrelative intensities of the peaks as a function of processing parameters. Thedegree of crystallinity (χ) was calculated by calorimetry and XRD methods (49). The differential scanningcalorimetry (DSC) data were measured at a scanning rate of 5°C/min using TAInstruments Q2000 DSC to determine the thermal and structural properties ofnylon-11 nanowires, from which the melting temperature (Tm)and the melt crystallization temperature (Tc) were recordedfrom the first heating. KPFM measurements were carried out using BrukerMultiMode 8 in the noncontact amplitude modulation (AM-KPFM) mode with 2-V ACsignal, and an antimony (n)-doped Si tip (MESP-RC-V2, Bruker) with anominal radius of ~35 nm, a resonant frequency of ~150 kHz, and a nominalspring constant of 5 N m−1 was used. The KPFM measurements were performedunder the same measuring conditions for all samples (temperature = 21°C,humidity = 17%). The rubbing procedure was pursued for one time in a contactmode with a scan rate of 1 Hz, a scan area of 5 μm2, and a contactforce of 30 nN. Film thickness was measured using a stylus surface profilometer(Veeco Dektak 6M).
SUPPLEMENTARY MATERIALS
Supplementary material forthis article is available at http://advances.sciencemag.org/cgi/content/full/6/24/eaay5065/DC1
This is an open-access articledistributed under the terms of the Creative Commons Attribution license, which permits unrestricteduse, distribution, and reproduction in any medium, provided the original workis properly cited.
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