CN114832161B - 一种具有自生压电场的异质结构声敏剂及其制备方法和应用 - Google Patents

一种具有自生压电场的异质结构声敏剂及其制备方法和应用 Download PDF

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CN114832161B
CN114832161B CN202210255209.7A CN202210255209A CN114832161B CN 114832161 B CN114832161 B CN 114832161B CN 202210255209 A CN202210255209 A CN 202210255209A CN 114832161 B CN114832161 B CN 114832161B
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李博
蔡心眉
憨勇
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Xian Jiaotong University
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Abstract

本发明公开了一种具有自生压电场的异质结构声敏剂及其制备方法和应用,所述具有双内建电场的异质结构声敏剂为由窄带隙半导体包覆自生压电势的压电材料形成的核壳异质结构;所述自生压电势的压电材料为氧化锌,所述窄带隙半导体为氧化钛。本发明的声敏剂结构稳定,制备方法简单,成本低廉,应用于声动力抗菌并治疗骨髓炎,抗菌效果优异。

Description

一种具有自生压电场的异质结构声敏剂及其制备方法和应用
技术领域
本发明属于钛基表面处理技术和生物医学应用领域,具体涉及一种具有自生压电场的异质结构声敏剂及其制备方法和应用。
背景技术
骨髓炎是一种由细菌感染引起骨质破坏的炎症性疾病。目前主要临床治疗方法有长时间高剂量的抗生素使用和手术清创。但是这些传统治疗方法存在诸多缺陷,例如复发率较高、导致大块骨缺损及耐药性细菌例如甲氧西林耐药性金黄色葡萄球菌的泛滥,给患者造成了极大的生理及心理痛苦于经济负担。因此,有必要提供一种无需抗生素并短时有效的方式杀灭细菌从而治疗骨髓炎。
近年来,基于活性氧(Reactive oxygen species/ROS,包括超氧阴离子、过氧化氢、单线氧以及羟基自由基)的声动力疗法成为用于抗菌治疗的新疗法。超声波可通过激活声敏剂与其周围的水和氧气发生氧化还原反应而产生具有毒性的ROS,引起细菌氧化应激从而破坏细菌膜通透性,导致蛋白泄露及DNA损伤,最终死亡。并且相比于光照,超声波可以穿透到更深的组织层(高达10cm)并最大限度地减小对周围健康组织的损伤,因此在治疗基于骨髓炎的深部组织感染中具有更大的优势和潜力。
目前,声敏剂主要分为有机小分子材料如卟啉等和无机材料,主要包括贵金属(Pt、Au、Ag等)和非金属氧化物等。相比于传统有机小分子和贵金属材料,无机金属氧化物例如TiO2作为声敏剂时,具有更稳定的化学性质和更优异的生物相容性。然而,单纯的TiO2由于较宽的带隙(3.2eV),所需激发电子从价带跃迁至导带的能量较大,而导致较低的ROS产率,极大的限制了其在声动力疗法中的应用。
目前,已经有许多策略对TiO2进行改性,提高其ROS产率。其中,缺陷工程可以通过引入氧空位在TiO2带隙之间引入缺陷态能级,从而显著缩短带隙。但是,过窄的带隙将会导致电子-空穴对复合过快,这对于ROS的产生是十分不利的。因此,缩窄带隙的同时,需要增大电子-空穴对分离的驱动力。当TiO2与另一个半导体结合形成异质结构时,由于二者功函数差异可在其界面处自发产生内建电场,从而有效驱动电子-空穴对分离。近年来,压电材料(例如ZnO等)极化产生的压电势被看做驱动电子-空穴对分离的新工具。然而,现有的研究往往需要借助外加装置产生机械力(如搅拌、震荡、弯曲等)诱发压电效应,而增加了体系的复杂性。
发明内容
本发明的目的在于提供一种具有自生压电场的异质结构声敏剂及其制备方法和应用,以克服现有技术存在的缺陷,本发明的声敏剂结构稳定,制备方法简单,成本低廉,应用于声动力抗菌并治疗骨髓炎,抗菌效果优异。
为达到上述目的,本发明采用如下技术方案:
一种具有自生压电场的异质结构声敏剂,所述具有双内建电场的异质结构声敏剂为由窄带隙半导体包覆自生压电势的压电材料形成的核壳异质结构;所述自生压电势的压电材料为氧化锌,所述窄带隙半导体为氧化钛。
一种具有自生压电场的异质结构声敏剂的制备方法,包括以下步骤:
1)采用微弧氧化工艺对金属钛基体进行处理,在金属钛基体表面形成富含Zn2+的氧化钛基涂层;
2)通过一次水热工艺在富含Zn2+的氧化钛基涂层上构建ZnO单晶纳米棒阵列化涂层;
3)通过原子层沉积工艺在ZnO单晶纳米棒阵列化涂层上保形地沉积一层氧化钛薄膜,形成ZnO/TiO2核壳异质结构涂层;
4)将ZnO/TiO2核壳异质结构涂层置于还原性气氛中退火,对氧化钛薄膜引入氧空位,形成ZnO/TiO2-x涂层;
5)对退火后的ZnO/TiO2-x涂层进行快速冷却,产生热应力,在ZnO单晶纳米棒内形成压电势,形成p-ZnO/TiO2-x涂层,即得到具有双内建电场的异质结构声敏剂。
进一步地,步骤1)中将金属钛基体置于电解液中进行微弧氧化处理,电解液为(CH3COO)2Zn和β-C3H7Na2O6P的复配溶液,所述复配溶液中(CH3COO)2Zn的浓度为0.2M,β-C3H7Na2O6P的浓度为0.02M;
所述微弧氧化处理具体为:采用直流脉冲电流,在正电压为530V,负电压为0V,频率为100Hz的条件下,对金属钛基体进行80s的微弧氧化处理。
进一步地,步骤2)中水热工艺的具体操作为:
将富含Zn2+的氧化钛涂层置于水热反应釜中,并加入浓度为0.03M的NaOH溶液,在140℃下水热处理4h,得到ZnO单晶纳米棒阵列化涂层。
进一步地,步骤3)中原子层沉积工艺的具体为:
将具有ZnO纳米棒阵列化涂层的金属钛基体置于原子层沉积反应腔体中,依次利用钛的前驱体与氧化剂,进行200个周期的原子层沉积步骤,以形成氧化钛薄膜,所述氧化钛薄膜的厚度为15纳米;
其中,在所述原子层沉积步骤中,原子层沉积反应腔体的温度保持于250℃。
进一步地,所述钛的前驱体采用TTIP,所述氧化剂采用双氧水;且所述TTIP在加热后通过载气通入原子层沉积反应腔体,加热温度为65℃,载气为高纯氮气;双氧水在常温状态下直接加入原子层沉积反应腔体;
每个周期的原子层沉积步骤为:TTIP脉冲时间为2s,吹扫时间为8s,双氧水脉冲时间为2s,吹扫时间为10s,吹扫所用气体为高纯氮气。
进一步地,步骤4)中还原性气氛为氩气;步骤4)中退火温度为450℃,时间为2h。
进一步地,步骤5)快速冷却具体为:将退火后的ZnO/TiO2-x直接置于冰水混合物中。
一种具有自生压电场的异质结构声敏剂在除菌上的应用,所述除菌在超声辐照条件下进行,所述超声辐照条件为1MHz,2.5W/cm2,时间为30min。
一种具有自生压电场的异质结构声敏剂在制备治疗骨髓炎所用骨植入体上的应用。
与现有技术相比,本发明具有以下有益的技术效果:
本发明在金属钛基体表面改性形成骨植入体涂层,可作为声动力疗法抗菌的声敏剂使用,并促进成骨,以治疗骨髓炎。对TiO2引入氧空位形成TiO2-x可显著缩窄其带隙从而降低其激发电子跃迁所需是能量;TiO2-x与ZnO形成核壳异质结构,由于二者功函数差异,可在其界面处自发产生内建电场;并且,由于二者热膨胀系数失配,在热处理后快速冷却过程中产生热应力,可使作为压电材料的ZnO内部正负电荷中心分离发生极化从而产生压电势,此双内建电场的结构,可有效驱动电子-空穴对分离,提高ROS产率及声动力治疗效果。
本发明将具有双内建电场的异质结构涂层作为声敏剂,植入骨髓炎模型的缺损部位后,在超声作用下,由于外层TiO2-x中氧空位的存在,可激发更多的电子进行跃迁;同时,ZnO/TiO2-x异质结构界面自生内建电场及ZnO内部由于热应力产生的压电势可协同促进电子-空穴对的分离,从而提高ROS产率并杀灭细菌,结合本发明声敏剂仿骨基质的纳米棒阵列化构型,可促进间充质干细胞的成骨分化,在治疗骨髓炎方面具有很大的应用前景。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本发明的某些实施例,因此不应被看作是对范围的限定,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图。
图1是本发明实施例所得产物的表面形貌、物相及ZnO/TiO2异质结构界面处TEM表征,其中(a),(b),(c)分别为ZnO,ZnO/TiO2及p-ZnO/TiO2-x SEM图,其中小图为低倍形貌图;图(d)为所得产物的XRD衍射图谱;(e),(f),(g)分别为ZnO/TiO2的TEM形貌图,界面处高分辨图及选区电子衍射图。
图2是本发明实施例所得产物的氧空位及热应力表征,其中(a),(b),(c)分别为XPS全频谱图,O 1s及Ti 2p的高分辨谱图;(d)为XRD图谱在2deg=30-35.5精细图谱;(e),(f)分别为Raman图谱及在波数为120-180cm-1的精细图谱。
图3是本发明ZnO/TiO2及p-ZnO/TiO2-x涂层在超声刺激下产ROS的效率对比示意图。
图4是本发明ZnO/TiO2及p-ZnO/TiO2-x涂层在超声刺激下的电化学性能测试图,其中(a)为超声电流响应图;(b)为电化学阻抗谱。
图5是本发明ZnO/TiO2及p-ZnO/TiO2-x涂层光学性能测试图,其中(a)为紫外-可见漫反射谱图;(b)为由(a)得到的Tauc图。
图6是本发明ZnO/TiO2及p-ZnO/TiO2-x涂层抗菌性能测试图。
具体实施方式
下面对本发明的实施方式做进一步详细描述:
一种具有自生压电场的异质结构声敏剂,由窄带隙半导体包覆自生压电势的压电材料形成的核壳异质结构,所述自生压电势的压电材料为氧化锌,所述窄带隙半导体为氧化钛,压电材料的自生压电势由核壳结构热膨胀系数失配形成的热应力产生,包覆半导体的窄带隙由引入表面氧空位形成。
一种具有双内建电场的异质结声敏剂的制备方法,包括如下步骤:
1)采用微弧氧化工艺对金属钛基体进行处理,使其表面形成富含Zn2+的氧化钛基涂层;微弧氧化处理时,电解液为0.2M的(CH3COO)2Zn和0.02M的β-C3H7Na2O6P(β-GP)溶液的复配溶液,以金属钛片为阳极、不锈钢为阴极置于电解液中,微弧氧化处理时的具体操作为:采用直流脉冲电流,在正电压为530V,负电压为0V,频率为100Hz,阴阳极板间距10cm、电解液温度25℃的条件下,对金属钛基体进行80s的微弧氧化处理。
2)通过一次水热工艺实现ZnO单晶纳米棒阵列化涂层的构建;一次水热工艺的溶液为0.03M的NaOH溶液,一次水热工艺的具体操作为:将表面富含Zn2+的氧化钛涂层置于水热反应釜中,并加入0.03M的NaOH溶液(淹没即可),在140℃下水热处理4h,即可直接得到ZnO单晶纳米棒阵列化涂层。
3)通过原子层沉积工艺于ZnO单晶纳米棒阵列化涂层上保形地沉积一层氧化钛薄膜,形成ZnO/TiO2核壳异质结构涂层;原子层沉积工艺的具体操作为:将具有ZnO纳米棒阵列化涂层的金属钛基体置于原子层沉积反应腔体中,依次利用钛的前驱体与氧化剂,进行200个周期的原子层沉积步骤,以形成该氧化钛层,其厚度为15纳米;原子层沉积反应腔体的温度保持于250℃,钛的前驱体包含TTIP,氧化剂包含双氧水,其中TTIP的加热温度为65℃,载气为高纯氮气;双氧水置于常温;原子层沉积步骤为:TTIP脉冲时间为2s,吹扫时间为8s,双氧水脉冲时间为2s,吹扫时间为10s,吹扫气体为高纯氮气。
4)将其置于气体流量为300sccm的氩气中退火,对氧化钛薄膜引入氧空位,形成ZnO/TiO2-x涂层;退火的工艺为:温度为450℃,时间为2h。
5)对退火后的ZnO/TiO2-x涂层进行快速冷却,快速冷却的具体操作为:将退火后的ZnO/TiO2-x直接置于冰水混合物中,产生热应力,在ZnO单晶纳米棒内形成压电势,形成p-ZnO/TiO2-x涂层。
使用上述方法制备的声敏剂与细菌接触,超声辐照,用于清除细菌及骨髓炎治疗目的,细菌为金黄色葡萄球菌,超声辐照条件为1MHz,2.5W/cm2,时间为30min。
下面结合实施例对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例
一.声敏剂的制备
本实施例所述具有双内建电场的异质结构声敏剂的制备方法,包括以下步骤:
1)采用微弧氧化和水热法制备ZnO纳米棒阵列化涂层:以0.2Mβ-C3H7Na2O6P(β-GP)溶液和0.02M(CH3COO)2Zn溶液的复配溶液作为电解液,以金属钛片为阳极、不锈钢为阴极置于电解液中;采用直流脉冲电源,在正电压530V、负电压0V、频率100Hz、阴阳极板间距10cm、电解液温度25℃的条件下,对钛片进行80s的微弧氧化处理,得到含有Zn2+的氧化钛基复合涂层;接下来,将含有Zn2+的氧化钛基复合涂层置于水热反应釜中,并加入0.03M NaOH溶液,在140℃下水热处理4h,即可直接得到ZnO纳米棒阵列化涂层。
2)采用原子层沉积技术构建ZnO/TiO2核壳异质结构:将具有ZnO纳米棒阵列化涂层的金属钛基体置于原子层沉积反应腔体中,以TTIP作为钛的前驱体,H2O2作为氧化剂,高纯N2作为吹扫气体,进行200个周期的原子层沉积步骤,以形成该氧化钛层。其中,在所述原子层沉积步骤中,TTIP脉冲时间为2s,吹扫时间为8s,双氧水脉冲时间为2s,吹扫时间为10s。该腔体的温度保持于250℃。TTIP的加热温度为65℃,载气为高纯氮气;双氧水置于常温。
3)采用退火工艺在TiO2中引入氧空位,形成ZnO/TiO2-x:将具有ZnO/TiO2异质结构涂层的钛基体置于管式炉中,并通入流量为300sccm还原性高纯Ar,在450℃温度下退火2h。
4)利用退火后快速降温产生热应力在ZnO中产生压电势,形成p-ZnO/TiO2-x:准备一个盛有冰水混合物的烧杯,将退火后的ZnO/TiO2-x直接置于其中进行快速冷却。
二.声敏剂的表征
由本实施例制备方法得到的ZnO纳米棒阵列化涂层、ZnO/TiO2核壳异质结构以及具有双内建电场的p-ZnO/TiO2-x分别进行扫描电镜及X射线衍射图谱的表征,结果如图1、图2所示。由图1(a),1(b),1(c),1(d)可知,原子层沉积及后续退火工艺并没有改变ZnO纳米棒涂层的阵列化构型及物相。由图1(e),1(f),1(g)可知,利用“微弧氧化-水热”法制得的ZnO(JCPDSNo.36-1451)纳米棒为单晶,且原子层沉积后形成的TiO2薄膜为锐钛矿(Anatase,JCPDSNo.21-1272)厚度约为15nm;同时,ZnO的(002)晶面与TiO2的(200)晶面直接接触,形成了核壳异质结构。
图2是本发明上述实施例提供的制备方法所得产物的氧空位及热应力表征。由XPS结果可得,p-ZnO/TiO2-x涂层中氧空位(OV)及三价钛离子(Ti3+)含量均明显高于ZnO/TiO2,说明在Ar气氛退火时,非常低的氧分压会促进晶格氧扩散至气氛中,因此在TiO2薄膜表面成功引入了氧空位;从图2(d)可知,p-ZnO/TiO2-x涂层中,位于2deg=34.5的代表ZnO(002)晶面的峰往高角度方向发生偏移,说明快速冷却过程中,由于ZnO的热膨胀系数小于TiO2-x,ZnO单晶沿着c轴方向受到了一定的压应力。图2(e-f)中p-ZnO/TiO2-x涂层的ZnO E2 high峰偏移也证实了以上结果。
材料性能测试
一.产ROS效率测试
利用有机染料甲基橙的降解情况检测本发明实施例1中所合成材料在超声刺激下的ROS生成情况。具体操作如下:
将所制得ZnO/TiO2、p-ZnO/TiO2-x样品置于300μL 5mg/L的甲基橙溶液中,在避光条件下施加超声辐照(1MHz,2.5W/cm2)80分钟,并以不加超声刺激及超声同样条件的纯甲基橙溶液(300μL 5mg/L)作为对照。取上清液检测462nm处的吸光度,检测结果如图3所示。
图3中,按照吸光度强度从高到低排序为:-U>+U80min>ZnO/TiO2+U80min>p-ZnO/TiO2-x+U80min。由此可知,甲基橙溶液在超声刺激下会轻微发生降解,这可能是由于超声空化效应及超声水解效应会产生少量ROS造成的;由于ZnO/TiO2的异质结构界面处的内建电场,使得超声刺激下,ROS产量大幅提升,甲基橙降解明显;当p-ZnO/TiO2-x涂层存在双内建电场时,ROS产量最大,即在该超声条件下甲基橙可完全降解。
二.超声电化学性能测试
使用电化学工作站测试超声产生的电流响应及阻抗谱,表征材料超声激发载流子(电子-空穴对)的产量及寿命。具体操作如下:
以所制得ZnO/TiO2或p-ZnO/TiO2-x样品作为工作电极,Pt电极作为对电极,Ag/AgCl作为参比电极,形成三电极体系,浸没于作为电解液的0.1MNa2SO4溶液中,并将该电化学体系置于超声清洗机中施加超声刺激,结果如图4所示。
图4(a)为超声刺激下产生的电流密度随时间变化图,可知存在双内建电场的p-ZnO/TiO2-x涂层在超声刺激下,电流密度显著高于ZnO/TiO2,说明压电势及氧空位的存在可以显著增强电荷转移动力学;图4(b)为超声刺激下电化学阻抗谱图,p-ZnO/TiO2-x显示出更小的圆弧半径,说明其具有更小的电荷转移阻抗,进一步验证了p-ZnO/TiO2-x的结构有利于促进超声产生的电子-空穴对分离,从而提高ROS产率。
三.光学性能测试
使用紫外可见分光光度计测量ZnO/TiO2及p-ZnO/TiO2-x样品的漫反射光谱,与此同时其带隙可由根据公式(1)得到的Tauc图计算得出。
(αhν)n=A(hν-Eg)   (1)
其中α表示吸收系数,A表示比例系数,h表示普朗克常数,ν表示光频率,Eg表示带隙。结果如图5所示。
由图5(a-b)可知,相比于ZnO/TiO2,p-ZnO/TiO2-x涂层具有更大的吸收范围,这可以归因于TiO2薄膜中引入了氧空位而显著缩短了其带隙。由此可知,p-ZnO/TiO2-x涂层需要吸收的供电子跃迁的能量更低。因此同等条件的超声刺激下,其发生电子跃迁产生电子-空穴对的数量必多于ZnO/TiO2
四.抗菌性能测试
本实施例以金黄色葡萄球菌为例,采用平板计数法评价所合成ZnO/TiO2及p-ZnO/TiO2-x样品在超声刺激下的抗菌性能,并以无抗菌性的纯钛作为对照。具体操作如下:
采用营养肉汤培养基培养金黄色葡萄球菌。样品用医用75%酒精消毒后置于24孔板。将300μL 105CFU/mL的细菌浊液滴加至样品表面。随后,超声组在超声条件为1MHz,2.5W/cm2下刺激30分钟,置于37℃培养3小时;不加超声组,直接置于37℃培养3小时。之后吸取菌液稀释并涂板计数。结果如图6所示。
由图6可知,不加超声刺激培养3h后,ZnO/TiO2及p-ZnO/TiO2-x样品均有较低的抗菌率,分别为19.66%,17.73%。这可能是由于纳米棒尖端对细菌的刺破效应导致的。而在超声刺激组中,纯钛样品表现出5.42%的抗菌率,这是由于超声波本身产生的空化效应及声水解效应将产生少量ROS导致的;然而ZnO/TiO2的抗菌率达到了30.69%,p-ZnO/TiO2-x的抗菌率则高达98.53%。
综上述结果可以看到,本申请实施例所提供的声敏剂p-ZnO/TiO2-x涂层,由于外层TiO2具有一定含量的氧空位,在超声刺激下可激发更多电子进行跃迁,并且在其双内建电场结构的驱动下,超声下产生的电子-空穴对更易分离,与环境中的水和氧气发生氧化还原反应,生成具有毒性的ROS,快速消灭细菌。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (8)

1.一种具有自生压电场的异质结构声敏剂的制备方法,其特征在于,包括以下步骤:
1)采用微弧氧化工艺对金属钛基体进行处理,在金属钛基体表面形成富含Zn2+的氧化钛基涂层;
2)通过一次水热工艺在富含Zn2+的氧化钛基涂层上构建ZnO单晶纳米棒阵列化涂层;
3)通过原子层沉积工艺在ZnO单晶纳米棒阵列化涂层上保形地沉积一层氧化钛薄膜,形成ZnO/TiO2核壳异质结构涂层;
4)将ZnO/TiO2核壳异质结构涂层置于还原性气氛中退火,对氧化钛薄膜引入氧空位,形成ZnO/TiO2-x涂层;
5)对退火后的ZnO/TiO2-x涂层进行快速冷却,产生热应力,在ZnO单晶纳米棒内形成压电势,形成p- ZnO/TiO2-x涂层,即得到具有双内建电场的异质结构声敏剂;
所述步骤1)中将金属钛基体置于电解液中进行微弧氧化处理,电解液为(CH3COO)2Zn和β-C3H7Na2O6P的复配溶液,所述复配溶液中(CH3COO)2Zn的浓度为0.2M,β-C3H7Na2O6P的浓度为0.02M;
所述微弧氧化处理具体为:采用直流脉冲电流,在正电压为530V,负电压为0V,频率为100Hz的条件下,对金属钛基体进行80s的微弧氧化处理;
所述步骤2)中水热工艺的具体操作为:
将富含Zn2+的氧化钛涂层置于水热反应釜中,并加入浓度为0.03M的NaOH溶液,在140℃下水热处理4h,得到ZnO单晶纳米棒阵列化涂层。
2.根据权利要求1所述的一种具有自生压电场的异质结构声敏剂的制备方法,其特征在于,步骤3)中原子层沉积工艺的具体为:
将具有ZnO纳米棒阵列化涂层的金属钛基体置于原子层沉积反应腔体中,依次利用钛的前驱体与氧化剂,进行200个周期的原子层沉积步骤,以形成氧化钛薄膜,所述氧化钛薄膜的厚度为15纳米;
其中,在所述原子层沉积步骤中,原子层沉积反应腔体的温度保持于250℃。
3.根据权利要求2所述的一种具有自生压电场的异质结构声敏剂的制备方法,其特征在于,所述钛的前驱体采用TTIP,所述氧化剂采用双氧水;且所述TTIP在加热后通过载气通入原子层沉积反应腔体,加热温度为65℃,载气为高纯氮气;双氧水在常温状态下直接加入原子层沉积反应腔体;
每个周期的原子层沉积步骤为:TTIP脉冲时间为 2s,吹扫时间为8s,双氧水脉冲时间为2s,吹扫时间为10s,吹扫所用气体为高纯氮气。
4.根据权利要求1所述的一种具有自生压电场的异质结构声敏剂的制备方法,其特征在于,步骤4)中还原性气氛为氩气;步骤4)中退火温度为450℃,时间为2h。
5.根据权利要求1所述的一种具有自生压电场的异质结构声敏剂的制备方法,其特征在于,步骤5)快速冷却具体为:将退火后的ZnO/TiO2-x直接置于冰水混合物中。
6.一种具有自生压电场的异质结构声敏剂,其特征在于,采用权利要求1-5任一项所述的所述一种具有自生压电场的异质结构声敏剂的制备方法制得,所述异质结构声敏剂具有双内建电场,所述异质结构声敏剂为由窄带隙半导体包覆自生压电势的压电材料形成的核壳异质结构;所述自生压电势的压电材料为氧化锌,所述窄带隙半导体为氧化钛。
7.权利要求6所述的一种具有自生压电场的异质结构声敏剂在除菌上的应用,其特征在于,所述除菌在超声辐照条件下进行,所述超声辐照条件为1MHz,2.5W/cm2,时间为30min。
8.权利要求6所述的一种具有自生压电场的异质结构声敏剂在制备治疗骨髓炎所用骨植入体上的应用。
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