CN111816718B - 一种阵列异质结的自组装生长方法 - Google Patents
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Abstract
本发明公开了一种阵列异质结的自组装生长方法,包括如下步骤:配置PSS溶液;将阵列基底置于PSS溶液中浸泡,形成PSS修饰的阵列基底,显负电性;配置聚乙烯亚胺辅助的金属离子前驱体溶液,形成带正电的离子团;将前驱体溶液滴加到PSS修饰的阵列基底上,正负基团的吸附作用将前驱体溶液吸附在阵列表面;热处理即可形成稳定牢固的异质结阵列。本发明首次公开了一种通过PSS修饰显负电性和PEI辅助形成的离子基团显正电性的金属离子前驱体溶液之间的正负吸引作用,将金属离子前驱体溶液与阵列表面相连热处理后形成稳定的异质结的自组装的生长方法,该方法形成的异质结表面均匀,可控性强,为异质结的生长提供了可选择的通用方法。
Description
技术领域
本发明属于半导体异质结技术领域,涉及一种阵列异质结薄膜的自组装的生长方法,更具体的涉及一种以聚苯乙烯磺酸钠和聚乙烯亚胺辅助形成金属离子前驱体溶液在阵列基底表面生长异质结薄膜的方法。
背景技术
纳米阵列如TiO2、ZnO等阵列相比于平面薄膜具有独特的结构、大的比表面积、对光有更高的捕获效率、更高的量子效应等特点,在太阳能电池、发光器件、光催化等领域有广泛的应用。然而单一材料具有自身的缺陷,在阵列表面生长另外一种材料形成阵列异质结则能结合两者的优点,取长补短,甚至会由于材料之间的独特的耦合机制而发挥出原有材料所不具备的新颖特性。
近年来的研究表明基于阵列异质结的应用领域广泛,也证明了阵列异质结相比于单一的阵列具有优异的性能。浙江大学的Xia课题组在TiO2阵列上生长Co9S8形成TiO2@Co9S8阵列异质结,用于氧/氢逸出反应中作为双功能催化剂具有优异的性能,参阅Adv. Sci.2018, 5, 1700772。上海交通大学的Li课题组在TiO2阵列表面修饰了ZnO形成Z-型异质结的光阳极,具有高的光吸收特性及高的光电化学水解性能,参阅Appl.Catal. B-Environ.2020,267,118599。复旦大学的Fang课题组生长了一种ZnO/NiO的异质结,成功地应用于自充电的透明紫外探测器,参阅J. Mater. Chem. C2019,7, 223。从此可知,阵列异质结在光电催化、光电探测等领域都有重要的贡献,但是上面我们所列举的这些阵列异质结的生长主要都集中在水热方法生长异质结,该方法可控性不强。目前为止,还没有公开的方法可以获得可控生长阵列异质结的通用方法。
发明内容
为了能实现在阵列表面形成均匀的薄膜与阵列形成核壳结构的异质结,本发明设计了一种用聚苯乙烯磺酸钠(PSS)和聚乙烯亚胺(PEI)金属离子络合物自组装的方法在阵列基底表面生长半导体化合物形成异质结的方法,从而实现了异质结吸收光子后产生电子空穴对,使电子空穴对快速分离,该方法能实现各种核壳结构的异质结,为生长异质结提供了可行的方案。
为达到上述发明创造目的,本发明采用下述技术方案:一种在阵列基底上通过聚苯乙烯磺酸钠和聚乙烯亚胺金属离子络合物自组装形成异质结的方法,包括如下步骤:
a.配置一定浓度的聚苯乙烯磺酸钠(PSS)溶液;
b.将清洗干净的阵列基底浸泡在聚苯乙烯磺酸钠(PSS)溶液中,使聚苯乙烯磺酸钠(PSS)吸附在阵列表面,形成聚苯乙烯磺酸钠(PSS)修饰的阵列基底,显负电性;
c.利用聚合物辅助沉积的技术将聚乙烯亚胺(PEI)及其衍生物与金属离子配位,形成含金属离子的前驱体溶液,金属离子基团显正电性;
d.将含金属离子的前驱体溶液滴加到浸泡过聚苯乙烯磺酸钠(PSS)溶液的基底上,正负离子的吸附作用将前驱体溶液吸附在阵列表面;
e.通过热处理使得金属离子前驱体溶液转变成金属氧化物、金属碳化物、金属氮化物及金属硫化物等等,从而与基底阵列材料形成异质结。
本发明首次公开了一种通过PSS修饰显负电性和PEI辅助形成的离子基团显正电性的金属离子前驱体溶液之间的正负吸引作用,将金属离子前驱体溶液与阵列表面相连热处理后形成稳定的异质结的自组装的生长方法,该方法形成的异质结表面均匀,可控性强,适用范围广,为异质结的生长提供了可选择的通用方法。
优选的,步骤a中聚苯乙烯磺酸钠(PSS)溶液的质量浓度不宜超过5%,溶液的溶剂为乙醇。
优选的,步骤b中浸泡所采用的温度为70-90℃,时间为2小时,所述基底可采用二氧化钛阵列、氧化铜阵列、氧化锌阵列等等。
优选的,步骤c中的前驱体溶液中金属离子与聚乙烯亚胺(PEI)能形成稳定的前驱体溶液,一般为金属氯化物及金属硝酸盐等与聚乙烯亚胺(PEI)反应后通过超滤将没有络合的金属离子超滤掉,溶液的粘度可根据实验中基底阵列的不同而调控,其中金属离子包括元素周期表中绝大部分金属元素如Ni、Fe、Ti、Cu、Nb、Zn、Sb、Sn、Mo等均能形成均匀稳定的前驱体溶液。
优选的,步骤d中金属离子前驱体溶液可以是Ni2+、Ti4+、Cu2+、Fe2+、Zn2+等一元金属离子也可以是如Zn2+和Fe2+等两种甚至多元金属离子混合的前驱体溶液与聚苯乙烯磺酸钠(PSS)修饰的基底之间形成均匀包覆的状态。
优选的,步骤e中可在不同的气氛中热处理,如在氧气或空气中热处理得到氧化物,在含硫气氛中得到硫化物,在含硒气氛中得到硒化物,在氨气气氛下得到氮化物等等化合物与阵列形成核壳结构的异质结。
对生长的异质结进行结构和性能的表征,得出通过这种方法能均匀的在阵列表面形成包覆层,从而形成异质结。在扫描电子显微镜下能清晰的看出原始的阵列表面光滑且呈立方柱结构,而通过该方法生长了异质结后,表面粗糙有明显的颗粒均匀的分布在表面,通过性能的表征发现与没有形成异质结的阵列基底比较,电子空穴能顺利的导出。
本发明首次实现了可控的方法在阵列基底表面生长均匀的薄膜与基底阵列之间形成异质结。通过这种PSS辅助的方法能均匀可控的在不规则基底表面形成均匀的薄膜,相对于其他方法具有明显的特色,本发明具有显著区别和突出优点:
1该方法中能与基底形成异质结的关键在于金属离子是否能与PEI及其衍生物形成稳定的前驱体溶液,而通过实验的实验发现元素周期表中绝大部分的金属离子都能与其形成温定的前驱体,每种前驱体在热处理后可形成氧化物、碳化物、氮化物、硫化物和硒化物等,因此该方法在阵列基底表面形成异质结具有通用性。
2异质结的薄膜厚度对电子与空穴的导出具有重要影响,本发明可通过调控金属离子的前驱体溶液的粘度、离子浓度等从而使得阵列表面的异质结层厚度不一样,可根据实际的需要生长不同厚度的包覆层,得到性能最优的阵列异质结。
附图说明
图1为实施例1的阵列异质结生长示意图;
图2为实施例扫描电子显微镜图,其中(a)为阵列基底扫描电子显微镜图,(b)为形成异质结的扫描电子显微镜图;
图3为实施例透射电子显微镜图,其中(a)为阵列基底的透射电子显微镜图,(b)为形成异质结的透射电子显微镜图;
图4为实施例的阵列异质结SEM,(a)为有PSS处理后生长的阵列异质结的扫描电子显微镜图,(b)为无PSS处理生长的阵列异质结的扫描电子显微镜图。
具体实施方式
实施例1
实施路线如图1所示,具体的步骤如下:
a,取一定量的PSS(平均分子量为70 000)粉末加入乙醇溶液中,配置质量浓度为5%的PSS溶液,在室温下充分搅拌使之均匀;
b, 将通过水热法生长的二氧化钛阵列柱(参阅Energy Environ. Sci., 2016,9, 2633)(如图2的(a)和图3的(a)所示的形貌)浸泡在上述PSS溶液中,置于平板加热器上90℃加热2小时,结束后自然降温至室温,烘干,形成PSS修饰的阵列基底;
c,将氯化镍加入含PEI(枝化聚乙烯亚胺,平均分子量为10 000)的水溶液(PEI的质量分数为20%-40%)中搅拌使之充分反应,PEI与金属离子通过络合的方式形成稳定的配位化合物,充分反应后将溶液通过超滤装置(分子量大于滤膜分子量要求的则不能通过滤膜,分子量小于滤膜分子量的则可被滤掉)将没有络合的镍离子滤掉形成最终的镍的前驱体溶液,最终的前驱体溶液在分子层面上均匀且稳定,镍的前驱体溶液的粘度和浓度可通过控制加入PEI的量来调控,其中PEI与氯化镍的质量比范围应在0.5~2:1(本实施例中PEI:氯化镍的质量比为1:1),前驱体溶液的镍离子浓度对包覆层的厚度有重要影响,浓度越大,则包覆层越厚,浓度过大则容易出现不能完全吸附。
d, 将前驱体溶液滴加到被PSS修饰的阵列基底上,静置一段时间,使溶液充分进去阵列柱之间,形成包覆层,通过提拉或旋涂的方式可使包覆层更加均匀,厚度可通过金属前驱体溶液的浓度及提拉或旋涂次数改变形成预制膜。
e, 将上述预制膜置于管式炉中进行热处理,热处理的气氛为氧气,反应温度为500℃,反应时间为2小时,结束后自然降温至室温,即可得到TiO2@TiNiO3的阵列异质结,最终的异质结薄膜形貌如图2的(b)和图3的(b)所示,TiNiO3均匀的包覆在TiO2阵列表面。
实施例2
a, 将通过水热法生长的二氧化钛阵列柱(参阅Energy Environ. Sci., 2016,9, 2633)清洗干净烘干待用。
b,将氯化镍加入含PEI(枝化聚乙烯亚胺,平均分子量为10 000)的水溶液(PEI的质量分数为20%-40%)中搅拌使之充分反应,PEI与金属离子通过络合的方式形成稳定的配位化合物,充分反应后将溶液通过超滤装置(分子量大于滤膜分子量要求的则不能通过滤膜,分子量小于滤膜分子量的则可被滤掉)将没有络合的镍离子滤掉形成最终的镍的前驱体溶液,最终的前驱体溶液在分子层面上均匀且稳定,镍的前驱体溶液的粘度和浓度可通过控制加入PEI的量来调控,其中PEI与氯化镍的质量比范围应在0.5~2:1(本实施例中PEI:氯化镍的质量比为1:1),前驱体溶液的镍离子浓度对包覆层的厚度有重要影响,浓度越大,包覆层越厚。
c, 将前驱体溶液滴加到步骤a中二氧化钛阵列基底上,静置一段时间,使溶液充分进去阵列柱之间,形成预制膜。
d, 将上述预制膜置于管式炉中进行热处理,热处理的气氛为氧气,反应温度为500℃,反应时间为2小时,结束后自然降温至室温,与PSS修饰处理过的阵列异质结SEM(如图4)比较发现,无PSS处理的阵列表面包覆不均匀。
实施例3
具体的步骤如下:
a,取一定量的PSS(平均分子量为70 000)粉末加入乙醇溶液中,配置质量分数5%的PSS溶液,在室温下充分搅拌使之均匀;
b, 将通过水热法生长的二氧化钛阵列柱(参阅Energy Environ. Sci., 2016,9, 2633)浸泡在上述PSS溶液中,置于平板加热器上90℃加热2小时,结束后自然降温至室温,烘干,形成PSS修饰的阵列基底;
c,将硝酸锌加入含PEI(枝化聚乙烯亚胺,平均分子量为10 000)的水溶液(PEI的质量分数为20%-40%)中搅拌使之充分反应,充分反应后将溶液通过超滤装置(分子量大于滤膜分子量要求的则不能通过滤膜,分子量小于滤膜分子量的则可被滤掉)将没有络合的锌离子滤掉形成最终的前驱体溶液,测试溶液中锌离子的浓度;同时制备铁的前驱体溶液,将氯化铁加入含PEI的水溶液中,搅拌使之充分反应,充分反应后将溶液通过超滤装置(分子量大于滤膜分子量要求的则不能通过滤膜,分子量小于滤膜分子量的则可被滤掉)将没有络合的铁离子滤掉形成最终的前驱体溶液,测试溶液中铁离子的浓度,根据需要生长的化合物如ZnFe2O4中Zn与Fe的原子比为1:2配成含Zn2+和Fe3+的前驱体溶液,由于每种金属离子均已与PEI形成了稳定的配位化合物,因此Zn2+和Fe3+的在分子层面上是均匀的;
d, 将ZnFe前驱体溶液滴加到被PSS修饰的阵列基底上,静置一段时间,使溶液充分进去阵列柱之间,形成包覆层,通过提拉或旋涂的方式可使包覆层更加均匀,厚度可通过金属前驱体溶液的浓度及提拉或旋涂次数改变形成预制膜。
e, 将上述预制膜置于管式炉中进行热处理,热处理的气氛为氧气,反应温度为700℃,反应时间为2小时,结束后自然降温至室温,即可得到TiO2@ZnFe2O4的阵列异质结,可实现ZnFe2O4均匀的包覆在TiO2阵列表面。
实施例4
a,取一定量的PSS(平均分子量为70 000)粉末加入乙醇溶液中,配置质量分数为5%的PSS溶液,在室温下充分搅拌使之均匀;
b, 将通过水热法生长的TiO2阵列柱(参阅Energy Environ. Sci., 2016, 9,2633)浸泡在上述PSS溶液中,置于平板加热器上90℃加热2小时,结束后自然降温至室温,烘干,形成PSS修饰的阵列基底;
c,将氯化锑加入含PEI(枝化聚乙烯亚胺,平均分子量为10 000)的水溶液(PEI的质量分数为20%—40%)中搅拌使之充分反应,充分反应后将溶液通过超滤装置(分子量大于滤膜分子量要求的则不能通过滤膜,分子量小于滤膜分子量的则可被滤掉)将没有络合的锑离子滤掉形成最终的前驱体溶液,溶液的粘度和浓度可通过控制加入PEI的量来调控,PEI与金属离子通过络合的方式形成稳定的配位化合物,因此最终的前驱体溶液在分子层面上均匀且稳定;
d, 将前驱体溶液滴加到被PSS修饰的阵列基底上,静置一段时间,使溶液充分进去阵列柱之间,形成包覆层,通过提拉或旋涂的方式可使包覆层更加均匀,厚度可通过金属前驱体溶液的浓度及提拉或旋涂次数改变形成预制膜。
e, 将上述预制膜置于管式炉中进行热处理,在硫粉提供硫蒸汽的气氛中,反应温度为500℃,反应时间为2小时,结束后自然降温至室温,即可得到TiO2@Sb2S3的阵列异质结,最终的异质结薄膜,可用于光催化及硫化锑薄膜太阳能电池中。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (7)
1.一种在阵列基底上通过聚苯乙烯磺酸钠和聚乙烯亚胺金属离子络合物自组装形成异质结的方法,包括如下步骤:
a.配置聚苯乙烯磺酸钠溶液;
b.将清洗干净的阵列基底浸泡在聚苯乙烯磺酸钠溶液中,使聚苯乙烯磺酸钠吸附在阵列表面,形成聚苯乙烯磺酸钠修饰的阵列基底,显负电性;
c.利用聚合物辅助沉积的技术将聚乙烯亚胺及其衍生物与金属离子配位,形成含金属离子的前驱体溶液,金属离子基团显正电性;
d.将含金属离子的前驱体溶液滴加到浸泡过聚苯乙烯磺酸钠溶液的基底上,正负离子的吸附作用将前驱体溶液吸附在阵列表面;
e.通过热处理使得金属离子前驱体溶液转变成金属氧化物、金属氮化物或金属硫化物,从而与基底阵列材料形成异质结。
2.根据权利要求1所述的方法,其特征在于:步骤a中,聚苯乙烯磺酸钠溶液的质量浓度不超过5%,溶液的溶剂为乙醇。
3.根据权利要求1所述的方法,其特征在于:步骤b中浸泡所采用的温度为70-90℃,时间为2小时,所述基底采用二氧化钛阵列、氧化铜阵列或氧化锌阵列。
4.根据权利要求1所述的方法,其特征在于:步骤c中的前驱体溶液中金属离子与聚乙烯亚胺能形成稳定的前驱体溶液;所述金属离子为金属氯化物或金属硝酸盐,所述金属离子与聚乙烯亚胺反应后通过超滤装置将没有络合的金属离子超滤掉,溶液的粘度根据实验中基底阵列的不同而调控,其中金属离子的金属元素包括Ni、Fe、Ti、Cu、Nb、Zn、Sb、Sn或Mo。
5.根据权利要求1所述的方法,其特征在于:步骤d中金属离子前驱体溶液是Ni2+、Ti4+、Cu2+、Fe2+和Zn2+中的任意一种一元金属离子或任意两种以上的多元金属离子混合的前驱体溶液。
6.根据权利要求1所述的方法,其特征在于:步骤e中在不同的气氛中热处理,在氧气或空气中热处理得到氧化物,在含硫气氛中得到硫化物,在氨气气氛下得到氮化物,与阵列形成核壳结构的异质结。
7.一种权利要求1所述方法制备出的在阵列基底上通过聚苯乙烯磺酸钠和聚乙烯亚胺金属离子络合物自组装形成异质结的用途,其特征在于:用于光电器件或光催化领域。
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