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一种室温溅射法制备二氧化钛薄膜的方法 【EN】A kind of method that room temperature sputtering method prepares titanium deoxid film

申请(专利)号:CN201610876611.1国省代码:上海 31
申请(专利权)人:【中文】中国科学院上海硅酸盐研究所【EN】SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES
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摘要:
【中文】本发明涉及一种室温溅射法制备二氧化钛薄膜的方法,采用直流磁控溅射法制备不同结晶度二氧化钛薄膜,其中靶材为纯钛靶,本底真空度在10‑4 Pa以下,溅射气体为氩气和氧气,总压强为0.5~2.5 Pa,氧分压为50%以下,靶材与基材的距离为7~20 cm,初始基材温度为15~35℃,施加于所述靶材上的直流电源的功率为300~900W,沉积时间为5~30分钟,获得完全非晶或部分结晶的二氧化钛薄膜。本发明的方法薄膜制备条件温和,设备简单,节约资源能源。 【EN】The present invention relates to a kind of method that room temperature sputtering method prepares titanium deoxid film, use direct current magnetron sputtering process to prepare different crystallinity titanium deoxid film, wherein target is pure titanium target, and background vacuum is 10‑4 Below Pa, sputter gas is argon and oxygen, total pressure is 0.5~2.5 Pa, partial pressure of oxygen is less than 50%, target is 7~20 cm with the distance of base material, and initial substrate temperature is 15~35 DEG C, and the power putting on the DC source on described target is 300~900W, sedimentation time is 5~30 minutes, it is thus achieved that the completely amorphous or titanium deoxid film of partially crystallizable.The method film preparation mild condition of the present invention, equipment is simple, and economize on resources the energy.

主权项:
【中文】1.一种室温溅射法制备二氧化钛薄膜的方法,其特征在于,采用直流磁控溅射法制备不同结晶度二氧化钛薄膜,其中靶材为纯钛靶,本底真空度在10Pa以下,溅射气体为氩气和氧气,总压强为0.5~2.5 Pa,氧分压为50 %以下,靶材与基材的距离为7~20 cm,初始基材温度为 15~35 ℃,施加于所述靶材上的直流电源的功率为 300~900 W,沉积时间为5~30分钟,获得完全非晶或部分结晶的二氧化钛薄膜。 【EN】1. the method that a room temperature sputtering method prepares titanium deoxid film, it is characterised in that use direct current magnetron sputtering process to prepare Different crystallinity titanium deoxid film, wherein target is pure titanium target, and background vacuum is 10Below Pa, sputter gas is argon And oxygen, total pressure is 0.5~2.5 Pa, and partial pressure of oxygen is 50 below %, and target is 7~20 cm with the distance of base material, first primordium Material temperature is 15~35 DEG C, and the power putting on the DC source on described target is 300~900 W, and sedimentation time is 5 ~30 minutes, it is thus achieved that the completely amorphous or titanium deoxid film of partially crystallizable.


说明书

【中文】

一种室温溅射法制备二氧化钛薄膜的方法

技术领域

本发明属于无机纳米材料领域,具体涉及一种室温溅射法制备不同结晶度二氧化钛薄膜的方法,用于钙钛矿太阳能电池致密层。

背景技术

近年来,在能源危机逐渐加剧,环境污染程度逐渐变深的背景下,全球光电研究领域取得了极大的进展,成为本世纪最具前景和战略意义的研究热点之一。在此领域中,由于成本低、工艺简单以及性能优秀,钙钛矿太阳能电池成为了光电器件领域的研究热点。该电池2009年首次提出的太阳光转换效率仅为4%,经过7年的发展如今认证效率已经高达22%,超过非晶硅太阳能电池和铜铟镓硒太阳能电池当前的光电转化效率,具有媲美单晶硅和多结砷化镓电池的潜力。因此,积极开展针对钙钛矿电池的研究,优化电池结构和组成材料,对今后国民经济可持续和创新发展有着重大的意义。实现电池具备高转换效率的基本途径就是提高光生载流子的提取,分离和运输的能力。

钙钛矿太阳能电池包含5层材料,这几层材料分别具有不同的性能。首先是透明导电电极,常用的是FTO(掺F二氧化锡)或者ITO(氧化铟锡)导电玻璃;随后是电子传输层,用于及时输运光生电子和阻挡光生空穴,抑制光生电子和光生空穴的复合;再次是钙钛矿吸收材料,主要是钙钛矿型有机铅卤化物(ABX3:A=CH3NH3,B=Pb,X=Cl,I,Br);再次是空穴传输层,用于及时输运光生空穴和阻挡光生电子,抑制光生电子和光生空穴的复合;最后是背电极,常用的是金,银和铜。因此,合适的电子传输层是高性能钙钛矿太阳能不可缺少的一部分。理想的电子传输层具有优秀的电子传输能力和空穴阻挡能力,在可见光范围内具备高透过率,较低的界面电阻,以及匹配钙钛矿吸收层导带位置的能级。到目前为止,二氧化钛和氧化锌是主要应用于电子传输层的材料。应用这两种材料作为电子传输层的钙钛矿太阳能电池具有比较高的转换效率,然而氧化锌材料长期不稳定性影响了其市场化推广。因此,二氧化钛是最主要的,也是被认为前景最广阔的电子传输材料。

目前为止,报道的制备二氧化钛电子传输层方法主要是旋涂法和喷雾热解法。针对这两种制备方法,在合成过程中均需要高温煅烧过程,以提高纳米粉体的结晶性和获得致密的结构。高温处理极大的限制了柔性衬底电池的制备与应用,以及提高了生产成本。与此同时,旋涂法虽然简便,但是受制于尺寸的限制。仅仅在有限的电池面积下,可以获得均匀的电子传输层。而喷雾热解法制备的电子传输层面积虽然相应有所提高,但是其设备非常复杂,对于未来的大规模生产来说,有很大的局限性。其他的方法包括原子层沉积,溶胶凝胶,微波辅助和丝网印刷,均需要高温处理工程,并且最终制备的电池性能弱于前面两种方法。因此寻找一种可以低温制备大尺寸高性能电子传输层的方法势在必行。

发明内容

针对现有技术中二氧化钛电子传输层合成温度高,条件苛刻的技术方法,本发明的目的在于提供一种不需要任何加热即可快速沉积制备不同结晶度二氧化钛纳米薄膜的方法。

在此,本发明提供一种室温溅射法制备不同结晶度二氧化钛薄膜的方法,采用直流磁控溅射法制备不同结晶度二氧化钛薄膜,其中靶材为纯钛靶,本底真空度在10-4Pa以下,溅射气体为氩气和氧气,总压强为0.5~2.5Pa,氧分压为50%以下,靶材与基材的距离为7~20cm,初始基材温度为15~35℃,施加于所述靶材上的直流电源的功率为300~900W,沉积时间为5~30分钟,获得完全非晶或部分结晶的二氧化钛薄膜。部分结晶的二氧化钛薄膜的结晶度可为0~50%(优选不为0)。

本发明采用了简单快捷且能够精确控制薄膜厚度和性质的室温溅射法,在低温下制备得到不同结晶性质且性能优异的TiO2纳米薄膜,基材初始的温度为室温,整个过程中不需要进行加热。相比于目前已经报道的完全非晶的二氧化钛薄膜,根据本发明的方法制备的二氧化钛薄膜的特点在于,可以自由调节二氧化钛薄膜的结晶度。本发明通过大量的对比试验发现,二氧化钛薄膜结晶度对基于该薄膜制备的钙钛矿太阳能电池性能有显著的影响。通过试验优化所得薄膜的结晶度,从而获得最佳的电池性能。因此本方案有显著的科学意义和实际意义。而且,由于更高的溅射功率,根据本发明的方法制备的部分结晶的二氧化钛纳米薄膜拥有更小的粗糙度,并且由于薄膜中存在的结晶纳米颗粒,因此该薄膜拥有更高的电子提取与转移效率,较小的界面电阻和价电子空穴复合能力。相比于广泛使用的溶液法,本发明的方法制备工艺更简便,不仅可以室温制备,而且薄膜更加致密和平坦,可以有效的降低薄膜的界面电阻。此外,磁控溅射法相比起溶液法制备的薄膜,致密高,表面粗糙度低,厚度连续可调,不受基材面积的影响,室温下可以即获得结晶的薄膜。

本发明中,通过控制溅射功率和/或气氛压力,提高溅射腔体中沉积粒子的能量,从而可以获得完全非晶和部分结晶的二氧化钛纳米薄膜。其中,控制靶材直流电源功率为500W~650W,控制总压强为1~1.5Pa,氧分压为15%~35%时,可以得到完全非晶的二氧化钛薄膜。

又,控制靶材直流电源功率为650W~750W,控制总压强为1~1.5Pa,氧分压为15%~35%时,可以得到部分结晶的二氧化钛薄膜。所述部分结晶的二氧化钛薄膜中结晶颗粒为锐钛矿相二氧化钛。

较佳地,所述总压强为0.5-2Pa,优选为1-2Pa。

较佳地,靶材直流电源功率为500W-700W。

上述制备方法中,氧气和氩气比例可以为1:1-1:10,优选为1:5-1:8,更优选为1:6。此外,所采用的氩气和氧气的纯度可为99.99%以上。

上述制备方法中,沉积前进行预溅射,所述预溅射的条件是:功率100-300W,时间5-30分钟,气氛是纯氩气,气体压力是0.5-1.5Pa。

较佳地,所述基材为FTO、AZO或ITO。

本发明还提供由上述方法制备得到的二氧化钛薄膜,所述薄膜为完全非晶或部分结晶的二氧化钛薄膜。所述二氧化钛薄膜的厚度为30nm-60nm。不同厚度的二氧化钛纳米薄膜可以通过控制溅射时间获得。溅射时间越长,厚度越大。

本发明的二氧化钛薄膜的可见光透过率在80%以上。此外,所述薄膜材料具备优异的电子分离和运输能力以及空穴阻挡能力,基于该薄膜材料制备的钙钛矿太阳能电池最佳光电转换效率大于15%。

本发明还提供一种钙钛矿太阳能电池的制备方法,所述方法包括:在透明导电基材上依次溅射电子传输层、钙钛矿吸收层、空穴传输层以及背电极,其中,所述电子传输层为二氧化钛薄膜,所述二氧化钛薄膜由上述室温溅射法制备二氧化钛薄膜的方法制备得到。

本发明的优点;

薄膜制备条件温和,设备简单,节约资源能源;

磁控溅射法制备周期短,可以连续控制,不受限制于衬底尺寸和薄膜均匀性;

磁控溅射法制备工艺简单,稳定高,重复性好,市场化应用前景美好;

本发明的二氧化钛薄膜均匀致密,表面粗糙度低,与基底材料结合牢固,在可见光区透过率好。具有优秀的电子传输能力和空穴阻挡能力。并且该薄膜表面润湿性好,可以很好的与钙钛矿吸收材料接触,极大的降低了界面接触电阻。

附图说明

图1:磁控溅射示意图;

图2A:磁控溅射制备的完全非晶二氧化钛薄膜断面SEM;图2B:磁控溅射制备的部分结晶二氧化钛薄膜断面SEM;图2C:磁控溅射制备的部分结晶二氧化钛薄膜表面SEM;图2D:磁控溅射制备的完全非晶二氧化钛薄膜、磁控溅射制备的部分结晶二氧化钛薄以及纯FTO的XRD图;

图3:磁控溅射制备的完全非晶二氧化钛薄膜、磁控溅射制备的部分结晶二氧化钛薄以及纯FTO的可见光透过率;

图4:基于磁控溅射法制备的完全非晶二氧化钛薄膜和部分结晶二氧化钛的太阳能电池性能。

具体实施方式

以下结合附图和下述实施方式进一步说明本发明,应理解,下述实施方式仅用于说明本发明,而非限制本发明。

本发明涉及一种采用直流磁控溅射物理气相沉积技术在低温下制备不同结晶性质TiO2纳米薄膜的方法。通过控制溅射功率和气氛压力,提高溅射腔体中沉积粒子的能量,从而可以获得结晶程度不同的二氧化钛纳米薄膜,可以用于钙钛矿太阳能电池电子传输层。通过控制溅射时间,可以获得不同厚度的二氧化钛纳米薄膜。根据本发明的方法制备的薄膜具有优秀的光生电子分离和传输效率,以及空穴阻挡效率。因此,相比于传统的制备方法,基于该薄膜的钙钛矿太阳能电池具有较高的填充因子和短路电流,电池光电转换效率更高。本发明的方法不仅简化传统电池制备工艺,节约成本,而且可以提高基于该薄膜电池性能,有利于促进钙钛矿太阳能电池的市场化应用。

以下,具体说明根据本发明的室温溅射法制备不同结晶度二氧化钛薄膜的方法。

首先,对基材进行清洗。本发明中,所述基材对尺寸和性状没有限制,可以为大面积的基材,另外,可以为刚性基材或柔性基材,例如可采用FTO、ITO、AZO或沉积有导电金属或者透明导电体的柔性衬底。

具体的,作为一个示例,清洗过程可以包括:将基材(例如FTO玻璃)超声清洗,分别用丙酮和无水乙醇超声清洗基材一定时间(例如各30分钟)。

接着,将清洗后的基材装入沉积所使用的直流磁控溅射系统设备中。图1示例性示出室温溅射法运行示意图。参见图1,沉积所使用的直流磁控溅射系统设备可以包括沉积腔室、进样室、载靶板、衬底板、直流电源、以及一系列的真空泵,其中载靶板与衬底板成一定角度,直流电源连接在载靶板上。具体的,作为一个示例,将清洗后的基材固定在衬底板上,放入进样室中,然后打开闸门装载到真空度(本底真空度)已达到10-4Pa时以下的沉积腔室中。

接着,进行沉积制备二氧化钛薄膜。其中,可以在制备薄膜前进行一定程度的预溅射。具体的,作为一个示例,整个系统中靶材预溅射的条件可以设置为:功率100-300W,时间5-30分钟,气氛是纯氩气,以及气体压力是0.5-1.5Pa。此外,靶材可以采用纯钛靶。

本发明中,采用直流磁控溅射法制备二氧化钛薄膜。室温溅射法简单快捷,同时又可以精确控制薄膜厚度和性质。具体的,作为一个示例,沉积过程可以包括:将高纯(例如99.99%以上)氩气和氧气混合气体通入沉积腔室中,控制总压强和氧分压分别在0.5-2.5Pa和50%以下的范围内,氧分压优选为20%以下;控制靶材与基材的距离为7-20cm,初始基材温度为室温,并且整个过程中不需要额外的加热;开启直流电源,控制直流电源的功率为300-900W或者功率密度为3.8~11.5W/cm2,溅射纯钛靶材。沉积时间可为15-60分钟,沉积结束时基材温度在80℃以下。

在一个优选方案中,总压强为0.5-2Pa,更优选为1-2Pa,最优选为1.5Pa。

又,在一个优选方案中,氧气和氩气比例为1:1-1:10,更优选为1:5-1:8,最优选为1:6。

又,在一个优选方案中,施加在上述靶材上的直流功率为500W-700W,更优选为700W。

通过控制溅射功率和/或气氛压力,提高溅射腔体中沉积粒子的能量,从而可以获得具备不同的结晶程度,包括完全非晶的二氧化钛纳米薄膜和部分结晶的二氧化钛纳米薄膜。例如,控制靶材直流电源功率为500W~650W,控制总压强为1~1.5Pa,氧分压为15%~35%时,可以得到完全非晶的二氧化钛薄膜。根据本发明的方法制备的完全非晶的二氧化钛薄膜。

或者,控制靶材直流电源功率为650W-750W,控制总压强为1~1.5Pa,氧分压为15%~35%时,可以得到部分结晶的二氧化钛薄膜。其中,部分结晶的二氧化钛纳米薄膜是指非晶薄膜中含有一系列不连续的二氧化钛结晶颗粒。结晶度可为0~50%。部分结晶的二氧化钛薄膜中,结晶颗粒为锐钛矿相二氧化钛。本发明的部分结晶的二氧化钛薄膜由于其不同的组成,电子传输和分离速率有明显的提高。由于更高的溅射功率,部分结晶的二氧化钛纳米薄膜拥有更小的粗糙度,并且由于薄膜中存在的结晶纳米颗粒,因此该薄膜拥有更高的电子提取与转移效率,较小的界面电阻和价电子空穴复合能力。部分结晶的样品拥有更好的电子传输效率,因此基于这种薄膜制备的钙钛矿太阳能电池具有更高的太阳能转换效率。通过测试稳态荧光光谱和瞬态荧光光谱,可以发现部分结晶的二氧化钛薄膜具有更高的电子分离和传递效率。

通过控制溅射时间,可以获得不同厚度的二氧化钛纳米薄膜。

本发明的二氧化钛薄膜厚度可为30-60nm,优选30-50nm。厚度在30-60nm的薄膜具有一下几个方面的优点。厚度小于30nm时,可能存在二氧化钛不能完全覆盖FTO衬底的情况,因而FTO与钙钛矿吸收材料存在一定程度的直接接触,会发生光生电子和光生空穴直接复合的情况,因此太阳能转换效率会急剧降低。当薄膜厚度过大时,光生电子的传递路线过长,相应的损耗增加,同样不利于电池性能。

沉积结束后,等衬底(基材)由于粒子轰击产生的温度降回到室温,取出基材。因而制得沉积在衬底上的二氧化钛纳米薄膜材料。

这种室温溅射制备的薄膜具有优秀的光生电子分离和传输效率,以及空穴阻挡效率。通过入射单色光子-电子转化效率测试,可以发现本方法获得电子传输层性能优越。此外,由于是室温下制备,可以选用柔性衬底,可以制备柔性薄膜。

相比于传统的制备方法,基于该薄膜的钙钛矿太阳能电池具有较高的填充因子和短路电流,电池光电转换效率更高。室温溅射法不仅简化传统电池制备工艺,节约成本,而且可以提高基于该薄膜电池性能,有利于促进钙钛矿太阳能电池的市场化应用。

本发明的优点;

薄膜制备条件温和,设备简单,节约资源能源;

磁控溅射法制备周期短,可以连续控制,不受限制于衬底尺寸和薄膜均匀性;

磁控溅射法制备工艺简单,稳定高,重复性好,市场化应用前景美好;

本发明的二氧化钛薄膜均匀致密,表面粗糙度低,与基底材料结合牢固,在可见光区透过率好。具有优秀的电子传输能力和空穴阻挡能力。通过测试该薄膜的接触角可以发现,接触角仅为40°,因此表明该薄膜表面润湿性好,可以很好的与钙钛矿吸收材料接触,极大的降低了界面接触电阻。

下面进一步例举实施例以详细说明本发明。同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的时间、温度、压力、功率等工艺参数也仅是合适范围中的一个示例,即本领域技术人员可以通过本文的说明做合适的范围内选择,而并非要限定于下文示例的具体数值。

实施例1

将基材(FTO玻璃)超声清洗,分别用丙酮和无水乙醇超声清洗基材各30分钟后,有序地固定在衬底板上,放入进样室中,然后打开闸门装载到真空度(本底真空度)已达到10-4Pa以下的沉积腔室中。通入比例为1:6的氧气与氩气,控制总压强为1.5Pa,靶材与基材的距离为8cm,初始的腔室温度保持在室温(15~35℃)条件下开启直流电源(电功率为675W),溅射纯钛靶材,沉积时间为15min,得到完全非晶的二氧化钛薄膜,如图2D所示。随后在通过真空蒸发制备钙钛矿吸收材料,旋涂制备空穴传输材料,以及真空蒸发制备背电极(Ag)。经过标准太阳能电池测试系统测试,该太阳能电池的光电转换效率为13.30%。

实施例2

将基材(FTO玻璃)超声清洗,分别用丙酮和无水乙醇超声清洗基材各30分钟后,有序地固定在衬底板上,放入进样室中,然后打开闸门装载到真空度(本底真空度)已达到10-4Pa以下的沉积腔室中。通入比例为1:6的氧气与氩气,控制总压强为1.5Pa,靶材与基材的距离为8cm,初始的腔室温度保持在室温条件下开启直流电源(电功率为700W),溅射纯钛靶材,沉积时间为15min,得到部分结晶的二氧化钛薄膜,XRD图谱如图2D所示,根据结晶度经验公式:

<math>

<mrow>

<mi>R</mi>

<mo>=</mo>

<mfrac>

<mrow>

<mi>X</mi>

<mo>/</mo>

<mi>Y</mi>

</mrow>

<mrow>

<mi>M</mi>

<mo>/</mo>

<mi>N</mi>

</mrow>

</mfrac>

</mrow>

</math>

(其中X和Y表示部分结晶样品和退火之后完全结晶样品XRD谱图中25.37°位置处峰的强度;M和N表示相应FTO的XRD谱图中37.8°位置处峰的强度值)可以知道结晶度为16.8%。随后在通过真空蒸发制备钙钛矿吸收材料,旋涂制备空穴传输材料,以及真空蒸发制备背电极(Ag)。经过标准太阳能电池测试系统测试,该太阳能电池的光电转换效率为13.30%。效率的提升主要是由于以下几个方面,首先,溅射功率提升,导致构成薄膜的粒子能量更高,因此薄膜更加致密,有利光生电子的传播。其次,高能粒子的持续轰击有利于促使薄膜表面更加平坦,有利于钙钛矿吸收材料在电子传输层表面润湿。最后也是最重要的,薄膜中存在大量个微晶颗粒,这些晶粒的存在可以富集电子的作用,是提升性能最主要的原因。

实施例3

将基材(FTO玻璃)超声清洗,分别用丙酮和无水乙醇超声清洗基材各30分钟后,有序地固定在衬底板上,放入进样室中,然后打开闸门装载到真空度(本底真空度)已达到10-4Pa以下的沉积腔室中。通入比例为1:6的氧气与氩气,控制总压强为1.5Pa,靶材与基材的距离为8cm,初始的腔室温度保持在室温条件下开启直流电源(电功率为725W),溅射纯钛靶材,沉积时间为15min,得到部分结晶的二氧化钛薄膜,基于结晶度经验计算公式,可得该薄膜的结晶度为32.3%。随后在通过真空蒸发制备钙钛矿吸收材料,旋涂制备空穴传输材料,以及真空蒸发制备背电极(Ag)。经过标准太阳能电池测试系统测试,该太阳能电池的光电转换效率为15.76%。相比于实施例2,基于该薄膜制备的太阳能电池性能进一步提升进一步证明伴随着结晶度的提高,结晶颗粒的比例提升与电池性能之间的关系。

实施例4

将基材(FTO玻璃)超声清洗,分别用丙酮和无水乙醇超声清洗基材各30分钟后,有序地固定在衬底板上,放入进样室中,然后打开闸门装载到真空度(本底真空度)已达到10-4Pa以下的沉积腔室中。通入比例为1:6的氧气与氩气,控制总压强为1Pa,靶材与基材的距离为8cm,初始的腔室温度保持在室温条件下开启直流电源(电功率为750W),溅射纯钛靶材,沉积时间为15min,得到部分结晶的二氧化钛薄膜,根据结晶度经验公式可以测得该薄膜结晶度为49.2%。随后在通过真空蒸发制备钙钛矿吸收材料,旋涂制备空穴传输材料,以及真空蒸发制备背电极(Ag)。经过标准太阳能电池测试系统测试,该太阳能电池的光电转换效率为14.02%。相比于实施例3,基于该薄膜制备的太阳能电池性能有所降低,这是因为大量的结晶晶粒的存在可能对电子有一定的散射作用,从而会相应的削弱电池性能。

实施例5

将基材(FTO玻璃)超声清洗,分别用丙酮和无水乙醇超声清洗基材各30分钟后,有序地固定在衬底板上,放入进样室中,然后打开闸门装载到真空度(本底真空度)已达到10-4Pa以下的沉积腔室中。通入比例为1:6的氧气与氩气,控制总压强为0.5Pa,靶材与基材的距离为8cm,初始的腔室温度保持在室温条件下开启直流电源(电功率为725W),溅射纯钛靶材,沉积时间为10min,得到部分结晶的二氧化钛薄膜。随后在通过真空蒸发制备钙钛矿吸收材料,旋涂制备空穴传输材料,以及真空蒸发制备背电极(Ag)。经过标准太阳能电池测试系统测试,该太阳能电池的光电转换效率为8.16%。与实施例3相比,本实施例的工作时间减少,即沉积的薄膜厚度减小,因此可能某些区域FTO与钙钛矿吸收材料直接接触。光生电子和光生空穴会在这些区域发生复合,而这会极大的削弱电池太阳能电池性能。

实施例6

将基材(FTO玻璃)超声清洗,分别用丙酮和无水乙醇超声清洗基材各30分钟后,有序地固定在衬底板上,放入进样室中,然后打开闸门装载到真空度(本底真空度)已达到10-4Pa以下的沉积腔室中。通入比例为1:6的氧气与氩气,控制总压强为1.5Pa,靶材与基材的距离为6cm,初始的腔室温度保持在室温条件下开启直流电源(电功率为725W),溅射纯钛靶材,沉积时间为20min,部分结晶的二氧化钛薄膜源(电功率为725W),溅射纯钛靶材,沉积时间为10min,得到部分结晶的二氧化钛薄膜。随后在通过真空蒸发制备钙钛矿吸收材料,旋涂制备空穴传输材料,以及真空蒸发制备背电极(Ag)。经过标准太阳能电池测试,统测试,该太阳能电池的光电转换效率为13.27%。与实施例3相比性能有所下降,这是由于随着溅射时间延长,薄膜的厚度增加,不利于电子的传递,因此太阳能电池相应的降低。

相比目前已经报导的非晶二氧化钛薄膜,本方案证明可以通过改进实验参数获得部分结晶的二氧化钛薄膜,并且基于这种薄膜可以获得更好的电池性能。通过对比试验,可以获得最佳的制备工艺。

表1示出基于磁控溅射法制备的完全非晶二氧化钛薄膜(实施例1)和部分结晶二氧化钛(实施例3)的太阳能电池性能数据,其中ISC、VOC、FF、PCE分别表示短路电流密度、断路电压、填充因子和电池转换效率。

表1

通过XRD分析(见图2D),可以表征根据本发明制备的二氧化钛纳米薄膜具有不同的结晶性质,包括纯非晶二氧化钛薄膜,部分结晶的二氧化钛薄膜。通过AFM分析,可以知道部分结晶的二氧化钛薄膜可以具有更小的粗糙度。通过XPS分析,可以知道薄膜组成是纯二氧化钛,没有其他价态的钛或者氧存在。通过场发射扫描电子显微镜(见图2A、B、C)可以研究薄膜的形貌。

基于上述优异的性能,本发明制备的二氧化钛电池应用于钙钛矿太阳能电池的致密层,可以有效的分离和传输电子。由以上可知,本发明提出方法制备的二氧化钛薄膜显著的提高了钙钛矿太阳能电池中电子分离和传输效率。

另外,通过XRD可以表征非晶薄膜和部分结晶的区别,AFM可以表征薄膜的粗糙度。因此基于部分结晶二氧化钛纳米薄膜制备的钙钛矿太阳能电池光电转换效率高于基于完全非晶二氧化钛纳米薄膜的电池。因此通过本发明的制备方法能提供一种制备不同性质二氧化纳米薄膜的方法,并且基于该薄膜制备的太阳能电池具备较高的光电转换效率。

产业应用性:本发明制备30-60nm非晶和部分结晶的二氧化钛纳米薄膜,并且薄膜表面均匀致密,粗糙度低,可见光范围内透过率高。更加重要的是该薄膜具有优秀的电子传输效率和空穴阻挡能力,可以有效的提高基于该薄膜钙钛矿太阳能电池的光电转换效率。因此本发明具有很大的应用与市场化前景。

【EN】

A kind of method that room temperature sputtering method prepares titanium deoxid film

Technical field

The invention belongs to field of inorganic nano material, be specifically related to a kind of room temperature sputtering method and prepare different crystallinity titanium dioxide

The method of titanium thin film, for perovskite solaode compacted zone.

Background technology

In recent years, gradually aggravate in energy crisis, under the background that environmental gradually deepens, whole world photoelectricity research neck

Territory achieves progress greatly, becomes one of study hotspot of most prospect in this century and strategic importance.In this area, due to

Low cost, technique is simple and excellent performance, and perovskite solaode becomes the study hotspot of field of photoelectric devices.This electricity

The sunlight conversion efficiency that pond proposes for 2009 first is only 4%, has been up to through the development of 7 years nowadays authentication efficiency

22%, exceed non-crystal silicon solar cell and the current electricity conversion of copper indium gallium selenium solar cell, there is the monocrystalline that matches in excellence or beauty

Silicon and the potentiality of multi-junction gallium arsenide battery.Therefore, actively develop the research for perovskite battery, optimize battery structure and composition

Material, and innovation and development sustainable to national economy from now on has great meaning.Realize battery and possess the base of high conversion efficiency

This approach is exactly to improve the extraction of photo-generated carrier, the ability separating and transporting.

Perovskite solaode comprises 5 layer materials, and these several layer materials are respectively provided with different performances.First it is transparent leading

Electricity electrode, conventional is FTO (mixing F tin ash) or ITO (tin indium oxide) electro-conductive glass;It is followed by electron transfer layer, uses

In transporting light induced electron in time and stopping photohole, suppression light induced electron and photohole compound;It is that perovskite is inhaled again

Receive material, mainly Ca-Ti ore type Organic leadP halogenide (ABX3:A=CH3NH3, B=Pb, X=Cl, I, Br);It is hole again

Transport layer, for transporting photohole in time and stopping light induced electron, suppression light induced electron and photohole compound;It is finally

Back electrode, conventional is gold, silver and copper.Therefore, suitable electron transfer layer is that high performance calcium titanium ore solar energy is indispensable

A part.Preferably electron transfer layer has outstanding electron transport ability and hole blocking ability, has in visible-range

Standby high permeability, relatively low interface resistance, and the energy level of coupling perovskite absorbed layer conduction band positions.Up to the present, dioxy

Change titanium and zinc oxide is the material being mainly used in electron transfer layer.Application both materials are as the perovskite of electron transfer layer

Solaode has the conversion efficiency that comparison is high, but zinc oxide material secular instability have impact on its marketization and promotes.

Therefore, titanium dioxide is topmost, the electron transport material that the prospect that is also considered as is the most wide.

So far, the titanic oxide electronic transport layer method of preparing of report is mainly spin-coating method and spray pyrolysis.Pin

To both preparation methoies, building-up process is required to high-temperature burning process, to improve crystallinity and the acquisition of nano-powder

Fine and close structure.High-temperature process significantly limit the preparation and application of flexible substrate battery, and improves production cost.With

This simultaneously, although spin-coating method is easy, but is limited by the restriction of size.Only under limited cell area, it is possible to obtain all

Even electron transfer layer.Although and electron transfer layer area prepared by spray pyrolysis increases accordingly, but its equipment is non-

The most complicated, for following large-scale production, there is significant limitation.Other method includes ald, colloidal sol

Gel, microwave-assisted and silk screen printing, be required to high-temperature process engineering, and the battery performance finally prepared is weaker than above two kinds

Method.Therefore find that a kind of can to prepare the method for large scale high-performance electronic transport layer with low temperature imperative.

Summary of the invention

High for titanic oxide electronic transport layer synthesis temperature in prior art, that condition is harsh technical method, the present invention

Purpose be to provide a kind of and need not any heating and fast deposition can prepare different crystallinity titanium dioxide nano-film

Method.

Here, the present invention provides a kind of method that room temperature sputtering method prepares different crystallinity titanium deoxid film, use straight

Stream magnetron sputtering method prepares different crystallinity titanium deoxid film, and wherein target is pure titanium target, and background vacuum is 10-4Pa with

Under, sputter gas is argon and oxygen, and total pressure is 0.5~2.5Pa, and partial pressure of oxygen is less than 50%, target and the distance of base material

Being 7~20cm, initial substrate temperature is 15~35 DEG C, and the power putting on the DC source on described target is 300~900W,

Sedimentation time is 5~30 minutes, it is thus achieved that the completely amorphous or titanium deoxid film of partially crystallizable.The titanium dioxide of partially crystallizable is thin

The degree of crystallinity of film can be 0~50% (not being the most 0).

Present invention employs simple and fast and can accurately control the room temperature sputtering method of film thickness and character, at low temperatures

Prepare different crystallographic property and the TiO of excellent performance2Nano thin-film, the initial temperature of base material is room temperature, whole during

It is made without heating.Compared at present it has been reported that completely amorphous titanium deoxid film, the method according to the invention system

The feature of standby titanium deoxid film is, can freely regulate the degree of crystallinity of titanium deoxid film.The present invention is by substantial amounts of

Contrast test finds, perovskite solar cell properties based on this film preparation is had significantly by titanium deoxid film degree of crystallinity

Impact.By the degree of crystallinity of assay optimization gained thin film, thus obtain optimal battery performance.Therefore this programme has significant section

Learn meaning and practical significance.It is additionally, since higher sputtering power, the dioxy of prepared according to the methods of the invention partially crystallizable

Change titanium nano thin-film and have a less roughness, and due to crystalline nanometer particle present in thin film, therefore this thin film has

Higher electron extraction and transfer efficiency, less interface resistance and valency electron hole-recombination ability.Compared to widely used

Solwution method, the method preparation technology of the present invention is easier, is possible not only to room temperature and prepares, and thin film is finer and close and smooth, can

To effectively reduce the interface resistance of thin film.Additionally, the thin film that magnetron sputtering method is prepared compared with solwution method, fine and close high, surface

Roughness is low, thickness continuously adjustabe, is not affected by base material area, can i.e. obtain the thin film of crystallization under room temperature.

In the present invention, by controlling sputtering power and/or atmosphere pressures, improve the energy of deposited particles in sputtering cavity,

It is hereby achieved that completely amorphous and partially crystallizable titanium dioxide nano-film.Wherein, controlling target DC source power is

500W~650W, controlling total pressure is 1~1.5Pa, when partial pressure of oxygen is 15%~35%, can obtain completely amorphous titanium dioxide

Titanium thin film.

Also, controlling target DC source power is 650W~750W, controlling total pressure is 1~1.5Pa, and partial pressure of oxygen is 15%

~when 35%, the titanium deoxid film of partially crystallizable can be obtained.Crystalline particle in the titanium deoxid film of described partially crystallizable

For anatase phase titanium dioxide.

It is preferred that described total pressure is 0.5-2Pa, preferably 1-2Pa.

It is preferred that target DC source power is 500W-700W.

In above-mentioned preparation method, oxygen and argon ratio can be 1:1-1:10, preferably 1:5-1:8, more preferably 1:

6.Additionally, the purity of the argon used and oxygen can be more than 99.99%.

In above-mentioned preparation method, carrying out pre-sputtering before deposition, the condition of described pre-sputtering is: power 100-300W, time

5-30 minute, atmosphere was pure argon, and gas pressure is 0.5-1.5Pa.

It is preferred that described base material is FTO, AZO or ITO.

The present invention also provides for the titanium deoxid film prepared by said method, and described thin film is completely amorphous or part

The titanium deoxid film of crystallization.The thickness of described titanium deoxid film is 30nm-60nm.The nano titania of different-thickness is thin

Film can obtain by controlling sputtering time.Sputtering time is the longest, and thickness is the biggest.

The visible light transmissivity of the titanium deoxid film of the present invention is more than 80%.Additionally, described thin-film material possesses excellent

Different is electrically separated and transport capacity and hole blocking ability, and the perovskite solaode prepared based on this thin-film material is

Good photoelectric transformation efficiency is more than 15%.

The present invention also provides for the preparation method of a kind of perovskite solaode, and described method includes: at electrically conducting transparent base

Electron transfer layer, perovskite absorbed layer, hole transmission layer and back electrode, wherein, described electron transfer layer is sputtered successively on material

For titanium deoxid film, the method that described titanium deoxid film is prepared titanium deoxid film by above-mentioned room temperature sputtering method is prepared into

Arrive.

Advantages of the present invention;

Film preparation mild condition, equipment is simple, and economize on resources the energy;

Magnetron sputtering method manufacturing cycle is short, can be unrestricted in substrate dimension with uniformity of film with continuous control;

Magnetron sputtering method preparation technology is simple, stable height, and reproducible, marketization application prospect is fine;

The titanium deoxid film even compact of the present invention, surface roughness is low, is firmly combined with base material, saturating in visible region

Cross rate good.There is outstanding electron transport ability and hole blocking ability.And this film surface wettability is good, can well

Contact with perovskite absorbing material, greatly reduce interface contact resistance.

Accompanying drawing explanation

Fig. 1: magnetron sputtering schematic diagram;

Completely amorphous titanium deoxid film section SEM prepared by Fig. 2 A: magnetron sputtering;Part knot prepared by Fig. 2 B: magnetron sputtering

Crystal titanium dioxide thin-membrane section SEM;Partially crystallizable titanium deoxid film surface SEM prepared by Fig. 2 C: magnetron sputtering;Fig. 2 D: magnetic

Thin and the pure FTO's of partially crystallizable titanium dioxide prepared by the completely amorphous titanium deoxid film of control sputtering preparation, magnetron sputtering

XRD figure;

Partially crystallizable titanium dioxide prepared by completely amorphous titanium deoxid film prepared by Fig. 3: magnetron sputtering, magnetron sputtering thin with

And the visible light transmissivity of pure FTO;

Fig. 4: the completely amorphous titanium deoxid film prepared based on magnetron sputtering method and the solar-electricity of partially crystallizable titanium dioxide

Pond performance.

Detailed description of the invention

The present invention is further illustrated, it should be appreciated that following embodiment is only used for below in conjunction with accompanying drawing and following embodiment

The present invention is described, and the unrestricted present invention.

The present invention relates to a kind of employing magnetically controlled DC sputtering physical gas phase deposition technology and prepare different crystallinity at low temperatures

Matter TiO2The method of nano thin-film.By controlling sputtering power and atmosphere pressures, improve the energy of deposited particles in sputtering cavity,

It is hereby achieved that the titanium dioxide nano-film that crystallization degree is different, may be used for perovskite solaode electric transmission

Layer.By controlling sputtering time, it is possible to obtain the titanium dioxide nano-film of different-thickness.Prepared according to the methods of the invention

Thin film has outstanding light induced electron and separates and efficiency of transmission, and hole barrier efficiency.Therefore, compared to traditional preparation side

Method, perovskite solaode based on this thin film has higher fill factor, curve factor and short circuit current, cell photoelectric conversion efficiency

Higher.The method of the present invention not only simplifies conventional batteries preparation technology, cost-effective, and can improve based on this hull cell

Performance, may advantageously facilitate the marketization application of perovskite solaode.

Hereinafter, the method that the room temperature sputtering method according to the present invention prepares different crystallinity titanium deoxid film is illustrated.

First, base material is carried out.In the present invention, size and character are not limited by described base material, can be big face

Long-pending base material, furthermore it is possible to be rigid substrate or flexible parent metal, such as, can use FTO, ITO, AZO or deposition to have conducting metal

Or the flexible substrate of transparent conductive body.

Concrete, as an example, cleaning process may include that base material (such as FTO glass) ultrasonic cleaning, respectively

With acetone and dehydrated alcohol ultrasonic cleaning base material certain time (the most each 30 minutes).

Then, the base material after cleaning loads in the DC magnetron sputtering system equipment that deposition is used.Fig. 1 is exemplary to be shown

Go out room temperature sputtering method and run schematic diagram.Seeing Fig. 1, the DC magnetron sputtering system equipment that deposition is used can include deposit cavity

Room, Sample Room, load target plate, underboarding, DC source and a series of vacuum pump, wherein carry target plate and become certain with underboarding

Angle, DC source is connected to carry on target plate.Concrete, as an example, the base material after cleaning is fixed on underboarding,

Put in Sample Room, then open gate and be loaded into vacuum (background vacuum) and reached 10-4Deposition chambers below during Pa

In.

Then, carry out deposition and prepare titanium deoxid film.Wherein it is possible to carry out a certain degree of pre-spatter before preparing thin film

Penetrate.Concrete, as an example, in whole system, the condition of target pre-sputtering could be arranged to: power 100-300W, time

5-30 minute, atmosphere was pure argon, and gas pressure is 0.5-1.5Pa.Additionally, target can use pure titanium target.

In the present invention, direct current magnetron sputtering process is used to prepare titanium deoxid film.Room temperature sputtering method simple and fast, the most again

Can accurately control film thickness and character.Concrete, as an example, deposition process may include that by high-purity (such as

More than 99.99%) argon and oxygen mixed gas are passed through in deposition chambers, control total pressure and partial pressure of oxygen respectively at 0.5-

In the scope of 2.5Pa and less than 50%, partial pressure of oxygen is preferably less than 20%;The distance controlling target and base material is 7-20cm, just

Beginning base material temperature is room temperature, and whole during need not extra heating;Open DC source, control the merit of DC source

Rate is 300-900W or power density is 3.8~11.5W/cm2, sputter pure titanium target.Sedimentation time can be 15-60 minute,

At the end of deposition, base material temperature is below 80 DEG C.

In a preferred version, total pressure is 0.5-2Pa, more preferably 1-2Pa, most preferably 1.5Pa.

Also, in a preferred version, oxygen and argon ratio are 1:1-1:10, more preferably 1:5-1:8, most preferably

1:6。

Also, in a preferred version, being applied to the dc power on above-mentioned target is 500W-700W, more preferably

700W。

By controlling sputtering power and/or atmosphere pressures, improve the energy of deposited particles in sputtering cavity, such that it is able to obtain

Must possess different crystallization degrees, the nano titania including completely amorphous titanium dioxide nano-film and partially crystallizable is thin

Film.Such as, control target DC source power be 500W~650W, control total pressure be 1~1.5Pa, partial pressure of oxygen be 15%~

When 35%, completely amorphous titanium deoxid film can be obtained.The titanium dioxide that prepared according to the methods of the invention is completely amorphous

Titanium thin film.

Or, controlling target DC source power is 650W-750W, and controlling total pressure is 1~1.5Pa, and partial pressure of oxygen is

When 15%~35%, the titanium deoxid film of partially crystallizable can be obtained.Wherein, the titanium dioxide nano-film of partially crystallizable is

Refer in noncrystal membrane containing a series of discontinuous titanium dioxide crystal granules.Degree of crystallinity can be 0~50%.The two of partially crystallizable

In thin film of titanium oxide, crystalline particle is anatase phase titanium dioxide.The titanium deoxid film of the partially crystallizable of the present invention is due to it

Different compositions, electric transmission and the rate of departure are significantly improved.Due to higher sputtering power, the titanium dioxide of partially crystallizable

Titanium nano thin-film has a less roughness, and due to crystalline nanometer particle present in thin film, therefore this thin film has more

High electron extraction and transfer efficiency, less interface resistance and valency electron hole-recombination ability.The sample of partially crystallizable has

Preferably electric transmission efficiency, therefore perovskite solaode based on this film preparation has the conversion of higher solar energy

Efficiency.By test steady-state fluorescence spectrum and transient state fluorescence spectrum, it appeared that the titanium deoxid film of partially crystallizable has more

High is electrically separated and transmission efficiency.

By controlling sputtering time, it is possible to obtain the titanium dioxide nano-film of different-thickness.

The titanium deoxid film thickness of the present invention can be 30-60nm, preferably 30-50nm.Thickness has at the thin film of 30-60nm

The advantage having the most several aspect.When thickness is less than 30nm, it is understood that there may be titanium dioxide can not be completely covered the feelings of FTO substrate

Condition, thus FTO exists with perovskite absorbing material and a certain degree of directly contacts, it may occur that light induced electron and photohole are direct

Compound situation, therefore solar energy conversion efficiency can drastically reduce.When film thickness is excessive, the transfer route mistake of light induced electron

Long, increase is lost accordingly, is unfavorable for battery performance equally.

After deposition terminates, wait substrate (base material) to roll back room temperature due to the temperature that particle bombardment produces, take out base material.Thus

Prepare the titanium dioxide nano-film material being deposited on substrate.

The thin film of this room temperature sputtering preparation has outstanding light induced electron and separates and efficiency of transmission, and hole barrier effect

Rate.Tested by incident monochromatic photon-electron transformation efficiency, it appeared that this method obtains electron transfer layer superior performance.This

Outward, owing to being to prepare under room temperature, flexible substrate can be selected, fexible film can be prepared.

Compared to traditional preparation method, perovskite solaode based on this thin film have higher fill factor, curve factor and

Short circuit current, cell photoelectric conversion efficiency is higher.Room temperature sputtering method not only simplifies conventional batteries preparation technology, cost-effective, and

And can improve based on this hull cell performance, may advantageously facilitate the marketization application of perovskite solaode.

Advantages of the present invention;

Film preparation mild condition, equipment is simple, and economize on resources the energy;

Magnetron sputtering method manufacturing cycle is short, can be unrestricted in substrate dimension with uniformity of film with continuous control;

Magnetron sputtering method preparation technology is simple, stable height, and reproducible, marketization application prospect is fine;

The titanium deoxid film even compact of the present invention, surface roughness is low, is firmly combined with base material, saturating in visible region

Cross rate good.There is outstanding electron transport ability and hole blocking ability.By testing the contact angle of this thin film it is found that connect

Feeler is only 40 °, therefore shows that this film surface wettability is good, can well contact with perovskite absorbing material, greatly

Reduce interface contact resistance.

Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this

Invention is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to this

Some nonessential improvement and adjustment that bright foregoing is made belong to protection scope of the present invention.Following example is concrete

The technological parameters such as time, temperature, pressure, power are the most only examples in OK range, i.e. those skilled in the art are permissible

Select in the range of being done suitably by explanation herein, and do not really want to be defined in the concrete numerical value of hereafter example.

Embodiment 1

By base material (FTO glass) ultrasonic cleaning, respectively with acetone and dehydrated alcohol ultrasonic cleaning base material after each 30 minutes, in an orderly manner

It is fixed on underboarding, puts in Sample Room, then open gate and be loaded into vacuum (background vacuum) and reached 10-4Pa

In following deposition chambers.The ratio of being passed through is oxygen and the argon of 1:6, and control total pressure is 1.5Pa, target and the distance of base material

For 8cm, initial chamber temp opens DC source (electrical power is 675W), sputtering under the conditions of being maintained at room temperature (15~35 DEG C)

Pure titanium target, sedimentation time is 15min, obtains completely amorphous titanium deoxid film, as shown in Figure 2 D.Passing through vacuum subsequently

Perovskite absorbing material is prepared in evaporation, and hole mobile material is prepared in spin coating, and back electrode (Ag) is prepared in vacuum evaporation.Through mark

Quasi-solar cell test system is tested, and the photoelectric transformation efficiency of this solaode is 13.30%.

Embodiment 2

By base material (FTO glass) ultrasonic cleaning, respectively with acetone and dehydrated alcohol ultrasonic cleaning base material after each 30 minutes, in an orderly manner

It is fixed on underboarding, puts in Sample Room, then open gate and be loaded into vacuum (background vacuum) and reached 10-4Pa

In following deposition chambers.The ratio of being passed through is oxygen and the argon of 1:6, and control total pressure is 1.5Pa, target and the distance of base material

For 8cm, initial chamber temp keeps opening DC source (electrical power is 700W) at ambient temperature, sputters pure titanium target,

Sedimentation time is 15min, obtains the titanium deoxid film of partially crystallizable, and XRD figure is composed as shown in Figure 2 D, public according to degree of crystallinity experience

Formula:

<math>

<mrow>

<mi>R</mi>

<mo>=</mo>

<mfrac>

<mrow>

<mi>X</mi>

<mo>/</mo>

<mi>Y</mi>

</mrow>

<mrow>

<mi>M</mi>

<mo>/</mo>

<mi>N</mi>

</mrow>

</mfrac>

</mrow>

</math>

(wherein X and Y is fully crystallized peak, 25.37 ° of positions in sample XRD spectra after representing part crystallized sample and annealing

Intensity;M and N represents the intensity level at peak, 37.8 ° of positions in the XRD spectra of corresponding FTO) it is known that degree of crystallinity is 16.8%.

Preparing perovskite absorbing material by vacuum evaporation subsequently, hole mobile material, and the vacuum evaporation preparation back of the body are prepared in spin coating

Electrode (Ag).Through standard solar cells test system and test, the photoelectric transformation efficiency of this solaode is 13.30%.

The lifting of efficiency is mainly due to the following aspects, and first, sputtering power promotes, and causes constituting the particle energy of thin film more

Height, therefore thin film is finer and close, the propagation of favourable light induced electron.Secondly, the constant bombardment of high energy particle is conducive to promoting thin film

Surface is more smooth, and beneficially perovskite absorbing material is at electron transfer layer moistened surface.Last is also most important, in thin film

There are a large amount of microcrystal grains, the existence of these crystal grain can be enriched with the effect of electronics, is an up the topmost reason of performance.

Embodiment 3

By base material (FTO glass) ultrasonic cleaning, respectively with acetone and dehydrated alcohol ultrasonic cleaning base material after each 30 minutes, in an orderly manner

It is fixed on underboarding, puts in Sample Room, then open gate and be loaded into vacuum (background vacuum) and reached 10-4Pa

In following deposition chambers.The ratio of being passed through is oxygen and the argon of 1:6, and control total pressure is 1.5Pa, target and the distance of base material

For 8cm, initial chamber temp keeps opening DC source (electrical power is 725W) at ambient temperature, sputters pure titanium target,

Sedimentation time is 15min, obtains the titanium deoxid film of partially crystallizable, based on degree of crystallinity empirical formula, and can this thin film

Degree of crystallinity be 32.3%.Preparing perovskite absorbing material by vacuum evaporation subsequently, hole mobile material is prepared in spin coating, with

And vacuum evaporation prepares back electrode (Ag).Through standard solar cells test system and test, the photoelectricity of this solaode turns

Changing efficiency is 15.76%.Compared to embodiment 2, solar cell properties based on this film preparation promotes further further

Proving the raising along with degree of crystallinity, the ratio of crystalline particle promotes the relation between battery performance.

Embodiment 4

By base material (FTO glass) ultrasonic cleaning, respectively with acetone and dehydrated alcohol ultrasonic cleaning base material after each 30 minutes, in an orderly manner

It is fixed on underboarding, puts in Sample Room, then open gate and be loaded into vacuum (background vacuum) and reached 10-4Pa

In following deposition chambers.The ratio of being passed through is oxygen and the argon of 1:6, and control total pressure is 1Pa, and target with the distance of base material is

8cm, initial chamber temp keeps opening DC source (electrical power is 750W) at ambient temperature, sputters pure titanium target, heavy

The long-pending time is 15min, obtains the titanium deoxid film of partially crystallizable, can record this thin film crystallization according to degree of crystallinity empirical equation

Degree is 49.2%.Preparing perovskite absorbing material by vacuum evaporation subsequently, hole mobile material, and vacuum are prepared in spin coating

Back electrode (Ag) is prepared in evaporation.Through standard solar cells test system and test, the photoelectric transformation efficiency of this solaode

It is 14.02%.Compared to embodiment 3, solar cell properties based on this film preparation decreases, this is because substantial amounts of

The existence of crystal grain may have certain scattering process to electronics, thus can weaken battery performance accordingly.

Embodiment 5

By base material (FTO glass) ultrasonic cleaning, respectively with acetone and dehydrated alcohol ultrasonic cleaning base material after each 30 minutes, in an orderly manner

It is fixed on underboarding, puts in Sample Room, then open gate and be loaded into vacuum (background vacuum) and reached 10-4Pa

In following deposition chambers.The ratio of being passed through is oxygen and the argon of 1:6, and control total pressure is 0.5Pa, target and the distance of base material

For 8cm, initial chamber temp keeps opening DC source (electrical power is 725W) at ambient temperature, sputters pure titanium target,

Sedimentation time is 10min, obtains the titanium deoxid film of partially crystallizable.Perovskite absorption material is being prepared subsequently by vacuum evaporation

Material, hole mobile material is prepared in spin coating, and back electrode (Ag) is prepared in vacuum evaporation.System is tested through standard solar cells

Test, the photoelectric transformation efficiency of this solaode is 8.16%.Compared with Example 3, the working time of the present embodiment reduces,

The film thickness i.e. deposited reduces, it is thus possible to some region FTO directly contacts with perovskite absorbing material.Light induced electron and light

Raw hole can occur compound in these regions, and this can weaken battery solar cell properties greatly.

Embodiment 6

By base material (FTO glass) ultrasonic cleaning, respectively with acetone and dehydrated alcohol ultrasonic cleaning base material after each 30 minutes, in an orderly manner

It is fixed on underboarding, puts in Sample Room, then open gate and be loaded into vacuum (background vacuum) and reached 10-4Pa

In following deposition chambers.The ratio of being passed through is oxygen and the argon of 1:6, and control total pressure is 1.5Pa, target and the distance of base material

For 6cm, initial chamber temp keeps opening DC source (electrical power is 725W) at ambient temperature, sputters pure titanium target,

Sedimentation time is 20min, the titanium deoxid film source (electrical power is 725W) of partially crystallizable, sputters pure titanium target, sedimentation time

For 10min, obtain the titanium deoxid film of partially crystallizable.Perovskite absorbing material, spin coating is being prepared subsequently by vacuum evaporation

Prepare hole mobile material, and back electrode (Ag) is prepared in vacuum evaporation.Testing through standard solar cells, unified test tries, should

The photoelectric transformation efficiency of solaode is 13.27%.Performance has declined compared with Example 3, and this is due to along with sputtering

Time lengthening, the thickness of thin film increases, is unfavorable for the transmission of electronics, and therefore solaode reduces accordingly.

Compare at present it has been reported that amorphous titanium deoxid film, this programme proves to obtain by improving experiment parameter

The titanium deoxid film of partially crystallizable, and more preferable battery performance can be obtained based on this thin film.By contrast test, can

To obtain optimal preparation technology.

Table 1 is illustrated based on completely amorphous titanium deoxid film (embodiment 1) and partially crystallizable two prepared by magnetron sputtering method

The solar cell properties data of titanium oxide (embodiment 3), wherein ISC、VOC, FF, PCE represent short-circuit current density, disconnected respectively

Road voltage, fill factor, curve factor and battery conversion efficiency.

Table 1

By XRD analysis (see Fig. 2 D), titanium dioxide nano-film prepared in accordance with the present invention can be characterized there is difference

Crystallographic property, including pure amorphous titanium deoxid film, the titanium deoxid film of partially crystallizable.Analyzed by AFM, it is known that

The titanium deoxid film of partially crystallizable can have less roughness.By XPS analysis, it is known that thin film composition is pure two

Titanium oxide, does not has titanium or the oxygen of other valence states.Can be ground by field emission scanning electron microscope (see Fig. 2 A, B, C)

Study carefully the pattern of thin film.

Performance based on above-mentioned excellence, titanium dioxide battery applications prepared by the present invention is in the cause of perovskite solaode

Close layer, can efficiently separate and transmit electronics.As known from the above, the titanium deoxid film that prepared by moving party's method of the present invention is notable

Improve in perovskite solaode and be electrically separated and efficiency of transmission.

It addition, can be characterized the difference of noncrystal membrane and partially crystallizable by XRD, AFM can characterize the roughness of thin film.

Therefore the perovskite solar cell photoelectric conversion efficiency prepared based on partially crystallizable titanium dioxide nano-film is higher than based on complete

The battery of full amorphous titanium dioxide nano-film.Therefore it is provided that one prepares heterogeneity two by the preparation method of the present invention

The method of oxidation nanometer thin film, and solaode based on this film preparation possesses higher photoelectric transformation efficiency.

Industrial applicability: the present invention prepares the titanium dioxide nano-film of 30-60nm amorphous and partially crystallizable, and thin film

Surface even compact, roughness is low, it is seen that in optical range, transmitance is high.It is more importantly that this thin film has outstanding electronics biography

Defeated efficiency and hole blocking ability, can effectively improve photoelectric transformation efficiency based on this thin film perovskites solaode.

Therefore the present invention has the biggest application and marketization prospect.

图1
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