CN110563028B - 一种铜锌锡硫薄膜的制备方法 - Google Patents
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000889 atomisation Methods 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000007921 spray Substances 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 238000007751 thermal spraying Methods 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 23
- 239000011135 tin Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
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- 239000000919 ceramic Substances 0.000 description 1
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- 238000004070 electrodeposition Methods 0.000 description 1
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- C01G19/00—Compounds of tin
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- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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Abstract
本发明属于光伏材料制备技术领域,具体涉及一种铜锌锡硫薄膜的制备方法。本发明提供的方法包括将铜源、锌源、锡源和硫源溶于水中,得到前驱体溶液;将所述前驱体溶液进行超声雾化,然后将所得雾滴喷镀在热衬底上,得到铜锌锡硫薄膜;整个方法操作简单,易于大规模生产。
Description
技术领域
本发明属于光伏材料制备技术领域,具体涉及一种铜锌锡硫薄膜的制备方法。
背景技术
铜锌锡硫Cu2ZnSnS4(CZTS)的禁带宽度约1.5eV,十分接近于半导体太阳能电池的最佳禁带宽度(1.45eV),是一种直接带隙半导体,光吸收系数超过104cm-1,并且CZTS中各元素在自然界中含量丰富且无毒,是一种理想的光电材料,因此成为近年来研究的热点。
CZTS的制备方法有很多,如蒸发法、溅射法以及脉冲激光沉积法、电化学沉积、溶胶-凝胶法、水热合成法以及热注入法等,上述方法虽然都可以制备出CZTS,但制备过程复杂,无法大规模生产。
发明内容
本发明的目的在于提供一种铜锌锡硫薄膜的制备方法,本发明能在不影响薄膜材料性能的基础上,简单快速的制成铜锌锡硫薄膜,有望实现大规模生产。
为了实现上述目的,本发明提供如下技术方案:
本发明提供了一种铜锌锡硫薄膜的制备方法,包括以下步骤:
将铜源、锌源、锡源和硫源溶于水中,得到前驱体溶液;
将所述前驱体溶液进行超声雾化,然后将所得雾滴喷镀在热衬底上,得到铜锌锡硫薄膜。
优选的,所述铜源包括氯化铜和/或硝酸铜;
所述锌源包括氯化锌和/或硝酸锌;
所述锡源包括氯化亚锡和/或硝酸亚锡;
所述硫源包括硫脲。
优选的,所述前驱体溶液中,铜离子、锌离子、亚锡离子和硫原子的摩尔比为2:1:1:(6~8)。
优选的,所述前驱体溶液的浓度为1~4mmol/L,以锌离子或亚锡离子计。
优选的,进行所述超声雾化时,超声的频率为45~50kHz。
优选的,进行所述喷镀时,喷头距离热衬底的高度为20~60mm。
优选的,进行所述喷镀时,喷头的移动速度为10~100mm/s。
优选的,进行所述喷镀时,雾滴的喷出速度为500~2000μL/min。
优选的,所述热衬底的温度为250~500℃。
优选的,所述喷镀在无气体保护和非真空条件下进行。
本发明提供了一种铜锌锡硫薄膜的制备方法,包括以下步骤:将铜源、锌源、锡源和硫源溶于水中,得到前驱体溶液;将所述前驱体溶液进行超声雾化,然后将所得雾滴喷镀在热衬底上,得到铜锌锡硫薄膜。本发明利用超声雾化技术对铜锌锡硫的前驱体溶液进行处理,形成微米级雾滴,易于均匀分散;在热衬底作用下,前驱体溶液中的溶剂挥发,溶质热分解,可得到铜锌锡硫薄膜,整个制备过程无需控制真空环境,降低了对设备的要求;也无需使用表面活性剂,确保了铜锌锡硫薄膜的纯度。
附图说明
图1为本发明实施例1制得的Cu2ZnSnS4薄膜的X射线衍射图;
图2为本发明实施例1制得的Cu2ZnSnS4薄膜的平面(a)及截面(b)SEM图;
图3为本发明实施例2制得的Cu2ZnSnS4薄膜的SEM图。
图4为本发明实施例3制得的Cu2ZnSnS4薄膜的SEM图。
具体实施方式
本发明提供了一种铜锌锡硫薄膜的制备方法,包括以下步骤:
将铜源、锌源、锡源和硫源溶于水中,得到前驱体溶液;
将所述前驱体溶液进行超声雾化,然后将所得雾滴喷镀在热衬底上,得到铜锌锡硫薄膜。
本发明将铜源、锌源、锡源和硫源溶于水中,得到前驱体溶液。在本发明中,所述铜源优选包括氯化铜和/或硝酸铜,所述铜源的纯度优选为分析纯;所述锌源优选包括氯化锌和/或硝酸锌,所述锌源的纯度优选为分析纯;所述锡源优选包括氯化亚锡和/或硝酸亚锡,所述锡源的纯度优选为分析纯;所述硫源包括硫脲,所述硫源的纯度优选为分析纯。
在本发明中,所述前驱体溶液中,铜离子、锌离子、亚锡离子和硫原子的摩尔比优选为2:1:1:(6~8),更优选为2:1:1:8。本发明优选添加过量的硫源,用于补偿硫源蒸发造成的硫原子损失,以得到组分为Cu2ZnSnS4的薄膜材料。在本发明中,以锌离子或亚锡离子的浓度计,所述前驱体溶液的浓度优选为1~4mmol/L,更优选为1.5~3.5mmol/L,再优选为2~3mmol/L。本发明通过对前驱体溶液的浓度进行控制,有利于形成质地均匀的Cu2ZnSnS4薄膜。
本发明对所述铜源、锌源、锡源和硫源在水中的溶解方式没有特殊要求,将各组分与水混合后,搅拌,得到的浅黄色溶液即为前驱体溶液。在本发明中,前驱体溶液中的水优选为去离子水,以减少杂质的引入。
得到前驱体溶液后,本发明将所述前驱体溶液进行超声雾化,然后将所得雾滴喷镀在热衬底上,得到铜锌锡硫薄膜。在本发明中,所述热衬底的温度优选为250~500℃,更优选为270~480℃,再优选为300~450℃。本发明将超声雾化后所得雾滴喷镀在热衬底上,雾滴中的溶剂受热蒸发,溶质经过热分解,在热衬底上形成铜锌锡硫薄膜。
在本发明中,所述热衬底的材质优选包括玻璃、导电玻璃、陶瓷或不锈钢中的一种。本发明对衬底的厚度没有特殊要求,采用本领域技术人员熟知的即可;对衬底的尺寸没有特殊要求,根据所需薄膜尺寸的大小选择衬底尺寸即可。
在本发明中,上述衬底在使用前,优选进行清洗处理;所述清洗处理优选包括依次进行的丙酮清洗、乙醇清洗和去离子水清洗,所述清洗优选在超声条件下进行,具体的超声参数采用本领域技术人员熟知的即可。本发明通过清洗处理,一方面去除衬底表面可能的杂质,避免杂质对薄膜纯度的影响,另一方面还有利于前驱体溶液在衬底的附着,对得到质地均匀的薄膜材料有利。
在本发明中,进行所述超声雾化时,超声的频率优选为45~50kHz,具体如45kHz、46kHz、47kHz、48kHz、49kHz或50kHz;进行所述喷镀时,喷头距离热衬底的高度优选为10~60mm,更优选为20~45mm;喷头的移动速度优选为10~100mm/s,更优选为50~80mm/s;雾滴的喷出速度优选为500~2000μL/s,更优选为1000~1500μL/s。本发明优选对超声雾化和喷镀参数进行上述控制,可得到微米级雾滴,并有利于雾滴在热衬底上的均分分散。喷镀过程中,本发明无需采取其他保护措施,也不需要进行真空操作,以空气为载体,将雾滴喷镀在加热的衬底上,雾滴中的溶剂受热蒸发,溶质受热分解,在衬底上固化后形成铜锌锡硫(Cu2ZnSnS4)薄膜,整个方法简单,易控。
本发明采用上述技术方案所述方法制备得到的Cu2ZnSnS4的薄膜纯度高,厚度均匀、可控,无需真空环境,降低了对设备的要求;也无需使用表面活性剂,减少了杂质,保证所得Cu2ZnSnS4薄膜的纯度,适合规模化生产。
为了进一步说明本发明,下面结合附图和实施例对本发明提供的一种铜锌锡硫薄膜的制备方法进行详细地描述,但不能将它们理解为对本发明保护范围的限定。
实施例1
按如下步骤制备Cu2ZnSnS4薄膜:
以玻璃为衬底,将玻璃依次在丙酮、无水乙醇和去离子水中超声清洗15min,备用;
室温下将氯化铜、氯化锌、氯化亚锡以及硫脲以摩尔比例为2∶1∶1∶8溶解于去离子水中,搅拌至澄清透明制得2.5mmol/L前驱体溶液;
以超声雾化器将前驱体溶液雾化成雾状液滴,以空气作为载气将雾滴喷镀在400℃的衬底上,喷镀时参数控制在如下条件:
超声的频率为50kHz;雾滴的喷出速度1500μL/min;喷头与衬底的垂直距离为25mm;喷头的移动速度为50mm/s;成膜区完全覆盖雾滴视为完成一次(层)喷镀,喷镀次数为10次,喷镀一层后,间隔5min,喷镀下一层;
雾滴经过溶剂的蒸发、溶质热分解等反应过程,最终在衬底上形成固体Cu2ZnSnS4薄膜。
实施例2
按照实施例1的方式制膜,不同之处在于衬底的温度为350℃。
实施例3
按照实施例1的方式制备铜锌锡硫薄膜,不同之处在于,前驱体溶液的浓度为1.5mol/L;衬底的温度为450℃。
利用X射线衍射仪对实施例1~3所得铜锌锡硫薄膜进行表征,其中实施例1所得产品的表征结果如图1所示。图1中,X射线衍射图谱在28.48°、47.47°和56.09°处的衍射峰分别对应Cu2ZnSnS4的(112)、(220)和(312)晶面(JCPDS card 26-0575),且无其他物相的衍射峰出现,说明采用本发明的方法可以制备出纯度较高的铜锌锡硫薄膜。实施例2和3的表征结果与实施例1相同,均得到了纯度较高的铜锌锡硫薄膜。
利用扫描电镜对实施例1~3所得铜锌锡硫薄膜的形貌进行表征,结果如图2~4所示。图2中,a为实施例1所得铜锌锡硫薄膜的平面SEM图,b为实施例1所得铜锌锡硫薄膜截面的形貌图。由图2(a)可以看出铜锌锡硫薄膜是由不规则的颗粒组成的,且颗粒大小一致,薄膜的均匀性较好;图2(b)中深色部分为衬底玻璃,浅色部分为铜锌锡硫薄膜,由图可看出,铜锌锡硫薄膜厚度约为700nm。本发明所得Cu2ZnSnS4薄膜导电类型为p型,载流子浓度高达1.21×1020cm-3,适合作为太阳能电池的吸收层。
图3和图4分别对应实施例2和3所得铜锌锡硫薄膜,从图中可以看出,实施例2和3均得到了均匀的铜锌锡硫薄膜。
由以上实施例可知,本发明提供的方法制备过程简单、易于控制;无需使用表面活性剂,制备的薄膜均匀,无杂相,提高了产物纯度,符合材料合成绿色化的要求;本发明提供的Cu2ZnSnS4薄膜的制备方法,不需要苛刻的真空环境,而且一步制备Cu2ZnSnS4薄膜,工艺简单适合于大规模生产。
尽管上述实施例对本发明做出了详尽的描述,但它仅仅是本发明一部分实施例,而不是全部实施例,人们还可以根据本实施例在不经创造性前提下获得其他实施例,这些实施例都属于本发明保护范围。
Claims (4)
1.一种铜锌锡硫薄膜的制备方法,包括以下步骤:
将铜源、锌源、锡源和硫源溶于水中,得到前驱体溶液;
将所述前驱体溶液进行超声雾化,然后将所得雾滴喷镀在热衬底上,得到铜锌锡硫薄膜;
进行所述超声雾化时,超声的频率为45~50kHz;进行所述喷镀时,喷头距离热衬底的高度为20~60mm;喷头的移动速度为10~100mm/s;雾滴的喷出速度为500~2000μL/min;
所述铜源为氯化铜和/或硝酸铜;所述前驱体溶液中,铜离子、锌离子、亚锡离子和硫原子的摩尔比为2:1:1:(6~8);所述前驱体溶液的浓度为1~4mmol/L,以锌离子或亚锡离子计。
2.如权利要求1所述的制备方法,其特征在于,所述锌源包括氯化锌和/或硝酸锌;
所述锡源包括氯化亚锡和/或硝酸亚锡;
所述硫源包括硫脲。
3.如权利要求1或2所述的制备方法,其特征在于,所述热衬底的温度为250~500℃。
4.如权利要求3所述的制备方法,其特征在于,所述喷镀在无气体保护和非真空条件下进行。
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