CN105118875A - 一种铜铟镓硒薄膜太阳电池无镉缓冲层的原子层沉积制备方法 - Google Patents
一种铜铟镓硒薄膜太阳电池无镉缓冲层的原子层沉积制备方法 Download PDFInfo
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- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000010409 thin film Substances 0.000 title claims abstract description 18
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000010408 film Substances 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 239000005361 soda-lime glass Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- QBJCZLXULXFYCK-UHFFFAOYSA-N magnesium;cyclopenta-1,3-diene Chemical compound [Mg+2].C1C=CC=[C-]1.C1C=CC=[C-]1 QBJCZLXULXFYCK-UHFFFAOYSA-N 0.000 abstract 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 7
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000005083 Zinc sulfide Substances 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- H01L31/02966—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe including ternary compounds, e.g. HgCdTe
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Abstract
本发明公开了一种铜铟镓硒薄膜太阳电池无镉缓冲层的沉积方法，该方法的特征是采用二乙基锌（DEZn）、双环戊二茂镁（MgCP2）、H2S作为Zn、Mg和S的前躯体源进行原子层沉积，得到Zn1-xMgxS缓冲层材料。此方法具有沉积速度稳定、薄膜致密性好、性能优异等特点。Zn1-xMgxS作为CIGS薄膜太阳电池的一种新型缓冲层材料，具有无镉、环境友好的特点；通过调节ZnS的Mg掺杂比例，可得到比ZnS更合适的晶格参数，降低了其与吸收层CIGS界面间的失配度，改善了界面质量；随着Mg含量x的变化，还能调节Zn1-xMgxS薄膜的带隙，弥补硫化锌带隙偏小的缺点；Zn1-xMgxS的带隙增加还可增强紫外区的透光率，进而提高铜铟镓硒薄膜太阳电池的光电转换效率；采用原子层沉积（ALD）制备的薄膜由于致密性好，还可抑制由于薄膜致密性不理想产生的微针孔而导致的电池内部短路现象，改善电池的性能。
Description
技术领域
本发明属于太阳电池领域，涉及一种以原子层沉积（ALD）技术制备铜铟镓硒（CIGS）薄膜太阳电池无镉缓冲层的方法，该缓冲层材料为Mg掺杂ZnS薄膜（Zn1-xMgxS）。
背景技术
太阳电池是一种根据光生伏打效应而将太阳能直接转化成电能的半导体器件。CIGS薄膜太阳电池是20世纪80年研发出的一种新型太阳电池，具有吸收层材料的吸收系数大、性能稳定、抗辐射能力强、光电转换效率高和弱光效应好等特点。目前，CIGS太阳电池的实验室转换效率已超过多晶硅，因此，其有着良好的应用前景。CIGS薄膜太阳电池的典型结构为：衬底（玻璃）/金属背电极（Mo）/光吸收层（CIGS）/缓冲层（CdS）/窗口层（ZnO）/透明前电极（AZO）/金属栅线电极（Al）。虽然缓冲层厚度一般只有50nm，但它能与吸收层形成异质结分离载流子以提高少子寿命，并保护吸收层。目前高效的CIGS太阳电池普遍采用硫化镉（CdS）为缓冲层材料，其实验室电池效率可达20%以上。CdS缓冲层一般采用化学水浴法（CBD）制备，与吸收层和窗口层的制备工艺不匹配，不利于流水线规模化生产；并且Cd有毒，不环保，不符合太阳电池的“环境友好”的要求；同时硫化镉的带隙小，对短波长的可见光有较强的吸收作用，不利于电池效率的进一步提升。为此，人们开始寻找CdS的替代物，并将重点放在硫化锌系化合物上，但硫化锌的带隙仍然偏小，同时由于其与吸收层的界面处存在较大的晶格失配，导致界面质量下降，电池效率降低。因此，有必要寻找性能比ZnS更好的无镉缓冲层材料。
原子层沉积（ALD）是一种可以将物质以单原子膜形式一层一层地镀在基底表面的方法。其优点主要有：可以通过控制反应周期数精确控制薄膜的厚度，形成达到原子层厚度精度的薄膜；不需要控制反应物流量的均一性；前驱体是饱和化学吸附，保证生成大面积均匀性的薄膜；可生成极好的三维保形性化学计量致密薄膜，缺陷少，可作为台阶覆盖和纳米孔材料的涂层；可以沉积多组份纳米薄层和混合氧化物；薄膜生长可在低温(室温到400℃)下进行。利用原子层沉积技术制备的Zn1-xMgxS薄膜具有致密性和保形性好、无针孔、带隙可调、薄膜厚度可精确控制等特点，从而可实现与吸收层较好的晶格匹配，改善界面质量，弥补硫化锌的带隙偏小的不足，增强紫外区的透过率，还可以抑制由于薄膜中存在的微针孔而导致的电池内部短路现象，提高电池的性能。
发明内容
本发明提供了一种以原子层沉积技术制备铜铟镓硒（CIGS）薄膜太阳电池无镉缓冲层材料—Zn1-xMgxS薄膜的方法，采用二乙基锌（DEZn）、双环戊二茂镁（MgCP2）、H2S作为Zn、Mg和S的前躯体源，使用高纯度N2作为载运和清洗气体进行原子层沉积，得到了较好的Zn1-xMgxS薄膜，作为铜铟镓硒薄膜太阳电池无镉缓冲层。制备方法如下。
在普通钠钙玻璃衬底上依次制备钼背电极和铜铟镓硒光吸收层，形成样片，将样片放入原子层沉积设备的反应室中。
将反应室真空抽到0.5pa以下，设置反应腔室温度为150-250℃。
采用二乙基锌（DEZn）、双环戊二茂镁（MgCP2）、H2S作为Zn、Mg和S的前躯体源，使用高纯度N2作为载运和清洗气体，携带气体流量100-300sccm，源瓶温度设置为室温到100℃，ZnS和MgS薄膜一个生长周期的脉冲时间分别为10-50ms，等待时间为3-10s。
分别生长300-500个周期，可得到厚度为40-70nm的Zn1-xMgxS薄膜，薄膜的Mg组分通过ZnS和MgS的周期数调节来实现。
本发明采用原子层沉积技术制备铜铟镓硒薄膜太阳电池无镉缓冲层，获得的Zn1-xMgxS缓冲层薄膜致密、无微针孔、均匀，厚度易于控制、薄膜性能优异，Mg组分易控、带隙可调，弥补了ZnS带隙偏小的不足，提高了其在紫外区的透光率；可实现其与吸收层材料的晶格匹配度，改善界面质量；还可抑制由于薄膜致密性不好而产生的电池内部短路现象。提高电池的效率，取代目前的CdS缓冲层。
具体实施方式
为使本发明的上述目的、特征和优点能够更加通俗易懂，下面结合具体实施方式对本发明做详细的说明。
实施例1
（1）在普通钠钙玻璃衬底上依次制备钼背电极和铜铟镓硒光吸收层，形成样片，将样片放入原子层沉积设备的反应室中；
（2）将反应室真空抽到0.5pa，设置反应腔室温度为180℃；
（3）采用二乙基锌（DEZn）、双环戊二茂镁（MgCP2）、H2S作为Zn、Mg和S的前躯体源，使用高纯度N2作为载运和清洗气体，携带DEZn和MgCP2气体流量均为150sccm，携带H2S气体流量为200sccm，分别设置ZnS和MgS薄膜一个生长周期的脉冲时间为20ms和25ms，等待时间分别为5s和10s；
（4）分别进行薄膜生长共500个周期，得到较好的Zn1-xMgxS薄膜。
实施例2
（1）在普通钠钙玻璃衬底上依次制备钼背电极和铜铟镓硒光吸收层，形成样片，将样片放入原子层沉积设备的反应室中；
（2）抽反应室真空到0.4pa，设置反应腔室温度为200℃；
（3）采用二乙基锌（DEZn）、双环戊二茂镁（MgCP2）、H2S作为Zn、Mg和S的前躯体源，使用高纯度N2作为载运和清洗气体，携带DEZn和MgCP2气体流量均为180sccm，携带H2S气体流量为220sccm，分别设置ZnS和MgS薄膜一个生长周期的脉冲时间为30ms和40ms，等待时间分别为5s和10s；
（4）分别进行薄膜生长共400个周期，得到较好的Zn1-xMgxS薄膜。
以上所述内容仅为本发明构思下的基本说明，而依据本发明所做的等效变换，均应属于本发明的保护范围。
Claims (3)
1.一种铜铟镓硒薄膜太阳电池无镉缓冲层的沉积方法，其制备步骤包括：在普通钠钙玻璃衬底上依次制备钼背电极和铜铟镓硒光吸收层，形成样片，将样片放入原子层沉积系统的反应室中，抽反应室真空到0.5pa以下，设置反应腔室温度为150-250℃，采用二乙基锌（DEZn）、双环戊二茂镁（MgCP2）、H2S作为Zn、Mg和S的前躯体源，使用高纯度N2作为载运和清洗气体，携带气体流量为100-300sccm，源瓶温度设置为室温到100℃，分别设置ZnS和MgS一个生长周期的脉冲时间为10-50ms，等待时间为3-10s，生长300-500个周期的薄膜，可得到厚度为40-70nm的Zn1-xMgxS薄膜，薄膜的Mg组分通过调节ZnS和MgS的生长周期数来实现。
2.根据权利要求1所述的铜铟镓硒薄膜太阳电池无镉缓冲层的沉积方法，其特征在于：采用二乙基锌（DEZn）、双环戊二茂镁（MgCP2）、H2S作为Zn、Mg和S的前躯体源，采用原子层沉积（ALD）技术制备优质Zn1-xMgxS薄膜。
3.根据权利要求1所述的铜铟镓硒薄膜太阳电池无镉缓冲层的沉积方法，其特征在于：携带气体流量100-300sccm，源瓶温度设置为室温到100℃；分别设置ZnS和MgS一个生长周期的脉冲时间为10-50ms，等待时间为3-10s；为满足缓冲层的使用要求，薄膜生长300-500个周期。
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