CN110176472A - 含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池及其制造方法 - Google Patents
含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池及其制造方法 Download PDFInfo
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Abstract
本发明公开了一种含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，叠层薄膜太阳能电池包括从上至下依次涂覆叠加的氧化铟锡电极层、氧化锌纳米粒子缓冲层、富勒烯衍生物与3‑己基噻吩聚合物构成的电子传输层、黑磷吸收层、3,4‑乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层、三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层、共用氧化铟锡电极层、n型掺氢纳米氧化硅层、i型掺氢非晶硅层、单晶硅吸收层、n型掺氢非晶硅层、p型掺氢纳米氧化硅层、掺铝的氧化锌减反层和银电极层构成。本发明使用了黑磷这一新型吸收层材料，通过光谱选择层减少了反射损失，显著提高了光电转换效率。
Description
技术领域
本发明涉及太阳能电池技术领域，具体地指一种含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池及其制造方法。
背景技术
目前的晶硅太阳能电池厚度较厚，不方便携带，并且的能量转换效率较低，在13％左右，另外，目前流行的钙钛矿/硅叠层太阳能电池有毒性，环保性能较差。
发明内容
本发明的目的就是要提供一种含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池及其制造方法，本发明使用了黑磷这一新型吸收层材料，通过光谱选择层减少了反射损失，显著提高了光电转换效率。
为实现此目的，本发明所设计的一种含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，所述叠层薄膜太阳能电池包括从上至下依次涂覆叠加的氧化铟锡电极层、氧化锌纳米粒子缓冲层、富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层、黑磷吸收层、3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层、三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层、共用氧化铟锡电极层、n型掺氢纳米氧化硅层、i型掺氢非晶硅层、单晶硅吸收层、n型掺氢非晶硅层、p型掺氢纳米氧化硅层、掺铝的氧化锌减反层和银电极层构成，其中，n型掺氢纳米氧化硅层与i型掺氢非晶硅层涂覆叠加，n型掺氢非晶硅层与p型掺氢纳米氧化硅层涂覆叠加并共同形成异质结。
一种上述含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池的制造方法，它包括如下步骤：
步骤1：在单晶硅上利用湿法腐蚀的方法制备单晶硅吸收层，单晶硅吸收层的光学带隙1.7～1.9eV；
步骤2：利用等离子体增强化学的气相沉积法(PECVD，Plasma Enhanced ChemicalVapor Deposition)和氢掺杂制备n型掺氢纳米氧化硅层、p型掺氢纳米氧化硅层、i型掺氢非晶硅层和n型掺氢非晶硅层，结构由上至下为：n型掺氢纳米氧化硅层、i型掺氢非晶硅层、单晶硅吸收层、n型掺氢非晶硅层和p型掺氢纳米氧化硅层；
步骤3：利用原子层沉积技术(ALD，Atomic layer deposition)在p型掺氢纳米氧化硅层的下端制备掺铝的氧化锌减反层；
步骤4：在掺铝的氧化锌减反层的下端制备银电极层；
步骤5：在已制备的n型掺氢纳米氧化硅层上端制备共用氧化铟锡电极层；
步骤6：在共用氧化铟锡电极层上端用沉积法制备三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层，其中第一层和第三层的折射率相同，第一层和第三层的折射率和消光系数都要大于第二层；
步骤7：用喷涂法在三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层上制备3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层，并将黑磷涂层到3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层上形成黑磷吸收层，黑磷吸收层的光学带隙2.2～2.6eV，然后用喷涂法在黑磷吸收层上制备富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层；
步骤8：在富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层上端用真空蒸汽镀氧化锌纳米粒子缓冲层，然后找氧化锌纳米粒子缓冲层上端制备氧化铟锡电极层。
相对于传统的硅太阳能电池，本发明能够通过在某些波段吸收效率更高的材料来组合提升整体吸收效率，并且明显降低电池厚度。同厚度情况下黑磷/硅叠层太阳能电池较硅基太阳能电池效率能提升10％，这其中加入的光谱选择层大约使整体效率提升了1％。此外，黑磷作为各向异性材料，当入射光的偏振方向平行于armchair方向时的吸收效率要高于垂直于该方向时的效率，这意味着可以通过光偏振调制以实现更高的吸收效率。
光谱选择层由不同折射率的氢化微晶氧化硅(μc-SiOx:H)组成，且它们的消光系数比较低，他们产生的光电流在整个结构中微乎其微。它的优点在于，所用材料易于制备；可以通过不同折射率的材料来对不同的叠层太阳能适配，灵活性较高；成本低廉，在叠层太阳能电池的吸收效率已经足够高的情况下，单纯使用增加吸收层的厚度来提升吸收效率的成本要比引入光谱选择层更高。
本发明利用了黑磷对短波高效吸收的光学特性，和硅基太阳能电池组成叠层太阳能电池，并使用了PCBM和PEDOT:PSS作为电子传输层和空穴传输层，在银基底上和顶端的氧化铟锡下沉积了氧化锌作为减反层，运用30nm的nc-SiOx:H和5nm的a-Si:H构成了异质结，大大提高了载流子的传输效率。
附图说明
图1为本发明的结构示意图；
图2为黑磷和晶硅叠层薄膜太阳能电池的功函数匹配图；
图3为黑磷不同偏振方向上的折射率示意图。
其中，1—氧化铟锡电极层、2—氧化锌纳米粒子缓冲层、3—富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层、4—黑磷吸收层、5—3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层、6—三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层、7—共用氧化铟锡电极层、8—n型掺氢纳米氧化硅层、9—i型掺氢非晶硅层、10—n型掺氢非晶硅层、11—p型掺氢纳米氧化硅层、12—单晶硅吸收层、13—掺铝的氧化锌减反层、14—银电极层。
具体实施方式
以下结合附图和具体实施例对本发明作进一步的详细说明：
如图1所示的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，所述叠层薄膜太阳能电池包括从上至下依次涂覆叠加的氧化铟锡电极层1(厚度为150nm)、氧化锌纳米粒子缓冲层2(厚度为40nm)、富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层3(PCBM，厚度为17nm)、黑磷吸收层4、3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层5(PEDOT:PSS，厚度为32nm)、三层不同折射率的掺氢微晶氧化硅(μc-SiOx:H)叠加构成的光谱选择层6、共用氧化铟锡电极层7(厚度为35nm)、n型掺氢纳米氧化硅层8(nc-SiOx:H/i)、i型掺氢非晶硅层9(a-Si:H)、单晶硅吸收层12、n型掺氢非晶硅层10(a-Si:H)、p型掺氢纳米氧化硅层11(nc-SiOx:H/i)、掺铝的氧化锌减反层13(ZnO:Al，厚度为80nm)和银电极层14构成，其中，n型掺氢纳米氧化硅层8与i型掺氢非晶硅层9涂覆叠加，n型掺氢非晶硅层10与p型掺氢纳米氧化硅层11涂覆叠加并共同形成异质结(即，n型掺氢纳米氧化硅层、i型掺氢非晶硅层涂覆、n型掺氢非晶硅层、p型掺氢纳米氧化硅层共同形成异质结)。
上述技术方案中，氧化铟锡电极层1为叠层薄膜太阳能电池做正极电极；
所述氧化锌纳米粒子缓冲层2用于对叠层薄膜太阳能电池的禁带宽度起过渡和缓冲作用，增加电池耗尽区的带宽，本身对入射光的吸收微乎其微，并不会影响吸收层的吸收；
所述富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层3用于将电子传输到黑磷吸收层4，并在黑磷吸收层4产生空穴，进而产生回路电流。
上述技术方案中，所述3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层5用于将黑磷吸收层4产生的空穴经三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层6传输到共用氧化铟锡电极层7；
三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层6用于优化叠层薄膜太阳能电池对太阳光谱的吸收效率，提高黑磷吸收层4对300nm～750nm波长光谱的吸收效率(可以提高到18％)，提高单晶硅吸收层12对750nm～1200nm波长光谱的吸收效率(可以提高到18％)。
上述技术方案中，所述黑磷吸收层4厚度为140～210nm，黑磷吸收层4的光学性质表现为各向异性。入射光在两个偏振方向上的折射率不同(如图3)，在仿真中使用了加权平均的方法模拟了无偏振光入射时的黑磷吸收层的吸收率。
上述技术方案中，所述共用氧化铟锡电极层7用于作为黑磷吸收层4和单晶硅吸收层12的共用电极；
所述异质结用于提高提高空穴电子传输对的传输效率；
所述掺铝的氧化锌减反层13用于减少入射光在叠层薄膜太阳能电池内部反射，增加叠层薄膜太阳能电池耗尽区带宽。
上述技术方案中，所述黑磷吸收层4为顶电池的吸收层，单晶硅吸收层12为底电池的吸收层；
银电极层14为叠层薄膜太阳能电池负极。
上述技术方案中，所述黑磷吸收层4的厚度为140～210nm，单晶硅吸收层12的厚度为250μm±10μm，单晶硅吸收层12厚度经优化后在降低了底电池厚度的基础上，能最大限度地表现出顶电池的吸收效率；
所述黑磷吸收层4的光学带隙为2.2～2.6eV，单晶硅吸收层12的光学带隙为1.1eV。
上述技术方案中，所述三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层6中，从上至下各层掺氢微晶氧化硅当入射光波长为750nm时折射率分别为2.17、1.77、2.17，高折射率材料在300～1200nm波长范围内的任意折射率和消光系数都高于低折射率材料，从上至下各层掺氢微晶氧化硅的厚度分别为50nm±1nm、80nm±1nm和30nm±1nm，该厚度可以平衡顶电池与底电池的短路电流；
所述n型掺氢纳米氧化硅层8和p型掺氢纳米氧化硅层11的厚度均为30nm±1nm，i型掺氢非晶硅层9和n型掺氢非晶硅层10的厚度均为5nm±0.1nm。
上述技术方案中，所述叠层薄膜太阳能电池的功函数沿电子传输方向递增，沿空穴传输方向递减。
一种上述含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池的制造方法，它包括如下步骤：
步骤1：在单晶硅上利用湿法腐蚀的方法制备单晶硅吸收层12，单晶硅吸收层12的光学带隙1.7～1.9eV；
步骤2：利用等离子体增强化学的气相沉积法和氢掺杂制备n型掺氢纳米氧化硅层8、p型掺氢纳米氧化硅层11、i型掺氢非晶硅层9和n型掺氢非晶硅层10，结构由上至下为：n型掺氢纳米氧化硅层8、i型掺氢非晶硅层9、单晶硅吸收层12、n型掺氢非晶硅层10和p型掺氢纳米氧化硅层11；
步骤3：利用原子层沉积技术在p型掺氢纳米氧化硅层11的下端制备掺铝的氧化锌减反层13；
步骤4：在掺铝的氧化锌减反层13的下端制备银电极层14；
步骤5：在已制备的n型掺氢纳米氧化硅层8上端制备共用氧化铟锡电极层7；
步骤6：在共用氧化铟锡电极层7上端用沉积法制备三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层6，其中第一层和第三层的折射率相同，第一层和第三层的折射率和消光系数都要大于第二层；
步骤7：用喷涂法在三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层6上制备3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层5，并将黑磷涂层到3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层5上形成黑磷吸收层4，黑磷吸收层4的光学带隙2.2～2.6eV，然后用喷涂法在黑磷吸收层4上制备富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层3；
步骤8：在富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层3上端用真空蒸汽镀氧化锌纳米粒子缓冲层2，然后找氧化锌纳米粒子缓冲层2上端制备氧化铟锡电极层1，并快速退火。
本发明的吸收率、反射率和短路电流进行了计算，并运用了控制变量法设定了未使用光谱选择层的结构作为对照。
其中，本设计的短路电流达到了16.4mA/cm2，相对于没有使用光谱选择层的结构提升了1.02mA/cm2，反射损失在500nm-1200nm波长范围内减少了4.2mA/cm2，即显著提升了长波波段的吸收效率进而提高了整个电池的吸收效率。
其中，通过分析其电场分布可知，通过引入光谱选择层，其电场分布整体下移，即底电池的电场活动要强于未使用光谱选择层的情况。
本说明书未作详细描述的内容属于本领域专业技术人员公知的现有技术。
Claims (10)
1.一种含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：所述叠层薄膜太阳能电池包括从上至下依次涂覆叠加的氧化铟锡电极层(1)、氧化锌纳米粒子缓冲层(2)、富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层(3)、黑磷吸收层(4)、3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层(5)、三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层(6)、共用氧化铟锡电极层(7)、n型掺氢纳米氧化硅层(8)、i型掺氢非晶硅层(9)、单晶硅吸收层(12)、n型掺氢非晶硅层(10)、p型掺氢纳米氧化硅层(11)、掺铝的氧化锌减反层(13)和银电极层(14)构成，其中，n型掺氢纳米氧化硅层(8)与i型掺氢非晶硅层(9)涂覆叠加，n型掺氢非晶硅层(10)与p型掺氢纳米氧化硅层(11)涂覆叠加并共同形成异质结。
2.根据权利要求1所述的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：氧化铟锡电极层(1)为叠层薄膜太阳能电池做正极电极；
所述氧化锌纳米粒子缓冲层(2)用于对叠层薄膜太阳能电池的禁带宽度起过渡和缓冲作用，增加电池耗尽区的带宽；
所述富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层(3)用于将电子传输到黑磷吸收层(4)，并在黑磷吸收层(4)产生空穴，进而产生回路电流。
3.根据权利要求1所述的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：所述3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层(5)用于将黑磷吸收层(4)产生的空穴经三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层(6)传输到共用氧化铟锡电极层(7)；
三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层(6)用于优化叠层薄膜太阳能电池对太阳光谱的吸收效率，提高黑磷吸收层(4)对300nm～750nm波长光谱的吸收效率，提高单晶硅吸收层(12)对750nm～1200nm波长光谱的吸收效率。
4.根据权利要求1所述的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：所述黑磷吸收层(4)厚度为140～210nm nm，黑磷吸收层(4)的光学性质表现为各向异性。
5.根据权利要求1所述的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：所述共用氧化铟锡电极层(7)用于作为黑磷吸收层(4)和单晶硅吸收层(12)的共用电极；
所述异质结用于提高提高空穴电子传输对的传输效率；
所述掺铝的氧化锌减反层(13)用于减少入射光在叠层薄膜太阳能电池内部反射，增加叠层薄膜太阳能电池耗尽区带宽。
6.根据权利要求1所述的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：所述黑磷吸收层(4)为顶电池的吸收层，单晶硅吸收层(12)为底电池的吸收层；
银电极层(14)为叠层薄膜太阳能电池负极。
7.根据权利要求1所述的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：单晶硅吸收层(12)的厚度为250μm±10μm；
所述黑磷吸收层(4)的光学带隙为2.2～2.6eV，单晶硅吸收层(12)的光学带隙为1.1eV。
8.根据权利要求1所述的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：所述三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层(6)中，从上至下各层掺氢微晶氧化硅当入射光波长为750nm时折射率分别为2.17、1.77、2.17，从上至下各层掺氢微晶氧化硅的厚度分别为50nm±1nm、80nm±1nm和30nm±1nm；
所述n型掺氢纳米氧化硅层(8)和p型掺氢纳米氧化硅层(11)的厚度均为30nm±1nm，i型掺氢非晶硅层(9)和n型掺氢非晶硅层(10)的厚度均为5nm±0.1nm。
9.根据权利要求1所述的含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池，其特征在于：所述叠层薄膜太阳能电池的功函数沿电子传输方向递增，沿空穴传输方向递减。
10.一种权利要求1所述含光谱选择层的黑磷和晶硅叠层薄膜太阳能电池的制造方法，其特征在于，它包括如下步骤：
步骤1：在单晶硅上利用湿法腐蚀的方法制备单晶硅吸收层(12)，单晶硅吸收层(12)的光学带隙1.7～1.9eV；
步骤2：利用等离子体增强化学的气相沉积法和氢掺杂制备n型掺氢纳米氧化硅层(8)、p型掺氢纳米氧化硅层(11)、i型掺氢非晶硅层(9)和n型掺氢非晶硅层(10)，结构由上至下为：n型掺氢纳米氧化硅层(8)、i型掺氢非晶硅层(9)、单晶硅吸收层(12)、n型掺氢非晶硅层(10)和p型掺氢纳米氧化硅层(11)；
步骤3：利用原子层沉积技术在p型掺氢纳米氧化硅层(11)的下端制备掺铝的氧化锌减反层(13)；
步骤4：在掺铝的氧化锌减反层(13)的下端制备银电极层(14)；
步骤5：在已制备的n型掺氢纳米氧化硅层(8)上端制备共用氧化铟锡电极层(7)；
步骤6：在共用氧化铟锡电极层(7)上端用沉积法制备三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层(6)，其中第一层和第三层的折射率相同，第一层和第三层的折射率和消光系数都要大于第二层；
步骤7：用喷涂法在三层不同折射率的掺氢微晶氧化硅叠加构成的光谱选择层(6)上制备3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层(5)，并将黑磷涂层到3,4-乙烯二氧噻吩与聚苯乙烯磺酸钠聚合物空穴传输层(5)上形成黑磷吸收层(4)，黑磷吸收层(4)的光学带隙2.2～2.6eV，然后用喷涂法在黑磷吸收层(4)上制备富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层(3)；
步骤8：在富勒烯衍生物与3-己基噻吩聚合物构成的电子传输层(3)上端用真空蒸汽镀氧化锌纳米粒子缓冲层(2)，然后找氧化锌纳米粒子缓冲层(2)上端制备氧化铟锡电极层(1)。
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