TW201424025A - 太陽能電池之製法 - Google Patents
太陽能電池之製法 Download PDFInfo
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- 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
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/543—Solar cells from Group II-VI materials
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Abstract
本發明提供一種太陽能電池之製法，包括以下步驟：提供一第一基板；形成一光吸收層前驅物於該第一基板之上；對該光吸收層前驅物進行一熱處理步驟以形成一光吸收層，其中該光吸收層包括一第一光吸收層與一第二光吸收層，且該第一光吸收層形成於該第一基板之上；形成一第二基板於該第二光吸收層之上；移除該第一基板，以暴露出該第一光吸收層之表面；形成一硫化鋅層於該第一光吸收層之表面上；以及形成一透明導電層於該硫化鋅層之上。
Description
本發明係有關於一種太陽能電池之製法，且特別是有關於一種將硫化鋅(ZnS)緩衝層形成於分層的光吸收層上之製法。
近年來由於受到全球氣候變遷、環境污染問題以及資源日趨短缺的影響，在環保意識高漲與能源危機的警訊下刺激了太陽光電產業的蓬勃發展。於各種太陽能電池中，由於硒化銅銦鎵電池(Cu(In,Ga)Se2,CIGS)具備高轉換效率、穩定性佳、低材料成本、可製成薄膜等優點，因此受到極大的重視。
CIGS化合物屬於黄銅礦(chalcopyrite)結構，其主要由IB-IIIA-VIA族化合物所組成，其為一種直接能隙(direct bandgap)半導體材料，可藉由調控組成而改變半導體之能隙，是目前作為光吸收層之主要材料。
傳統製法上形成緩衝層於光吸收層之上，緩衝層之作用在於與光吸收層結合成為適當的異質接面，以增加短波長光的吸收效率。然而，硫化鎘(CdS)由於具有毒性，以逐漸被無毒緩衝材料所取代，例如硫化鋅(ZnS)。
然而，於製作CIGS太陽能電池的過程中，使用溶液塗佈法搭配熱處理製程(selenization process)，會使得光吸收層產生結構分層(delamination)的問題。若要將硫化鋅(ZnS)緩衝層形成於分層的光吸收層之上，通常要提高製程溫度
或對光吸收層進行後硫化處理(post-sulfurization process)，提高製程溫度會減少基板的選擇性，而後硫化處理則需使用毒化物硫化氫。
因此，本發明提供一種太陽能電池之製法，以解決結構分層之光吸收層與硫化鋅(ZnS)緩衝層無法搭配的問題
本發明提供一種太陽能電池之製法，包括以下步驟：提供一第一基板；形成一光吸收層前驅物於該第一基板之上；對該光吸收層前驅物進行一熱處理步驟以形成一光吸收層，其中該光吸收層包括一第一光吸收層與一第二光吸收層，且該第一光吸收層形成於該第一基板之上；形成一第二基板於該第二光吸收層之上；移除該第一基板，以暴露出該第一光吸收層之表面；形成一硫化鋅(ZnS)層於該第一光吸收層之表面上；以及形成一透明導電層(transparent conducting oxide,TCO)於該硫化鋅(ZnS)層之上。
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細說明如下：
本發明提供一種太陽能電池之製法，請參見第1A-1F圖，首先提供第一基板102，第一基板102包括玻璃、高分子基板、金屬基板或上述之組合。
接著，請參見第1A圖，形成光吸收層104於第一基板102之上，其中形成光吸收層104之方法包括溶液塗佈法，例如旋轉塗佈(spin coating)、棒狀塗佈(bar coating)、浸漬塗佈(dip coating)、滾筒塗佈(roll coating)、噴霧塗佈(spray coating)、凹版式塗佈(gravure coating)、噴墨印刷(ink jet printing)、狹縫塗佈(slot coating)或刮刀塗佈(blade coating)。
於一實施例中，可先製備光吸收層前驅物(precursor)，藉由將含有IB族、IIIA族與VIA族之氧化物混合於溶液中而得，(其中IB族包括銅(Cu)、銀(Ag)、金(Au)或上述之組合，IIIA族包括鋁(Al)、銦(In)、鎵(Ga)或上述之組合，VIA族包括硫(S)、硒(Se)、碲(Te)或上述之組合)，而溶液包括水、醇類、酮類或醚類。接著，將光吸收層前驅物塗佈於第一基板102之上，塗佈前驅物漿料厚度為約0.1~10 μm。
之後，請參見第1B圖，對光吸收層前驅物進行熱處理(包括除碳，還原，硒化等步驟)以形成光吸收層104，於硒化製程中，因前驅物中每個成份的反應速度不同，而形成兩層光吸收層(104a,104b)，使光吸收層104包括第一光吸收層104a與第二光吸收層104b，其中第一光吸收層104a形成於第一基板102之上。
於一實施例中，若以銅銦鎵硒化合物(CIGS)為光吸收層，第一光吸收層104a為富含鎵之光吸收層(例如CuGaSe2)，第二光吸收層則為富含銦之光吸收層(例如
CuInSe2)。
上述之熱處理步驟包括以下步驟：將已塗佈前驅物之第一基板102置於包括ⅥA族氣體之氣氛(atmosphere)中，以進行熱處理步驟。VIA族氣體包括硒化氫(H2Se)、硫化氫(H2S)、硒(Se)蒸氣、硫(S)蒸氣、碲(Te)蒸氣或上述之組合。熱處理步驟之溫度為約450-550℃，熱處理步驟之時間為約10-60分鐘。
進行熱處理步驟之後，因第二光吸收層104b之組成富含銦，故晶粒成長較為容易，因此第二光吸收層104b之粒徑大於第一光吸收層104a之粒徑，其中第一光吸收層104a之粒徑大小為約50-500 nm，第二光吸收層104b之粒徑大小為約1 μm-10 μm，其中晶粒大小會受到熱處理溫度的影響。此外，因第二光吸收層104b中富含銦，因此其能隙(energy gap)小於第一光吸收層104a之能隙。
於一實施例中，第一光吸收層104a為CGS層，其能階為約1.7 eV，第二光吸收層104b為CIS層，其能階為約1.0 eV。
之後，請參見第1C圖，形成第二基板106於第二光吸收層104b之上。形成第二基板106之步驟包括塗佈導電膠105於第二光吸收層104b之上；以及形成於第二基板106於導電膠105之上。
上述之第二基板106包括高分子基板、金屬基板或上述之組合，其中高分子基板包括聚亞醯胺(polyimide,PI)、聚對苯二甲酸乙二酯(poly(ethylene terephthalate),PET)、聚
碳酸酯(poly carbonate,PC)、聚甲基丙烯酸甲酯(poly(methyl methacrylate),PMMA)或上述之組合。
接著，請參見第1D圖，移除第一基板102，以暴露第一光吸收層104a之表面。由於第二基板106之材質可為可撓式基板，因此，可將第二基板固定於滾筒(roll)，透過捲對捲製程(roll-to-roll process)，以移除第一基板102並取出光吸收層104。
請參見第1E圖，形成硫化鋅(ZnS)層110於第一光吸收層104a之表面上。於一實施例中，硫化鋅層110中的硫可以被氧取代，亦即硫化鋅層110中尚包括氧(ZnS1-xOx,x=0-1)。
請參見第1F圖，形成透明導電層(TCO)112於硫化鋅(ZnS)層110上，其中透明導電層(TCO)包括氧化銦錫(ITO)、氧化銦(In2O3)、氧化錫(SnO2)、氧化鋅(ZnO)、氧化鎘(CdO)、摻鋁之氧化鋅(AZO)、氧化銦鋅(IZO)或上述之組合。
須注意的是，習知進行熱處理之溫度需大於600℃，以避免光吸收層分層，之後才能將硫化鋅(ZnS)層形成於光吸收層之上。而本發明不利用高溫製程改善光吸收層分層的問題，而是藉由結構反轉的(reversal structure)步驟，將硫化鋅(ZnS)層形成於第一光吸收層104a之上(CGS)，因此，相對於習知技術，本發明不需要使用高溫製程(本案熱處理溫度為約450-550℃)，即可將光吸收層與硫化鋅(ZnS)層搭配。
再者，太陽能電池的能階分佈為入光處為較高能階材料，隨著深度增加，材料的能階依序遞減。本發明比較例中，將硫化鋅(ZnS)層110形成於能階較低的第二光吸收層104b(CIS)之上時，因能階障礙的關係導致電流輸出困難，因此利用該結構所製備之電池光電轉換效率極低(~0%)，由此可知，將硫化鋅(ZnS)層110(能階為約3.6 eV)形成於能階較低的第二光吸收層104b之上(相對於第一光吸收層104a)，並無法製成太陽能電池。
綜上所述，本發明所提供之太陽能電池之製法，藉由結構反轉的製法步驟，解決結構分層之光吸收層與硫化鋅(ZnS)緩衝層無法搭配的問題。
以不鏽鋼作為第一基板，並以濺鍍法製作厚度約800 nm之鉻(Cr)層，再濺鍍約800 nm的鉬(Mo)層於鉻(Cr)層上。
之後，使用奈米漿料塗佈法配合熱處理製程，製作厚度為約2500nm之CIGS光吸收層，其中CIS層厚度約為1500nm，CGS厚度約為1000nm。
接著，於CIGS光吸收層上方均勻塗佈銀膠(silver glue)，並將聚亞醯胺(PI)基板覆蓋於其上，再加熱至130℃並維持10分鐘，以黏合聚亞醯胺(PI)基板和CIGS光吸收層。
移除不鏽鋼基板之方法為利用圓形滾筒(roll)纏繞PI
膜，透過滾動滾筒即可撕離光吸收層。
之後，將硫化鋅(ZnS)緩衝層製作於光吸收層之上。ZnS緩衝層配方為0.002M硫酸鋅，0.05M硫脲以及2.5M氨水進行反應，於75℃反應並維持20分鐘。
後續使用濺鍍法製作透明導電膜(IZO和AZO)，之後使用印刷方式網版印刷銀電極(作為上電極)。
實施例所得之太陽能電池進行切割並定義面積，所製備之太陽能電池之光電轉換效率於AM1.5，照度為100 mW/cm2下進行量測。
表1顯示實施例所得之太陽能電池之開路電壓(open-circuit voltage，Voc)為0.35 V、短路電流(short-circuit current，Jsc)為14.06 mA/cm2、填充因子(fill factor)為28.2%、光電轉換效率(photo-electric conversion)為1.578%、並聯電阻(shunt resistance，Rsh)為72.72 Ohm、串聯電阻(series resistance，Rs)為48.97 Ohm。
本發明實施例之太陽能電池中，其中CIS層(第二光吸收層)厚度為約1000nm、CGS層(第一光吸收層)厚度為約1500nm、硫化鋅(ZnS)層厚度為約10~20nm、IZO厚度為約50nm以及AZO厚度為約400nm。
請參見第2圖，其顯示本發明實施例之太陽能電池之掃描式電子顯微鏡(scanning electron microscope,SEM)圖。由第2圖中可知，因為ZnS和IZO層鍍膜厚度過薄，因此無法明顯觀察到ZnS緩衝層和IZO層。此外，圖中顯示CGS(第一光吸收層)、ZnS緩衝層與透明導電層(TCO)之接合相當完整，並沒有層與層之間的剝離現象發生，顯示使用本發明所提供之製法所製作之CIGS太陽電池應有不錯的品質。
以不鏽鋼做為基板，並以濺鍍法製作厚度約800 nm之鉻(Cr)層，再濺鍍約800 nm的鉬(Mo)層於鉻(Cr)層上。
之後，使用奈米漿料塗佈法配合熱處理製程，製作厚度為約2500nm之CIGS吸收層。其中CIS層(第二光吸收層)厚度為約1000nm、CGS層(第一光吸收層)厚度為約1500nm，之後，進行硫化鋅(ZnS)緩衝層製作。ZnS緩衝層配方同實施例。
後續使用濺鍍法製作透明導電膜(IZO和AZO)，之後使用印刷方式網版印刷銀電極(作為上電極)。
比較例之結構的光電轉換效率為0%，由此可知，將硫化鋅(ZnS)層製作於能階較低的第二吸收層(CIS)之上，並無法製出太陽能電池。
雖然本發明已以數個較佳實施例揭露如上，然其並非
用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
102‧‧‧第一基板
104‧‧‧光吸收層
104a‧‧‧第一光吸收層
104b‧‧‧第二光吸收層
105‧‧‧導電膠
106‧‧‧第二基板
110‧‧‧硫化鋅(ZnS)層
112‧‧‧透明導電層(transparent conducting oxide,TCO)
第1A~1F圖為一系列剖面圖，用以說明本發明之太陽能電池之製法。
第2圖顯示本發明之太陽能電池之掃描式電子顯微鏡(scanning electron microscope,SEM)圖。
104‧‧‧光吸收層
104a‧‧‧第一光吸收層
104b‧‧‧第二光吸收層
105‧‧‧導電膠
106‧‧‧第二基板
110‧‧‧硫化鋅(ZnS)層
112‧‧‧透明導電層(transparent conducting oxide,TCO)
Claims (18)
- 一種太陽能電池之製法，包括以下步驟：提供一第一基板；形成一光吸收層前驅物於該第一基板之上；對該光吸收層前驅物進行一熱處理步驟以形成一光吸收層，其中該光吸收層包括一第一光吸收層與一第二光吸收層，且該第一光吸收層形成於該第一基板之上；形成一第二基板於該第二光吸收層之上；移除該第一基板，以暴露出該第一光吸收層之表面；形成一硫化鋅(ZnS)層於該第一光吸收層之表面上；以及形成一透明導電層(transparent conducting oxide,TCO)於該硫化鋅(ZnS)層之上。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該光吸收層包括銅銦鎵硒化合物(CIGS)。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該第一光吸收層包括富含鎵之光吸收層(CGS)，且該第二光吸收層包括富含銦之光吸收層(CIS)。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該第一基板包括玻璃、高分子基板、金屬基板或上述之組合。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中形成該光吸收層之方法包括旋轉塗佈(spin coating)、棒狀塗佈(bar coating)、浸漬塗佈(dip coating)、滾筒塗佈(roll coating)、噴霧塗佈(spray coating)、凹版式塗佈(gravure coating)、噴墨印刷(ink jet printing)、狹縫塗佈(slot coating)或刮刀塗佈(blade coating)。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該熱處理步驟包括以下步驟：將該第一基板置於包括ⅥA族氣體之氣氛(atmosphere)中，以進行該熱處理步驟。
- 如申請專利範圍第6項所述之太陽能電池之製法，其中該VIA族氣體包括硒化氫(H2Se)、硫化氫(H2S)、硒(Se)蒸氣、硫(S)蒸氣、碲(Te)蒸氣或上述之組合。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該熱處理步驟之溫度為約450-550℃。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該熱處理步驟之時間為約10-60分鐘。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該第二光吸收層之粒徑大於該第一光吸收層之粒徑。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該第一光吸收層之粒徑大小為約50-500 nm。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該第二光吸收層之粒徑大小為約1 μm-10 μm。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該第二光吸收層之能階(energy gap)小於該第一光吸收層之能階。
- 如申請專利範圍第1項所述之太陽能電池之製 法，其中該硫化鋅層中尚包括氧(ZnS1-xOx,x=0-1)。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該第二基板包括高分子基板、金屬基板或上述之組合。
- 如申請專利範圍第15項所述之太陽能電池之製法，其中該高分子基板包括聚亞醯胺(polyimide,PI)、聚對苯二甲酸乙二酯(poly(ethylene terephthalate),PET)、聚碳酸酯(poly carbonate,PC)、聚甲基丙烯酸甲酯(poly(methyl methacrylate),PMMA)或上述之組合。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中該透明導電層(TCO)包括氧化銦錫(ITO)、氧化銦(In2O3)、氧化錫(SnO2)、氧化鋅(ZnO)、氧化鎘(CdO)、摻鋁之氧化鋅(AZO)、氧化銦鋅(IZO)或上述之組合。
- 如申請專利範圍第1項所述之太陽能電池之製法，其中形成該第二基板於該第二光吸收層之上，包括以下步驟：塗佈一導電膠於該第二光吸收層之上；以及形成於第二基板於該導電膠之上。
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