TW201203583A - CIGS solar cell and the method for making the same - Google Patents
CIGS solar cell and the method for making the same Download PDFInfo
- Publication number
- TW201203583A TW201203583A TW099121861A TW99121861A TW201203583A TW 201203583 A TW201203583 A TW 201203583A TW 099121861 A TW099121861 A TW 099121861A TW 99121861 A TW99121861 A TW 99121861A TW 201203583 A TW201203583 A TW 201203583A
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- Prior art keywords
- solar cell
- cigs solar
- semiconductor layer
- type semiconductor
- array
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- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000004065 semiconductor Substances 0.000 claims abstract description 77
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- 229910052802 copper Inorganic materials 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 230000003213 activating effect Effects 0.000 claims 2
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims 2
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- 238000000277 atomic layer chemical vapour deposition Methods 0.000 claims 1
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- 229910000831 Steel Inorganic materials 0.000 description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- YNLHHZNOLUDEKQ-UHFFFAOYSA-N copper;selanylidenegallium Chemical compound [Cu].[Se]=[Ga] YNLHHZNOLUDEKQ-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- UNRNJMFGIMDYKL-UHFFFAOYSA-N aluminum copper oxygen(2-) Chemical compound [O-2].[Al+3].[Cu+2] UNRNJMFGIMDYKL-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- NMHFBDQVKIZULJ-UHFFFAOYSA-N selanylideneindium Chemical compound [In]=[Se] NMHFBDQVKIZULJ-UHFFFAOYSA-N 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- 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
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- 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
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- 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
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- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
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- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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- 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
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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
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- Engineering & Computer Science (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
Description
201203583 六、發明說明: 【發明所屬之技術領域】 本發明是有關於一種電池及其製造方法’且特別是有 關於一種太陽能電池及其製造方法。 【先前技術】 太陽能為一種環保的再生性能源,可轉換為其他形式 之能量如熱及電,且太陽能電池應用的範圍非常廣,大到 發電系統,小到消費性電子產品,但以太陽能作為在經濟 上具有競爭力的再生性能源,仍受到太陽能電池將光能轉 換為電能時之低效率所阻礙,因此,有效地提高太陽能電 池的產電效率,並降低太陽能電池的生產成本,已成為太 陽能電池的發展目標。 有關CIGS太陽能電池之先前技術如美國專利號碼 第 7018858 所揭露之 Light absorbing layer producing method專利,該專利用一種沉積前驅物層之雙靶式濺鍍法 〉儿積設備,採取一種雙把直立面對面設置進行共錢鍵 (co-sputter)的鍍膜方式,但因該方式將基板設置於靶材下 方,沉積過程若有污染顆粒產生,則容易發生該污染顆粒 順勢沉降至基板的缺點。 又如台灣專利號瑪第200917508號所揭露之光伏打接 收器專利,該技術之缺點在於太陽能接收器及光入射點之 間之焦距或點極大’故需大量空間及體積以安裝此接收 器’又,該製造方法於匯集陽光時所產生的熱度,必須另 外設置一冷卻系統來維持低於一特定溫度,否則所產生之 201203583 熱能將不利於太陽能電池的光轉電效率。 有鑑於此,得知CIGS太陽能電池仍未_完善,本發 明之目的係提供一高效率之CIGS太陽能電池結構與製作 方法。 【發明内容】 通常太陽能電池是由p型半導體層、本質半導體層 (intrinsic semiconductor layer )以及η型半導體層堆聂而 • 成,且Ρ型半導體層、本質半導體層以及η型半導體層皆 為非晶矽(amorphous silicon )材料。而以非晶石夕為材料的 半導體層往往存在著光吸收效果不佳的缺點,進而導致產 電效率不佳,為改善此問題,常利用增加本質半導體層厚 度的方式來增加光吸收效果’但同時也增加太陽能電池的 整體厚度與生產成本。有鑑於此,本發明在不增加本質半 導體層厚度與整體體積的條件之下,利用結構與形成方式 上的研發,藉由增加光吸收面積而提升光吸收量,也因^ Φ 增加光電轉換效率來提高產電效率,並可大幅降低生產成 本而提高太陽光能之經濟價值。 緣以達成上述目的之一,本發明在提供一種太陽能電 池結構,可使光電轉換效率增加,該發明之主要結構包含 玻璃基板、光吸收表面與光電轉換結構,其中,該玻璃1 - 板之至少一表面具有多個陣列式凹凸部,且該陣^式凹^ 部之最頂端延伸至最底端之距離為一預定深度;該光吸收 表面包含陣列式凹凸部最頂端所形成之表面、陣列式凹凸 部最頂端延伸至最底端所形成之表面、以及陣列式凹凸部 201203583 最底端基板除陣列式凹凸部所形成表面之集合;該光電轉 換結構由η型半導體層、p型半導體層與i型半導體層所 組成。其中,該η型半導體層為一 CIGS類化合物且位於
該光吸收表面之上方,該ρ型半導體層位於該η型半導體 層之上方且為一氧化物’且該i型半導體層位於該η型半 導體層與該ρ型半導體層間並為一氧化物,而該光電轉換 結構所形成之n-i-p結構則可促進各該層表面之接合效 果’藉以產生良好的界面接觸’進一步減少界面孔洞的形 成,因此增加量子效率,而能提高光電轉換效率。 再者’本發明之另一目的是在提供一種CIGS太陽能 電池之製造方法’由在玻璃基板表面產生之陣列式凹凸 部,該陣列式凹凸部之外形為幾何圖形柱體,例如圓柱體 或多邊形柱體等,藉以增加整體光吸收表面面積而增加光 吸收量’因此提高太陽能電池的產電效率。 又,本發明為一種CIGS太陽能電池之製造方法,該 方法包含下列步驟:提供一玻璃基板,塗佈一預定形狀之 ㈣膜於該玻縣板之狀位置處,並㈣璃基板於 #,劑中’於—預定時間後取出該玻璃基板清洗且去除 該膜’使該玻縣板之預定位置處形成多個預定形狀 ^列式凹凸部’纟中,該些陣列式凹凸部之最頂端所形 面1¾凹凸部之最頂端延伸至最底端所形成表面、以 人部^最底端基板除陣列式凹凸部所形成表面之集 穑霜y該光吸收表面;再者,依序於減吸收表面上沉 電於該下電極上沉積覆蓋-中間層,於該 曰,儿積覆蓋-光電轉換結構,其中,該光電轉換結 201203583 構包含有η型半導體層、p型半導體層與i型半導體層;最 後,於該光電轉換結構上沉積覆蓋一上電極’並於該上電 極上形成一導線,以及於該導線上沉積覆蓋一抗反射層。 綜上所述,本發明於結構與形成方式上的改變,可以 增加太陽能電池之光吸收量、光電轉換效率與其產電效率。 【實施方式】 為能更清楚地說明本創作之CIGS太陽能電池結構, • 茲舉較佳實施例並配合圖示詳細說明如後。 請參照第1A、1B、2A與2B圖,為本發明之一較佳 實施例,其分別繪示本發明CIGS太陽能電池之剖面示意 圖、局部剖面示意圖、本發明之玻璃基板俯視圖與第2A圖 玻場基板之側視圖。其中: 該CIGS太陽能電池1〇〇包含玻璃基板11〇、光吸收 表面120與光電轉換結構130。該玻璃基板11〇之至少一 表面包含多個陣列式凹凸部112,各該陣列式凹凸部112 之最頂端延伸至最底端之距離為一預定深度h,於本實施 ^中,該縣深度hh釐米以上,其中又以米為最 =又各該陣列式凹凸部之間具有相同之預定間距w與寬 其中間距以0.625釐米為最佳;且各該陣列式凹凸部 卜形為圓柱體之相同幾何圖案柱體,換言之,每一個陣 歹J式凹凸部112的外型與大小 板no之表面。 彳n且均佈於該玻璃基 另外,該光吸收表面12〇包含夂钫睡m 端所形成表面122、各該陣列式凹凸部: 201203583 最底端所形成表面124,以及各該陣列式凹凸部ii2最底 端基板除凹凸部112所形成表面126之集合。综上所述, 本發明之太陽能電池可藉由該陣列式凹凸部112之形成而 增加該玻璃基板之光吸收表面之表面積。 其中:光電轉換結構130由η型半導體層132、p型半 ' 導體層134與i型半導體層136所組成。該η型半導體層 132位於光吸收表面120上方,且該η型半導體層132為 一 CIGS類化合物,該CIGS類化合物之化學式為 φ Sn:Cu(Ini-xGax)Se2,於本實施例中,該化學式X值為 0.18〜0.3 ;又,該CIGS類化合物包含第一前驅化合物與第 二前驅化合物;其中該第一前驅化合物包含銅(Cu)、鎵 (Ga)與硒(Se)等元素’例如銅鎵硒合金,且該第二前 驅化合物包含姻(In)與碼(Se)等元素,例如铜砸合金。 再者,該光電轉換結構130之該p型半導體層134位 於該η型半導體層132之上方,且該p型半導體層134為 一氧化物’例如含銅與鋁之氧化物;又該光電轉換結構13〇 φ 之該.丨型半導體層136則位於η型半導體層132與ρ型半 導體層134間,且為一氧化物。 於本實施例中,該CIGS類化合物之厚度為15〇〇〜2500 奈米,能階為1.17eV,該i型半導體層為氧化亞銅(cU2〇), 其能階為2.1 eV,其厚度為5〜5〇奈米,該p型半導體層 134為氧化銅鋁(CuA1〇2),其厚度為3〇〜12〇夺米,苴能 •階,3,5 eV,使得太陽能所產生之π波長可依其波;高 低各自被η半導體層、i半導體層、ρ半導體層所吸收。 由於該Ρ型半導體層134與該η型半導體層132的能 201203583 階差異大,因此’利用i型半導體層136的氧化物使得p 型半導體層134 # η型半導體層132具有較好的接合界 面,並在界面上有較低之載子復合機率產生,進而提高量 子效率。 _ 上述實施方式乃藉由於玻璃基板上設置陣列式凹凸 . 部,在不增加CIGS太陽能電池的整體體積下,達到增加 光吸收表面積的目的。(表一)係列出比較例與多個實施 例,與其各自所增加的總表面積比例,於該表列出當玻璃 •基板尺寸為10〇平方公分時,在具有不同的陣列式凹凸部 的數目、寬度以及兩兩陣列式凹凸部間的間距條件下所 產生的總表面積與總表面積增加比例之計算結果;據此得 知,在相同尺寸之玻璃基板上,隨著陣列式凹凸部的數目 增加、寬度減少、以及排列越密集,則所增加的總表面積 越多,亦即表示此種態樣可增加CIGS太陽能電池的光吸 收表面積。 (表一) 陣列式凹凸部 寬度 間距 古riE 數量 總表面積 總表面積增加 (公分) (公分) --- (公分) (個) (平方公分) 比例 比較例1 0 0 0 0 100 實施例1 0.5 _ 0.5 0.2 64 120.1 20% 實施例2 0.25 0.25 0.2 256 140.2 40% 實施例3 0.125 0.125 0.2 1024 180.4 80% ----- 201203583 實施例4 0.0625 0.0625 0.2 4096 260,8 160% 再請參照第3圖為本發明CIGS太陽能電池之另一實 施方式,係同於第1A圖中所標示範圍Μ之剖面結構示意 圖。該CIGS太陽能電池200包含有玻璃基板210、光吸收 • 表面220、下電極230、中間層240、光電轉換結構250、 上電極260、導線270與抗反射層280等結構。其中,該 玻璃基板210、該光吸收表面220與該光電轉換纟士構250 φ 之結構皆與前述之實施方式相同’下列敘述僅針對不同之 處進行說明。
該下電極230位於該玻璃基板210且為該光吸收表 面220之上,且該下電極230可為一金屬材質或為一非金 屬氧化物。若該下電極230係為一金屬材質,: (Ti)、鉬(Mo)、鈕(Ta)或上述任意合金, (Mo)為優選材質;又,該中間層240位於光 250與下電極230之間,其材質包含錫(Sn) 或鉛(Pb)等元素,其中以錫(Sn)為優選材 其中又以鉬 電轉換結構 、碲(Te) 質。
π本貫施例T π」〜川奈米。 中’該中間層240位於該下電極230上,且 入bj ,, 卜電極230 金屬材質,則該基板中的鈉(Na)元素會藉由熱擴散穿 該下電極,以致於該下電極230與該光電轉換結、構 具有較好的介面接觸效果,並減少界面孔洞的形成。 另外,第4圖為本發明CIGS太陽能電池之又一 方式,係同於第1A圖中所標示範圍μ之剖面結構示 圖。請參照第4圖所示,若該下電極23〇係 … : 、,一非金屬 201203583 化物,例如氧化鋼錫(IT0),因氧化物具有阻礙納(Na)元素 擴散的效果,所以必須增設一納化合物層242於該中間層 240與該光電轉換結構25〇之間,例如氟化鈉(NaF),藉由 鈉源之補充以輔助吸收| CIGS的成長,糾之太陽能電 池具備吸收層前後皆可透光的特性,可增進吸收層的陽光 - 吸收效益。 且該上電極260位於該光電轉換結構25〇之上方,於 本實施例中,該上電極260之厚度為4〇〇〜12〇〇奈米,材質 籲係為銘摻雜氧化鋅(AZ0,Zn〇:A1);該導線27❹則位於上 電極260之上方;該抗反射層28〇則位於導線27〇之上方, 於本實施例中,該抗反射層280之厚度為8〇〜15〇奈米,材 質為氮化矽(Si3N4:H)。 再者,為了能清楚地說明本創作之CIGS太陽能電池 之製造方法,茲舉較佳實施例並配合圖示詳細說明如後。 請參照第5圖係為一種CIGS太陽能電池製造方法之 流程示思圖。該太陽能電池製造方法之步驟包含提供 φ 玻璃基板(步驟31 〇 )、形成陣列式凹凸部(步驟32〇 )、形 成下電極(步驟330 )、形成中間層(步驟340 )、形成光電 轉換結構(步驟350)、形成上電極(步驟36〇)、形成導線 (步驟370)與形成抗反射層(步驟38〇)。 另請加參照第6圖係為該CIGS太陽能電池製造方法 • 中,形成陣列式凹凸部(步驟320)之流程400示意圖。 首先’於一玻璃基板410表面之預定位置處塗佈保護膜420 為一預定形狀,於本實施例中該保護膜42〇係為石蠟;再 將該玻璃基板410浸泡於一蝕刻劑例如氫氟酸水溶液中一 201203583
預定時間進行酸蝕,藉以於該玻璃基板410之表面形成多 個陣列式凹凸部430 ;然而隨著浸泡之時間越長,所形成 的陣列式凹凸部之最頂端延伸至最底端距離的深度越大; 接著取出該玻璃基板410清洗並藉由例如曱醇加以去除該 保護膜420,即可產生一具有多個陣列式凹凸部430之玻 璃基板410,此時該陣列式凹凸部430之最頂端所形成表 面432、最頂端延伸至最底端所形成之表面434與最底端 基板除陣列式凹凸部430所形成表面436之集合,即為本 發明之光吸收表面440。 又於該光吸收表面440之輪廓向外延伸方向沉積覆蓋 形成一下電極(步驟330),其中該下電極之材質可選自金 屬材質或非金屬氧化物二者之一;又於該下電極上沉積覆 蓋一中間層(步驟34〇),其中,該中間層可選自錫、碲或 鉛等兀素:於此實施例中,其厚度設定為5〜50奈米,若 該:電極係為一非金屬氧化物,貝需增設-鈉化合物層於 1二二該光電轉換結構之間;接著沉積覆蓋一光電轉 二=驟350)於該中間層之上,其中,該光電轉換 人^成n型半導體層、丨型半導體層與ρ型半導體層 該η型半導體層之形成步驟係包含於中間層上形 藉IS以二前驅物膜’並於似族元素之氣氛下’ I ^ .式形成一 CIGS類化合物,該CIGS類化合物 :式為Sn:Cu(Ini你抑2,其中χ值為〇」8〜〇 3 ’此 時使該中間層擴散摻入該⑽類化合物;於此 歹1 ,該第一前驅物膜包含銅、鎵與硒元素,該第二 [S3' 12 201203583 前驅物膜包含銦與硒元素,且該η型半導體層之厚度為 1500〜2500奈米。 又,該第一與第二前驅物膜之形成方法可為電鍍、無 電電鍵、原子層沉積、化學氣相沉積、金屬一有機化學氣 相沉積或物理氣相沉積,其中以物理氣象沉積為優選;而 前述熱處理步驟係利用活化一激發源將VIA族元素蒸氣活 性化,而該活化激發源之方式可為電子束、離子束、電漿 共振裝置或熱裂解,其中以熱裂解搭配電漿共振裝置為優 選,此時熱處理之實際溫度為380 °C〜600 °C。 另外,該i型半導體層之形成方式為以原子層沈積法 (Atomic layer deposition,ALD )於 η型半導體層上沈積 銅膜,再通入氧氣以180°C進行熱氧化處理,而形成氧化 亞銅層;於本實施例中,所形成之氧化亞銅層厚度為5〜50 奈米;該p型半導體層則以濺鍍法沈積於i型半導體層上, 該p型半導體層包含銅與鋁之氧化物。 承上依序於該光電轉換結構(步驟350)上沉積覆蓋 該上電極(步驟360)、於該上電極上形成該導線(步驟 370)、以及於該導線上沉積覆蓋該抗反射層(步驟380)。 於本實施例中,該上電極與該抗反射層皆利用濺鍍法沈積。 再者,依(表一)之實施例4所示簡述如下:將玻璃基 板表面塗佈圓形圖樣之石臘,該圓形直徑為0.0625公分, 兩圓形間的間隔為0.0625公分;待石臘硬固,將玻璃基板 整個浸入氫氟酸水溶液中進行蝕刻,約30 - 40分鐘後,於 玻璃基板表面形成2公釐高之圓柱凸出物,此時玻璃基板 之表面積增加約160%。 m 13 201203583 接著’進行元件製程。於玻璃基板之具有圓柱凸出物 表面以濺鍵法沉積1 y m之背電極。隨後分別沉積錫薄膜 (中間層)、銅鎵硒膜(CuGaSe)與銦硒(InSe)膜於背電 極表面’並對玻璃基板進行熱處理°該熱處理利用兩階段 • 溫度來使錫薄膜、銅鎵硒膜與銦硒膜交互擴散與化合反 • 應;第一階段通入高溫活化後的硒蒸氣以進行硒化,其溫 度約為400°C。第二階段則為同時通入高溫活化後的硒蒸 氣與硫蒸氣,進行硒化與硫化溫度之約為580°c ;最後形 φ 成表面硫化的銅銦鎵硒層,厚度約2000奈米;此時
Cu/(In+Ga)值為 0.85〜0.90,Ga/(In+Ga)則約為 0.25。 又利用原子層沉積法於180°C下沉積銅膜;於180°C下 通入氧氣進行熱氧化處理,使銅銦鎵硒層上形成厚度約3〇 奈米的氧化亞鋼薄膜;此時CuA102與AZO薄膜均以濺鍍 法沉積製作。 待元件製作完成後,以l〇〇mW/cm2(AM1.5)之光源進 行電性量測。請參照第7圖所示為上述實施例之電性量測 φ 結果圖。該實施例之開路電壓(Voc)為0.47 V,填充因子 (Fill Factor,FT)為64.54%,其太陽能電池效率為10.52 %。 由上述本發明實施方式可知,應用本發明具有下列優 點: 第一 ’利用蝕刻技術使得太陽能電池表面具有陣列式 凹凸部’增大整體太陽能電池之光吸收表面,以增加光吸 收量’進而提高太陽能電池的產電效率。 第二’於下電極與光電轉換結構間沈積中間層,使得 201203583 下電極表面濕潤,因而使下電極與光電轉換結構間具有較 好的接合效果,減少下電極與光電轉換結構的界面孔洞。 第三,i型半導體層的氧化物使得p型半導體層與η 型半導體層具有較好的接合界面,進而提高量子效率。 • 雖然本發明已以實施方式揭露如上,然其並非用以限 - 定本發明,任何熟習此技藝者,在不脫離本發明之精神和 範圍内,當可作各種之更動與潤飾,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。 【圖式簡單說明】 為讓本發明之上述和其他目的、特徵、優點與實施例 能更明顯易懂,所附圖式之說明如下: 第1Α圖係繪示本發明一較佳實施例的一種CIGS太陽 能電池之剖面示意圖。 第1Β圖係繪示第1Α圖之CIGS太陽能電池中,局部 剖面示意圖。 • 第2Α圖係繪示第1Α圖之CIGS太陽能電池中,玻璃 基板之俯視圖。 第2B圖係繪示第2A圖之玻璃基板的側視圖。 第3圖為本發明CIGS太陽能電池之另一實施方式, 係同於第1A圖中所標示範圍Μ之剖面結構示意圖。
• 第4圖為繪示本發明又一實施方式依照之一種CIGS • 太陽能電池,同於第1A圖中所標示範圍Μ之剖面結構示 意圖。 L S] 15 201203583 第5圖係為一種CIGS太陽能電池製造方法之流程示 意圖。 第6圖係繪示第5圖之CIGS太陽能電池製造方法中, 形成陣列式凹凸部之流程示意圖。 • 第7圖係繪示上述實施例之電性量測結果圖。 【主要元件符號說明】 100 : CIGS太陽能電池 φ 112 :陣列式凹凸部 122 :表面 126 :表面 132 : η型半導體層 136 : i型半導體層 210 :玻璃基板 230 :下電極 242 :納化合物層 φ 260 :上電極 280 :抗反射層 310 - 380 :步驟 410 :玻璃基板 430 :陣列式凹凸部 434 :側面 434 440 :光吸收表面 h:預定深度 w :預定間距 110 :玻璃基板 120 :光吸收表面 124 :側面 130 :光電轉換結構 134 : p型半導體層 200 : CIGS太陽能電池 220 :光吸收表面 240 :中間層 250 :光電轉換結構 270 :導線 300 :太陽能電池製造方法 400 :流程 420 :保護膜 432 :最頂端表面 436 :最底端表面 d :寬度 Μ :範圍
Claims (1)
- 201203583 七、申請專利範圍: 1. 一種CIGS太陽能電池,包含: 一玻璃基板,該玻璃基板之至少一表面包含複數個陣 . 列式凹凸部,該些陣列式凹凸部之最頂端延伸至最底端之 _ 距離為一預定深度; 一光吸收表面,包含該些陣列式凹凸部最頂端形成表 面、該些陣列式凹凸部由最頂端延伸至最底端所形成表面 與該些陣列式凹凸部最底端基板除陣列式凹凸部所形成表 $面之集合;以及 一光電轉換結構,該光電轉換結構由下列各層所組成: 一 η型半導體層,位於該光吸收表面上方,且η型 半導體層為一 CIGS類化合物; 一 ρ型半導體層,位於該η型半導體層上方,且該 Ρ型半導體層為一氧化物;以及 一 i型半導體層,位於該η型半導體層與該ρ型半 | 導體層間,且該i型半導體層為一氧化物。 2. 如請求項1所述之CIGS太陽能電池,更包含: 一下電極,位於該玻璃基板與該光電轉換結構之間, 且該下電極為一金屬。 • 3.如請求項2所述之CIGS太陽能電池,其中該金屬係 選自鈦、鉬、组或由上述任意合金所組成之組合。 m 17 201203583 4. 如請求項1所述之CIGS太陽能電池,更包含: 一下電極,位該玻璃基板與該光電轉換結構之間,且 該下電極為一非金屬氧化物;以及 一鈉化合物層,位於該下電極與該光電轉換結構之間。 5. 如請求項1所述之CIGS太陽能電池,更包含: 一上電極,位於該下電極上方。 6. 如請求項1所述之CIGS太陽能電池,更包含: 一中間層,位於該光電轉換結構與該下電極之間。 7. 如請求項6所述之CIGS太陽能電池,其中該中間層 材質為錫、碲或鉛。 8. 如請求項5所述之CIGS太陽能電池,更包含: 一導線,位於該上電極之上方。 9. 如請求項8所述之CIGS太陽能電池,更包含: 一抗反射層,位於該導線之上方。 10. 如請求項1所述之CIGS太陽能電池,其中該預定 深度為1釐米以上。 11. 如請求項1所述之CIGS太陽能電池,其中該CIGS 18 201203583 類化合物包含一第一前驅化合物與一第二前驅化合物。 12. 如請求項11所述之CIGS太陽能電池,其中該第一 前驅化合物包含銅、鎵與硒。 13. 如請求項11所述之CIGS太陽能電池,其中該第二 前驅化合物包含姻與砸。 14. 如請求項1所述之CIGS太陽能電池,其中該 CIGS類化合物之化學式為SniCi^InkGaJSey其中X值為 0.18 - 0.3 。 15. 如請求項1所述之CIGS太陽能電池,其中該p 型半導體層包含銅與鋁之氧化物。 16. 如請求項1所述之CIGS太陽能電池,其中該些 ® 陣列式凹凸部具有相同之一預定間距。 17. 如請求項16所述之CIGS太陽能電池,其中該預 定間距為0.625釐米。 18. 如請求項1所述之CIGS太陽能電池,其中該些陣 列式凹凸部之外形為幾何圖形柱體。 19 201203583 19. 如請求項18所述之CIGS太陽能電池,其中該些 陣列式凹凸部之外形為圓形柱體。 20. —種CIGS太陽能電池之製造方法,包含: ' 提供一玻璃基板; • 形成複數個陣列式凹凸部於該玻璃基板之至少一表 面,其中,該些陣列式凹凸部最頂端形成表面、由最頂端 延伸至最底端所形成表面與最底端基板除陣列式凹凸部所 φ 形成表面的集合為一光吸收表面; 沉積覆蓋一下電極於該光吸收表面上; 沉積覆蓋一中間層於該下電極上; 沉積覆蓋一光電轉換結構於該中間層上,該光電轉換 結構包含一 η型半導體層、一 p型半導體層與一 i型半導 體層; 沉積覆蓋一上電極於該光電轉換結構上; 形成一導線於該上電極上;以及 • 沉積覆蓋一抗反射層於該導線上。 21. 如請求項20所述之CIGS太陽能電池之製造方法, 其中該些陣列式凹凸部之形成步驟包含: 塗佈一保護膜於該玻璃基板之一預定位置處; 浸泡該玻璃基板於一蝕刻劑中,於一預定時間後取出 « 並清洗;以及 去除該保護膜。 m 20 201203583 22.如請求項20所述之CIGS太陽能電池之製造方法, 其中該些陣列式凹凸部之最頂端延伸至最底端方向之距離 為1釐米以上。 - 23.如請求項20所述之CIGS太陽能電池之製造方 法,其中該下電極為一金屬。 φ 24.如請求項23所述之CIGS太陽能電池之製造方法, 其中該金屬係選自鈦、鉬、组或其上述任意合金。 25. 如請求項20所述之CIGS太陽能電池之製造方法, 其中該下電極為一非金屬氧化物;以及更形成一鈉化合物 層於該下電極與該光電轉換結構之間。 26. 如請求項20所述之CIGS太陽能電池之製造方法, • 其中該中間層為錫、碲或鉛。 27.如請求項20所述之CIGS太陽能電池之製造方法, 其中該η型半導體層係在VIA族元素之氣氛下,將一第一 前驅物膜以及一第二前驅物膜經熱處理方式後形成。 28.如請求項27所述之CIGS太陽能電池之製造方法, 其中該第一前驅物膜包含銅、鎵與硒。 21 201203583 29. 如請求項27所述之CIGS太陽能電池之製造方法, 其中該第二前驅物膜包含銦與硒。 30. 如請求項27所述之CIGS太陽能電池之製造方法, 其中形成該第一與該第二前驅物膜之方法選自電鍍、無電 電鍵、原子層沉積、化學氣相沉積、金屬_有機化學氣相 沉積或物理氣相沉積。 31. 如請求項27所述之CIGS太陽能電池之製造方法, 其中該熱處理步驟包含: 活化一激發源以將VIA族元素之蒸氣活性化,活化激 發源之方式為電子束、離子束、電漿共振裝置或熱裂解。 32. 如請求項27所述之CIGS太陽能電池之製造方法, 其中該熱處理之溫度為380 °C - 600 °C。 33. 如請求項20所述之CIGS太陽能電池之製造方法, 其中該η型半導體層包含SmCi^InkGadSes,X為0.18 -0.3。 34.如請求項20所述之CIGS太陽能電池之製造方法, 其中該p型半導體層包含銅與鋁之氧化物。 22 201203583 35. 如請求項20所述之CIGS太陽能電池之製造方法, 其中該些陣列式凹凸部間具有相同之一預定間距。 36. 如請求項20所述之CIGS太陽能電池之製造方法, 其中該些陣列式凹凸部之外形為幾何圖形柱體。m 23
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