TWI548102B - 形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法 - Google Patents
形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法 Download PDFInfo
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- TWI548102B TWI548102B TW103124862A TW103124862A TWI548102B TW I548102 B TWI548102 B TW I548102B TW 103124862 A TW103124862 A TW 103124862A TW 103124862 A TW103124862 A TW 103124862A TW I548102 B TWI548102 B TW I548102B
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Description
本發明是有關於一種太陽電池元件的形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法,更詳細而言,本發明是有關於一種可減少作為半導體基板的矽基板的內應力、抑制結晶粒界(crystal grain boundary)的損壞、抑制結晶缺陷(crystal defects)的增長及抑制翹曲的p型擴散層形成技術。
對先前的矽太陽電池元件的製造步驟進行說明。
首先,為了促進光學侷限效應(confinement effect)來謀求高效率化,準備形成有紋理構造(texture)的p型矽基板,繼而於氧氯化磷(POCl3)、氮氣、氧氣的混合氣體環境下以800℃~900℃進行幾十分鐘的處理,從而於基板上同樣地形成n型擴散層。於該先前的方法中,因使用混合氣體進行磷的擴散,故不僅於表面形成n型擴散層,而且於側面、背面亦形成n型擴散層。由於這些原因,需要側蝕
刻(side etching)來移除側面的n型擴散層。另外,需將背面的n型擴散層轉換成p+型擴散層,因此於背面印刷鋁膏,然後對其進行煅燒(燒結),以使n型擴散層轉變成p+型擴散層並同時獲得歐姆接觸。
但是,由鋁膏所形成的鋁層的導電率低,為了降低薄片電阻(sheet resistance),通常形成於整個背面的鋁層於煅燒後必需具有10μm~20μm左右的厚度。進而,若如上述般形成較厚的鋁層,則由於矽的熱膨脹係數與鋁的熱膨脹係數相差較大,因此這種差別導致於煅燒及冷卻的過程中在矽基板中產生較大的內應力,而促進了結晶粒界的損壞、結晶缺陷的增長及翹曲。
為了解決該問題,存在減少膏組成物的塗佈量,使背面電極層變薄的方法。但是,若減少膏組成物的塗佈量,則自p型矽半導體基板的表面擴散至內部的鋁的量變得不充分。其結果,無法達成所期望的背面電場(Back Surface Field,BSF)效果(生成載子(carrier)的收集效率(collection efficiency)因p+型擴散層的存在而提高的效果),因此產生太陽電池的特性下降的問題。
因此,例如於日本專利特開2003-223813號公報中提出有一種膏組成物,其包含鋁粉末,有機媒劑(organic vehicle),以及熱膨脹係數小於鋁且熔融溫度、軟化溫度及分解溫度中的任一者高於鋁的熔點的無機化合物粉末。
但是,當使用日本專利特開2003-223813號公報中所記載的膏組成物時,亦存在無法充分地抑制翹曲的情況。
本發明是鑒於以上的先前的問題點而完成的發明,其課題在於提供一種於使用矽基板的太陽電池元件的製造步驟中,可抑制矽基板中的內應力、基板的翹曲的產生,並形成p型擴散層,且於具有藉此所獲得的p型擴散層的基板中載子的生命週期(lifetime)不會大幅下降的形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法。
解決上述課題的方法如下。
<1>一種形成p型擴散層的組成物,其包括:含有受體元素(acceptor element)且生命週期殺手元素(lifetime killer)的總量為1000ppm以下的玻璃粉末、以及分散介質。
<2>如上述<1>所述之形成p型擴散層的組成物,其中上述受體元素是選自B(硼)、Al(鋁)及Ga(鎵)中的至少一種。
<3>如上述<1>或<2>所述之形成p型擴散層的組成物,其中含有上述受體元素的玻璃粉末包括:選自B2O3、Al2O3及Ga2O3中的至少一種含有受體元素的物質,以及選自SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、SnO、ZrO2、及MoO3中的至少一種玻璃成分物質。
<4>如<1>~<3>中任一項所述之形成p型擴散層的組成物,其中上述生命週期殺手元素是選自Fe(鐵)、Cu(銅)、Ni(鎳)、Mn(錳)、Cr(鉻)、W(鎢)、及Au(金)中的至少一種。
<5>一種p型擴散層的製造方法,其包括:塗佈如上述
<1>~<4>中任一項所述之形成p型擴散層的組成物的步驟、以及實施熱擴散處理的步驟。
<6>一種太陽電池元件的製造方法,其包括:於半導體基板上塗佈如上述<1>~<4>中任一項所述之形成p型擴散層的組成物的步驟、實施熱擴散處理來形成p型擴散層的步驟、以及於所形成的上述p型擴散層上形成電極的步驟。
根據本發明,於使用矽基板的太陽電池元件的製造步驟中,可抑制矽基板中的內應力、基板的翹曲,並形成p型擴散層,且在已形成p型擴散層的基板中,載子的生命週期不會大幅下降。
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂,下文特舉較佳實施例,並配合所附圖式,作詳細說明如下。
首先,對本發明的形成p型擴散層的組成物進行說明,其次對使用形成p型擴散層的組成物的p型擴散層及太陽電池元件的製造方法進行說明。
再者,於本說明書中,「步驟(process)」這一用語不僅是指獨立的步驟,亦包含在無法與其他步驟明確地加以區分的情況下,
若該步驟能達成所預期的作用,則亦包含於本用語中。
另外,於本說明書中,「~」表示分別包括其前後所記載的數值作為最小值及最大值的範圍。
進而,於本說明書中,當論及組成物中的各成分的量時,在組成物中存在多個相當於各成分的物質的情況下,只要事先無特別說明,則表示組成物中所存在的該多個物質的合計量。
本發明的形成p型擴散層的組成物包括至少含有受體元素且生命週期殺手元素的總量為1000ppm以下的玻璃粉末(以下,有時僅稱為「玻璃粉末」)、以及分散介質,進而考慮塗佈性等,亦可視需要含有其他添加劑。
此處,所謂形成p型擴散層的組成物,是指含有受體元素,且可藉由例如塗佈於矽基板上後進行熱擴散處理(煅燒/燒結)而使該受體元素熱擴散來形成p型擴散層的材料。藉由使用本發明的形成p型擴散層的組成物,可分離p+型擴散層的形成步驟與歐姆接觸的形成步驟,從而拓展了對用於形成歐姆接觸的電極材料的選擇,並且還拓展了對電極構造的選擇。例如,若將銀等低電阻材料用於電極時,能夠以較薄的膜厚達成低電阻。另外,電極亦無需形成於整個面上,亦可如梳型等形狀般部分地形成梳型電極。藉由如以上般形成薄膜或梳型形狀等部分形狀,可一面抑制矽基板中的內部應力、基板的翹曲的產生,一面形成p型擴散層。
因此,若應用本發明的形成p型擴散層的組成物,則抑制先前廣泛採用的方法中所產生於基板中的內應力及基板的翹曲的產
生,前述之先前廣泛採用的方法為:印刷鋁膏,然後對其進行煅燒,與使n型擴散層變成p+型擴散層的同時獲得歐姆接觸的方法。
進而,玻璃粉末中的受體成分於煅燒中亦難以揮發(sublimation),因此抑制p型擴散層因揮發氣體的產生而形成至所期望的區域以外的情況。其原因可認為由於受體成分與玻璃粉末中的元素結合、或者被導入至玻璃中,因此難以揮發。
進而,因本發明的形成p型擴散層的組成物中所包含的玻璃粉末中的生命週期殺手元素的總量為1000ppm以下,故形成有p型擴散層的基板中的載子的生命週期不會大幅下降。生命週期殺手元素的詳細情況將後述。
對本發明的含有受體元素的玻璃粉末進行詳細說明。
所謂受體元素,是指藉由摻雜於矽基板中而可形成p型擴散層的元素。受體元素可使用第13族的元素,例如可列舉:B(硼)、Al(鋁)及Ga(鎵)等。
作為用於將受體元素導入至玻璃粉末中的含有受體元素的物質,可列舉B2O3、Al2O3、及Ga2O3,較佳為使用選自B2O3、Al2O3及Ga2O3中的至少一種。
另外,玻璃粉末可視需要調整成分比率,藉此控制熔融溫度、軟化點、玻璃轉移點、化學耐久性等。較佳為進而包含以下所述的成分。
作為玻璃成分物質,可列舉:SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、V2O5、SnO、ZrO2、
MoO3、La2O3、Nb2O5、Ta2O5、Y2O3、TiO2、GeO2、TeO2及Lu2O3等,較佳為使用選自SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、SnO、ZrO2、及MoO3中的至少一種。
作為含有受體元素的玻璃粉末的具體例,可列舉包括上述含有受體元素的物質與上述玻璃成分物質兩者的體系,可列舉:B2O3-SiO2體系(以含有受體元素的物質-玻璃成分物質的順序記載,以下相同)、B2O3-ZnO體系、B2O3-PbO體系、B2O3單獨體系等包含B2O3作為含有受體元素的物質的體系,Al2O3-SiO2體系等包含Al2O3作為含有受體元素的物質的體系,Ga2O3-SiO2體系等包含Ga2O3作為含有受體元素的物質的體系等的玻璃粉末。
另外,亦可為如Al2O3-B2O3體系、Ga2O3-B2O3體系等般,玻璃粉末也可以包含兩種以上的含有受體元素的物質的玻璃粉末。
於上述中例示了包含一種成分的玻璃或包含兩種成分的複合玻璃,但亦可為如B2O3-SiO2-Na2O體系、B2O3-SiO2-CeO2體系等般,包含三種成分以上的物質的玻璃粉末。
使載子(carrier)的生命週期下降的元素(生命週期殺手元素)於玻璃粉末中的總量為1000ppm以下,較佳為500ppm以下,更佳為100ppm以下,進而更佳為50ppm以下。
作為生命週期殺手元素,可列舉:Fe、Cu、Ni、Mn、Cr、W及Au。該些的元素量可藉由感應耦合電漿(Inductively Coupled Plasma,ICP)質量分析裝置、ICP發光分析裝置、原子吸光分析裝置來分析。另外,載子的生命週期可藉由微波光電導衰減法(Microwave
Photoconductivity Decay,μ-PCD法)來測定。
玻璃粉末中的玻璃成分物質的含有比率較理想的是考慮熔融溫度、軟化溫度、玻璃轉移溫度、化學耐久性而適宜設定,一般而言,較佳為0.1質量%以上至95質量%以下,更佳為0.5質量%以上至90質量%以下。
玻璃粉末的軟化溫度就擴散處理時的擴散性、滴液(dripping)的觀點而言,較佳為200℃~1000℃,更佳為300℃~900℃。玻璃粉末的軟化溫度可藉由公知的示差熱分析裝置(Differential Thermal Analyzer,DTA),根據其吸熱波峰來測定。
作為玻璃粉末的形狀,可列舉:大致球狀、扁平狀、塊狀、板狀、及鱗片狀等,就製成形成p型擴散層的組成物時的對於基板的塗佈性或均勻擴散性的觀點而言,較理想的是大致球狀、扁平狀、或板狀。
玻璃粉末的粒徑較理想的是50μm以下。當使用具有50μm以下的粒徑的玻璃粉末時,易於獲得平滑的塗膜。進而,玻璃粉末的粒徑更理想的是10μm以下。再者,下限並無特別限制,但較佳為0.01μm以上。
此處,玻璃的粒徑表示平均粒徑,可藉由雷射散射繞射法(laser scattering diffraction method)粒度分布(particle size distribution)測定裝置等來測定。
含有受體元素的玻璃粉末是藉由以下的程序來製作。
首先,稱量原料並將其填充至坩堝中。坩堝的材質可列舉
鉑、鉑-銠、銥、氧化鋁、石英、碳等,可考慮熔融溫度、環境、與熔融物質的反應性等而適宜選擇。
其次,藉由電爐以對應於玻璃組成的溫度進行加熱而製成熔液。此時,較理想的是以使熔液變得均勻的方式進行攪拌。
繼而,使所獲得的熔液流出至氧化鋯基板或碳基板等上而將熔液玻璃化。
最後,粉碎玻璃而形成粉末狀。粉碎可應用噴射磨機、珠磨機、球磨機等公知的方法。
形成p型擴散層的組成物中的含有受體元素的玻璃粉末的含有比率是考慮塗佈性、受體元素的擴散性等而決定。一般而言,形成p型擴散層的組成物中的玻璃粉末的含有比率較佳為0.1質量%以上至95質量%以下,更佳為1質量%以上至90質量%以下。
其次,對分散介質進行說明。
所謂分散介質,是指於組成物中使上述玻璃粉末分散的介質。具體而言,採用黏合劑或溶劑等作為分散介質。
作為黏合劑,例如可適宜選擇:(甲基)丙烯酸二甲基胺基乙酯聚合物、聚乙烯醇、聚丙烯醯胺類、聚乙烯醯胺類、聚乙烯吡咯啶酮、聚(甲基)丙烯酸類、聚環氧乙烷類、聚磺酸、丙烯醯胺烷基磺酸、纖維素醚類、纖維素衍生物、羧甲基纖維素、羥乙基纖維素、乙基纖維素、明膠、澱粉及澱粉衍生物、海藻酸鈉類(sodium alginate)、三仙膠(xanthan)、瓜爾膠及瓜爾膠衍生物、硬葡聚糖及硬葡聚糖衍生物、黃蓍膠及黃蓍膠衍生物、糊精及糊精衍生物、丙烯酸樹脂、丙烯酸酯
樹脂、丁二烯樹脂、苯乙烯樹脂、及該些的共聚物、以及二氧化矽等。該些可單獨使用一種、或者組合兩種以上來使用。
黏合劑的分子量並無特別限制,較理想的是鑒於作為組成物的所期望的黏度而適宜調整。
作為溶劑,例如可列舉:丙酮、甲基乙基酮、甲基-正丙基酮、甲基-異丙基酮、甲基-正丁基酮、甲基-異丁基酮、甲基-正戊基酮、甲基-正己基酮、二乙基酮、二丙基酮、二-異丁基酮、三甲基壬酮、環己酮、環戊酮、甲基環己酮、2,4-戊二酮、丙酮基丙酮等酮系溶劑;二乙醚、甲基乙基醚、甲基-正丙醚、二-異丙醚、四氫呋喃、甲基四氫呋喃、二噁烷、二甲基二噁烷、乙二醇二甲醚、乙二醇二乙醚、乙二醇二-正丙醚、乙二醇二丁醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、二乙二醇甲基-正丙醚、二乙二醇甲基-正丁醚、二乙二醇二-正丙醚、二乙二醇二-正丁醚、二乙二醇甲基-正己醚、三乙二醇二甲醚、三乙二醇二乙醚、三乙二醇甲基乙基醚、三乙二醇甲基-正丁醚、三乙二醇二-正丁醚、三乙二醇甲基-正己醚、四乙二醇二甲醚、四乙二醇二乙醚、四-二乙二醇甲基乙基醚、四乙二醇甲基-正丁醚、二乙二醇二-正丁醚、四乙二醇甲基-正己醚、四乙二醇二-正丁醚、丙二醇二甲醚、丙二醇二乙醚、丙二醇二-正丙醚、丙二醇二丁醚、二丙二醇二甲醚、二丙二醇二乙醚、二丙二醇甲基乙基醚、二丙二醇甲基-正丁醚、二丙二醇二-正丙醚、二丙二醇二-正丁醚、二丙二醇甲基-正己醚、三丙二醇二甲醚、三丙二醇二乙醚、三丙二醇甲基乙基醚、三丙二醇甲基-正丁醚、三丙二醇二-正丁醚、三丙二醇甲基-正己醚、四丙
二醇二甲醚、四丙二醇二乙醚、四-二丙二醇甲基乙基醚、四丙二醇甲基-正丁醚、二丙二醇二-正丁醚、四丙二醇甲基-正己醚、四丙二醇二-正丁醚等醚系溶劑;乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸第二丁酯、乙酸正戊酯、乙酸第二戊酯、乙酸3-甲氧基丁酯、乙酸甲基戊酯、乙酸2-乙基丁酯、乙酸2-乙基己酯、乙酸2-(2-丁氧基乙氧基)乙酯、乙酸苄酯、乙酸環己酯、乙酸甲基環己酯、乙酸壬酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙酸二乙二醇單甲醚、乙酸二乙二醇單乙醚、乙酸二乙二醇單-正丁醚、乙酸二丙二醇單甲醚、乙酸二丙二醇單乙醚、乙二醇二乙酸酯、乙氧基三甘醇乙酸酯、丙酸乙酯、丙酸正丁酯、丙酸異戊酯、草酸二乙酯、草酸二-正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丁酯、乳酸正戊酯、乙二醇甲醚丙酸酯、乙二醇乙醚丙酸酯、乙二醇甲醚乙酸酯、乙二醇乙醚乙酸酯、二乙二醇甲醚乙酸酯、二乙二醇乙醚乙酸酯、二乙二醇-正丁醚乙酸酯、丙二醇甲醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯、二丙二醇甲醚乙酸酯、二丙二醇乙醚乙酸酯、γ-丁內酯、γ-戊內酯等酯系溶劑;乙腈、N-甲基吡咯酮、N-乙基吡咯酮、N-丙基吡咯酮、N-丁基吡咯酮、N-己基吡咯酮、N-環己基吡咯酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸等非質子性極性溶劑;甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇、正戊醇、異戊醇、2-甲基丁醇、第二戊醇、第三戊醇、3-甲氧基丁醇、正己醇、2-甲基戊醇、第二己醇、2-乙基丁醇、第二庚醇、正辛醇、2-乙基己醇、第二辛醇、正壬醇、正癸醇、第二-十一醇、三甲基壬醇、第二-十四醇、
第二-十七醇、苯酚、環己醇、甲基環己醇、苄醇、乙二醇、1,2-丙二醇、1,3-丁二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇等醇系溶劑;乙二醇甲醚、乙二醇乙醚、乙二醇單苯醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單-正丁醚、二乙二醇單-正己醚、乙氧基三甘醇、四乙二醇單-正丁醚、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇單乙醚、三丙二醇單甲醚等二醇單醚系溶劑;α-萜品烯、α-萜品醇、月桂油烯、別羅勒烯(allo-ocimene)、檸檬烯、雙戊烯、α-蒎烯、β-蒎烯、松脂醇(terpineol)、香旱芹酮、羅勒烯、水芹烯等萜烯系溶劑;水等。該些可單獨使用一種、或者組合兩種以上來使用。
當製成形成p型擴散層的組成物時,就對於基板的塗佈性的觀點而言,可列舉α-萜品醇、二乙二醇單-正丁醚、乙酸2-(2-丁氧基乙氧基)乙酯作為較佳的溶劑。
形成p型擴散層的組成物中的分散介質的含有比率是考慮塗佈性、受體濃度而決定。
考慮到塗佈性,形成p型擴散層的組成物的黏度較佳為10mPa.S以上至1000000mPa.S以下,更佳為50mPa.S以上至500000mPa.S以下。
再者,當上述玻璃粉末中的生命週期殺手元素的總量為1000ppm以下時,p型擴散層形成組成物中的生命週期殺手元素的總量大概成為1100ppm以下。因此,上述p型擴散層形成組成物中的生命週期殺手元素的總量較佳為500ppm以下,更佳為100ppm以下。
其次,對本發明的p型擴散層及太陽電池元件的製造方法
進行說明。
首先,對作為p型半導體基板的矽基板賦予鹼性溶液來去除損壞層,並藉由蝕刻而獲得紋理構造。
詳細而言,利用20質量%苛性鈉去除自鑄錠進行切片時所產生的矽表面的損壞層。繼而,利用1質量%苛性鈉與10質量%異丙醇的混合液進行蝕刻,形成紋理構造。太陽電池元件藉由在受光面(表面)側形成紋理構造,而可促進光學侷限效應,謀求高效率化。
其次,於氧氯化磷(POCl3)、氮氣、氧氣的混合氣體環境下以800℃~900℃進行幾十分鐘的處理,從而同樣地形成n型擴散層。此時,於使用氧氯化磷環境的方法中,磷的擴散亦到達側面及背面,n型擴散層不僅形成於表面,而且亦形成於側面、背面。因此,為了去除側面的n型擴散層而實施側蝕。
然後,於p型半導體基板的背面,即與受光面為相反側的面的n型擴散層上塗佈上述形成p型擴散層的組成物,形成了形成p型擴散層的組成物層。於本發明中,塗佈方法並無限制,例如有印刷法、旋塗法、毛刷塗佈、噴霧法、刮刀法、輥塗機法、噴墨法等。
上述形成p型擴散層的組成物的塗佈量並無特別限制。例如,作為玻璃粉末量,可設定為0.01g/m2~100g/m2,較佳為0.1g/m2~10g/m2。
再者,根據形成p型擴散層的組成物的組成,亦可設置用以於塗佈後,使組成物中所含有的溶劑揮發的乾燥步驟。於該情況下,於80℃~300℃左右的溫度下,當使用加熱板時乾燥1分鐘~10分鐘,
當使用乾燥機等時乾燥10分鐘~30分鐘左右。該乾燥條件依存於形成n型擴散層的組成物的溶劑組成,於本發明中並不特別限定於上述條件。
於600℃~1200℃下對塗佈了上述形成p型擴散層的組成物的半導體基板進行熱擴散處理。藉由該熱擴散處理,受體元素向半導體基板中擴散,而形成p+型擴散層。熱擴散處理可應用公知的連續爐、分批式爐等。另外,熱擴散處理時的爐內環境亦可適宜調整成空氣、氧氣、氮氣等。
熱擴散處理時間可對應於形成p型擴散層的組成物中所含有的受體元素的含有率等而適宜選擇。例如,可設定為1分鐘~60分鐘,更佳為5分鐘~30分鐘。
由於在所形成的p+型擴散層的表面形成有玻璃層,故藉由蝕刻而去除該玻璃層。蝕刻可應用浸漬於氫氟酸等酸中的方法、浸漬於苛性鈉等鹼中的方法等公知的方法。
另外,於先前的製造方法中,於背面印刷鋁膏,然後對其進行煅燒,使n型擴散層轉變成p+型擴散層的同時獲得歐姆接觸。但是,由鋁膏所形成的鋁層的導電率低,為了降低薄片電阻,通常形成於整個背面的鋁層於煅燒後必需具有10μm~20μm左右的厚度。進而,若如上述般形成較厚的鋁層,則由於矽的熱膨脹係數與鋁的熱膨脹係數相差較大,因此於煅燒及冷卻的過程中,在矽基板中產生較大的內應力,而成為翹曲的原因。
存在該內應力對結晶的結晶粒界造成損傷、電力損失變大
的課題。另外,翹曲於模組製程中的太陽電池元件的搬送、或者與被稱為分支線路(tab wire)的銅線的連接過程中,容易使太陽電池元件破損。近年來,由於切片加工技術的提高,因此矽基板的厚度正被薄型化,而存在太陽電池元件更加容易破裂的傾向。
但是,根據本發明的製造方法,於藉由上述本發明的形成p型擴散層的組成物將n型擴散層轉換成p+型擴散層後,在該p+型擴散層上另外設置電極。因此,用於背面的電極的材料並不限定於鋁,例如可應用Ag(銀)或Cu(銅)等,背面的電極的厚度亦可比先前的厚度更薄地形成,並且另外亦無需形成於整個面上。因此,可減少於煅燒及冷卻的過程中所產生的矽基板中的內應力及翹曲。
於上述所形成的n型擴散層上形成抗反射膜。抗反射膜是應用公知的技術而形成。例如,當抗反射膜為氮化矽膜時,藉由將SiH4與NH3的混合氣體作為原料的電漿化學氣相沈積(Chemical Vapor Deposition,CVD)法來形成。此時,氫於結晶中擴散,不參與矽原子之鍵結的軌道,即懸鍵與氫鍵結,而使缺陷鈍化(氫鈍化)。
更具體而言,於上述混合氣體流量比NH3/SiH4為0.05~1.0,反應室的壓力為0.1Torr~2Torr,成膜時的溫度為300℃~550℃,使電漿放電的頻率為100kHz以上的條件下形成。
於表面(受光面)的抗反射膜上,藉由網版印刷法印刷塗佈表面電極用金屬膏並使其乾燥,而形成表面電極。表面電極用金屬膏是將金屬粒子與玻璃粒子作為必需成分,且視需要包含樹脂黏合劑、其他添加劑等。
繼而,於上述背面的p+型擴散層上亦形成背面電極。如上所述,本發明中背面電極的材質或形成方法並無特別限定。例如,可塗佈包含鋁、銀或銅等金屬的背面電極用膏,並使其乾燥而形成背面電極。此時,為了模組製程中的單元間的連接,亦可於背面的一部分上設置形成銀電極的銀膏。
對上述電極進行煅燒,製成太陽電池元件。若於600℃~900℃的範圍內煅燒幾秒~幾分鐘,則於表面側,作為絕緣膜的抗反射膜因電極用金屬膏中所含有的玻璃粒子而熔融,進而矽表面的一部分亦熔融,膏中的金屬粒子(例如銀粒子)與矽基板形成接觸部並凝固。藉此,所形成的表面電極與矽基板被導通。將此稱為燒透(fire through)。
對表面電極的形狀進行說明。表面電極是由匯流條電極、以及與該匯流條電極交叉的指狀電極構成。
此種表面電極可藉由例如上述金屬膏的網版印刷、或者電極材料的鍍敷、高真空中的利用電子束加熱的電極材料的蒸鍍等方法而形成。眾所周知,包含匯流條電極與指狀電極的表面電極一般是用作受光面側的電極,可應用受光面側的匯流條電極及指狀電極的公知的形成方法。
再者,於上述的p型擴散層及太陽電池元件的製造方法中,為了於作為p型半導體基板的矽基板上形成n型擴散層,而使用氧氯化磷(POCl3)、氮氣及氧氣的混合氣體,但亦可使用形成n型擴散層的組成物來形成n型層。於形成n型擴散層的組成物中,含有P(磷)
或Sb(銻)等第15族的元素作為施體(donor)元素。
於將形成n型擴散層的組成物用於n型擴散層的形成的方法中,首先,於作為p型半導體基板的表面的受光面塗佈形成n型擴散層的組成物,於背面塗佈本發明的形成p型擴散層的組成物,然後於600℃~1200℃下進行熱擴散處理。藉由該熱擴散處理,施體元素於表面向p型半導體基板中擴散而形成n型擴散層,受體元素則於背面擴散而形成p+型擴散層。除該步驟以外,藉由與上述方法相同的步驟來製作太陽電池元件。
再者,藉由參照而將日本申請案2010-100223中所揭示的全部內容引用於本說明書中。
本說明書中所記載的所有文獻、專利申請案、及技術規格是以與具體地且個別地記載藉由參照而引用各個文獻、專利申請案、及技術規格時相同的程度,藉由參照而引用於本說明書中。
以下,更具體地說明本發明的實例,但本發明並不受該些實例限制。再者,只要事先無特別記述,則化學品全部使用試劑。另外,只要事先無說明,則「%」表示「mol%」。
再者,以下所示的「載子的生命週期」是以相對值來表示實例或比較例中所製作的具有p型擴散層的n型矽基板的載子的生命週期相對於將含有B2O3的塗佈液塗佈於n型矽基板並進行熱擴散處理而形成p型擴散層的n型矽基板的載子的生命週期。載子的生命週期就實用的觀點而言,將70%以上設定為合格。
使用自動乳缽混練裝置將粒子形狀為大致球狀,平均粒徑為3.3μm的SiO2-B2O3體系玻璃(SiO2:50mol%,B2O3:50mol%,生命週期殺手元素為980ppm)粉末20g與乙基纖維素3g、乙酸2-(2-丁氧基乙氧基)乙酯77g加以混合並膏化,製成形成p型擴散層的組成物。
再者,玻璃粉末中的生命週期殺手元素是藉由高頻感應耦合電漿發光分光分析裝置及高頻感應耦合電漿質量分析裝置,分析其含量及元素的種類。於以下實例中相同。玻璃粉末中含有Fe、Cu、Ni作為生命週期殺手元素。
另外,玻璃粒子形狀是使用日立高科技(Hitachi High-Technologies)(股份)製造的TM-1000型掃描型電子顯微鏡進行觀察並判定。玻璃的平均粒徑是使用Beckman Coulter(股份)製造的LS 13 320型雷射散射繞射法粒度分布測定裝置(測定波長:632nm)來算出。
其次,藉由網版印刷將所製備的膏狀物(形成p型擴散層的組成物)塗佈於n型矽基板的表面,並於150℃的加熱板上乾燥5分鐘。繼而,利用設定成1000℃的電爐進行10分鐘熱擴散處理,然後,為了去除玻璃層而將基板浸漬於氫氟酸中5分鐘,進行流水清洗,其後進行乾燥。
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為80Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000
Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,載子的生命週期為74%。進而,未產生基板的翹曲。
將所使用的玻璃粉末替換成SiO2-B2O3體系玻璃粉末(SiO2:50mol%,B2O3:50mol%,生命週期殺手元素為530ppm,大致球狀,平均粒徑為3.8μm),除此以外,以與實例1相同的方式形成p型擴散層。玻璃粉末中含有Fe、Cu、Ni作為生命週期殺手元素。
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為82Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,載子的生命週期為82%。進而,未產生基板的翹曲。
將所使用的玻璃粉末替換成SiO2-B2O3體系玻璃粉末(SiO2:50mol%,B2O3:50mol%,生命週期殺手元素為470ppm,大致球狀,平均粒徑為3.3μm),除此以外,以與實例1相同的方式形成p型擴散層。玻璃粉末中含有Fe、Cu、Ni作為生命週期殺手元素。
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為78Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,載子的生命週期為87%。進而,未產生基板的翹曲。
將所使用的玻璃粉末替換成SiO2-B2O3體系玻璃粉末
(SiO2:50mol%,B2O3:50mol%,生命週期殺手元素為120ppm,大致球狀,平均粒徑為3.7μm),除此以外,以與實例1相同的方式形成p型擴散層。玻璃粉末中含有Fe、Cu、Ni作為生命週期殺手元素。
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為81Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,載子的生命週期為91%。進而,未產生基板的翹曲。
將所使用的玻璃粉末替換成SiO2-B2O3體系玻璃粉末(SiO2:50mol%,B2O3:50mol%,生命週期殺手元素為85ppm,大致球狀,平均粒徑為3.5μm),除此以外,以與實例1相同的方式形成p型擴散層。玻璃粉末中含有Fe、Cu、Ni作為生命週期殺手元素。
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為80Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,載子的生命週期為95%。進而,未產生基板的翹曲。
將所使用的玻璃粉末替換成SiO2-B2O3體系玻璃粉末(SiO2:50mol%,B2O3:50mol%,生命週期殺手元素為20ppm,大致球狀,平均粒徑為3.2μm),除此以外,以與實例1相同的方式形成p型擴散層。玻璃粉末中含有Fe、Cu、Ni作為生命週期殺手元素。
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為
85Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,載子的生命週期為98%。進而,未產生基板的翹曲。
將所使用的玻璃粉末替換成SiO2-B2O3體系玻璃粉末(SiO2:50mol%,B2O3:50mol%,生命週期殺手元素為8ppm,大致球狀,平均粒徑為3.5μm),除此以外,以與實例1相同的方式形成p型擴散層。玻璃粉末中含有Fe、Cu、Ni作為生命週期殺手元素。
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為81Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000Ω/□以上而無法測定,判斷為實質上未形成p型擴散層。另外,載子的生命週期為100%。進而,未產生基板的翹曲。
將粒子形狀為大致球狀,平均粒徑為3.3μm的SiO2-B2O3體系玻璃(SiO2:50mol%,B2O3:50mol%,生命週期殺手元素為1180ppm)粉末20g與乙基纖維素3g、乙酸2-(2-丁氧基乙氧基)乙酯77g加以混合並膏化,製成形成p型擴散層的組成物。玻璃粉末中含有Fe、Cu、Ni作為生命週期殺手元素。
其次,藉由網版印刷將所製備的膏狀物(形成p型擴散層的組成物)塗佈於n型矽基板的表面,於150℃的加熱板上乾燥5分鐘。繼而,利用設定成1000℃的電爐進行10分鐘熱擴散處理,然後,為了去除玻璃層而將基板浸漬於氫氟酸中5分鐘,進行流水清洗,其
後進行乾燥。
塗佈有形成p型擴散層的組成物之側的表面的薄片電阻為80Ω/□,B(硼)擴散而形成p型擴散層。背面的薄片電阻為1000000Ω/□以上而無法測定,未形成p型擴散層。但是,載子的生命週期為68%而較低。
雖然本發明已以較佳實施例揭露如上,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內,當可作些許之更動與潤飾,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。
Claims (6)
- 一種形成p型擴散層的組成物,包括:含有受體元素且生命週期殺手元素的總量為1000ppm以下的玻璃粉末;以及分散介質。
- 如申請專利範圍第1項所述的形成p型擴散層的組成物,其中上述受體元素是選自B(硼)、Al(鋁)及Ga(鎵)中的至少一種。
- 如申請專利範圍第1項所述的形成p型擴散層的組成物,其中含有上述受體元素的玻璃粉末含有:選自B2O3、Al2O3及Ga2O3中的至少一種含有受體元素的物質;以及選自SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、SnO、ZrO2、及MoO3中的至少一種玻璃成分物質。
- 如申請專利範圍第1項所述的形成p型擴散層的組成物,其中上述生命週期殺手元素是選自Fe(鐵)、Cu(銅)、Ni(鎳)、Mn(錳)、Cr(鉻)、W(鎢)、及Au(金)中的至少一種。
- 一種p型擴散層的製造方法,包括:塗佈如申請專利範圍第1項至第4項中任一項所述的形成p型擴散層的組成物的步驟;以及實施熱擴散處理的步驟。
- 一種太陽電池元件的製造方法,其包括: 於半導體基板上塗佈如申請專利範圍第1項至第4項中任一項所述的形成p型擴散層的組成物的步驟;實施熱擴散處理來形成p型擴散層的步驟;以及於所形成的上述p型擴散層上形成電極的步驟。
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TW103124862A TWI548102B (zh) | 2010-04-23 | 2011-04-22 | 形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法 |
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EP (2) | EP2562793B1 (zh) |
JP (2) | JP5573946B2 (zh) |
KR (1) | KR101868163B1 (zh) |
CN (1) | CN102859659B (zh) |
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JP5814558B2 (ja) * | 2010-06-30 | 2015-11-17 | 株式会社神戸製鋼所 | 酸化物半導体薄膜の評価方法、及び酸化物半導体薄膜の品質管理方法 |
JP6645470B2 (ja) * | 2017-04-17 | 2020-02-14 | 株式会社村田製作所 | 外部電極用導電性ペーストおよびその外部電極用導電性ペーストを用いて製造する電子部品の製造方法 |
CN111977982B (zh) * | 2020-09-11 | 2022-04-22 | 南通天盛新能源股份有限公司 | 一种n型银铝浆用玻璃粉及其制备方法 |
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- 2011-04-22 JP JP2012511720A patent/JP5573946B2/ja not_active Expired - Fee Related
- 2011-04-22 WO PCT/JP2011/059970 patent/WO2011132778A1/ja active Application Filing
- 2011-04-22 EP EP11772109.2A patent/EP2562793B1/en not_active Not-in-force
- 2011-04-22 US US13/642,526 patent/US20130071968A1/en not_active Abandoned
- 2011-04-22 TW TW100114099A patent/TWI495118B/zh not_active IP Right Cessation
- 2011-04-22 TW TW103124862A patent/TWI548102B/zh not_active IP Right Cessation
- 2011-04-22 KR KR1020127028224A patent/KR101868163B1/ko active IP Right Grant
- 2011-04-22 EP EP15168121.0A patent/EP2930740A1/en not_active Withdrawn
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US20140065761A1 (en) | 2014-03-06 |
JPWO2011132778A1 (ja) | 2013-07-18 |
EP2562793A4 (en) | 2013-09-11 |
WO2011132778A1 (ja) | 2011-10-27 |
JP5573946B2 (ja) | 2014-08-20 |
US20130071968A1 (en) | 2013-03-21 |
TW201138128A (en) | 2011-11-01 |
JP2014099660A (ja) | 2014-05-29 |
EP2562793A1 (en) | 2013-02-27 |
KR101868163B1 (ko) | 2018-06-15 |
EP2562793B1 (en) | 2017-08-30 |
US20150214418A1 (en) | 2015-07-30 |
US9520529B2 (en) | 2016-12-13 |
TWI495118B (zh) | 2015-08-01 |
TW201448237A (zh) | 2014-12-16 |
EP2930740A1 (en) | 2015-10-14 |
CN102859659B (zh) | 2017-07-28 |
KR20130098142A (ko) | 2013-09-04 |
CN102859659A (zh) | 2013-01-02 |
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