CN104599956B - 通过包含聚合物膜的掺杂剂掺杂基材 - Google Patents
通过包含聚合物膜的掺杂剂掺杂基材 Download PDFInfo
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- CN104599956B CN104599956B CN201410412614.0A CN201410412614A CN104599956B CN 104599956 B CN104599956 B CN 104599956B CN 201410412614 A CN201410412614 A CN 201410412614A CN 104599956 B CN104599956 B CN 104599956B
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Abstract
通过包含聚合物膜的掺杂剂掺杂基材。本文公开了一种用于掺杂基材的方法,所述方法包括在基材上设置包含含掺杂剂聚合物和非极性溶剂的组合物的涂层;在750‑1300℃的温度下退火1秒至24小时,以使所述掺杂剂扩散到基材中;其中所述含掺杂剂聚合物是具有共价结合的掺杂剂原子的聚合物,所述含掺杂剂聚合物不含氮和硅;所述方法不包括在退火步骤之前在涂层上形成氧化物封盖层的步骤。
Description
技术领域
本发明涉及通过含掺杂剂的聚合物膜掺杂基材,所述聚合物膜被设置在基材上。
发明背景
将电子装置缩小为纳米级(尺寸小于100纳米(nm))的挑战之一是在小于10纳米的尺寸范围内实现半导体材料的受控掺杂。例如,随着晶体管栅极长度快速接近小于10纳米尺寸范围,使用纳米长度尺寸的高导电超浅结来缩小晶体管尺寸,从而实现更快的晶体管速度和更高的封装密度。此外,已提出的一系列小型化电子应用结合使用利用掺杂的纳米线结构模块或其他非平面导电纳米结构。
现有的方法不适用于掺杂至小于10nm的深度。离子注入法包括用能替代基材晶格中硅原子的高能掺杂离子轰击硅基材。但是,该方法也会产生晶格中的点缺陷和空位,其与掺杂剂相互作用使结分布(junction profile)变宽,从而限制形成小于10nm的掺杂分布。此外,离子注入法与非平面的纳米结构材料不相容,这是因为能量离子很可能完全渗透通过纳米结构,而不保留在晶格中,并导致明显的晶体损坏。另一方面,当掺杂在小于10nm的深度进行时,常规的固源扩散法缺少控制和均一性。
单层掺杂法克服了现有技术的缺点并实现高质量的小于5nm的掺杂分布,同时具有高的面均一性。该方法中,在硅表面上形成高度均匀的共价结合的单层含掺杂剂的小分子。在后续的热退火步骤中,掺杂剂原子扩散到硅晶格中。该方法得到了证明是迄今为止同时对p-和n-型掺杂具有低的方块电阻率(sheet resistivity)的最浅的结,它与非平面的尺寸受限的纳米结构基材相容。但是,单层掺杂策略要利用数个繁琐的步骤。首先,在无氧气氛下(即,在惰性气氛中或在真空中)进行包含小分子的掺杂剂的沉积,以防止氧化污染。另外,在退火步骤之前在表面官能化的硅基材顶部蒸发硅氧化物封盖层,以使掺杂剂原子有效地扩散到硅基材中。封盖层的蒸发需要大约10-6托的高真空。
日本专利申请JP 2005-123431公开了通过在基材上涂覆溶解在极性有机溶剂或水或其混合物的酸式有机磷酸酯聚合物(聚合度小于或等于500)膜,接着在低于磷扩散温度的第一温度下加热一段时间,然后在高于所述第一温度但低于所述磷扩散温度的第二温度下在氧化气氛中加热一段时间,接着在高于所述第二温度的第三温度下在非氧化气氛中加热一段时间以使磷扩散到基材中而形成n-型扩散区。这是一种复杂的方法,需要三种不同的加热循环并在各循环间转换气氛。同样,使用这种极性溶剂通常与半导体制造中采用的标准方法是不相容的,很可能导致差的膜涂层。如果该膜在基材上涂覆不完全,那么基材的磷掺杂很可能不均匀。
相应地,需要开发一种在环境条件下掺杂基材的方法,不使用高真空并且不使用刻蚀。
发明内容
本文公开了一种用于掺杂基材的方法,所述方法包括在基材上设置包含聚合物和非极性溶剂的组合物的涂层,所述聚合物包含掺杂剂;在750-1300℃的温度使基材退火1秒至24小时,以使所述掺杂剂扩散到基材中;其中含掺杂剂的聚合物是具有共价结合的掺杂剂原子的聚合物,所述含掺杂剂的聚合物不含氮和硅;所述方法不包括在退火步骤之前在涂层上形成氧化物封盖层的步骤。
附图说明
图1A和1B是p-型(硼)(图1A)和n-型(磷)(图1B)掺杂的硅基材的方块电阻(sheetresistance)RS随退火时间和温度变化的图。
图2A和图2B是硅基材中磷掺杂原子的深度分布在固定退火时间为30秒的情况下(图2A)随退火温度变化的图,以及在固定退火温度为1000℃的情况下(图2B)随退火时间变化的图。退火前聚合物膜的厚度为16nm。对照实验采用进行快速热退火步骤的无聚合物膜的硅基材进行;
图3A和3B是采用不同厚度的聚合物膜的情况下,掺杂的硅基材中磷原子的深度分布(图3A)和硼-和磷-掺杂的硅基材的方块电阻(图3B)的图。所有基材在1000℃下退火30秒;
图4是进行不同退火时间在1000℃退火的掺杂硅基材中硼原子的深度分布图。退火前聚合物膜的厚度为20nm;
图5显示在1000℃退火30秒的掺杂硅基材的磷和硅SIMS分布,采用16nm含磷聚合物膜;以及
图6A和6B显示本发明的含硼聚合物(图6A)和含磷聚合物(图6B)的热重分析结果图。
具体实施方式
术语“包括”包括了术语“由…组成”以及”基本上由…组成”。本文中使用的术语“和/或”用来表示“和”以及“或”。例如,“A和/或B”表示A、B或A和B。
本文公开了一种用于实现半导体基材掺杂的方法,该方法通过用含掺杂剂的聚合物膜涂覆基材,并在升高的温度下对所述基材进行退火来进行。所述聚合物膜包括包含所述掺杂剂的聚合物。所述掺杂剂与所述聚合物共价结合。加热所述基材促进掺杂剂从聚合物扩散到基材中。该方法的优点在于工艺中不需要真空。所述聚合物膜本身能作为封盖层,从而消除了对使用在其他的市场上已有的比较工艺中使用的封盖层的需求。换言之,所述方法不包括在退火步骤之前在聚合物膜上形成氧化物封盖层的步骤。通过采用低退火温度和短退火时间,可以在基材上得到最浅至5nm的掺杂结。该方法特别有益于例如形成用于源/漏晶体管栅极和用于掺杂硅纳米结构(例如纳米导线)的高导电超浅结,以制备多种小型化电子装置。所述聚合物膜在本文中也成为聚合物涂层或聚合物层。
所述基材是半导体基材。合适的半导体基材的例子是无定形硅,砷化镓,锗硅,碳化硅,砷、硒和碲的混合物等。用作基材的示例性半导体是硅。
所述基材用含掺杂剂的聚合物膜涂覆,其中所述基材是用该掺杂剂掺杂的。掺杂剂可以包括硼、磷、砷、铋、锑、镓或其组合。所述掺杂剂与聚合物共价连接,在下文中将被称为含掺杂剂的聚合物。在一个实施方式中,所述掺杂剂是聚合物骨架的一部分,而在另一个实施方式中,掺杂剂是聚合物骨架上的取代基。在又一个实施方式中,掺杂剂是聚合物骨架的一部分以及是聚合物骨架上的取代基。在优选的实施方式中,所述掺杂剂是磷或硼,包含这些掺杂剂的聚合物在下文中将被称为含硼聚合物或含磷聚合物。
含掺杂剂的聚合物可以是热塑性聚合物,热塑性聚合物的掺混物、热固性聚合物,或者热塑性聚合物与热固性聚合物的掺混物。所述含掺杂剂的聚合物还可以是含掺杂剂的聚合物的掺混物,含掺杂剂的共聚物,含掺杂剂的三元共聚物或者包含至少一种上述聚合物的组合。含掺杂剂的聚合物还可以是低聚物、均聚物或者共聚物,所述共聚物可以是交替共聚物、嵌段共聚物、无规共聚物或接枝共聚物。含掺杂剂的聚合物可以是直链状、树枝状、星状、支链状或环状等。在一个实施方式中,热固性膜(含掺杂剂)可以施用于基材作为热塑性膜并在膜退火期间进行交联(即变为热固性)。
含硼聚合物可以是通过聚合有机硼复合物(complex),将有机硼复合物或含硼部分结合到聚合物骨架上或者将有机硼复合物或含硼部分作为取代基结合到聚合物骨架上得到的聚合物。
用于衍生含硼聚合物的有机硼复合物的例子有硼烷、乙烯基硼烷、乙烯基硼酸、环硼氮烷(borazine)、乙烯基环硼氮烷、环二硼吖嗪(cyclodiborazane)、喹啉合硼、二酮酸硼、吡唑硼(pyrazabole)、二吡咯甲烷硼(boron dipyrromethane)和碳硼烷(carborane)等。如果需要的话,上述有机硼复合物可以是取代的。可以通过上述有机硼复合物的聚合得到的聚合物的例子有聚[2-(乙烯基)戊硼烷)]、聚乙烯基环硼氮烷、聚亚硼烷(polyborazylene)、聚环二硼吖嗪、含环二硼吖嗪的聚合物、喹啉合硼聚合物、含吡唑硼的聚合物、含碳硼烷的聚合物、聚(乙烯基硼酸)等,或包括至少一种上述聚合物的组合。如果需要的话,所述聚合物可以是取代的。
优选的含硼聚合物是聚(乙烯基硼酸)。优选的取代的含硼聚合物是聚(乙烯基硼酸频哪醇酯)(poly(vinylboronic acid pinacol ester))。
含磷聚合物包括磷腈(phosphazene)聚合物、磷酸酯聚合物、磷酸聚合物、膦酸聚合物(例如,聚(偏乙烯基-1,1-二-膦酸))等,或包含至少一种前述聚合物的组合。
所述磷腈聚合物的分子中具有—P═N—键。磷腈聚合物可以是由下式(1)表示的环状聚合物,或由下式(2)表示的直链状聚合物;以及通过至少一种选自以下式(1)和(2)表示的苯氧基磷腈物质与由下式(1)表示的交联基团交联得到的交联的苯氧基磷腈化合物:
式(1)中,m表示3-25的整数,R1和R2相同或不同,R1和R2独立地是氢、羟基、C7-30芳基、C1-12烷氧基或C1-12烷基。
链状苯氧基磷腈由以下式(2)表示:
在式(2)中,X1表示—N═P(OPh)3基团或—N═P(O)OPh基团,Y1表示—P(OPh)4基团或—P(O)(OPh)2基团,n表示3-10000的整数,Ph表示苯基,R1和R2相同或不同,R1和R2独立地是氢、卤素、C1-12烷氧基或C1-12烷基。
苯氧基磷腈还可具有由下式(3)表示的交联基团:
在式(3)中,A表示—C(CH3)2—,—SO2—,—S—或—O—,以及q是0或1。
在一个实施方式中,磷酸聚合物具有式(4)结构:
其中e为1-500的整数。
希望含掺杂剂的聚合物不含氮和硅。当含掺杂剂的聚合物是均聚物时,优选其包含无羟基、胺、氨基、硫醇和羧酸基团的单体作为聚合单元。当含掺杂剂的聚合物是共聚物时,优选其包含小于50wt%的包含选自以下取代基的任意单体作为聚合单元:羟基、胺、氨基、硫醇、羧酸和它们的组合。
膦酸聚合物的例子是聚(偏乙烯基-1,1-二-膦酸)或聚(乙烯基膦酸二乙酯)。示例性的含磷聚合物是聚(乙烯基膦酸二乙酯)。
含掺杂剂的聚合物可以在设置在基材上之前与其他不含掺杂剂的聚合物共聚或者与其他不含掺杂剂的聚合物掺混。在一个实施方式中,含掺杂剂的聚合物可以与不含掺杂剂的聚合物共聚,然后与其他的不含掺杂剂的聚合物掺混。
在设置到半导体基材上之前,该共聚或掺混促进所述含掺杂剂的聚合物在溶剂中的溶解。
不含掺杂剂的聚合物可以是热塑性聚合物或热固性聚合物。
热塑性聚合物的例子是聚缩醛、聚烯烃、聚丙烯酸类热塑性聚合物、聚苯乙烯、聚芳基砜、聚醚砜、聚苯硫醚、聚氯乙烯、聚砜、聚四氟乙烯、聚醚酮、聚醚醚酮、聚醚酮酮、聚苯酞(polyphthalide)、聚缩醛、聚酐、聚乙烯基醚、聚乙烯基硫醚、聚乙烯基醇、聚乙烯基酮、聚卤乙烯、聚乙烯酯、聚磺酸盐(polysulfonate)、聚硫醚(polysulfide)、聚硫酯(polythioester)、聚砜、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、乙烯-丙烯二烯橡胶、聚四氟乙烯、氟化乙烯丙烯、全氟烷氧基乙烯、聚氯三氟乙烯、聚偏二氟乙烯等,或包含至少一种前述热塑性聚合物的组合。
热固性聚合物的例子包括环氧聚合物、乙烯基聚合物、苯并环丁烯聚合物、丙烯酸类热固性聚合物、醇酸树脂、酚-醛聚合物、酚醛树脂清漆(novolacs)、甲阶酚醛树脂、羟甲基呋喃、邻苯二甲酸二烯丙酯等,或包含至少一种前述热固性聚合物的组合。
在一个实施方式中,所述不含掺杂剂的聚合物的重量分数和嵌段长度可以变化,以使不同量和不同浓度的掺杂剂递送到基材具体部分上。当含掺杂剂的聚合物与另一种不含掺杂剂的聚合物共聚和/或掺混时,以所述共聚物和/或掺混物的总重量为基准计,所述含掺杂剂的聚合物的量通常为20-95重量%,优选35-85重量%,更优选45-75重量%。
在一个实施方式中,在掺杂所述半导体基材的一个方法中,所述聚合物溶解在溶剂中并被设置在基材上。然后对其上设置有聚合物的基材进行退火(以称为加热)以去除溶剂,并促进半导体基材的掺杂。
所述溶剂优选是非极性溶剂。使用偶极矩或介电常数来表征溶剂极性,介电常数小于17.5,优选小于10,更优选小于5的溶剂通常被认为是非极性的。示例性的非极性溶剂包括但不限于:芳族烃、酯、醚等。示例性的极性溶剂有戊烷、环戊烯、己烷、环己烷、苯、甲苯、1,4-二噁烷、氯仿、四氢呋喃、乙醚、二甲苯、均三甲苯、丙二醇甲基醚乙酸酯、乙酸正丁酯等或包含至少一种前述溶剂的组合。示例性的非极性溶剂是四氢呋喃。
当含掺杂剂的聚合物与非极性溶剂混合时,以所述溶剂和含掺杂剂的聚合物的总重量为基准计,所述聚合物的量为0.0005-5重量%。在一个优选的实施方式中,以所述溶剂和含掺杂剂的聚合物的总重量为基准计,所述聚合物的量为0.001-0.02重量%。
可以对含掺杂剂的聚合物-非极性溶剂溶液(以下称为聚合物-溶剂溶液)进行搅拌,并升高温度以促进聚合物溶剂化。所述聚合物-溶剂溶液再被设置到基材表面上。在其上设置所述聚合物-溶剂溶液之前,所述基材表面可以通过在溶剂中加热或清洗而预清洁。
所述聚合物-溶剂溶液可以通过旋涂、刮刀刮涂、喷涂、浸渍涂覆、丝网印刷、刷涂等设置到基材上。用于涂覆所述基材的优选的方法是通过旋涂进行。溶剂可以从基材表面上蒸发,留下设置在基材上的聚合物涂层。所述聚合物涂层包含所述掺杂剂。
所述聚合物涂层作为其自身的封盖层,不需要高真空蒸发通常在现有的单层掺杂工艺中使用的金属氧化物层,例如氧化硅层。此外,由于半导体基材用聚合物膜涂覆而非共价结合,也不需要非氧化性环境条件。
所述聚合物涂层的厚度范围可以是几纳米至几百纳米(nm),优选3-250nm,更优选5-200nm,更优选6-120nm。但是,预期可以使用较薄的膜,只要小心地避免会导致非均匀掺杂的针孔(pinhole)即可。如果需要的话,在小心地尽量减少退火后半导体基材上增加的有机残留物的情况下,也可以使用较厚的膜。
然后,对基材和其上设置的聚合物涂层进行退火,在500-1500℃,优选700-1300℃退火2秒至24小时,优选4秒至12小时,更优选10秒至3分钟。退火可以采用加热对流、传导加热或辐射加热进行。在退火工艺中优选对流加热。
退火可以在真空中进行或者在惰性气氛中进行。合适的惰性气氛包括氮气、氩气、氖气(zeon)、氦气、氮气或二氧化碳。在一个优选的实施方式中,所述退火在包含氮气的惰性气氛下进行。
得到的基材中掺杂剂的浓度分布是对基材和聚合物涂层进行扩散的退火温度和时间的函数。其他的影响因素是退火温度下半导体基材中掺杂剂分子的溶解度和退火温度下掺杂剂分子的扩散系数。这样退火时间和温度可以根据需要变化以实现所需的掺杂剂分布。从而可以使用适当的低退火温度和短退火时间得到浅至小于-5nm的掺杂结。
退火过程中,所有残留溶剂从聚合物涂层中蒸发,仅留下聚合物。所述掺杂剂从含掺杂剂的聚合物中扩散至基材0.01-1000nm的深度,优选0.05-100nm,优选0.09-50nm,更优选0.1-10nm。
这种掺杂方法促进电子装置和制品例如晶体管中源和漏延伸区域的结的形成,具有快速转换速度和高的堆积密度。其他的应用包括但不限于晶体管栅极、纳米结构、二极管、光检测器、光电池和集成电路。
以下通过非限制性的实施例描述本发明所述的掺杂方法。
实施例
实施例1
本实施例证明含硼聚合物的制备。按照如下所述合成含硼聚合物,聚(乙烯基硼酸频哪醇酯)(PVBAPE)。在室温下在分子筛(1.0g)作用下,在二氯甲烷(50mL)中搅拌稍微摩尔过量的频哪醇(2.1g)24小时,将乙烯基硼酸(2.5g)转化为频哪醇酯。通过可逆加成断裂链转移聚合在70℃下聚合酯化单体(1.0g)16小时,使用2-十二烷基硫烷基(sulfanyl)硫代碳基硫烷基-2-甲基丙酸作为链转移剂(0.0155g)、偶氮二异丁腈(AIBN)作为引发剂(0.0011g)和无水苯甲醚作为溶剂(1mL)。将得到的聚合物通过沉淀至冷(-20℃)己烷中进行分离。得到的数均分子量MN和多分散度分别为10kg/mol和1.28,采用凝聚渗透色谱法(GPC)和聚苯乙烯分子量标准。首先,合成一系列具有不同分子量的聚合物。使用数均分子量Mn=10kg/mol的PVBAPE进行本发明所述的所有掺杂测试。
实施例2
本实施例证明含磷聚合物的制备。通过乙烯基膦酸二乙酯的阴离子聚合(DEVP)来合成含磷聚合物,聚(乙烯基膦酸二乙酯)(PDEVP)。分别采用3次冷冻-抽吸-解冻(freeze-pump-thaw)循环对DEVP(6.0mL)和二苯基乙烯(DPE,0.5mL)脱气,通过分子筛或氢化钙作用下搅拌过夜进行干燥,并蒸馏到火焰干燥的安瓶中。无水四氢呋喃(THF,125mL)脱气并用仲丁基锂(300μL)在-78℃下清洗30分钟(然后加热至室温过夜)。DPE套管转移至-78℃的THF中,然后用仲丁基锂(150μL 1.4M环己烷溶液)引发。30分钟后,DEVP转移至反应容器,在用甲醇终止之前聚合进行3小时。将得到的聚合物沉淀至冷(0℃)己烷中。根据使用的单体和引发剂的量计算理论数均分子量为31kg/mol。但是,由于聚合物黏附在柱上,不能通过GPC确定实际分子量。
实施例3
该实施例证明聚合物膜设置在基材上和掺杂基材。聚合物膜(PVBAPE或PDEVP)由甲苯或氯仿的稀溶液旋涂到(100)平面上的高电阻率(>10,000ohm-cm)硅基材上。所述硅基材由美国加利福尼亚州圣克拉拉市的硅谷微电子公司(Silicon ValleyMicroelectronics;Santa Clara,CA)获得。未掺杂的硅基材先用稀HF 28(约1%)处理以去除本身的氧化物层。采用浓度范围1-20mg/mL,2000转每分钟(rpm)的旋涂速度获得6-120nm的厚度,该厚度通过椭圆光度法测得。使用Heatpulse210T RTA系统对涂覆有聚合物膜的基材在氮气吹扫下进行快速热退火。温度经过20秒(sec)从室温升至950℃、1000℃或1050℃,然后在退火温度下保持10、30或60秒,再经过大约20秒冷却回到室温。
实施例4
接着进行测试,如对得到的方块电阻RS的四点探针测试所证明,本发明的聚合物膜掺杂法能得到p-或n-型高度掺杂的基材。例如,涂覆有17nm厚含硼聚合物膜并在1000℃退火30秒的硅基材的RS为2.2*103Ω/方块(Ω/square)(同样示于附图中,以Ω/□计)。在误差范围内,这与使用同样的退火温度和时间的现有单层掺杂工艺得到的p-掺杂基材的RS是相同的。涂覆有18nm厚含磷聚合物膜并在1000℃退火30秒的硅基材的RS为5.4*102Ω/方块,其与现有的单层n-型掺杂工艺得到的方块电阻相比较高,但在同样的数量级上。应注意对于给定的退火条件来说,n-型掺杂基材具有较低的方块电阻,这是由于与硼相比,磷在硅中的溶解度和扩散系数更高。
通过调节退火条件可以控制硅基材中的掺杂剂分布。如图1A和1B所示,n-型和p-型掺杂硅基材的方块电阻随着退火时间和温度的增加而降低。随着温度降低是由于在升高的温度下,掺杂剂在硅中的溶解度和扩散增加,而随着时间降低是由于掺杂剂分子扩散到硅基材中的可用时间较长。
测量掺杂后硅基材中掺杂剂原子的深度分布的二次离子质谱(SIMS)实验确认对于较高的退火温度和较长的退火时间,硅基材中掺杂剂原子浓度较高(见图2A和2B)。这也显示由于扩散改善和扩散时间更长,掺杂剂原子更深地渗透到硅基材中。
在磷掺杂基材的情况下,虽然对于较高的退火温度和更长的退火时间,磷的总体浓度增加,但表面上磷的浓度实际上略微降低(见图2A和2B)。换言之,在快速热退火步骤中,聚合物膜不能提供足够的磷原子将硅基材表面正下方(just under)的磷浓度维持在磷的平衡溶解度。本研究中1000℃时测定的表面浓度范围为3*1020至8*1020原子/cm3,这取决于退火时间,而之前测得的1000℃时硅中磷的平衡溶解度为1*1021原子/cm3。
为了增加磷掺杂量,我们通过增加磷膜厚度来增加磷“源”。如图3A和3B所示,结合到硅基材中的磷量确实随着膜厚度的增加而增加,相应地测得的RS降低。对于膜厚在大约40-90nm的情况,RS似乎在约3*102Ω/方块时趋平,在此条件下表面磷浓度仍低于平衡溶解度(RS仍是使用现有的单层掺杂工艺得到的两倍)。
与磷掺杂不同,硼掺杂与聚合物膜厚度无关(见图3B)。因此,对于本研究中考察的退火温度和时间,硼掺杂可描述为“恒定源”扩散模型,这表示即使对于最薄的膜,聚合物膜提供了足够的掺杂原子,这样硅基材表面正下方的硼原子浓度等于硼在硅中的最大溶解度。掺杂剂分布则仅取决于退火时间和温度。如图4所示,恰好在掺杂的硅基材表面上的硼浓度对各种退火时间均是恒定的,并接近于2*1020至4*1020原子/cm3的平衡溶解度,而硅基材更深处的硼浓度随着较长的退火时间而增加。
具有较高磷含量的聚合物膜可用于改进磷掺杂,以及不同的聚合物化学性质以促进“自-封盖”。通过监测对于Si的二次离子强度来测定基材表面,其在硅基材表面迅速增加,然后保持恒定。取对于Si的二次离子强度达到平台值的75%时的基材表面。图5显示在1000℃退火30秒的掺杂硅基材的磷和硅SIMS分布,采用16nm含磷聚合物膜。在硅信号达到其平台值的75%时的深度对基材表面进行设计。较浅深度处的磷信号可能是由于基材顶部残留的有机材料造成的。
图6A和6B显示含硼聚合物(图6A)和含磷聚合物(图6B)的热重分析结果图。温度以5℃/分钟的速率增加。两种聚合物在类似的温度下降解。两步降解法归因于侧链的初步降解和聚合物主链的二次降解。
测试显示本发明的硼-和磷-掺杂的基材的碳含量与对照基材相比没有明显不同,所述对照基材进行快速热退火工艺,但其上未沉积前述的聚合物膜。
总之,采用含掺杂剂的聚合物薄膜的硅掺杂能提供常规方法无法实现的优异的纳米级n-型和p-型掺杂,通过消除对无空气化学和高真空沉积氧化硅封盖层的需求改进了现有技术(特别是单层掺杂)。该方法特别有益于例如形成用于源/漏晶体管栅极和用于掺杂硅纳米结构(例如纳米导线)的高导电超浅结,以用于多种小型化电子装置。以上示出的掺杂分布通常具有几十纳米的总深度,预期可以对本发明方法的退火条件进行调节以得到仅几纳米的深度分布。
Claims (9)
1.一种对基材进行掺杂的方法,该方法包括:
在基材上设置组合物涂层,所述组合物包含含掺杂剂的聚合物和非极性溶剂;以及
在750-1300℃的温度对所述基材进行退火1秒至24小时,以使掺杂剂扩散到基材中;
其中所述含掺杂剂的聚合物是具有共价结合的掺杂剂原子的聚合物;所述含掺杂剂的聚合物不含氮和硅;并且所述方法不包括在退火步骤之前在所述涂层上形成氧化物封盖层的步骤。
2.如权利要求1所述的方法,其特征在于,所述掺杂剂选自硼、磷、砷、铋、锑和镓。
3.如权利要求1所述的方法,其特征在于,所述基材是半导体基材。
4.如权利要求3所述的方法,其特征在于,所述基材包括硅、镓和锗中的一种或多种。
5.如权利要求1所述的方法,其特征在于,进行单次退火步骤。
6.如权利要求1所述的方法,其特征在于,所述掺杂剂扩散到基材≤10nm的深度。
7.如权利要求1所述的方法,其特征在于,所述非极性溶剂的介电常数(ε)≤17.5。
8.如权利要求1所述的方法,其特征在于,所述聚合物包含小于50重量%的选自羟基、硫醇、羧酸或其组合的单体。
9.如权利要求1所述的方法,其特征在于,所述退火步骤在含氧气氛下进行。
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JP6348801B2 (ja) | 2018-06-27 |
US9076719B2 (en) | 2015-07-07 |
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JP2015053480A (ja) | 2015-03-19 |
KR101622590B1 (ko) | 2016-05-19 |
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