CN1341279A - 半导体器件 - Google Patents

半导体器件 Download PDF

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Publication number
CN1341279A
CN1341279A CN00804230A CN00804230A CN1341279A CN 1341279 A CN1341279 A CN 1341279A CN 00804230 A CN00804230 A CN 00804230A CN 00804230 A CN00804230 A CN 00804230A CN 1341279 A CN1341279 A CN 1341279A
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Prior art keywords
semiconductor device
oneself
resin composition
group
photosensitive resin
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CN00804230A
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CN1198334C (zh
Inventor
平野孝
山本景寿
番场敏夫
真壁裕明
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract

本发明改进了在生产倒装片中的操作问题并提供了各种可靠性高的半导体器件。将一种包含100重量份聚酰胺和1至100重量份光敏重氮醌化合物的正光敏树脂组合物涂布在形成器件的表面、图形化并固化。所得用于器件保护的聚苯并噁唑树脂薄膜和凸点电极用于模塑半导体器件。

Description

半导体器件
技术领域
本发明涉及具有高敏感性、能够给出高残余薄膜比图形的正光敏性树脂组合物并提供凸点电极的半导体器件。
背景技术
在常规半导体芯片中，形成无机膜(例如SiO2膜或SiN膜)用于电路保护。此外，涂覆聚酰亚胺树脂以缓解在封装步骤(例如传递模塑)中遇到的物理损伤。此外，近年来随着半导体芯片的输入端增加，已出现了使用倒装片安装，包括在裸芯片上形成块，并将所得芯片面向下安装于基材上。
然而，当在上述半导体芯片结构中使用以倒装片安装为代表的裸芯片安装时，存在的问题的是：聚酰亚胺树脂的高吸水性导致随着时间的推移损害介电强度并降低可靠性。
还存在的一个问题是，形成聚酰亚胺图形需要长操作时间，此外精确加工性差。
本发明目的在于减轻上述在生产倒装片中的操作问题，并提供各种可靠性优异的半导体器件。
本发明公开
本发明涉及一种半导体器件，包括：
(a)一种用于芯片保护的聚苯并噁唑树脂薄膜，它通过在电路形成芯片上涂覆正光敏树脂组合物，将涂覆的组合物形成图形和固化获得，所述正光敏树脂组合物包括100重量份下面通式(1)表示的聚酰胺和1至100重量份光敏重氮醌化合物，和
(b)凸点(bump)电极：
Figure A0080423000061
其中X为四价芳基；Y为二价芳基；Z为
Figure A0080423000062
(R1和R2各自为二价有机基团，R3和R4各自为单价有机基团)；E为具有至少一个链烯基或链炔基的羧基脂族、脂环族或芳族基团；a和b各自为摩尔分数，a+b＝100mol％，a＝60.0至100.0mol％，b＝0至40.0mol％，和n＝2至500。
正光敏树脂组合物优选包含下面通式(2)表示的双酚化合物和下面通式(3)表示的三酚化合物，其总量为1至30重量份：
Figure A0080423000063
其中R5和R6各自为氢或烷基，R7、R8、R9和R10各自为选自氢原子、卤原子、羟基、烷氧基、环烷基和烷基的原子或基团，和
Figure A0080423000064
其中R11为氢原子或烷基；R12、R13、R14、R15、R16和R17各自为选自氢原子、卤原子、羟基、烷基、烷氧基和环烷基的原子或基团。
双酚化合物与三酚化合物的比例优选为10∶90至90∶10。聚酰胺的X选自如下基团：聚酰胺的Y选自如下基团：
其中A为-CH2-、-C(CH3)2-、-O-、-S-、-SO2-、-CO-、-NHCO-或-C(CF3)2-。该正光敏树脂组合物在温度280至440℃下固化。
附图的简要描述
图1为本发明半导体器件的一个例子的焊盘(pad)部分的截面图。
图2a至2d为表示本发明半导体器件的一个例子的生产步骤的截面图。
图3a至3c为表示本发明半导体器件的一个例子的生产步骤的截面图。
图4a和4b为表示本发明半导体器件的一个例子的生产步骤的截面图。
图1至4中使用的标号具有下面的含义：1：硅片，2：Al焊盘，3：钝化膜，4：缓冲涂膜；5：金属(例如Cr或Ti)膜，6：布线(例如Al或Cu)；7：绝缘膜；8：阻挡金属；9：抗蚀剂；10：焊料；11：助熔剂(flux)；12：焊料凸点
本发明详细描述
式(1)的聚酰胺由具有结构X的双氨基苯酚、具有结构Y的二羧酸和具有结构E的酸酐组成。该聚酰胺当在约280至440℃下加热时，发生脱水和闭环并转化为称为聚苯并噁的耐热树脂。
本发明的聚酰胺(1)的X为例如下面中的任何一种：
Figure A0080423000081
其中A为-CH2-、-C(CH3)2-、-O-、-S-、-SO2-、-CO-、-NHCO-或-C(CF3)2-。然而，X不受其限制。
在上面的例子中，特别优选的一种为选自如下的：式(1)的Y为例如下面的任何一种：
Figure A0080423000092
其中A为-CH2-、-C(CH3)2-、-O-、-S-、-SO2-、-CO-、-NHCO-或-C(CF3)2-。然而，Y不受其限制。
在上面的例子中，特别优选的一种为选自如下的：
Figure A0080423000101
式(1)的E包括例如如下的：然而，E不受其限制。在上面的例子中，特别优选的一种选自如下的：
在本发明中，将具有结构Y的二羧酸衍生物与具有结构X的双氨基苯酚反应合成聚酰胺，然后将聚酰胺的端氨基用具有至少一个式(1)的E表示的链烯基或链炔基的酸酐封端。
此外，式(1)的Z为例如下面的任何一种：
Figure A0080423000112
然而，Z不受其限制。
例如，当对基材(例如硅片)需要非常高的粘结性时，需要使用式(1)的Z。使用的Z的比例b为40mol％或更低。当该比例高于40mol％时，所得树脂具有非常低的溶解性，导致产生渣滓同时不形成图形。此外，使用的各X、Y、E和Z可通过单一物质或两种或多种物质的混合物给出。
本发明中使用的光敏重氮醌化合物为具有1，2-苯醌二叠氮化物或1，2-萘醌二叠氮化物结构的化合物与作为基体的苯酚类化合物之间的反应产品。
在本发明的正光敏树脂组合物中，重要的是使该组合物含光敏重氮醌化合物，这样特别在该组合物显影期间可获得高敏感性和高残余薄膜比。该正光敏树脂的显影利用树脂曝光与未曝光部分之间的溶解度差异进行。为获得高敏感性和高残余薄膜比，必须使曝光部分具有高溶解性和未曝光部分具有高不溶性，这样曝光与未曝光部分之间的溶解度差异变得尽可能大。曝光与未曝光部分之间的溶解度差异主要取决于作为基体的苯酚类化合物的结构。因此，对具有能够促进曝光部分溶解、抑制未曝光部分溶解并由此得到足够的残余薄膜比例的基体的光敏重氮醌化合物进行了研究。结果，发现下面的化合物具有高敏感性并且得到高残余薄膜比例。
该光敏重氮醌化合物包括如下化合物，但并不限于这些化合物：
Figure A0080423000121
Figure A0080423000131
其中各Q选自氢原子、和在各化合物中，至少一个Q为：
光敏重氮醌化合物相对于聚酰胺的比例为每100重量份聚酰胺1至100重量份。当该比例低于1重量份时，所得树脂的图形形成性能差。当该比例大于100重量份时，出现敏感性大幅度降低且所得薄膜的拉伸伸长明显降低。
本发明的正光敏树脂组合物，若必要，可含有更高光敏性的二氢吡啶衍生物。对于二氢吡啶衍生物，例如可提及2，6-二甲基-3，5-二乙酰基-4-(2′-硝基苯基)-1，4-二氢吡啶、4-(2′-硝基苯基)-2，6-二甲基-3，5-二乙氧羰基-1，4-二氢吡啶和4-(2′，4′-二硝苯基)-2，6-二甲基-3，5-二甲氧羰基-1，4-二氢吡啶。
本发明的正光敏树脂组合物进一步优选含有通式(2)表示的双酚化合物和通式(3)表示的三酚化合物。通过将通式(2)和(3)表示的这些苯酚化合物加入由聚苯并噁唑前体和重氮醌化合物构成的正光敏树脂组合物中，可获得具有如下性能的正光敏树脂组合物：即该组合物具有与封装树脂的高粘结力，显影时显示高敏感性并给出高残余薄膜比例，和甚至在-60至-50℃的低温下贮存也不会造成苯酚沉积并具有优良的贮存稳定性。
甚至当仅加入通式(2)和(3)表示的苯酚化合物之一时，也可获得一定程度的与封装树脂的高粘结力。然而，当仅加入通式(2)表示的双酚化合物时，增加加入量趋于在-60至-50℃的低温下贮存该树脂组合物时造成苯酚沉积。当仅加入通式(3)表示的三苯酚化合物时，增加加入量造成残余薄膜比例明显降低。相反，当将通式(2)表示的双酚化合物和通式(3)表示的三酚化合物结合使用时，会减轻由单一化合物带来的问题，并且可获得更高的光敏性和与封装树脂的优良粘结力。
相对于100重量份通式(1)表示的聚酰胺，苯酚化合物的加入量，按通式(2)表示的双酚化合物和通式(3)表示的三酚化合物总量计为1至30重量份。当两种苯酚化合物的加入量大于30重量份时，如上所述在该树脂组合物低温(-60至-50℃)贮存期间产生沉积物，并且在显影期间出现残余薄膜比例明显降低。当加入量低于1重量份时，不仅出现与封装树脂的粘结力降低，而且在显影期间敏感性也降低。
双酚化合物与三酚化合物的比例为10∶90至90∶10。当双酚化合物的比例低于10时，出现残余薄膜比例降低。当该比例高于90时，发生沉积。
对于通式(2)表示的双酚化合物，例如可提及如下化合物。然而，双酚化合物(2)并不仅限于这些。
Figure A0080423000171
在上述化合物中，特别优选的是：
Figure A0080423000181
对于通式(3)表示的化合物，可提及，例如如下化合物。然而，化合物(3)不仅限于这些。
Figure A0080423000191
Figure A0080423000201
Figure A0080423000211
在上述化合物中，特别优选的是：
Figure A0080423000221
本发明的正光敏树脂组合物，若必要，可含有添加剂如流平剂、硅烷偶联剂等。
在本发明中，将这些组分溶于溶剂中并以清漆状态使用。对于溶剂，可提及N-甲基-2-吡咯烷酮、γ-丁内酯、N，N-二甲基乙酰胺、二甲亚砜、二甘醇二甲基醚、二甘醇二乙基醚、二甘醇二丁基醚、丙二醇单甲基醚、一缩二丙二醇单甲基醚、丙二醇单甲基醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、甲基-1，3-丁二醇乙酸酯、1，3-丁二醇-3-单甲基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯等。这些溶剂可单独或以混合物形式使用。
在使用本发明的正光敏树脂组合物中，首先将该组合物涂于合适的基材，例如硅片、陶瓷基材或铝基材上。在生产半导体器件中，涂布的组合物的量应使固化后最终薄膜的厚度变为0.1至20μm。当薄膜的厚度低于0.1μm时，薄膜不能足够显示作为半导体芯片的保护表面薄膜的功能。当薄膜的厚度大于20μm时，难以获得细微图形，同时加工时间长，导致低生产率。
对于涂布方法，有使用旋涂机的旋涂方法、使用喷涂机的喷涂法、浸涂法、印刷涂布法、辊涂法等。
然后，在温度60至130℃下进行预烘烤，接着以所需的图形施加光化射线。对于光化射线，可使用X-射线、电子束、紫外光、可见光等；然而，优选波长200至500nm的光化射线。然后，将已施加光化射线的部分溶解并用显影溶液除去，由此获得凸起图形。
对于显影溶液，可优选使用碱水溶液，这些碱的例子是无机碱，例如氢氧化钠、氢氧化钾、碳酸钠、硅酸钠、偏硅酸钠、氨水或其类似物；伯胺如乙胺、正丙胺或其类似物；仲胺如二乙基胺、二正丙基胺或其类似物；叔胺如三乙胺、甲基二乙基胺或其类似物；醇胺如二甲基乙醇胺、三乙醇胺或其类似物；或季铵盐如氢氧化四甲基铵、氢氧化四乙基铵或其类似物，或通过将合适量的水溶性有机溶剂如醇(例如甲醇、乙醇或其类似物)或表面活性剂加入上述水溶液中获得的水溶液。对于显影方法，可使用诸如喷雾、搅拌漂洗(paddle)、浸渍、超声波等方法。
然后，将通过显影形成的凸起图像进行漂洗。将蒸馏水用作漂洗液体，然后施加280至440℃的热处理形成噁唑环，由此获得最终的高耐热图形。热处理优选在350至440℃下进行，因为后面进行的凸点形成步骤特别包括暴露于化学物质如助熔剂和高温热处理。当热处理(固化)温度低于280℃时，固化需要很长的时间。当温度高于440℃时，所得薄膜的性能差。
实施本发明的最佳方式
下面，参照附图，对于使用本发明的用于半导体器件的光敏树脂组合物的实施例进行描述。图1为本发明具有凸点的半导体器件的焊盘部分的放大截面图。如图1所示，在硅片1上形成用于输入和输出的Al焊盘2；在其上形成钝化膜3；并在钝化膜3内形成通过孔。在其上形成聚苯并噁唑树脂薄膜(缓冲涂膜)4；进一步形成金属(例如Cr或Ti)薄膜5，如此与Al焊盘2接触；在焊料凸点12周围通过刻蚀除去金属膜5，以确保焊盘之间绝缘。形成阻挡金属8和焊料凸点12以使焊盘绝缘。
本发明通过下面的实施例具体描述。
实施例1*合成聚酰胺
在设置有温度计、搅拌器、原料入口和干燥氮气导入管的四颈可分烧瓶中，加入366.3g(1.0mol)六氟-2，2-双(3-氨基-4-羟苯基)丙烷和443.2g(0.9mol)通过1mol二苯基醚-4，4′-二羧酸与2mol1-羟基-1，2，3-苯并三唑反应获得的二羧酸衍生物。加入3,000g N-甲基-2-吡咯烷酮以使上述化合物溶解。然后，通过使用油浴使反应在75℃下反应12小时。
接着，加入溶于500g N-甲基-2-吡咯烷酮中的32.8g(0.2mol)5-降冰片烯-2，3-二羧酸酐，并搅拌12小时以使反应完成。将该反应混合物过滤，然后倒入水/甲醇＝3/1的溶液中。过滤收集所得沉淀物，用水充分洗涤，并在真空下干燥，得到预期的聚酰胺(A-1)。*制备正光敏树脂组合物
将100g上面合成的聚酰胺(A-1)和25g具有下面提及的结构的重氮醌(B-1)溶于250g N-甲基-2-吡咯烷酮中。将所得溶液通过0.2-μm聚四氟乙烯过滤器过滤，得到光敏树脂组合物。在上面的结构中，各个Q为氢原子或
Figure A0080423000242
和70％的所有Q为：
Figure A0080423000251
*性能评估
将上述正光敏组合物用旋涂机涂覆于硅片上，接着在热板上于120℃下干燥4分钟，得到厚度约5μm的涂膜。在该涂膜上用g-线步进器，NSR-1505G3A(Nikon Corporation的产品)通过标准片(reticle)施加400mJ/cm2的光。
然后，将所得材料浸入1.40％氧化铵四甲基氢水溶液中以溶解并除去曝光部分，并用纯水漂洗30秒。结果，所得残余薄膜的比例[(显影后的薄膜厚度/(显影前的薄膜厚度))×100非常高，为93.1％。
然后，将所得材料在氮气气氛下于干净的烘箱中在150℃下固化30分钟，并在400℃下固化30分钟。固化薄膜的吸水量为0.3％。然后，然后将钝化薄膜通过活性离子刻蚀技术(RIE)进行刻蚀。然后通过溅射在其上形成Cr单一物质薄膜。(图2b)。
如图2c所示，通过镀覆形成布线金属薄膜。随后，如图2d所示，涂布正光敏树脂组合物并通过照相平版印刷技术形成图形(绝缘膜)7。随后，如图3b所示，通过镀覆，顺序形成阻挡金属8和焊料10。随后，如图4a所示，涂布助熔剂11并通过加热使焊料10熔化。随后，通过洗涤除去助熔剂11形成焊料凸点(如图4b所示)，并沿划痕线进行划线，得到单个芯片。
实施例2
按照与实施例1相同的方式进行制备和评估，不同的是，在实施例1的聚酰胺合成中，将通过1mol二苯基醚-4，4′-二羧酸与2mol1-羟基-1，2，3-苯并三唑反应获得的二羧酸衍生物，用通过1mol己二酸与2mol 1-羟基-1，2，3-苯并三唑反应获得的二羧酸衍生物取代，由此合成聚酰胺(A-2)。实施例3
按照与实施例1相同的方式进行制备和评估，不同的是，在实施例1的聚酰胺合成中，将六氟-2，2-双(3-氨基-4-羟苯基)丙烷用3，3′-二氨基-4，4′-二羟基二苯基砜取代，由此合成聚酰胺(A-3)。
实施例4
按照与实施例1相同的方式进行制备和评估，不同的是，在实施例1的聚酰胺合成中，将5-降冰片烯-2，3-二羧酸酐用马来酸酐取代以合成聚酰胺(A-4)，并将固化条件变为在氮气气氛下150℃×30min和420℃×30min。
实施例5
按照与实施例1相同的方式进行制备和评估，不同的是，将光敏树脂组合物中的光敏重氮醌化合物B-1变为下述化合物B-2，并如表1所示改变所使用的该化合物的量，并将固化条件变为在氮气气氛下150℃×30min和380℃×30min。
B-2：在上面的通式中，各个Q为氢原子或
Figure A0080423000262
和70％的所有Q为：
Figure A0080423000271
实施例6
按照与实施例1相同的方式进行制备和评估，不同的是，将光敏树脂组合物中的光敏重氮醌化合物B-1变为下述化合物B-3，并将固化条件变为在氮气气氛下150℃×30min和350℃×30min。在上面的通式中，各个Q为氢原子或
Figure A0080423000273
和60％的所有Q为：
Figure A0080423000274
实施例7
按与实施例1相同的方式进行制备和评估，不同的是，如表1所示改变光敏树脂组合物中的光敏重氮醌化合物B-1的量。
实施例8
按与实施例1相同的方式进行制备和评估，不同的是，将10g下面的双酚化合物C-1加入到实施例1的光敏树脂组合物中。
Figure A0080423000281
比较例1
采用对光不敏感的聚酰亚胺树脂CRC-6061(Sumitomo Bakelite有限公司的产品)生产类似于实施例1的倒装片。于其中已在钝化薄膜中用刻蚀剂形成通过孔的硅片上用旋涂机制备涂层，接着在热板上于140℃下干燥4分钟，得到厚度约5μm的涂膜。在其上用旋涂机涂布正刻蚀剂OFPR-800(Tokyo Ohka Kogyo Co.，Lid的产品)，接着在热板于100℃下干燥2分钟，得到厚度约2μm的涂膜。在该涂膜上用g-线步进器，NSR-1505G3A(Nikon Corporation的产品)通过标准片施加400mJ/cm2的光。然后，将所得材料浸入2.38％氢氧化四甲基铵水溶液中60秒以溶解并除去曝光部分，并用纯水漂洗30秒。
然后将所得材料在清洁烘箱中于氮气下在150℃下固化30分钟，并在400℃下固化30分钟。固化薄膜的吸水量为2.0％。
对光不敏感的聚酰亚胺导致加工精确性差，这样不能使用缓冲涂层作为活性离子刻蚀(RIE)的光掩模；因此必须通过使用刻蚀剂在钝化薄膜中形成通过孔。该固化膜具有高吸水性，因此可靠性差。比较例2
按与实施例1相同的方式进行制备和评估，不同的是将固化条件变为在氮气气氛下150℃×30min和270℃×30min。形成凸点后在缓冲涂膜中出现裂缝。
实施例和比较例中的测量结果在表1中给出。表1
 聚酰胺(A)(g) 光敏重氮醌(B)(g) 苯酚化合物(C)(g)   吸水量(％)  固化温度(℃)
实施例1  A-1  100     B-1  25      -     0.3     400
实施例2  A-2  100     B-1  25      -     0.2     400
实施例3  A-3  100     B-1  25      -     0.6     400
实施例4  A-4  100     B-1  25      -     0.3     420
实施例5  A-1  100     B-2  35      -     0.3     380
实施例6  A-1  100     B-3  25      -     0.3     350
实施例7  A-1  100     B-1  20      -     0.3     400
实施例8  A-1  100     B-1  25     10     0.3     400
比较例1   -      -      -     2     400
比较例2  A-1  100     B-1  25      -     0.3     270
(吸水量按照JIS K 6911测定)
从上表可以明显看出，在本发明中，将钝化层通过用光敏缓冲涂覆树脂(一种聚苯并噁唑树脂前体)刻蚀作为光掩模；因此，与常规技术相比，本发明能够显著减少操作步骤。此外，本发明的聚苯并噁唑树脂吸水量低且与封装树脂的粘结力优异，因此可提供价廉且高可靠性的半导体器件。
工业实用性
本发明具有正光敏树脂组合物并设置有凸点电极的半导体器件可用于电或电子产品如计算机(包括个人计算机)、电视、视频组件(videodecks)等中。

Claims (6)

1.一种半导体器件，包括：
(a)用于芯片保护的聚苯并噁唑树脂薄膜，它通过在电路形成芯片上涂覆正光敏树脂组合物，和将涂覆的组合物进行图形化并固化获得，所述正光敏树脂组合物包括100重量份下面通式(1)表示的聚酰胺和1至100重量份光敏重氮醌化合物，和
(b)凸点电极：其中X为四价芳基；Y为二价芳基；Z为(R1和R2各自为二价有机基团，R3和R4各自为单价有机基团)；E为具有至少一个链烯基或链炔基的羧基脂族、脂环族或芳族基团；a和b各自为摩尔分数，a+b＝100mol％，a＝60.0至100.0mol％，b＝0至40.0mol％，和n＝2至500。
2.根据权利要求1的半导体器件，其中正光敏树脂组合物包含下面通式(2)表示的双酚化合物和下面通式(3)表示的三酚化合物，其总量为1至30重量份：
Figure A0080423000023
其中R5和R6各自为氢原子或烷基，R7、R8、R9和R10各自为选自氢原子、卤原子、羟基、烷氧基、环烷基和烷基的原子或基团，和
Figure A0080423000031
其中R11为氢原子或烷基；R12、R13、R14、R15、R16和R17各自为选自氢原子、卤原子、羟基、烷基、烷氧基和环烷基的原子或基团。
3.根据权利要求2的半导体器件，其中所述双酚化合物与三酚化合物的比例优选为10∶90至90∶10。
4.根据权利要求1的半导体器件，其中所述聚酰胺的X选自如下基团：
Figure A0080423000032
5.根据权利要求1或2的半导体器件，其中所述聚酰胺的Y选自如下基团：
其中A为-CH2-、-C(CH3)2-、-O-、-S-、-SO2-、-CO-、-NHCO-或-C(CF3)2-。
6.根据权利要求1的半导体器件，其中该正光敏树脂组合物在280至440℃的温度下固化。
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