CN109216228B - 激光加工用保护膜剂 - Google Patents
激光加工用保护膜剂 Download PDFInfo
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Abstract
使得在激光加工时可以确实地被覆并保护晶片上的包括器件在内的表面,加工处理后可以用水清洗除去,可以进行在晶片表面见不到碎屑等附着的加工处理。一种激光加工用保护膜剂,所述激光加工用保护膜剂是在水溶性粘合剂的溶液中加入水溶性的激光吸收剂使波长355nm的吸光度(换算成200倍稀释溶液的吸光度)达到0.3~3而得到的。该保护膜确实地吸收所照射的激光,减少碎屑的发生,可以进行确实的加工。上述水溶性粘合剂可以是将聚乙烯醇和聚‑N‑乙烯基乙酰胺混合而得的粘合剂,以成分量计可以按照100~200:1的比例混合。
Description
技术领域
本发明涉及对晶片(ウェーハ)照射激光而进行划线(スクライビング)、切割(ダイシング)、切槽(开槽,グルービング)等加工时用于被覆并保护晶片表面的保护膜剂。
背景技术
以硅或蓝宝石等化合物为基板的LSI、CMOS、功率器件等带图案的晶片,各器件(デバイス,设备)通过切割道(ストリート)区分而形成多个。将这种以切割道纵横分离的器件通过切割道分割而单片化(個片化)成各个的器件时,通过刀片(ブレード)或激光照射进行切割,再通过激光进行处理也是有效的方法。
通过激光进行切割时,由于激光的照射,晶片的吸收了激光的部位会发生爆炸(爆発),爆炸的物质在晶片表面形成异物(碎屑,デブリ),附着在形成于切割道的加工槽附近,但有时也会附着在器件表面。
作为针对上述问题的处置方法,以往已知有下述方法:为了创造因爆炸而升华的碎屑飞散而不会附着于晶片的环境,吹辅助气体使从晶片表面飞散的碎屑通过气氛气体进行分解、气化的方法;或者真空抽吸或减压下的加工方法等。然而,在这些方法中,存在着装置的设置、装置的开动、运转操作的繁杂等,即使采用这种方法,有时也无法充分除去碎屑,期望改良。
由于上述情况,人们逐渐采用下述方法:在照射激光之前用树脂被覆、保护形成有各种器件的晶片表面,之后进行上述加工,加工后除去上述保护膜。
在该方法中,使用水溶性树脂液作为保护膜剂,利用旋转涂布机等将保护膜剂涂布在形成有器件的晶片表面以保护表面,再进行激光加工,之后冲洗掉碎屑和保护膜剂。(专利文献1)
另外,还已知:在上述保护膜剂中混合少量的激光吸收剂,以有效地进行碎屑的去除。(专利文献2)
但是,在这种方法中,虽然对于防止碎屑在切割道周边的晶片上粘结具有相当的效果,但碎屑会飞散并粘结在远离切割道的器件芯片的中心部,或者由于热变化有时会产生烤焦(ヤケ)、焦烧(コゲ)等,存在对芯片的保护性尚不充分的问题。
特别是,在相机所使用的摄像元件(图像传感器)中,即使在芯片表面的镜头上附着少许由如上述碎屑产生的污垢,也会降低元件的性能,成为不良率上升的重要原因,希望针对这种情况进行进一步的改良。
现有技术文献
专利文献
专利文献1:日本特开2007-73670号公报;
专利文献2:日本专利第4571850号公报。
发明内容
发明所要解决的课题
本发明想要获得在激光加工时将晶片表面以不仅包括沿着切割道的部分、还包括芯片中心部在内的表面可以更确实地被覆并保护,在切割等加工处理后用水清洗而将其除去,可以得到见不到碎屑附着的洁净的晶片表面的激光加工用保护膜剂。
用于解决课题的手段
本发明涉及激光加工用保护膜剂,所述激光加工用保护膜剂是在水溶性粘合剂的溶液中加入水溶性的激光吸收剂使波长355nm的吸光度(换算成200倍稀释溶液的吸光度)达到0.3~3而得到的。
上述水溶性粘合剂可以是将聚乙烯醇和聚-N-乙烯基乙酰胺混合而得的粘合剂,以成分量计可以按照100~200:1的比例混合。
另外,上述激光加工用保护膜剂的溶液优选使其pH值为5~8。
发明效果
根据本发明,可以在通过保护膜剂被覆并保护晶片表面的状态下进行划线、切割、切槽等激光加工。通过该保护膜剂可以抑制在激光加工中所产生的碎屑的发生,碎屑很少会飞散到晶片上的器件芯片上,即使碎屑飞散,也可以通过保护膜剂保护器件,之后通过水洗可以容易地将碎屑与保护膜剂一同除去,可以得到具有洁净的表面的晶片。而且,加工切割道的宽度也可以变窄,使得器件的更有效制造成为可能。
另外,在认为随着各种加工而产生的异物的再附着的各种激光加工处理操作中,可以广泛使用该保护膜剂。而且,对于Low-K膜等绝缘膜的通过激光切槽进行的、切槽工序(溝入れ工程)也可以使用该保护膜剂。
而且,该保护膜剂作为可以用水容易地清洗除去的水溶性保护膜,还可用于防止表面损伤等。
具体实施方式
在本发明的激光加工用保护膜剂中使用水溶性粘合剂的溶液。
作为水溶性粘合剂,可以使用各种粘合剂,例如有:聚乙烯醇、聚-N-乙烯基乙酰胺。该聚乙烯醇可以与聚-N-乙烯基乙酰胺混合使用。
作为上述聚-N-乙烯基乙酰胺,优选为N-乙烯基乙酰胺的均聚物。该聚-N-乙烯基乙酰胺的分解起始温度为约350℃,具有耐热性。
上述聚-N-乙烯基乙酰胺通常使用溶解于溶剂中的溶液态聚-N-乙烯基乙酰胺,上述聚乙烯醇与聚-N-乙烯基乙酰胺的混合比以其成分量计为100~200:1左右,优选120~170:1左右,可以少量使用聚-N-乙烯基乙酰胺。
对上述聚乙烯醇的重均分子量没有特别限定,通常可以使用5,000~30,000左右、优选7,000~20,000左右、进一步优选10,000~17,000左右的分子量。
另外,上述聚-N-乙烯基乙酰胺可以使用绝对分子量为10,000~1,800,000左右、优选20,000~700,000左右、更优选30,000~500,000左右、进一步优选40,000~270,000左右的聚-N-乙烯基乙酰胺。
上述聚乙烯醇和聚-N-乙烯基乙酰胺均为水溶性,作为其溶剂可以使用纯水,可以将纯水和异丙醇等醇类、甘油类、丙二醇单甲醚等二醇醚类等的一种或多种一同混合使用。混合这些物质时,可以改良在利用激光加工用保护膜剂来保护晶片表面时的润湿性或延展性等而提高涂布性等。
在上述的水溶性粘合剂的溶液中,加入吸收加工用激光的水溶性激光吸收剂。
作为进行激光加工时的激光的波长,已知有355nm的紫外线、532nm的可见光线、790nm或1064nm的红外线等。
作为对应于这些激光的激光吸收剂,例如,用于紫外线吸收的有三嗪类、二苯甲酮类、苯并三唑类、蒽类、二苯乙烯基联苯衍生物等,用于红外线吸收的可以列举1,1,5,5,-四[4-(二乙基氨基)苯基]-1,4-戊二烯-3-鎓对甲苯磺酸盐等。
作为上述二苯甲酮类激光吸收剂,有2-羟基-4-甲氧基二苯甲酮-5-磺酸(三水合物)等。
另外,还有其他的通常作为紫外线、可见光线、红外线的吸收剂而已知的吸收剂或色素、染料等。
上述激光吸收剂的使用量例如可以以上述波长355nm的吸光度(换算成200倍稀释溶液的吸光度)达到0.3~3左右、优选0.3~1.5左右的量使用,该使用量多于以往认为的吸光剂的使用量,达到了较高的浓度。上述吸光度是指通过后述(试验)中采用的方法测得的吸光度。
这种激光加工用保护膜剂通过利用旋转涂布机涂布、或者利用喷雾器涂布在晶片表面,可以得到均匀的涂布面,特别是不需要进行烘烤操作即可使用。
另外,如上所述,该激光加工用保护膜剂可以通过旋转涂布机、喷雾器等涂布在晶片表面,但为了防止从晶片表面迸开(はじかれる)、使润湿性良好而提高涂布性、进而提高溶液的保存稳定性,可以添加表面活性剂等。作为该表面活性剂,只要呈水溶性即可,可以使用非离子类、阳离子类、阴离子类、两性类的表面活性剂。
作为上述非离子类表面活性剂,例如可以列举:壬基苯酚类、高级醇类、多元醇类、聚氧亚烷基二醇类、聚氧乙烯烷基酯类、聚氧乙烯烷基醚类、聚氧乙烯烷基苯基醚类、聚氧乙烯脱水山梨糖醇烷基酯类等。
另外,作为阳离子类表面活性剂,例如有:季铵盐、胺盐;作为阴离子类表面活性剂,例如有:烷基苯磺酸及其盐、烷基硫酸酯盐、甲基牛磺酸盐、醚磺酸盐等;作为两性类表面活性剂,例如可以列举:咪唑啉甜菜碱类、酰胺丙基甜菜碱类、氨基二丙酸盐类等。这些表面活性剂可以适宜选择其一种或两种以上进行使用。通常,相对于保护膜剂总量,以有效成分计,该表面活性剂可以使用0.05质量%~5质量%。
另外,若需要,则可以为了增加保存性而加入苯基乙二醇等防腐剂。而且,还可以根据需要使用增塑剂、有机酸等。
关于该激光加工用保护膜剂,对作为溶液的pH值没有特别限定,但使其处于优选pH5~8左右、进一步优选为pH6~8左右的所谓中性区时,容易操作,对晶片处理装置的影响小,容易保守装置,对装置的损伤也小。上述pH值是指通过后述的(试验)中采用的方法测得的pH值。
对调节pH值的调节剂没有特别限定,可以使用各种pH值调节剂,在下述的实施例、比较例中,使用三乙醇胺来调节pH值。
如上所述,将激光加工用保护膜剂通过旋转涂布机、其他的涂布方法被覆在设有摄像元件等器件的晶片上而形成保护膜,从其上对切割道部分照射激光时,激光的确被充分地含有激光吸收剂的激光加工用保护膜剂所吸收,可以对切割道部分进行确实地加工用处理,还可以减少碎屑的发生、散发。
另外,在激光加工中,在相同的切割道多次往返,逐渐增加切入深度时,晶片的蒸发成分在切割道上部气氛化,因此一部分激光发生散射而照射在器件部分,从而还可以抑制在器件部产生污垢或发生烤焦等不良情形。
进行激光加工处理后,使用水清洗激光加工用保护膜剂或碎屑等。在进行这样的清洗时可以使用刷子、或者施加超声波、或者利用压榨空气或氮等气体与水的混合液进行清洗。由此,有时还可以有效地将保护膜与通过加工处理产生的上述碎屑一同除去。
为了制作下述的实施例、比较例,准备了以下的材料。
1. 聚乙烯醇(PVA):重均分子量为约15,000;
2. 聚-N-乙烯基乙酰胺-1 (PNVA-1):含有12.5质量%的绝对分子量为300,000的成分的溶液;
3. 聚-N-乙烯基乙酰胺-2 (PNVA-2):含有10质量%的绝对分子量为50,000的成分的溶液;
4. 激光吸收剂:2-羟基-4-甲氧基二苯甲酮-5-磺酸(三水合物) (355nm的激光的吸收剂);
5. 三乙醇胺(TEA) (pH值调节剂);
6. 苯基乙二醇(防腐剂);
7. 丙二醇单甲醚(PGM);
8. 纯水(离子交换水)。
实施例
(实施例1)
将16.2质量%的PVA、0.8质量%的PNVA-1、1.5质量%的激光吸收剂、0.6质量%的TEA、1.0质量%的苯基乙二醇、15.0质量%的PGM、64.9质量% (balance)的纯水充分混合,得到了激光加工用保护膜剂。
(实施例2~4)
按照实施例1,根据表1所示的配比,得到了实施例2~4的激光加工用保护膜剂。
(实施例5)
将13.1质量%的PVA、1.0质量%的PNVA-2、1.85质量%的激光吸收剂、0.75质量%的TEA、1.0质量%的苯基乙二醇、15.0质量%的PGM、67.3质量%(balance)的纯水充分混合,得到了激光加工用保护膜剂。
(实施例6、7)
按照实施例5,根据表2所示的配比,得到了实施例6、7的激光加工用保护膜剂。
(比较例1)
将16.2质量%的PVA、0.8质量%的PNVA-1、1.18质量%的激光吸收剂、0.5质量%的TEA、1.0质量%的苯基乙二醇、15.0质量%的PGM、65.32质量% (balance)的纯水充分混合,得到了激光加工用保护膜剂。
为了观察实施例和比较例的性状、性能,进行了以下的试验。
(试验)
1. 粘度
根据JIS K6833,测定了25℃下的粘度(mPa·s)。
2. pH值
根据JIS Z8802,测定了25℃下的pH值。
3. 吸光度
制作实施例和比较例的激光加工用保护膜剂的200倍稀释液,根据JIS K0115,在25℃下测定了355nm的吸光度(Abs)。
4. 综合评价
使用旋转涂布机在形成有照相机中使用的摄像元件(图像传感器)的晶片表面涂布上述实施例和比较例所示的激光加工用保护膜剂,通过355nm的激光进行切割处理,再进行清洗处理,对于所得物,使用激光显微镜检查了激光加工性是否良好和摄像元件的表面状态。
秀(◎):激光加工性良好,在器件表面未见碎屑附着,作为摄像元件优良。
优(○):与上述秀(◎)相比激光加工性稍差,在器件表面未见碎屑附着,作为摄像元件优良。
不良(×):与上述优(○)相比激光加工性差,在器件表面可见少许的碎屑附着。
(试验结果)
上述实验的结果见表1、表2。
(考察)
在实施例1的激光加工用保护膜剂中,PVA与PNVA-1的成分混合比为162:1,粘度为95.4、pH值为6.07、吸光度为0.369,综合评价为优。与实施例1相比,在实施例2的激光加工用保护膜剂中由于增加了激光吸收剂和TEA的添加量,而粘度为104.0、pH值为6.31(几乎相同程度),但吸光度高达0.450,综合评价为优。
在实施例3中,PVA与PNVA-1的成分混合比为120:1,激光吸收剂的添加量与实施例2相同,但TEA的添加量减少而粘度低至46.0及pH值低至4.15,吸光度为0.441,综合评价为优。
与实施例3相比,在实施例4中,PVA与PNVA-1的成分混合比为140:1,粘度高达69.2,pH值为4.41,吸光度为0.452,综合评价为优。
另外,在实施例1~4的激光加工用保护膜剂的溶液中确认到了少许的混浊。
在实施例5~7的激光加工用保护膜剂中,使用与PNVA-1相比绝对分子量小的PNVA-2,PVA与PNVA-2的成分混合比为131:1,在实施例5的激光加工用保护膜剂中,激光吸收剂的添加量与实施例3~4相同,由于TEA的添加量增加,而粘度为59.2、pH值为6.07,吸光度为0.442,综合评价为秀。
与实施例5相比,在实施例6的激光加工用保护膜剂中由于增加了激光吸收剂和TEA的添加量,而粘度为64.5、pH值为6.31(几乎相同程度),但吸光度增大达到0.628,综合评价为秀。
与实施例6相比,在实施例7的激光加工用保护膜剂中由于激光吸收剂和TEA的添加量进一步增加,而粘度为69.0、pH值为6.31(几乎相同程度),但吸光度增大达到0.940,综合评价为秀。
另外,与实施例1~4不同,在实施例5~7的激光加工用保护膜剂的溶液中没有确认到混浊。
如上述的实施例5~7所示的激光加工用保护膜剂中,在吸光度高达0.45~0.94左右、且激光加工用保护膜剂中的激光吸光度大的激光加工用保护膜剂中,碎屑的发生亦少,摄像元件等形成于晶片表面的器件的污染少,可以判断为得到了进一步优选的结果、即得到了优良的器件。另外,还可判断为:粘度优选60~70左右、且pH值优选6~6.4左右。
相对于此,在比较例1的激光加工用保护膜剂中,相对于实施例1而言,由于激光吸收剂和TEA的添加量减少,而粘度为99.6、pH值为6.15,与实施例1几乎相同程度,但吸光度只有0.280,综合评价为不良,判断为没有得到优选的结果。
需要说明的是,在比较例1的激光加工用保护膜剂的溶液中确认到了少许的混浊。
[表1]
[表2]
Claims (3)
1.激光加工用保护膜剂,所述激光加工用保护膜剂是在水溶性粘合剂的溶液中加入水溶性的激光吸收剂而得到的,其中上述水溶性粘合剂是将聚乙烯醇和聚-N-乙烯基乙酰胺以成分量计按照100~200:1的比例混合而得的,所述激光加工用保护膜剂的波长355nm的吸光度为0.628~3,所述吸光度是换算成200倍稀释溶液后的吸光度。
2.权利要求1所述的激光加工用保护膜剂,其中,上述聚-N-乙烯基乙酰胺的绝对分子量为10,000~1,800,000。
3.权利要求1或2所述的激光加工用保护膜剂,其中,上述激光加工用保护膜剂的溶液的pH值为5~8。
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JP2006140311A (ja) * | 2004-11-12 | 2006-06-01 | Tokyo Ohka Kogyo Co Ltd | レーザーダイシング用保護膜剤及び該保護膜剤を用いたウエーハの加工方法 |
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KR102375502B1 (ko) | 2022-03-17 |
US20190006295A1 (en) | 2019-01-03 |
US10700016B2 (en) | 2020-06-30 |
TW201906940A (zh) | 2019-02-16 |
JP2019012807A (ja) | 2019-01-24 |
CN109216228A (zh) | 2019-01-15 |
KR20190004206A (ko) | 2019-01-11 |
TWI647289B (zh) | 2019-01-11 |
SG10201804882RA (en) | 2019-02-27 |
JP6718174B2 (ja) | 2020-07-08 |
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