CN114214131A - 一种晶圆衬底抛光制程后清洗液 - Google Patents
一种晶圆衬底抛光制程后清洗液 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/004—Surface-active compounds containing F
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/008—Polymeric surface-active agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
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- C11D2111/22—
Abstract
本发明公开了一种用于晶圆衬底抛光制程后使用的清洗液,属于湿电子化学品领域,主要应用于大尺寸的半导体晶圆制程中。其关键在于羟基有机酸,5%‑15%阳离子表面活性剂3%‑10%,Gemini非离子表面活性剂1%‑5%,螯合剂2‑5%,余量为去离子水。该清洗液能有效替代现有的SC‑2清洗工艺,环保高效、使用简单,性能稳定、易清洗不残留,满足大尺寸晶圆制程使用。
Description
技术领域
本发明属于半导体工业化学清洗领域,具体涉及一种晶圆衬底抛光制程后清洗液。
技术背景
晶圆是制造半导体器件的基础性原材料,极高纯度的多晶硅经过拉晶、切片等工序制备成为晶圆,晶圆经过一系列半导体制造工艺形成极微小的电路结构,再经切割、封装、测试成为芯片,广泛应用到各类电子设备中。
晶圆制造过程主要包括7个相互独立的工艺流程:光刻、刻蚀、薄膜生长、扩散、离子注入、化学机械抛光(CMP)、金属化。作为晶圆制造的关键制程工艺之一,化学机械抛光指的是,通过化学腐蚀与机械研磨的协同配合作用,实现晶圆表面多余材料的高效去除与全局纳米级平坦化。当前CMP已经广泛应用于集成电路制造中对各种材料的高精度抛光。抛光时,抛光头将晶圆待抛光面压抵在粗糙的抛光垫上,借助抛光液腐蚀、微粒摩擦、抛光垫摩擦等耦合实现全局平坦化。抛光盘带动抛光垫旋转,通过先进的终点检测系统对不同材质和厚度的磨蹭实现3~10nm分辨率的实时厚度测量防止过抛,使晶圆衬底抛光后表面达到超高平整度。此外制程线宽不断缩减和抛光液配方愈加复杂均导致抛光后更难以清洗,在CMP工艺中,抛光液中的磨料和被去除的材料作为外来颗粒是CMP工艺的污染源,CMP后清洗的重点是去除抛光过程中带有的所有污染物,如果没有洗净,在表面形成小到几十纳米的微小颗粒,大到几百微米的冗余物颗粒。这些颗粒在光刻时会遮挡光线,造成集成电路结构上的缺陷,污染物可能会附着在晶圆表面,造成图案的不完整,影响芯片的电气特性,直接导致接下来制程的产品质量和良率降低。随着对CMP清洗后的颗粒物要求呈指数级降低,因此在12英寸及更大尺寸晶圆的CMP后清洗,需要具备更强大的清洁能力来实现更彻底的清洁效果。
目前较为普遍的清洗方法为RCA清洗,其清洗分为两步:
一、标准清洗液1(SC-1)清洗,是氨水、双氧水和水的混合物,主要去除有机物膜污染、金属等颗粒;
二、标准清洗液2(SC-2)清洗,是盐酸、双氧水和水的混合物,功能是去除无机物、一些碱金属和重金属。
但由于新制程的特殊需求,以及大尺寸硅片对清洗要求的提高,通过现有清洗液SC-1和SC-2的组合清洗方法,难以高效除去表面附着的冗余物,导致晶圆表面颗粒缺陷较多,影响后续生产。
发明内容
为解决上述技术问题,本发明提供一种晶圆衬底抛光制程后清洗液,用来替代SC-2清洗,其清洗过程简单,对环境友好,清洗效果优异,可以有效除去抛光后附着于晶圆表面的污染物颗粒且不残留,满足大尺寸晶圆的生产制程要求。
本发明解决其技术问题所采用的方案为:
一种晶圆衬底抛光制程后清洗液,以质量百分含量计,其组成如下:
羟基有机酸 5%-15%;
阳离子表面活性剂 3%-10%
Gemmi非离子表面活性 1%-5%;
螯合剂 2%-5%;
去离子水 余量;
总质量分数之和为100%。
上述晶圆衬底抛光制程后清洗液中,所述羟基有机酸是选自羟基乙酸、羟基丙酸、2-羟基丙二酸、2-羟基丁二酸中的一种,其中优选羟基丙二酸。羟基有机酸含有亲水的羟基,再除去SC-1残留的碱性物质同时,具备更优异的水溶性,在后续水洗阶段清洗液不残留;同时有机酸根具有配合作用,与抛光液残留的过渡性金属元素结合时,也可形成可溶性的配合物,其溶解性大大增加,有效避免了清洗后的污染物颗粒二次污染。
上述晶圆衬底抛光制程后清洗液中,所述阳离子表面活性烷基三甲基溴化铵,具体的表面活性剂为:十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵中的一种。烷基三甲基溴化铵类的阳离子表面活性剂具有较好的pH适应性,渗透性优良,并且具有抗静电性,保证不会产生二次污染,提高清洗后产品后续制程的良率;烷基甲基溴化铵类阳离子表面活性剂也不会引入其他金属离子,不会因清洗不净导致生产率和可靠性收到影响。
上述晶圆衬底抛光制程后清洗液中,所述的Gemini双子表面活性剂为氟碳型Gemini双子表面活性剂,其如结构式1表示:
式1 甘八醇二全氟丙酸酯
式1的氟碳型Gemini双子表面活性剂通过八甘醇将两个全氟丙酸分子连接起来,降低了极性基团之间的平衡距离,克服了离子头基间的电荷斥力或水化作用引起的分离倾向,促进其在界面或分子聚集体中的紧密排列,更加有效地降低表面能,因此其有更低的临界胶束浓度(cmc)和更高的表面活性,氟原子具有高电负性,C-F键键能很高,与一般非离子表面活性剂相比具有高热稳定性和化学稳定性,其更高的浊点的特性能有效适用于不同工艺不同温度的清洗设备使用。
上述晶圆衬底抛光制程后清洗液中,所述螯合剂为二己烯三胺五甲叉膦酸,该螯合剂具有极佳的水溶性和优异的热稳定性,可以和多个金属离子螯合,形成多个立体结构大分子螯合物,松散溶于水,有效防止抛光液残留的金属类颗粒物再次聚集,导致二次污染。
上述高效CF显影液组合物中,所述的去离子水为电子级去离子水,在25℃时,其电阻率不低于18MΩ。
本发明的显著优点在于:羟基有机酸含有亲水的羟基,具有更优异的水溶性,在后续水洗阶段清洗液不残留;通过添加特定氟碳的Gemini双子表面活性剂,提高了清洗剂对于晶圆表面顽固的冗余物颗粒的清洗能力;阳离子表面活性剂的能更有效提高清洗后的细小颗粒物分散性,不团聚造成二次污染,同时使晶圆表面带正电荷,提高下一工序金属化的均一性;螯合剂的选用大分子的有机膦酸类也是充分考虑到易清洗、稳定性和二次污染等因素的同时,尽量减少磷的相对含量。该晶圆衬底抛光制程后清洗液整体材料绿色环保,化学性能稳定,适合用于不同的工艺参数和清洗方法,清洗效果能满足大尺寸晶圆的工艺制程要求。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚完整的描述,本发明的示意性实施方式及其说明仅用于解释本发明,并不作为本发明的限定。
其中氟碳型Gemini双子表面活性剂的合成方法如下所示:
其制备方法为:
向200mL的三口瓶中加入0.22mol的八甘醇、0.1mol的全氟丙酸、80mL甲苯溶剂和加入0.01moL的对甲苯磺酸催化剂。三口瓶氮气保护下,接温度计、分水器、冷凝管,搅拌条件下以升温至回流,并保持回流条件下反应6~8小时,至分水器中不再有水生成,停止反应。
减压蒸馏除去甲苯溶剂后冷却至室温,以50mL饱和碳酸钠水溶液水洗多次,直至pH为中性,再用饱和氯化钠水溶液清洗。
将产物置于真空干燥箱,在80℃,-0.1MPa条件下干燥1h,四氢呋喃(THF)溶解粗品,减压抽滤,除去固体颗粒杂质。再用旋转蒸发仪旋除THF,得到最终产物Gemini非离子八甘醇氟碳表面活性剂。
根据1H NMR(δ, DMSO, 300 MHz)分析,其化学位移为(δ):3.52(s, 24H, O-CH2-CH2);3.63(t, 4H, O-CH2);4.20(t,4H, O=C-O- CH2)。
根据13C NMR(δ, DMSO, 300 MHz)分析,其化学位移δ为66.5;69.0;70.8;119.5;134.5;163.5
根据IR分析,3401.65cm-1,O-H伸缩振动吸收峰;2914.64cm-1,亚甲基伸缩振动吸收峰;1769.80cm-1,羰基伸缩振动吸收峰;1232.13cm-1,C-O深说振动吸收峰;1174.87和1119.49,C-F伸缩振动吸收峰。
实施例和比较例:用于晶圆衬底抛光制程后清洗液。
根据下表1所示的组成和质量百分含量分别制备了实施例和比较例的晶圆衬底抛光制程后清洗液。其配制方法为:常温下先将去离子水加入搅拌釜,在60r/m的转速下依次加入羟基有机酸、螯合剂、Gemini非离子表面活性剂、阳离子表面活性剂。每种材料投入后搅拌至体系澄清后再添加下一种材料;全部添加完毕后,继续搅拌30分钟。然后再依次通过孔径为1μm和0.2μm的两道滤芯进行过滤,最终获得所述清洗液。
DTAB--十二烷基三甲基溴化铵、
TTAB--十四烷基三甲基溴化铵、
CTAB--十六烷基三甲基溴化铵、
Gemini--甘八醇二全氟丙酸酯
BHMTPMPA--二己烯三胺五甲叉膦酸
TEBAC--苄基三乙基氯化铵
Tx-10--烷基酚聚氧乙烯(10)醚
TO5--BASF的异构十三醇聚醚
EDTA--乙二胺四乙酸
实验例:清洗液清洗性能测定
为了评价上述实施例1-5和对比例1-8的清洗液对抛光后晶圆的清洗能力,通过下述实验进行清洗液清洗能力的测定。
1、清洗液稳定性。
将10mL清洗液加入带有温度计的试管中,置入搅拌的水浴锅中,水浴锅缓慢升温(2℃/min),同时观察试管内的清洗液,如出现浑浊或分层,则记录当前温度。温度越高,稳定性越好。
评价效果如下:
○:>65℃
△:50~65℃
×:<50℃
2、抑泡测试
清洗和清洗后的漂洗制程,清洗剂若起泡性太强会影响清洗效果,而且容易残留。因此在保证清洗效果的同时,低泡清洗剂更有优势。具体发泡力测试如下:
在试管中分别装入5mL不同配方的清洗剂30%水溶液,用力摇动15s,测试摇动后的泡沫高度以及静置30秒后的泡沫高度,泡沫高度越低越好。泡沫高度评判结果如下:
○:停止时泡沫高度<2cm,静置后<1cm
△:停止时泡沫高度2~5cm,静置后<1.5cm
×:停止时泡沫高度>5cm,静置后>1.5cm
3、清洗能力测试
将抛光后的晶圆先经过SC-1清洗,不同的清洗液稀释至10%,在超声清洗槽中加热到50℃,设置超声频率为28Hz,浸泡3min。将晶圆取出后以超纯水冲洗30s,超纯水流速为1.5L/min。脱水干燥后卸片,以AOI全自动晶粒镜检机进行晶圆表面颗粒检测,对颗粒数据进行统计,颗粒数越少越好。评判结果如下:
○:<1000个
△:>1000个,<5000个
×:>5000个
通过表1表2对比可以分析出,与实施例4相比:对比例1的用不含羟基的有机酸,由于其酸性和水溶性都稍差,所以在清洗能力上有所不足;对比例2没有添加阳离子表面活性剂,体系的稳定性变差和抑泡性有所减弱,同时清洗后的二次污染导致清洗能力下降;对比例3采用其他类型阳离子表面活性剂,并不能达到TTAB的使用效果;对比例4和对比例5都选用了其他类型的非离子表面活性剂,从稳定性、抑泡性和清洗能力都无法和Gemini氟碳类的表面活性剂相提并论,也可以看出氟碳端基的Gemini表面活性剂对晶圆颗粒污渍的直接清洗效果决定作用;对比例7没有添加螯合剂,表面洗净的晶圆收到颗粒沉降与静电吸附,导致了二次污染;对比例8添加了常见的EDTA当螯合剂,EDTA对抛光液中的铈离子螯合能力欠佳,清洗效果不佳。
综上,本发明的积极进步结果在于:通过添加端基氟碳型Gemini双子表面活性剂,提高清洗液的浸润和渗透能力,有效清除晶圆表面附着的各类冗余污染物;通过阳离子表面活性剂提高体系稳定性,同时与螯合剂,能有效防止清洗脱落的污染物二次附着于晶圆表面而造成的污染;羟基有机酸有更好的水溶性和更强的酸性,有效清洗SC-1残留的碱性物质和其他微粒污染物。该清洗剂清洗效果好,产品性能稳定,泡沫少,适应不同的工艺参数,而且清洗液所选材料大都是环保或易降解的、对环境友好。
上述实施例对本发明进行了详细描述,但其只是作为范例,并非因此限制本发明的专利范围。凡是利用本发明说明书对本发明进行的等同任何修改和替代也都在本发明的范畴之中,均包括在本发明的专利保护范围内。
Claims (9)
1.一种晶圆衬底抛光制程后清洗液,其特征在于,以质量百分含量计,其组成如下:
羟基有机酸 5%-15%;
阳离子表面活性剂 3%-10%;
Gemmi非离子表面活性 1%-5%;
螯合剂 2%-5%;
去离子水 余量;
总质量分数之和为100%。
2.根据权利要求1所述的晶圆衬底抛光制程后清洗液,其特征在于,所述羟基有机酸为羟基乙酸、羟基丙酸、2-羟基丙二酸、2-羟基丁二酸中的一种。
3.根据权利要求2所述的晶圆衬底抛光制程后清洗液,其特征在于,所述羟基有机酸为羟基丙二酸。
4.根据权利要求1所述的晶圆衬底抛光制程后清洗液,其特征在于,所述阳离子表面活性为烷基三甲基溴化铵。
5.根据权利要求4所述的晶圆衬底抛光制程后清洗液,其特征在于,所述阳离子表面活性为十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵中的任意一种。
7.根据权利要求1所述的晶圆衬底抛光制程后清洗液,其特征在于,所述螯合剂为二己烯三胺五甲叉膦酸。
8.根据权利要求1所述的晶圆衬底抛光制程后清洗液,其特征在于,所述去离子水为电子级去离子水,在25℃时,其电阻率不低于18MΩ。
9.一种如权利要求书1-8任一项所述的晶圆衬底抛光制程后清洗液的制备方法,其特征在于,在常温下,先将去离子水加入搅拌釜,在60r/m的转速下依次加入羟基有机酸、螯合剂、Gemini非离子表面活性剂、阳离子表面活性剂,每种材料投入后搅拌至体系澄清后再添加下一种材料;全部添加完毕后,继续搅拌30分钟,然后再依次通过孔径为1μm和0.2μm的两道滤芯进行过滤,即获得晶圆衬底抛光制程后清洗液。
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