CN101335206A - 在平板显示器制造工艺中在基底上制造铜层的改进的方法 - Google Patents
在平板显示器制造工艺中在基底上制造铜层的改进的方法 Download PDFInfo
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Abstract
本发明涉及在平板显示器制造工艺中在基底上制造铜层的方法和装置,其中铜无电极地沉积在基底上以形成铜互连层。使用铜溶液在基底上形成铜互连层,该铜溶液含有:作为铜源的CuSO45H2O,作为络合剂的酒石酸钾钠或柠檬酸三钠,作为还原剂的乙醛酸盐/酯、乙醛酸或磷酸钠,作为稳定剂的硫有机化合物,和pH调节剂。
Description
相关申请的交叉引用
本申请要求007年4月4日提交的美国临时申请系列第10/910,091号的权益,该文献经引用完全并入本文。
技术领域
概括而言,本发明涉及TFT-LCD平板显示器制造领域。更具体地,本发明涉及在基底上沉积铜互连层的方法。
背景技术
使用多种蚀刻方法制造晶体管。但是,铜的干蚀刻不够有效,因为多数铜类物质不是挥发性的和/或蚀刻气体和副产物在多数情况下是腐蚀性的。在半导体工业中,已经开发出镶嵌法,其中首先制造通孔,然后通过干法(溅射)和湿法(电镀)的组合将铜填入孔中。在平板显示器工业中,铜的使用被认为如在半导体工业中那样降低了信号延迟,但是镶嵌法被认为不合适,因为这种方法需要比现有布线法多得多的步骤,且对于大的基底(例如对于G5TFT-LCD板,1.5米×1.8米)并不总是有效。这种方法的使用预计会产生一些技术障碍并提高制造成本。另一方面,也研究了铜的湿蚀刻。但是,更难于控制铜互连的形状,因为湿蚀刻不是各向异性而是各向同性的。
无电极镀铜在PCB(印刷线路板)工业中具有长的历史,且镀敷技术本身已经成熟。镀敷在相对较低成本和低工艺温度下产生共形的、高质量的铜。可以购得许多用于铜互连的铜溶液。多数传统铜溶液含有福尔马林作为还原剂和/或含有乙二胺四乙酸(或“EDTA”)作为络合剂。从环境、健康和安全(EHS)角度来说,福尔马林是应该尽可能减少应用的产品,因为其已知是人类的致癌产品。为了使其更有效,推荐将含有这种产品的溶液加热以提高铜的镀敷速率。但是,其在环境温度下已经是高度挥发性的,在加热时更增加了对人类的危险。
EDTA也是出于不同原因受到关注的产品:EDTA能够形成稳定的络合物,难以用废物处理设备处理。该产品的使用受到限制,因为必须使用大量氧化剂使这类稳定络合物分解。但是,EDTA用于TFT-LCD制造的应用需要极大量的氧化剂,这使得该方法成本太高。
这些市售铜溶液对于TFT-LCD用途不是令人满意的。因为所得互连厚度均匀性差,与基础层的粘合性差,表面粗糙度高和/或缺乏镀敷可再现性。
因此,需要比现有方法更环境友好、且不存在目前用于相同用途的溶液的缺陷的用于TLF-LCD铜互连的铜镀敷溶液。
发明概要
本文描述了在平板TFT-LCD制造环境中制造镀铜基底的新型方法。
在一个实施方案中,提供了在制造平板显示器时使用的制造镀铜基底的方法,其中该方法包括提供基底,在部分基底上提供催化层。然后通过使基底的至少被催化的部分暴露于铜溶液而将铜层无电极地施用到这部分上。该铜溶液包含:作为铜源的CuSO45H2O;络合剂,可包括酒石酸钾钠4H2O或柠檬酸三钠2H2O;还原剂,可包括乙醛酸盐/酯、乙醛酸(glyoxilicacid)或磷酸钠H2O;作为稳定剂的硫有机化合物;和pH调节剂,其在室温下将溶液pH值调节至9至12.5。
本发明的其它实施方案可以包括但不限于下列一种或多种特征:
-将催化层在大约15℃至大约35℃的温度调节大约5秒至大约3分钟的时长;
-通过将镀铜基底在包含大约1体积%至大约3体积%的氢(余量为氮)的气氛下加热而将镀铜基底退火;
-在铜层上提供抑制氧化的覆盖层,其中该覆盖层是NiP或NiXP层(其中X是选自W、Mo或Re的难熔金属),且覆盖层为大约100纳米至大约300纳米厚;
-通过使基础层暴露于AgNO3在NH4OH溶液中的混合物而在基础层上提供薄催化银层,由此提供催化层,其中所述混合物包含在大约0.01%至大约1%NH4OH溶液中的大约0.1克/升至大约10克/升的AgNO3,所述混合物更优选包含在大约0.1%至大约0.5%NH4OH溶液中的大约1克/升至大约5克/升的AgNO3;
-通过使基础层暴露于(NH3)4PdCl2在NH4OH溶液中的混合物而在基础层上提供薄的催化钯层,由此提供催化层,其中所述混合物包含在大约0.01%至大约1%NH4OH溶液中的大约0.1克/升至大约1.0克/升的(NH3)4PdCl2,所述混合物更优选包含在大约0.01%至大约1%NH4OH溶液中的大约0.3克/升至大约0.7克/升的(NH3)4PdCl2;
-镀铜溶液进一步包含大约0.1克/升至大约10克/升NiSO46H2O;
-使催化层暴露于包含在溶液中的大约0.01%至大约5%、更优选大约0.1%至大约2%的乙醛酸盐/酯或次膦酸盐/酯(phosphinate)的混合物,由此调节催化层;
-使催化层暴露于包含在溶液中的大约0.1克/升至大约5克/升、更优选大约0.5克/升至大约3克/升的二甲胺硼烷(DMAB)的混合物,由此调节催化层;
-铜溶液包含大约2克/升至大约15克/升的CuSO45H2O;
-铜溶液包含大约40克/升至大约100克/升、更优选大约65克/升至大约85克/升的酒石酸钾钠4H2O;
-铜溶液包含大约10克/升至大约100克/升、更优选大约50克/升至大约90克/升的柠檬酸三钠2H2O;
-铜溶液包含大约0.01体积%至大约5体积%的乙醛酸盐/酯或乙醛酸;
-铜溶液包含大约5克/升至大约50克/升的次膦酸钠(sodiumphosphinate);
-稳定剂包含大约1ppb至大约100ppb的硫脲;
-在不加热铜溶液的情况下基本在室温、优选大约15℃至大约35℃下提供铜层;和
-通过不含福尔马林或乙二胺四乙酸(EDTA)的铜溶液提供铜层。
上文相当广泛地列出了本发明的特征和技术优点,以便更好理解下列发明详述。下文将描述构成本发明权利要求的主题的本发明其它特征和优点。本领域技术人员应该理解的是,可以容易地利用所公开的概念和具体实施方案作为修改或设计用于实现本发明的相同目的的其它结构的基础。本领域技术人员还应该认识到,这类同等构造不背离所附权利要求所列的本发明的实质和保护范围。
附图简述
为了进一步理解本发明的性质和目的,应该联系附图参看下列详述,在附图中为类似元件提供相同或类似的附图标记,其中:
图1显示了根据本发明在基底上提供铜层的一个实施方案的示意图。
优选实施方案描述
概括而言,本发明涉及在制造平板显示器时使用的制造镀铜基底的方法,其中该方法包括提供基底、在部分基底上提供催化层。然后通过使基底的至少被催化的部分暴露于铜溶液而将铜层无电极地施用到这部分上。所述铜溶液包含:作为铜源的CuSO45H2O;络合剂,可包括酒石酸钾钠4H2O或柠檬酸三钠2H2O;还原剂,可包括乙醛酸盐/酯、乙醛酸或磷酸钠H2O;作为稳定剂的硫有机化合物;和pH调节剂,其在室温将溶液pH值调节至9至12.5。
在一些实施方案中,催化步骤在15℃至大约35℃的室温进行。在一个实施方案中,可以使用在NH4OH溶液中的AgNO3在基础层上制造薄催化银层(其中基础层可以是NiP和NiXP层,其中X是诸如W、Mo或Re的难熔金属),该基础层在催化之前沉积在基底上。例如,使用在0.01%至1%NH4OH溶液中的0.1克/升至10克/升的AgNO3;更优选使用在0.1%至0.5%NH4OH溶液中包含1克/升至5克/升AgNO3的溶液。
在另一实施方案中,可以使用在NH4OH溶液中的(NH3)4PdCl2将薄催化钯层沉积在NiP或NiXP基础层上。例如,使用在0.01%至1%NH4OH溶液中的0.1克/升至1.0克/升的(NH3)4PdCl2,更优选在0.1%至0.5%NH4OH溶液中的0.3克/升至0.7克/升的(NH3)4PdCl2。各个催化步骤可以进行例如5秒至3分钟的合适时间。然后,将其用DIW(去离子水)清洗。
在一些实施方案中,可以通过使催化层暴露于调节溶液而调节催化层。该步骤通常在15℃至35℃的室温进行大约10秒至大约5分钟的时长。根据一个实施方案,可以使用包含0.01%至5%、更优选0.1%至2%的乙醛酸盐/酯或次膦酸盐/酯的溶液作为调节溶液。根据另一实施方案,可以使用包含0.1克/升至5克/升、更优选0.5克/升至3克/升的DMAB(二甲胺硼烷)溶液作为调节溶液。
在一些实施方案中,镀铜溶液包含2克/升至15克/升CuSO45H2O作为铜源。该溶液还可以包含络合剂,例如酒石酸盐或柠檬酸盐化合物。例如,该溶液可以含有40克/升至100克/升的酒石酸钾钠4H2O或10克/升至100克/升的柠檬酸三钠2H2O。
在一些实施方案中,铜溶液还可以包含选自由乙醛酸盐/酯和次膦酸盐/酯化合物组成的组的还原剂。例如,该溶液可以含有0.01%至5%的乙醛酸或5克/升至50克/升次膦酸钠H2O。
在一些实施方案中,可以在溶液中加入镍化合物以促进镀铜。例如,该溶液可以含有0.1克/升至10克/升的NiSO46H2O。该溶液还可以含有充当稳定剂的硫有机化合物。例如,该溶液可以含有大约1ppb至大约100ppb的硫脲。可以使用碱性溶液,例如NaOH或NH4OH,将溶液的pH值调节至9至12.5。
当对至少部分催化层施用铜溶液时,其可以无电极地施用,因为镀敷通过接触发生而不使用电极。镀敷时间通常由所需厚度决定,该时间通常为1分钟至60分钟,更优选3分钟至30分钟,以获得数百纳米的铜层。然后可以用DIW清洗基底以去除过量铜溶液。
在一些实施方案中,可以在施用铜层后将基底退火。可以在进行镀铜步骤后以传统方式加热样品,例如在400℃加热1小时或在150℃加热3小时。退火可以在包含1-10%氢和余量氮的气氛下,在大气压或真空压力下进行。
在一些实施方案中,可以在铜层上添加覆盖层以避免铜层的任何化学反应(即氧化)。根据一个实施方案,可以在铜层上无电极地施用10纳米至300纳米的NiP或NiXP(其中X是诸如W、Mo、Re的难熔金属)。
在一些实施方案中,制备镀铜溶液并在接近室温的温度条件(例如大约15℃至大约35℃)下提供铜层。
在一些实施方案中,镀铜溶液不含福尔马林——一种具有已知的环境、健康和安全问题的已知致癌物质。同样地,镀铜溶液不含乙二胺四乙酸(EDTA)--另一常用作络合剂的物质,其具有许多安全问题。
现在参看图1,下文将描述根据本发明的在制造平板显示器时使用的在基底上提供铜层的方法的实施方案。通常,图1显示了平板显示器制造法中的几个步骤的示意图,参考字母(a)-(h)是指这些步骤的一种时间次序。
在一个实施方案中,提供基底1,然后在其上提供NiP或NiPX的基础层2。在基础层2上提供催化层3,其通常比基础层2薄。然后可以任选地调节催化层3。然后可在催化层3上无电极地沉积铜层4。通常,通过使至少部分催化层与镀铜溶液接触而提供铜层。根据本领域技术人员已知的方法,在铜层4上沉积光致抗蚀剂5的图案,以画出沟槽7和8的图案。然后,同样根据本领域技术人员已知的方法,通过湿蚀刻溶液去除位于沟槽7和8下方的层2、3和4。然后将层5和6的剩余部分溶解,以在基底1上提供两叠互连轨道,分别为2a、3a、4a和2b、3b和4b。然后可以用热源9热处理基底1和轨道。然后可用保护层10和11将互连轨道覆盖。
实施例
提供下列非限制性实施例以进一步例示本发明的实施方案。但是,这些实施例不是完全穷尽的,且不是要限制本文所述的本发明的保护范围。
实施例1:
在镀铜之前,使用公知的无电极镀敷法在基底上镀敷50纳米NiP层。然后将样品在AgNO3溶液(在0.3%NH4OH中的1.5克/升AgNO3)中浸渍30秒,然后用去离子水(DIW)清洗,并浸入镀铜溶液,该镀铜溶液包含:
a)CuSO45H2O:7.5克/升;
b)C4H4KNaO65H2O:85克/升;
c)NiSO46H2O:1克/升;
d)乙醛酸:0.8重量%;和
e)硫脲:5ppb。
用NaOH将溶液pH值调节至12,并将该溶液保持在室温下。
然后将样品在H2/N2气氛(1%-99%)下在150℃下退火3小时。镀在NiP层上的铜表现出与基底的良好粘合性。通过原子力显微镜(AFM)进行的表面分析表现出小的粗糙度。通过俄歇电子能谱(AES)进行的深度分布分析表明铜层中仅有轻微杂质。
实施例2:
使用包含60克/升C4H4KnaO65H2O并具有11.5的pH值的铜溶液,所有其它条件与实施例1中相同。镀在NiP层上的铜表现出与基底的良好粘合性。通过AFM的表面分析表现出小的粗糙度。通过AES的深度分布分析表明铜层中仅有轻微杂质。
实施例3:
按照与实施例1中相同的条件进行镀铜步骤,不同的是乙醛酸浓度为0.2%。镀在NiP层上的铜表现出与基底的良好粘合性。通过AFM的表面分析表现出小的粗糙度。通过AES的深度分布分析表明铜层中仅有轻微杂质。还原剂浓度(乙醛酸)的降低导致较低的镀敷速率。
实施例4:
按照与实施例1中相同的条件进行镀铜步骤,不同的是该溶液的pH值保持至11.0且乙醛酸浓度为1.8%(较高的乙醛酸浓度提高了镀敷速率)。镀在NiP层上的铜表现出与基底的良好粘合性。通过AFM的表面分析表现出小的粗糙度。通过AES的深度分布分析表明铜层中仅有轻微杂质。
实施例5:
按照与实施例1中相同的条件进行镀铜步骤,不同的是在镀铜步骤之前在基底上镀敷50纳米NiXP(X是W、Mo或Re)而非NiP。镀在NiXP层上的铜表现出与基底的良好粘合性。通过AFM的表面分析表现出小的粗糙度。通过AES的深度分布分析表明铜层中仅有轻微杂质。
实施例6:
在镀铜之前,使用公知的无电极镀敷法在基底上镀敷50纳米NiP层。然后将样品在(NH3)4PdCl2溶液(在0.2%NH4OH中的0.6克/升(NH3)4PdCl2)中浸渍2分钟,然后浸入镀铜溶液中,该镀铜溶液包含:
a)CuSO45H2O:6.0克/升;
b)Na3C6H5O72H2O:15.3克/升;
c)NiSO46H2O:0.5克/升;和
d)NaH2PO2H2O:28.6克/升。
通过添加H3BO3和NaOH缓冲剂将溶液pH值调节至9.5,并保持在65℃。
在NiP层上镀铜,且铜层如实施例1至5中那样表现出良好的性质。
按照与实施例1中相同的条件进行对比例,但具有下列差别:
对比例1:
不预先沉积NiP或NiXP层,尝试在基底上镀铜。铜沉积据观察具有差的均匀性和/或与基底的粘合性差。
对比例2:
在不进行催化步骤的情况下在基底上镀铜。没有观察到铜沉积。
按照类似方式进行催化步骤,其中AgNO3的浓度超出了对于AgNO3的0.1克/升至10克/升的范围,和/或NH4OH的浓度超出了对于NH4OH的0.01%至1%的范围,此时,铜层沉积的可再现性不令人满意。
对比例3:
在低于0.01%的乙醛酸浓度下,尝试在基底上镀铜。观察到的镀敷速率太低或没有发生铜沉积。相反,当乙醛酸浓度增至高于5%时,镀敷速率保持良好,但溶液变得不稳定并迅速分解。
对比例4:
不在铜溶液中加入硫有机化合物。
铜沉积或铜层在基底上的均匀性或粘合性没有显著变化。但是,铜溶液变得更不稳定并在短时间内分解。相反,当硫有机化合物浓度高于100ppb时,镀敷速率变得太低以致不能获得合适的铜层厚度。
对比例5:
铜溶液在高于35℃下加热。镀敷速率仍然足够好,但溶液变得不稳定并迅速分解。
对比例6:
C4H4KNaO65H2O浓度保持低于40克/升,但铜溶液然后非常迅速地不规则地产生了意料外的沉淀。相反,当所述物质浓度保持高于100克/升时,镀敷再现性变差。
对比例7:
将铜溶液的pH值调节至低于9。没有观察到镀铜。另一方面,当pH值保持高于12.5时,镀敷速率变高,但观察到较差的铜层粘合性和较短的溶液贮存寿命。
尽管已经显示和描述了本发明的实施方案,但本领域技术人员可以在不背离本发明的实质或教导的情况下对其作出修改。本文所述的实施方案仅是示例性而非限制性的。该组合物和方法的许多变动和修改是可能的并在本发明的范围内。相应地,保护范围不限于本文所述的实施方案,而是仅受下列权利要求的限制,其范围应包括权利要求的主题的所有对等物。
Claims (20)
1.通过在基底上无电极地沉积铜互连层而在用于制造平板显示器的基底上制造铜层的方法,包括:
a)提供基底;
b)在至少部分基底上提供催化层;和
c)通过使所述被催化的部分暴露于铜溶液,在基底的至少部分被催化的部分上提供铜层,并由此形成镀铜基底,其中所述铜溶液包含:
1)作为铜源的CuSO45H2O;
2)络合剂,包含酒石酸钾钠4H2O或柠檬酸三钠2H2O;
3)还原剂,包含选自由乙醛酸盐/酯、乙醛酸或磷酸钠H2O组成的组中的至少一种;
4)稳定剂,包含硫有机化合物;和
5)pH调节剂,其在室温将铜溶液的pH值调节为9至12.5。
2.权利要求1的方法,进一步包括在提供铜层之前调节催化层,其中在大约15℃至大约35℃进行调节,且其中调节进行大约5秒至大约3分钟的时间。
3.权利要求1的方法,进一步包括将镀铜基底退火,其中退火包括在包含大约1体积%至大约3体积%的氢(余量为氮)的气氛下加热该基底。
4.权利要求1的方法,进一步包括在铜层上提供抑制氧化的覆盖层,其中:
a)覆盖层是NiP或NiXP层,其中X是选自由W、Mo和Re组成的组的难熔金属;且
b)覆盖层的厚度为大约100纳米至大约300纳米。
5.权利要求1的方法,进一步包括在提供催化层之前在基底上提供基础层,其中基础层包含NiP或NiXP层,且X是选自由W、Mo和Re组成的组的难熔金属。
6.权利要求5的方法,其中提供催化层包括通过使基础层暴露于AgNO3在NH4OH溶液中的混合物而在基础层上提供薄催化银层,其中该混合物包含在大约0.01%至大约1%NH4OH溶液中的大约0.1克/升至大约10克/升的AgNO3。
7.权利要求5的方法,其中提供催化层包括通过使基础层暴露于(NH3)4PdCl2在NH4OH溶液中的混合物而在基础层上提供薄催化钯层,其中该混合物包含在大约0.01%至大约1%NH4OH溶液中的大约0.1克/升至大约1.0克/升的(NH3)4PdCl2。
8.权利要求1的方法,其中所述镀铜溶液进一步包含大约0.1克/升至大约10克/升的NiSO46H2O。
9.权利要求2的方法,进一步包括通过使催化层暴露于调节混合物而调节催化层,所述调节混合物包含在溶液中的大约0.01%至大约5%的乙醛酸盐/酯或次膦酸盐/酯。
10.权利要求2的方法,进一步包括通过使催化层暴露于调节混合物而调节催化层,所述调节混合物包含在溶液中的大约0.1克/升至大约5克/升的二甲胺硼烷(DMAB)。
11.权利要求1的方法,其中所述铜溶液包含大约2克/升至大约15克/升的CuSO45H2O。
12.权利要求1的方法,其中所述铜溶液包含大约40克/升至大约100克/升的酒石酸钾钠4H2O。
13.权利要求12的方法,其中所述铜溶液包含大约65克/升至大约85克/升的酒石酸钾钠4H2O。
14.权利要求1的方法,其中所述铜溶液包含大约10克/升至大约100克/升的柠檬酸三钠2H2O。
15.权利要求14的方法,其中所述铜溶液包含大约50克/升至大约90克/升的柠檬酸三钠2H2O。
16.权利要求1的方法,其中所述铜溶液包含大约0.01体积%至大约5体积%的乙醛酸盐/酯或乙醛酸。
17.权利要求1的方法,其中所述铜溶液包含大约5克/升至大约50克/升的次膦酸钠。
18.权利要求1的方法,其中所述稳定剂包含大约1 ppb至大约100ppb的硫脲。
19.权利要求1的方法,进一步包括在不加热铜溶液的情况下在室温提供铜层。
20.权利要求1的方法,进一步包括用不含福尔马林或乙二胺四乙酸(EDTA)的铜溶液提供铜层。
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US4617205A (en) * | 1984-12-21 | 1986-10-14 | Omi International Corporation | Formaldehyde-free autocatalytic electroless copper plating |
JP2001181854A (ja) * | 1999-12-22 | 2001-07-03 | Ebara Corp | 無電解めっき液及びこれを用いた配線形成方法 |
JP2003013247A (ja) * | 2001-04-24 | 2003-01-15 | Murata Mfg Co Ltd | 無電解銅めっき浴及び高周波用電子部品 |
US6887776B2 (en) * | 2003-04-11 | 2005-05-03 | Applied Materials, Inc. | Methods to form metal lines using selective electrochemical deposition |
US7008871B2 (en) * | 2003-07-03 | 2006-03-07 | International Business Machines Corporation | Selective capping of copper wiring |
US20050006339A1 (en) * | 2003-07-11 | 2005-01-13 | Peter Mardilovich | Electroless deposition methods and systems |
US7256111B2 (en) * | 2004-01-26 | 2007-08-14 | Applied Materials, Inc. | Pretreatment for electroless deposition |
-
2007
- 2007-11-30 US US11/948,320 patent/US20080248194A1/en not_active Abandoned
-
2008
- 2008-03-25 TW TW097110501A patent/TW200901293A/zh unknown
- 2008-04-01 CN CNA2008100902166A patent/CN101335206A/zh active Pending
- 2008-04-01 SG SG200802533-0A patent/SG146600A1/en unknown
- 2008-04-02 JP JP2008096455A patent/JP2009009097A/ja active Pending
- 2008-04-03 KR KR1020080031392A patent/KR20080090351A/ko not_active Application Discontinuation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106169386A (zh) * | 2015-05-22 | 2016-11-30 | Ls产电株式会社 | 用于制备含镀Ag CNTs的电触头材料的方法 |
CN106169386B (zh) * | 2015-05-22 | 2019-01-22 | Ls 产电株式会社 | 用于制备含镀Ag CNTs的电触头材料的方法 |
US10210965B2 (en) | 2015-05-22 | 2019-02-19 | Lsis Co., Ltd. | Method for electrical contact materials including Ag plated CNTs |
CN108267870A (zh) * | 2016-12-30 | 2018-07-10 | 财团法人工业技术研究院 | 铜箔复材 |
Also Published As
Publication number | Publication date |
---|---|
TW200901293A (en) | 2009-01-01 |
SG146600A1 (en) | 2008-10-30 |
KR20080090351A (ko) | 2008-10-08 |
JP2009009097A (ja) | 2009-01-15 |
US20080248194A1 (en) | 2008-10-09 |
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