CN112813416A - 薄膜制造方法 - Google Patents

薄膜制造方法 Download PDF

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Publication number
CN112813416A
CN112813416A CN202011015851.5A CN202011015851A CN112813416A CN 112813416 A CN112813416 A CN 112813416A CN 202011015851 A CN202011015851 A CN 202011015851A CN 112813416 A CN112813416 A CN 112813416A
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film
thin film
growth inhibitor
precursor
forming
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CN202011015851.5A
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Inventor
延昌峰
郑在善
边惠兰
宋泰浩
金素贞
李锡宗
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Soulbrain Co Ltd
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Soulbrain Co Ltd
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
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    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
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Abstract

涉及薄膜制造方法，其包括：步骤(ⅰ)，使薄膜形成用生长抑制剂吸附在基板表面；以及步骤(ⅱ)，使金属膜前体、金属氧化膜前体、金属氮化膜前体或硅氮化膜前体吸附在吸附有生长抑制剂的基板表面，薄膜形成用生长抑制剂由化学式1表示，金属为选自钨、钴、铬、铝、铪、钒、铌、锗、镧系元素、锕系元素、镓、钽、锆、钌、铜、钛、镍、铱以及钼中的一种以上。本发明通过抑制副反应，降低薄膜生长速率，并通过去除薄膜内的工艺副产物，即便在具有复杂结构的基板上形成薄膜时，也大幅提高阶梯覆盖率及薄膜的厚度均匀性。化学式1：AnBmXoA为碳或硅，B为氢或碳原子数为1至3的烃基，X为卤素，n为1至15的整数，o为1以上的整数，m为0至2n+1。

Description

薄膜制造方法
技术领域
本发明涉及薄膜制造方法，更详细涉及通过抑制副反应，适当地降低薄膜生长速率，并通过去除薄膜内的工艺副产物，防止腐蚀及劣化，即便在具有复杂结构的基板上形成薄膜时，也大幅提高阶梯覆盖率(step coverage)及薄膜的厚度均匀性的薄膜制造方法。
背景技术
存储及非存储半导体元件的集成度在日趋提高，随着其结构变得越来越复杂，在将多种薄膜沉积到基板时，阶梯覆盖率(step coverage)的重要性越来越高。
所述半导体用薄膜由金属氮化物、金属氧化物、金属硅化物等形成。所述金属氮化物薄膜有氮化钛(TiN)、氮化钽(TaN)、氮化锆(ZrN)等薄膜，所述薄膜通常用于被掺杂的半导体的硅层与用作层间配线材料的铝(Al)、铜(Cu)等之间的防扩散膜(diffusionbarrier)。只是，当将钨(W)薄膜沉积到基板时，用作粘结层(adhesion layer)。
为了使沉积到基板的薄膜获得优秀且均匀的物性，所形成的薄膜需具备优秀的阶梯覆盖率。因此，比起主要利用气相反应的化学气相沉积(CVD，chemical vapordeposition)工艺，更多地采用利用表面反应的原子层沉积(ALD，atomic layerdeposition)工艺，但在实现100％的阶梯覆盖率(step coverage)方面仍然存在问题。
另外，为了沉积在所述金属氮化物中具有代表性的氮化钛(TiN)而使用四氯化钛(TiCl4)，此时，所制造的薄膜内会残留氯化物等工艺副产物，从而诱发铝等金属的腐蚀，并因生成非挥发性副产物而导致膜质的劣化。
因此，需要开发一种薄膜的制造方法，该方法能够形成结构复杂的薄膜且不腐蚀层间配线材料。
在先技术文献
专利文献
(专利文献0001)韩国公开专利第2006-0037241号
发明内容
技术问题
为了解决如上所述的现有技术的问题，本发明的目的在于提供一种薄膜制造方法，该方法通过抑制副反应，适当地降低薄膜生长速率，并通过去除薄膜内的工艺副产物，防止腐蚀及劣化，即便在具有复杂结构的基板上形成薄膜时，也大幅提高阶梯覆盖率(stepcoverage)及薄膜的厚度均匀性。
能够通过以下说明的本发明，实现本发明的上述目的及其他目的。
技术方案
为了实现上述目的，本发明提供一种薄膜制造方法，其包括：步骤(ⅰ)，使薄膜形成用生长抑制剂吸附在基板表面；以及步骤(ⅱ)，使金属膜前体、金属氧化膜前体、金属氮化膜前体或硅氮化膜前体吸附在吸附有薄膜形成用生长抑制剂的基板表面，其中，所述薄膜形成用生长抑制剂由化学式1表示，所述金属为选自钨、钴、铬、铝、铪、钒、铌、锗、镧系元素、锕系元素、镓、钽、锆、钌、铜、钛、镍、铱以及钼中的一种以上，
化学式1：
AnBmXo
其中，所述A为碳或硅，所述B为氢或碳原子数为1至3的烃基，所述X为卤素，所述n为1至15的整数，所述o为1以上的整数，m为0至2n+1。
另外，本发明提供一种薄膜制造装置，其包括：ALD(原子层沉积)腔室；第一汽化器，使薄膜形成用生长抑制剂汽化；第一移送单元，将汽化的薄膜形成用生长抑制剂移送至ALD腔室内；第二汽化器，使金属膜前体、金属氧化膜前体、金属氮化膜前体或硅氮化膜前体汽化；以及第二移送单元，将汽化的所述前体移送至ALD腔室内。
有益效果
本发明提供一种薄膜制造方法，该方法通过抑制副反应并降低沉积速度，适当地降低薄膜生长速率，并通过去除薄膜内的工艺副产物，防止腐蚀及劣化，即便在具有复杂结构的基板上形成薄膜时，也大幅提高阶梯覆盖率(step coverage)及薄膜的厚度均匀性。
附图说明
图1是用于说明现有的ALD工艺的工艺图。
图2是用于说明本发明的一实施例的ALD工艺的工艺图。
图3是示出本发明的实施例7(SP-TiCl4)及比较例1(TiCl4)的薄膜厚度随ALD周期增加而变化的图。
图4是示出本发明的实施例7-1至7-3及比较例1的沉积速度随每ALD周期薄膜形成用生长抑制剂(SP)的供给(feeding)时间变化的图。
图5是在本发明的实施例1(SP-TiCl4)及比较例1(TiCl4)中所沉积的TiN薄膜的透射电子显微镜(TEM)照片。
图6是示出本发明的附加实施例2及附加比较例1的沉积速度
Figure BDA0002699029710000031
随每ALD周期薄膜形成用生长抑制剂(SP)的供给(feeding)时间(s)变化的图。
具体实施方式
以下，对本发明的薄膜制造方法进行详细的说明。
本发明的发明人确认了在将膜前体化合物吸附到装载于ALD腔室内部的基板表面之前，使具有规定结构的卤代化合物作为生长抑制剂先吸附于该基板表面时，经沉积后形成的薄膜的生长速率降低，且作为工艺副产物残留的卤化物大幅减少，从而大幅提高阶梯覆盖率等，基于此，进一步进行研究，完成了本发明。
本发明的薄膜制造方法包括：步骤(ⅰ)，使薄膜形成用生长抑制剂吸附在基板表面；以及步骤(ⅱ)，使金属膜前体、金属氧化膜前体、金属氮化膜前体或硅氮化膜前体吸附在吸附有薄膜形成用生长抑制剂的基板表面，其中，所述薄膜形成用生长抑制剂由化学式1表示，所述金属为选自钨、钴、铬、铝、铪、钒、铌、锗、镧系元素、锕系元素、镓、钽、锆、钌、铜、钛、镍、铱以及钼中的一种以上，
化学式1：
AnBmXo
其中，所述A为碳或硅，所述B为氢或碳原子数为1至3的烃基，所述X为卤素，所述n为1至15的整数，所述o为1以上的整数，m为0至2n+1。在这种情况下，当形成薄膜时，通过抑制副反应，降低薄膜生长速率，并通过去除薄膜内的工艺副产物，减少腐蚀及劣化，即便在具有复杂结构的基板上形成薄膜时，也大幅提高阶梯覆盖率及薄膜的厚度均匀性。
在所述使薄膜形成用生长抑制剂吸附在基板表面的步骤(ⅰ)中，每周期对基板表面的薄膜形成用生长抑制剂的供给时间(Feeding Time)优选为1至10秒，更优选为1至5秒，更加优选为2至5秒，进一步优选为2至4秒，在此范围内，薄膜生长速率低，阶梯覆盖率及经济性优秀。
在本发明中，薄膜形成用生长抑制剂的供给时间(Feeding Time)以15至20L的腔室体积及0.5至5mg/s的流量为基准，更加具体而言，以18L的腔室体积及1至2mg/s的流量为基准。
作为优选的一例，在所述使薄膜形成用生长抑制剂吸附在基板表面的步骤(ⅰ)中，可以包括将薄膜形成用生长抑制剂注入到ALD腔室内并使其吸附到被装载(loading)的基板表面的步骤，在这种情况下，通过抑制副反应并降低沉积速度，降低薄膜生长速率，并去除薄膜内的工艺副产物。
在所述使薄膜形成用生长抑制剂吸附在基板表面的步骤(ⅰ)中，优选利用吹扫气体吹扫未被吸附到基板表面的残留的薄膜形成用生长抑制剂，此时，其优点在于，当形成薄膜时，通过抑制副反应，降低薄膜生长速率，并通过去除薄膜内的工艺副产物，减少腐蚀及劣化，即便在具有复杂结构的基板上形成薄膜时，也大幅提高阶梯覆盖率及薄膜的厚度均匀性。
另外，在所述吸附金属膜前体、金属氧化膜前体、金属氮化膜前体或硅氮化膜前体(以下，称作“膜前体”)的步骤(ⅱ)中，优选利用吹扫气体吹扫未被吸附的残留的前体。
所述薄膜制造方法可以优选包括如下步骤：使膜前体吸附在基板表面之后，供给反应气体；以及利用吹扫气体吹扫膜前体与反应气体的反应副产物。
作为优选的一实施例，所述薄膜制造方法可以包括如下步骤：a)使所述薄膜形成用生长抑制剂汽化并使其吸附到装载于ALD腔室内的基板表面；b)利用吹扫气体第一次吹扫所述ALD腔室内部；c)使膜前体汽化并使其吸附到装载于ALD腔室内的基板表面；d)利用吹扫气体第二次吹扫所述ALD腔室内部；e)向所述ALD腔室内部供给反应气体；以及f)利用吹扫气体第三次吹扫所述ALD腔室内部。在这种情况下，其优点在于，适当地降低薄膜生长速率，即便当形成薄膜时沉积温度升高，也有效地去除所生成的工艺副产物，从而减小薄膜的电阻率且大幅提高阶梯覆盖率(step coverage)。
所述薄膜形成用生长抑制剂及膜前体可以优选通过VFC方式、DLI方式或LDS方式被移送至ALD腔室内，即基板表面，更优选通过LDS方式被移送至ALD腔室内。
所述薄膜形成用生长抑制剂与膜前体化合物在ALD腔室内的投入量(mg/cycle)之比可以优选为1∶1.5至1∶20，更优选为1∶2至1∶15，更加优选为1∶2至1∶12，进一步优选为1∶2.5至1∶10，在此范围内，每周期薄膜生长速率(GPC)的减小率高且工艺副产物的减少效果好。
当所述膜前体为常用于ALD(原子层沉积方法)的膜前体时，没有特别的限制。
作为一例，所述金属膜前体、金属氧化膜前体以及金属氮化膜前体可以分别是选自金属卤化物、金属醇盐、烷基金属化合物、金属氨基化合物、金属羰基化合物以及被取代或未被取代的环戊二烯基金属化合物中的一种以上，但不限于此。
作为一具体例，所述金属膜前体、金属氧化膜前体以及金属氮化膜前体可以分别是选自四氯化钛(tetrachlorotitan)、四氯化锗(tetrachlorogermanium)、四氯化锡(tetrchlorotin)、三(异丙基)乙基甲基氨基锗(tris(isopropyl)ethylmethylaminogermanium)、四乙氧基锗(tetraethoxylgermanium)、四甲基锡(tetramethyl tin)、四乙基锡(tetraethyl tin)、二乙酰丙酮锡(bisacetylacetonate tin)、三甲基铝(trimethylaluminum)、四(二甲氨基)锗(tetrakis(dimethylamino)germanium)、二(正丁氨基)锗(bis(n-butylamino)germanium)、四(乙基甲基氨基)锡(tetrakis(ethylmethylamino)tin)、四(二甲氨基)锡(tetrakis(dimethylamino)tin)、Co2(CO)8(八羰基二钴，dicobalt octacarbonyl)、Cp2Co(双环戊二烯钴，biscyclopentadienylcobalt)、Co(CO)3(NO)(三羰基亚硝酰基钴，cobalt tricarbonylnitrosyl)以及CpCo(CO)2(二羰基环戊二烯基钴，cobalt dicarbonyl cyclopentadienyl)中的一种以上，但不限于此。
作为一例，所述硅氮化膜前体可以是选自(NH2)Si(NHMe)3、(NH2)Si(NHEt)3、(NH2)Si(NHnpr)3、(NH2)Si(NHipr)3、(NH2)Si(NHnbu)3、(NH2)Si(NHibu)3、(NH2)Si(NHtbu)3、(NMe2)Si(NHMe)3、(NMe2)Si(NHEt)3、(NMe2)Si(NHnpr)3、(NMe2)Si(NHipr)3、(NMe2)Si(NHnbu)3、(NMe2)Si(NHibu)3、(NMe2)Si(NHtbu)3、(NEt2)Si(NHMe)3、(NEt2)Si(NHEt)3、(NEt2)Si(NHnpr)3、(NEt2)Si(NHipr)3、(NEt2)Si(NHnbu)3、(NEt2)Si(NHibu)3、(NEt2)Si(NHtbu)3、(Nnpr2)Si(NHMe)3、(Nnpr2)Si(NHEt)3、(Nnpr2)Si(NHnpr)3、(Nnpr2)Si(NHipr)3、(Nnpr2)Si(NHnbu)3、(Nnpr2)Si(NHibu)3、(Nnpr2)Si(NHtbu)3、(Nipr2)Si(NHMe)3、(Nipr2)Si(NHEt)3、(Nipr2)Si(NHnpr)3、(Nipr2)Si(NHipr)3、(Nipr2)Si(NHnbu)3、(Nipr2)Si(NHibu)3、(Nipr2)Si(NHtbu)3、(Nnbu2)Si(NHMe)3、(Nnbu2)Si(NHEt)3、(Nnbu2)Si(NHnpr)3、(Nnbu2)Si(NHipr)3、(Nnbu2)Si(NHnbu)3、(Nnbu2)Si(NHibu)3、(Nnbu2)Si(NHtbu)3、(Nibu2)Si(NHMe)3、(Nibu2)Si(NHEt)3、(Nibu2)Si(NHnpr)3、(Nibu2)Si(NHipr)3、(Nibu2)Si(NHnbu)3、(Nibu2)Si(NHibu)3、(Nibu2)Si(NHtbu)3、(Ntbu2)Si(NHMe)3、(Ntbu2)Si(NHEt)3、(Ntbu2)Si(NHnpr)3、(Ntbu2)Si(NHipr)3、(Ntbu2)Si(NHnbu)3、(Ntbu2)Si(NHibu)3、(Ntbu2)Si(NHtbu)3、(NH2)2Si(NHMe)2、(NH2)2Si(NHEt)2、(NH2)2Si(NHnpr)2、(NH2)2Si(NHipr)2、(NH2)2Si(NHnbu)2、(NH2)2Si(NHibu)2、(NH2)2Si(NHtbu)2、(NMe2)2Si(NHMe)2、(NMe2)2Si(NHEt)2、(NMe2)2Si(NHnpr)2、(NMe2)2Si(NHipr)2、(NMe2)2Si(NHnbu)2、(NMe2)2Si(NHibu)2、(NMe2)2Si(NHtbu)2、(NEt2)2Si(NHMe)2、(NEt2)2Si(NHEt)2、(NEt2)2Si(NHnpr)2、(NEt2)2Si(NHipr)2、(NEt2)2Si(NHnbu)2、(NEt2)2Si(NHibu)2、(NEt2)2Si(NHtbu)2、(Nnpr2)2Si(NHMe)2、(Nnpr2)2Si(NHEt)2、(Nnpr2)2Si(NHnpr)2、(Nnpr2)2Si(NHipr)2、(Nnpr2)2Si(NHnbu)2、(Nnpr2)2Si(NHibu)2、(Nnpr2)2Si(NHtbu)2、(Nipr2)2Si(NHMe)2、(Nipr2)2Si(NHEt)2、(Nipr2)2Si(NHnpr)2、(Nipr2)2Si(NHipr)2、(Nipr2)2Si(NHnbu)2、(Nipr2)2Si(NHibu)2、(Nipr2)2Si(NHtbu)2、(Nnbu2)2Si(NHMe)2、(Nnbu2)2Si(NHEt)2、(Nnbu2)2Si(NHnpr)2、(Nnbu2)2Si(NHipr)2、(Nnbu2)2Si(NHnbu)2、(Nnbu2)2Si(NHibu)2、(Nnbu2)2Si(NHtbu)2、(Nibu2)2Si(NHMe)2、(Nibu2)2Si(NHEt)2、(Nibu2)2Si(NHnpr)2、(Nibu2)2Si(NHipr)2、(Nibu2)2Si(NHnbu)2、(Nibu2)2Si(NHibu)2、(Nibu2)2Si(NHtbu)2、(Ntbu2)2Si(NHMe)2、(Ntbu2)2Si(NHEt)2、(Ntbu2)2Si(NHnpr)2、(Ntbu2)2Si(NHipr)2、(Ntbu2)2Si(NHnbu)2、(Ntbu2)2Si(NHibu)2、(Ntbu2)2Si(NHtbu)2、Si(HNCH2CH2NH)2、Si(MeNCH2CH2NMe)2、Si(EtNCH2CH2NEt)2、Si(nprNCH2CH2Nnpr)2、Si(iprNCH2CH2Nipr)2、Si(nbuNCH2CH2Nnbu)2、Si(ibuNCH2CH2Nibu)2、Si(tbuNCH2CH2Ntbu)2、Si(HNCHCHNH)2、Si(MeNCHCHNMe)2、Si(EtNCHCHNEt)2、Si(nprNCHCHNnpr)2、Si(iprNCHCHNipr)2、Si(nbuNCHCHNnbu)2、Si(ibuNCHCHNibu)2、Si(tbuNCHCHNtbu)2、(HNCHCHNH)Si(HNCH2CH2NH)、(MeNCHCHNMe)Si(MeNCH2CH2NMe)、(EtNCHCHNEt)Si(EtNCH2CH2NEt)、(nprNCHCHNnpr)Si(nprNCH2CH2Nnpr)、(iprNCHCHNipr)Si(iprNCH2CH2Nipr)、(nbuNCHCHNnbu)Si(nbuNCH2CH2Nnbu)、(ibuNCHCHNibu)Si(ibuNCH2CH2Nibu)、(tbuNCHCHNtbu)Si(tbuNCH2CH2Ntbu)、(NHtbu)2Si(HNCH2CH2NH)、(NHtbu)2Si(MeNCH2CH2NMe)、(NHtbu)2Si(EtNCH2CH2NEt)、(NHtbu)2Si(nprNCH2CH2Nnpr)、(NHtbu)2Si(iprNCH2CH2Nipr)、(NHtbu)2Si(nbuNCH2CH2Nnbu)、(NHtbu)2Si(ibuNCH2CH2Nibu)、(NHtbu)2Si(tbuNCH2CH2Ntbu)、(NHtbu)2Si(HNCHCHNH)、(NHtbu)2Si(MeNCHCHNMe)、(NHtbu)2Si(EtNCHCHNEt)、(NHtbu)2Si(nprNCHCHNnpr)、(NHtbu)2Si(iprNCHCHNipr)、(NHtbu)2Si(nbuNCHCHNnbu)、(NHtbu)2Si(ibuNCHCHNibu)、(NHtbu)2Si(tbuNCHCHNtbu)、(iprNCH2CH2Nipr)Si(NHMe)2、(iprNCH2CH2Nipr)Si(NHEt)2、(iprNCH2CH2Nipr)Si(NHnpr)2、(iprNCH2CH2Nipr)Si(NHipr)2、(iprNCH2CH2Nipr)Si(NHnbu)2、(iprNCH2CH2Nipr)Si(NHibu)2、(iprNCH2CH2Nipr)Si(NHtbu)2、(iprNCHCHNipr)Si(NHMe)2、(iprNCHCHNipr)Si(NHEt)2、(iprNCHCHNipr)Si(NHnpr)2、(iprNCHCHNipr)Si(NHipr)2、(iprNCHCHNipr)Si(NHnbu)2、(iprNCHCHNipr)Si(NHibu)2以及(iprNCHCHNipr)Si(NHtbu)2中的一种以上，但不限于此。
所述nPr表示正丙基，iPr表示异丙基，nBu表示正丁基，iBu表示异丁基，tBu表示叔丁基。
作为优选的一例，所述金属卤化物可以是四卤化钛，作为一具体例，可以是选自TiF4、TiCl4、TiBr4以及TiI4中的至少一种以上，例如，TiCl4在经济性方面优选，但不限于此。
只是，由于所述四卤化钛热稳定性优秀，在常温下不会分解并以液态存在，可以很好地作为ALD(原子层沉积)方法的膜前体来沉积薄膜。
作为一例，所述膜前体可以与非极性溶剂混合并投入到腔室内，此时，能够容易地调节膜前体的粘度及蒸气压。
所述非极性溶剂可以优选为选自烷烃及环烷烃中的一种以上，在这种情况下，含有反应性及溶解度低且易于水分管理的有机溶剂，同时，即便在形成薄膜时沉积温度升高，也提高阶梯覆盖率(step coverage)。
作为一更优的一例，所述非极性溶剂可以包含C1-C10的烷烃(alkane)或C3-C10的环烷烃(cycloalkane)，优选C3-C10的环烷烃(cycloalkane)，此时，反应性及溶解度低且易于水分管理。
在本发明中，C1、C3等表示碳原子数。
所述环烷烃可以优选为C3-C10的单环烷烃，在所述单环烷烃中，环戊烷(cyclopentane)在常温下为液体且蒸气压最高，因此，在气相沉积工艺中优选，但不限于此。
作为一例，所述非极性溶剂在水中的溶解度(25℃)为200mg/L以下，优选为50至200mg/L，更优选为135至175mg/L，在此范围内，对于膜前体的反应性低且易于水分管理。
在本发明中，当溶解度基于本发明所属技术领域常用的测量方法或基准时，没有特别的限制，作为一实施例，能够通过HPLC法测量饱和溶液。
以膜前体与非极性溶剂的总重量之和为基准，所述非极性溶剂的含量可以优选为5至95重量％，更优选为10至90重量％，更加优选为40至90重量％，最优选为70至90重量％。
当投入的所述非极性溶剂的含量大于上述上限值时，会产生杂质，导致电阻和薄膜内的杂质数值增加，当投入的所述有机溶剂的含量小于上述下限值时，因添加溶剂而发生的提高阶梯覆盖率的效果及减少氯(Cl)离子等杂质的效果不佳。
作为一例，在所述薄膜制造方法中，通过数学式1计算出的每周期薄膜生长速率
Figure BDA0002699029710000081
的减小率为-5％以下，优选为-10％以下，更优选为-20％以下，更加优选为-30％以下，进一步优选为-40％以下，最优选为-45％以下，在此范围内，阶梯覆盖率及膜的厚度均匀性优秀。
数学式1：
每周期薄膜生长速率的减小率(％)＝[(使用薄膜形成用生长抑制剂时的每周期薄膜生长速率－未使用薄膜形成用生长抑制剂时的每周期薄膜生长速率)/未使用薄膜形成用生长抑制剂时的每周期薄膜生长速率]×100
在所述薄膜制造方法中，基于SIMS测量的经200周期之后所形成的薄膜内的残留卤素强度(c/s)可以优选为10,000以下，更优选为8,000以下，更加优选为7,000以下，进一步优选为6,000以下，在此范围内，防止腐蚀及劣化的效果优秀。
在本发明中，吹扫优选为1,000至10,000sccm，更优选为2,000至7,000sccm，更加优选为2,500至6,000sccm，在此范围内，每周期薄膜生长速率减小至优选的范围，并减少工艺副产物。
所述ALD(原子层沉积)工艺在需要高纵横比的集成电路(IC：IntegratedCircuit)制作中非常有利，尤其是基于自限性薄膜生长机制，具有优秀的阶梯涂覆性(conformality)、均匀的覆盖率(uniformity)以及精密的厚度控制等优点。
作为一例，所述薄膜制造方法能够在50至900℃范围的沉积温度下实施，优选在300至700℃范围的沉积温度下实施，更优选在350至600℃范围的沉积温度下实施，更加优选在400至550℃范围的沉积温度下实施，进一步优选在400至500℃范围的沉积温度下实施，在此范围内，能够实现ALD工艺特性并生长为具有优秀的膜质的薄膜。
作为一实施例，所述薄膜制造方法能够在0.1至10Torr范围的蒸汽压力下实施，优选在0.5至5Torr范围的蒸汽压力下实施，更优选在1至3Torr范围的蒸汽压力下实施，在此范围内，能够获得厚度均匀的薄膜。
在本发明中，沉积温度及沉积压力可以通过沉积腔室内的温度及压力来测量，也可以通过施加于沉积腔室内的基板的温度及压力来测量。
所述薄膜制造方法可以优选包括：在将所述薄膜形成用生长抑制剂投入腔室内之前，使腔室内的温度升温至沉积温度的步骤；以及/或在将所述薄膜形成用生长抑制剂投入腔室内之前，向腔室内注入惰性气体以进行吹扫的步骤。
另外，本发明涉及薄膜制造装置，该装置能够实现所述薄膜制造方法，包括：ALD腔室；第一汽化器，使薄膜形成用生长抑制剂汽化；第一移送单元，将汽化的薄膜形成用生长抑制剂移送至ALD腔室内；第二汽化器，使金属膜前体、金属氧化膜前体、金属氮化膜前体或硅氮化膜前体汽化；以及第二移送单元，将汽化的所述前体移送至ALD腔室内。其中，当汽化器及移送单元属于本发明所属技术领域中常用的汽化器及移送单元时，没有特别的限制。
通过一具体例，对所述薄膜制造方法进行说明。
首先，使上部待形成薄膜的基板位于能够进行原子层沉积的沉积腔室内。
所述基板可以包括硅基板、氧化硅等半导体基板。
所述基板可以在其上部进一步形成有导电层或绝缘层。
为了在位于所述沉积腔室内的基板上沉积薄膜，分别准备上述薄膜形成用生长抑制剂和膜前体或该膜前体与非极性溶剂的混合物。
然后，将所准备的薄膜形成用抑制剂注入到汽化器内之后，使其变为蒸汽相，并移送至沉积腔室，从而吸附到基板上，吹扫(purging)未被吸附的薄膜形成用抑制剂。
然后，将准备的膜前体或该膜前体与非极性溶剂的混合物注入到汽化器内之后，使其变为蒸汽相，并移送至沉积腔室，从而吸附到基板上，吹扫(purging)未被吸附的薄膜形成用组合物。
作为一例，在本发明中，将薄膜形成用抑制剂及膜前体等移送至沉积腔室的方式可以采用利用气相流量控制(Mass Flow Controller；MFC)方法移送被挥发的气体的方式(Vapor Flow Control；VFC)或利用液相流量控制(Liquid Mass Flow Controller；LMFC)方法移送液体的方式(Liquid Delivery System；LDS)，优选使用LDS方式。
此时，用于将薄膜形成用抑制剂及膜前体等移送至基板上的运载气体或稀释气体可以使用选自氩气(Ar)、氮气(N2)、氦气(He)中的一种或两种以上的混合气体，但不限于此。
作为一例，在本发明中，吹扫气体可以采用惰性气体，可以优选使用所述运载气体或稀释气体。
然后，供给反应气体。当所述反应气体为本发明所属技术领域常用的反应气体时，没有特别的限制，优选包括还原剂、氮化剂或氧化剂。所述还原剂与吸附到基板的膜前体进行反应，形成金属薄膜，通过所述氮化剂，形成金属氮化物薄膜，通过所述氧化剂，形成金属氧化物薄膜。
优选地，所述还原剂可以是氨气(NH3)或氢气(H2)，所述氮化剂可以是氮气(N2)，所述氧化剂可以是选自H2O、H2O2、O2、O3以及N2O中的一种以上。
然后，利用惰性气体吹扫未参与反应的残留的反应气体。以此方式，不仅能够去除过量的反应气体，还能够一同去除所生成的副产物。
如上所述，以使薄膜形成用抑制剂吸附在基板上的步骤、吹扫未被吸附的薄膜形成用抑制剂的步骤、使膜前体吸附在基板上的步骤、吹扫未被吸附的薄膜形成用组合物的步骤、供给反应气体的步骤、吹扫残留的反应气体的步骤为单位周期，并且为了形成具有所需厚度的薄膜，能够重复所述单位周期。
作为一例，可以进行所述单位周期100至1000次，优选100至500次，更优选150至300次，在此范围内，很好地表达所需薄膜特性。
图1是用于说明现有的ALD工艺的工艺图，图2是用于说明本发明的一实施例的ALD工艺的工艺图。参照图1，当如现有的ALD工艺那样没有在吸附膜前体(例如，TiCl4)之前先吸附本发明的薄膜形成用生长抑制剂(Inhibitor)以保护(protection)基板表面时，在与反应气体(例如，NH3)进行反应而形成的薄膜(例如，TiN)中会残留HCl等工艺副产物，从而因腐蚀及劣化，降低基板性能。然而，当如图2所示，当在吸附膜前体(例如，TiCl4)之前先吸附本发明的薄膜形成用生长抑制剂(Inhibitor；TSI)以进行基板表面保护(SurfaceProtection；SP)时，能够将在形成薄膜(例如，TiN)的过程中通过与反应气体(例如，NH3)进行反应而生成的HCl等工艺副产物与薄膜形成用生长抑制剂一同去除，从而防止基板的腐蚀及劣化，进而适当地降低每周期薄膜生长速率，并改善阶梯覆盖率及薄膜厚度的均匀性。
本发明的薄膜形成用生长抑制剂优选为由化学式1表示的化合物，
化学式1：
AnBmXo
其中，所述A为碳或硅，所述B为氢或碳原子数为1至3的烃基，所述X为卤素，所述n为1至15的整数，所述o为1以上的整数，m为0至2n+1。在这种情况下，当形成薄膜时，通过抑制副反应，降低薄膜生长速率，并通过去除薄膜内的工艺副产物，减少腐蚀及劣化，即便在具有复杂的结构的基板上形成薄膜时，也大幅提高阶梯覆盖率及薄膜的厚度均匀性。
所述B优选为氢或甲基，所述n优选为2至15的整数，更优选为2至10的整数，更加优选为2至6的整数，进一步优选为4至6的整数，在此范围内，工艺副产物去除效果好，且阶梯覆盖率优秀。
作为一例，在所述化学式1中，X可以是选自F、Cl、Br以及I中的一种以上，可以优选为Cl(氯)，此时，抑制副反应，并有效地去除工艺副产物。
在所述化学式1中，所述o可以优选为1至5的整数，更优选为1至3的整数，更加优选为1或2，在此范围内，沉积速度的降低效果好，因此，对改善阶梯覆盖率更加有效。
所述m优选为1至2n+1，更优选为3至2n+1，在此范围内，工艺副产物去除效果好，且阶梯覆盖率优秀。
由所述化学式1表示的化合物可以优选为支链化合物、环状化合物或芳香族化合物，作为一具体实施例，为选自1,1-二氯乙烷、1,2-二氯乙烷、二氯甲烷、2-氯丙烷、1-氯丙烷、1,2-二氯丙烷、1,3-二氯丙烷、2,2-二氯丙烷、1-氯戊烷、2-氯戊烷、3-氯戊烷、氯代环戊烷、正丁基氯、叔丁基氯、仲丁基氯、异丁基氯、1,2-二氯苯、1,4-二氯苯、三甲基氯硅烷、三氯丙烷、2-氯-2-甲基丁烷以及2-甲基-1-戊烷中的一种以上，此时，其优点在于，工艺副产物去除效果好，且阶梯覆盖率优秀。
由所述化学式1表示的化合物优选用于原子层沉积(ALD)工艺，此时，其优点在于，不阻碍膜前体的吸附，同时，作为生长抑制剂，有效地保护基板的表面(SurfaceProtection；SP)，并有效地去除工艺副产物。
由所述化学式1表示的化合物可以优选在常温(22℃)下为液体，密度为0.8至1.5g/cm3，蒸气压(20℃)为1至300mmHg，在水中的溶解度(25℃)为200mg/L以下，在此范围内，阶梯覆盖率及薄膜的厚度均匀性优秀。
更优选地，由所述化学式1表示的化合物可以是密度为0.85至1.3g/cm3，蒸气压(20℃)为1至260mmHg，在水中的溶解度(25℃)为160mg/L，在此范围内，阶梯覆盖率及薄膜的厚度均匀性优秀。
本发明的半导体基板通过本发明的薄膜制造方法制造而成，在这种情况下，通过抑制副反应，适当地降低薄膜生长速率，并通过去除薄膜内的工艺副产物，防止腐蚀及劣化，并且阶梯覆盖率(step coverage)及薄膜的厚度均匀性十分出色。
优选地，上述制造的薄膜的厚度为20nm以下，电阻率值为0.1至400μ
Ω·cm，卤素含量为10,000ppm以下，阶梯覆盖率为90％以上，在此范围内，作为防扩散膜，性能出色，并且减少金属配线材料的腐蚀，但不限于此。
作为一例，所述薄膜的厚度可以是5至20nm，优选为10至20nm，更优选为15至18.5nm，更加优选为17至18.5nm，在此范围内，薄膜特性优秀。
作为一例，所述薄膜的电阻率值可以是0.1至400μΩ·cm，优选为50至400μΩ·cm，更优选为200至400μΩ·cm，更加优选为300至400μΩ·cm，进一步优选为330至380μΩ·cm，最优选为340至370μΩ·cm，在此范围内，薄膜特性优秀。
所述薄膜的卤素含量可以更优选为9,000ppm以下或1至9,000ppm，更加优选为8,500ppm以下或100至8,500ppm，进一步优选为8,200ppm以下或1,000至8,200ppm，在此范围内，薄膜特性优秀，并且减少金属配线材料的腐蚀。
作为一例，所述薄膜的阶梯覆盖率为80％以上，优选为90％以上，更优选为92％以上，在此范围内，即便是结构复杂的薄膜也能够容易地沉积到基板，因此能够应用于新一代半导体装置。
作为一例，所述所制造的薄膜可以是金属氮化膜或金属氧化膜，作为一具体例，可以是TiN薄膜或TiO2薄膜。
以下，为了帮助理解本发明，提出优选的实施例及附图，然而本领域技术人员清楚以下实施例及附图仅用于对本发明进行例示，能够在本发明的范畴及技术思想范围内进行多种变更及修改，且这种变形及修改也毫无疑问地属于所附权利要求范围。
实施例
实施例1至7
分别准备下表1记载的薄膜形成用生长抑制剂和作为膜前体的TiCl4。将准备的薄膜形成用生长抑制剂装入罐中，在常温下利用LMFC(Liquid Mass Flow Controller，液体质量流量控制器)，以0.05g/min的流速供给到加热至150℃的汽化器。将在汽化器中汽化为蒸汽相的薄膜形成用生长抑制剂向装载有基板的沉积腔室投入3秒之后，将氩气以3000sccm供给6秒，以氩气进行吹扫。此时，将反应腔室内的压力控制为1.3Torr。然后，将准备的TiCl4装入另一罐中，在常温下利用LMFC(Liquid Mass Flow Controller)，以0.05g/min的流速，供给到加热至150℃的另一汽化器。将在汽化器中汽化为蒸汽相的TiCl4向沉积腔室投入3秒之后，将氩气以3000sccm供给6秒，以氩气进行吹扫。此时，将反应腔室内的压力控制为1.3Torr。然后，将氨气作为反应气体向所述反应腔室投入5秒之后，以氩气吹扫10秒。此时，将待形成金属薄膜的基板加热至460℃。将这种工艺重复200次，从而形成作为自限性原子层的TiN薄膜。
表1
类别 薄膜形成用生长抑制剂
实施例1 2-氯-2-甲基丁烷(2-chloro-2-methylbutane)
实施例2 正丁基氯(n-butyl chloride)
实施例3 三甲基氯硅烷(trimethylchlorosilane)
实施例4 2-氯丙烷(2-chloropropane)
实施例5 1,2,3-三氯丙烷(1,2,3-trichloropropane)
实施例6 2-甲基-1-戊烷(2-methyl-1-pentane)
实施例7 1,2-二氯苯(1,2-dichlorobenzene)
比较例1
除了未使用实施例1的薄膜形成用生长抑制剂并由此省略了吹扫未被吸附的薄膜形成用生长抑制剂的步骤以外，以与实施例1相同的方法在基板上形成了TiN薄膜。
比较例2及3
除了未使用上表1记载的实施例1的薄膜形成用生长抑制剂而是使用戊烷(Pentane)或环戊烷(cyclopentane)以外，以与实施例1相同的方法在基板上形成了TiN薄膜。
实验例
1)沉积评价
参照下表2，对于将2-氯-2-甲基丁烷用作薄膜形成用生长抑制剂的实施例1与不包含其的比较例1进行比较。其结果，沉积速度为
Figure BDA0002699029710000151
与比较例1相比，沉积速度降低了55.5％以上。能够确定其余实施例2至7也具有与实施例1类似的沉积速度。另外，可以确定未使用本发明的薄膜形成用生长抑制剂而是使用了戊烷或环戊烷的比较例2及3也具有与比较例1相同的沉积速度。此时，沉积速度降低表示将CVD沉积特性改变为ALD沉积特性，因此能够用作阶梯覆盖特性改善的指标。
表2
Figure BDA0002699029710000152
另外，如下表3所示，能够确定，随着作为薄膜形成用生长抑制剂的2-氯-2-甲基丁烷的注入量增加，沉积速度持续减小。其中，除了每周期薄膜形成用生长抑制剂的注入量以外，以与实施例1相同的方法实施实施例1-1。
表3
Figure BDA0002699029710000153
2)杂质减少特性
为了比较在实施例1及比较例1中所沉积的TiN薄膜的杂质减少特性，即工艺副产物减少特性，进行了SIMS分析，其结果见下表4。
表4
类别 实施例1 比较例1
每ALD周期注入量(mg/cycle) 1.6 0
Cl强度(c/s) 5907.05 17270.25
如上表4所示，能够确定使用了本发明的薄膜形成用生长抑制剂的实施例1的Cl强度降低至未使用本发明的薄膜形成用生长抑制剂的比较例1的1/3。
另外，图3是示出本发明的实施例7(SP-TiCl4)及比较例1(TiCl4)的薄膜厚度随ALD周期增加而变化的图，能够确定实施例7的薄膜的厚度大幅变薄。
另外，图4是示出本发明的实施例7-1至7-3及比较例1的沉积速度随每ALD周期薄膜形成用生长抑制剂(SP)的供给(feeding)时间变化的图，能够确定当如比较例1那样未使用本发明的薄膜形成用抑制剂时，每周期沉积速度约为
Figure BDA0002699029710000161
在将本发明的薄膜形成用抑制剂分别投入0.7秒、1秒、2秒的实施例7-1、7-2、7-3的情况下，沉积速度分别大幅降低至
Figure BDA0002699029710000162
Figure BDA0002699029710000163
其中，除了薄膜形成用生长抑制剂的投入量以外，以与实施例7相同的方法实施实施例7-1、7-2、7-3。
3)阶梯覆盖特性
利用TEM，确定了在实施例1及比较例1中所沉积的TiN薄膜的阶梯覆盖率，其结果见下表5及图5。
表5
类别 实施例1 比较例1
阶梯覆盖率(％) 92％ 78％
如上表5所示，能够确定使用了本发明的薄膜形成用生长抑制剂的实施例1与未使用本发明的薄膜形成用生长抑制剂的比较例1相比，阶梯覆盖率显著地高。另外，参照图5的TEM照片，能够确定在实施例1(SP-TiCl4)中所沉积的TiN薄膜的顶部(Top)和底部(bottom)的厚度均匀度与在比较例1(TiCl4)中所沉积的TiN薄膜相比，阶梯覆盖率(conformality)更优秀。
附加实施例1
除了使用三(二甲氨基)环戊二烯基锆(Tris(dimethylamino)cyclopentadienylzirconium；CpZr)以替代上述实施例1中作为膜前体的TiCl4，并且将薄膜形成用生长抑制剂的腔室内注入量设为12mg/sec，使用臭氧以替代作为反应气体的氨气，将待形成金属薄膜的基板加热至280至340℃以外，以与上述实施例1相同的方法实施工艺，从而形成锆氧化膜(ZrO2薄膜)。
附加实施例2
除了将附加实施例1中的薄膜形成用生长抑制剂的腔室内注入量设为2.3mg/sec并分别注入1至7秒和将待形成金属薄膜的基板加热至310℃以外，以与所述附加实施例1相同的方法实施工艺，从而形成锆氧化膜(ZrO2薄膜)。
附加比较例1
除了在上述附加实施例1中未使用薄膜形成用生长抑制剂以外，以与上述附加实施例1相同的方法实施工艺，从而形成锆氧化膜(ZrO2薄膜)。
对于在上述附加实施例1、2以及附加比较例1中所沉积的锆氧化膜的沉积速度、减小率(％)以及厚度均匀度(％)进行了测量，其结果见下表6及图6。此时，厚度均匀度(％)通过数学式2计算。
数学式2：
厚度均匀度(％)＝[(MAX－MIN)/(2×AVERAGE)]×100％
所述MAX、MIN、AVERAGE表示厚度的最大值、最小值、平均值，各厚度为利用椭偏仪所测量的光学厚度。
表6
Figure BDA0002699029710000171
如上表6所示，使用本发明的薄膜形成用生长抑制剂所形成的锆氧化膜(附加实施例1)与没有使用本发明的薄膜形成用生长抑制剂的锆氧化膜(附加比较例1)相比，基于沉积温度的ALD每周期薄膜厚度为0.508至
Figure BDA0002699029710000181
非常恒定，同时减小率大幅降低至34.6％至42.3％范围，并且膜厚度的均匀度(uniformity)在1.1％至2.1％范围内，变动幅度非常小。
另外，图6是示出附加实施例2及附加比较例1的沉积速度
Figure BDA0002699029710000182
随每ALD周期薄膜形成用生长抑制剂(SP)的供给(feeding)时间(s)变化的图，能够确定，当如附加比较例1那样不使用本发明的薄膜形成用抑制剂时，每周期沉积速度约为
Figure BDA0002699029710000183
而在将本发明的薄膜形成用抑制剂分别投入1秒、3秒、5秒、7秒的附加实施例2的情况下，沉积速度分别降低至约
Figure BDA0002699029710000184
其中，SP-P-SF-P-OF-P表示将薄膜形成用生长抑制剂(SP)的投入、吹扫气体(P)的投入、膜前体(SF)的投入、吹扫气体(P)的投入、反应气体(OF)的投入、吹扫气体(P)的投入进行一个周期，X-2X-5-10-3-6表示各步骤的投入时间(s)，X为0至7的整数。

Claims (16)

1.一种薄膜制造方法，其特征在于，包括：
步骤(ⅰ)，使薄膜形成用生长抑制剂吸附在基板表面；以及
步骤(ⅱ)，使金属膜前体、金属氧化膜前体、金属氮化膜前体或硅氮化膜前体吸附在吸附有薄膜形成用生长抑制剂的基板表面，
其中，所述薄膜形成用生长抑制剂由化学式1表示，
所述金属为选自钨、钴、铬、铝、铪、钒、铌、锗、镧系元素、锕系元素、镓、钽、锆、钌、铜、钛、镍、铱以及钼中的一种以上，
化学式1：
AnBmXo
其中，所述A为碳或硅，所述B为氢或碳原子数为1至3的烃基，所述X为卤素，所述n为1至15的整数，所述o为1以上的整数，m为0至2n+1。
2.根据权利要求1所述的薄膜制造方法，其特征在于，
在所述使薄膜形成用生长抑制剂吸附在基板表面的步骤(ⅰ)中，对基板表面的薄膜形成用生长抑制剂的供给时间(Feeding Time)为1至10秒。
3.根据权利要求1所述的薄膜制造方法，其特征在于，
在所述使薄膜形成用生长抑制剂吸附在基板表面的步骤(ⅰ)中，将薄膜形成用生长抑制剂注入到ALD(原子层沉积)腔室内并使其吸附到被装载(loading)的基板表面。
4.根据权利要求1所述的薄膜制造方法，其特征在于，
在所述使薄膜形成用生长抑制剂吸附在基板表面的步骤(ⅰ)中，利用吹扫气体吹扫未被吸附到基板表面的残留的薄膜形成用生长抑制剂。
5.根据权利要求1所述的薄膜制造方法，其特征在于，
在所述吸附膜前体的步骤(ⅱ)中，利用吹扫气体吹扫未被吸附的残留的膜前体。
6.根据权利要求1所述的薄膜制造方法，其特征在于，包括如下步骤：
使所述膜前体吸附在基板表面之后，供给反应气体；以及
利用吹扫气体吹扫所述膜前体与反应气体的反应副产物。
7.根据权利要求6所述的薄膜制造方法，其特征在于，
所述反应气体为还原剂、氮化剂或氧化剂。
8.根据权利要求1所述的薄膜制造方法，其特征在于，
所述薄膜形成用生长抑制剂及所述膜前体通过VFC方式、DLI方式或LDS方式被移送至基板表面。
9.根据权利要求1所述的薄膜制造方法，其特征在于，
所述薄膜形成用生长抑制剂与所述膜前体的向基板表面的投入量(mg/cycle)之比为1∶1.5至1∶20。
10.根据权利要求1所述的薄膜制造方法，其特征在于，
在所述化学式1中，X为氯(Cl)。
11.根据权利要求1所述的薄膜制造方法，其特征在于，
在所述化学式1中，所述o为1至5的整数。
12.根据权利要求1所述的薄膜制造方法，其特征在于，
由所述化学式1表示的化合物为支链化合物、环状化合物或芳香族化合物。
13.根据权利要求1所述的薄膜制造方法，其特征在于，
由所述化学式1表示的化合物在常温22℃下为液体，密度为0.8至1.5g/cm3，在20℃下的蒸气压为1至300mmHg，在25℃下水中的溶解度为200mg/L以下。
14.根据权利要求1所述的薄膜制造方法，其特征在于，
通过下述数学式1计算出的每周期薄膜生长速率
Figure FDA0002699029700000031
的减小率为-5％以下，
数学式1：
每周期薄膜生长速率的减小率(％)＝[(使用薄膜形成用生长抑制剂时的每周期薄膜生长速率－未使用薄膜形成用生长抑制剂时的每周期薄膜生长速率)/未使用薄膜形成用生长抑制剂时的每周期薄膜生长速率]×100。
15.根据权利要求1所述的薄膜制造方法，其特征在于，
基于SIMS测量的经200周期之后所形成的薄膜内残留卤素强度(c/s)为10,000以下。
16.一种薄膜制造装置，其特征在于，包括：
ALD(原子层沉积)腔室；
第一汽化器，使薄膜形成用生长抑制剂汽化；
第一移送单元，将汽化的薄膜形成用生长抑制剂移送至ALD腔室内；
第二汽化器，使金属膜前体、金属氧化膜前体、金属氮化膜前体或硅氮化膜前体汽化；以及
第二移送单元，将汽化的所述前体移送至ALD腔室内。
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