CN105899711B - 在无氧化剂情况下的含硅和氧的膜的沉积 - Google Patents
在无氧化剂情况下的含硅和氧的膜的沉积 Download PDFInfo
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- CN105899711B CN105899711B CN201580004037.4A CN201580004037A CN105899711B CN 105899711 B CN105899711 B CN 105899711B CN 201580004037 A CN201580004037 A CN 201580004037A CN 105899711 B CN105899711 B CN 105899711B
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- osih
- siloxane
- oxygen
- silicon
- bonds
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- 239000001301 oxygen Substances 0.000 title claims abstract description 57
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000010703 silicon Substances 0.000 title claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 10
- 230000008021 deposition Effects 0.000 title abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 82
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000000977 initiatory effect Effects 0.000 claims abstract description 30
- 238000000151 deposition Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims description 58
- 239000007789 gas Substances 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 15
- -1 acyclic siloxane Chemical class 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910018557 Si O Inorganic materials 0.000 claims description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 7
- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 claims description 6
- HVXTXDKAKJVHLF-UHFFFAOYSA-N silylmethylsilane Chemical compound [SiH3]C[SiH3] HVXTXDKAKJVHLF-UHFFFAOYSA-N 0.000 claims description 6
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims description 5
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 claims description 5
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 39
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 19
- 239000000377 silicon dioxide Substances 0.000 abstract description 19
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 66
- 210000002381 plasma Anatomy 0.000 description 58
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 238000009826 distribution Methods 0.000 description 19
- 239000011261 inert gas Substances 0.000 description 12
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000004050 hot filament vapor deposition Methods 0.000 description 3
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001227 electron beam curing Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
通过以下步骤在不存在氧化剂的情况下沉积含硅和氧的膜,诸如二氧化硅膜:将硅氧烷前体引入等离子体处理腔室中并且例如通过将所述硅氧烷前体暴露于低能等离子体来离解所述硅氧烷前体的Si‑H键中的至少一些。可以在不氧化易氧化的表面的情况下,在所述易氧化的表面上形成所述含硅和氧的膜。所沉积的含硅和氧的膜可以用作二氧化硅块状层的初始层,使用常规二氧化硅沉积技术(诸如将所述硅氧烷前体暴露于含氧等离子体)在所述初始层的顶部上形成所述二氧化硅块状层。在所述块状层沉积之前或之后,所述初始层可被后处理或被固化以减小Si‑H键的浓度。
Description
背景
技术领域
本公开的实施例总体涉及含硅和氧的膜的沉积,并且更具体地涉及在不存在氧化剂的情况下的含硅和氧的膜(诸如二氧化硅)的沉积。
背景技术
减小集成电路几何形状的尺寸的障碍在于无法在不氧化易氧化的材料的情况下在易于氧化的材料上使用常规沉积技术来沉积含氧的膜,诸如含Si-O-Si键合的膜,例如二氧化硅膜。含Si-O-Si键的膜在本文中称为含硅和氧的膜。含氧等离子体工艺、高温氧化蒸气退火和用于涂覆含氧的膜的其他技术可容易地使界面层处的下层材料氧化,因为这些源可能甚至穿透沉积的单层。在一些情况(诸如集成电路的制造)中,下层的氧化可能不利于器件的性能。
多种技术已用于在不存在氧化剂的情况下形成膜。例如,在存在惰性气体的情况下,已经使用直接等离子体沉积技术来沉积膜,并且在不存在氧化环境的情况下,已经使用电容耦合的等离子体和电感耦合的等离子体腔室来沉积膜。然而,前述技术无法形成含硅和氧的膜(诸如二氧化硅、氧化硅和其他含硅和氧的膜)所期望的Si-O-Si键合。
因此,需要一种在不使下层材料氧化的情况下沉积含氧的膜(诸如含硅和氧的膜,例如,二氧化硅)的方法。
发明内容
本文所公开的实施例通过以下步骤在不存在氧化剂的情况下在表面(诸如易氧化的表面)上形成含硅和氧的膜:将硅氧烷前体(诸如,具有通式SixOx-1H2x+2的无环硅氧烷前体和具有通式SixOxH2x的环状硅氧烷前体)引入处理腔室中;以及选择性地离解(dissociate)一种或多种硅氧烷前体的Si-H键中的至少一些,诸如通过将所述一种或多种硅氧烷前体暴露于低能等离子体进行离解。所沉积的含硅和氧的膜可以用作二氧化硅块状层的初始层,块状使用常规二氧化硅沉积技术(诸如将硅氧烷前体暴露于含氧的等离子体)将所述二氧化硅块状层形成在所述初始层的顶部上。所述初始层可被后处理(诸如通过紫外线处理或离子注入)以便减小Si-H键的浓度。
附图说明
因此,为了能够详细地理解本发明的上述特征的方式,可参考多个实施例得出上文简要概述的本发明的更具体的描述,并且在附图中示出实施例中的一些。然而应当注意,所附附图仅示出本发明的典型实施例,并且因此不应视为对本发明范围的限制,因为本发明可允许其他等效实施例。
图1是适合于实践本公开的实施例的等离子体处理腔室的一个实施例的横截面图。
具体实施方式
对本公开的各种实施例的描述出于说明的目的而被呈现并且不意在排他性。在不背离所述实施例的范围和精神的情况下,许多的修改和变型将对本领域的普通技术人员是显而易见的。本文所使用的术语被选择来最好地解释市场上出现的技术的实施例的原理、实际应用或技术改进,或使本领域的其他普通技术人员能够理解本文所公开的实施例。
本文所公开的实施例总体提供用于在不存在氧化剂的情况下形成含硅和氧的膜的方法。更具体地,硅氧烷前体被引入等离子体处理腔室中,并且随后被暴露于低能等离子体或远程的非氧自由基源以沉积初始层。低能等离子体或远程的非氧自由基源选择性地离解硅氧烷前体的Si-H键中的至少一些,从而允许在不存在氧自由基或离子的情况下的膜的沉积。硅氧烷前体是具有Si-O-Si键合的分子,因此具有Si-O键和Si-H键两者。硅氧烷前体可以是例如具有通式SixOx-1H2x+2的无环硅氧烷前体和/或具有通式SixOxH2x的环状硅氧烷前体。通过对温度和激活能量进行控制,可在维持Si-O键的同时使Si-H键断裂。由于Si-O键未断裂,因此氧不变为活性物种(例如,氧离子或氧自由基)。因此,结合中的氧将不会可测量地氧化表面。
等离子体处理腔室可以是能够产生低能等离子体或将硅氧烷前体暴露于远程的非氧自由基源的任何等离子体处理腔室。所沉积的含硅和氧的膜可以用作二氧化硅块状层的初始层,块状可以使用常规二氧化硅沉积技术(诸如通过将硅氧烷前体暴露于含氧的等离子体)将所述二氧化硅块状层形成在初始层的顶部上。也可以使用不同的前体气体或方法将其他成分的块状层沉积在初始层的顶部上。本文所公开的实施例允许在不氧化易氧化的表面的情况下,在所述易氧化的表面上沉积含硅和氧的膜。易氧化的表面可例如由金属(诸如铜、银、金、铝、钛或钽)构成。如果表面的任何部分易于氧化,那么这个表面就会被视为是易氧化的。在块状二氧化硅层的沉积过程中,初始层会保护易氧化的表面。在所述块状层的沉积之前或之后,所述初始层可被后处理或被固化以减小Si-H键的浓度。
图1描绘可用来实践本文所公开的实施例的等离子体处理腔室100。可适于执行所公开的实施例的一种等离子体处理腔室是可从加利福尼亚州的圣克拉拉市的应用材料公司(Applied Materials,Santa Clara,Calif.)获得的SiconiTM腔室。构想到,可以在其他适当地适配的等离子体处理腔室(包括从其他制造商处获得的那些)中实践本文所述的方法。合适的等离子体处理腔室包括配置成产生低能等离子体的任何处理腔室或耦合到配置成生成非氧自由基的远程自由基源的任何处理腔室。例如,处理腔室可以是电容耦合或电感耦合的等离子体增强化学气相沉积(PECVD)腔室。PECVD腔室可以是直接等离子体腔室或者包括远程等离子体腔室。如本文所定义,低能等离子体是以250W或更小(诸如小于100W,诸如在约10W与约50W之间)的RF源或偏置功率生成的等离子体。如果使用远程自由基源,那么所述远程自由基源可以是例如电容耦合或电感耦合的远程等离子体源、远程微波等离子体辅助CVD(MPCVD)腔室、远程热丝化学气相沉积(HW-CVD)腔室或远程电子回旋共振(ECR)源。远程等离子体源和远程自由基源分别在与发生沉积的区域空间上分开的区域中生成等离子体和自由基。
等离子体处理腔室100包括腔室主体102、盖组件104和基板支撑组件106。盖组件104设置在腔室主体102的上端,并且基板支撑组件106至少部分地设置在腔室主体102内。盖组件104可用作远程等离子体源。
腔室主体102包括狭缝阀开口108,所述狭缝阀开口108形成在腔室主体的侧壁中,以便接取处理腔室100的内部。选择性地打开和关闭狭缝阀开口108以允许由晶片搬运机械手(未示出)接取腔室主体102的内部。腔室主体102可进一步包括衬里112,所述衬里112包围基板支撑组件106。衬里112可以包括一个或多个孔隙114以及形成在其中的与真空系统流体地连通的泵送通道116。孔隙114提供使气体进入泵送通道116的流动路径,这为处理腔室100内的气体提供出口。腔室主体还包括了介于基座124与分配板168之间的工艺区域109。
真空系统可以包括真空泵118和节流阀120以调节通过处理腔室100的气体的流量。真空泵118耦接到设置在腔室主体102中的真空端口122,并且因此,与形成在衬里112内的泵送通道116流体地连通。除非另外指出,否则术语“气体”和“多种气体”可互换地使用,并且指代一种或多种前体、反应剂、催化剂、载体、净化剂、清洁剂、它们的组合、以及引入腔室主体102中的任何其他流体。
基板支撑组件106包括耦接到轴组件126的基座124。基座124具有适于支撑基板(未示出)的上表面。基座124还可包括RF电极,所述RF电极被配置为阴极并由导电材料制成。阴极可以包括铝板。阴极可直接耦接到轴组件126的中心轴128,从而将RF能量通过连接器150从RF功率源148提供到阴极。屏蔽构件125可绕基座124的外围来设置。屏蔽构件125可以包含诸如铝之类的导电材料。
轴组件126可以包括至少三个管状构件,所述管状构件在腔室主体102内竖直地移动。例如,屏蔽构件125可耦接到轴部分127,所述轴部分127设置在腔室主体102中的开口中。中心轴128设置在轴组件126内并且包括中空部分或芯129。中心轴128由诸如铝之类的导电材料制成并且用作RF电流运载构件。屏蔽构件125的中心轴128和轴部分127被设置在这两者之间的绝缘轴130电气地分离。用于绝缘轴130的材料可以包括对热量和工艺化学物质有抵抗性的陶瓷或聚合物材料,以及其他工艺耐受材料。
基座124可通过连接器150和中心轴128连接到RF功率源148。当RF功率源148不包括集成匹配电路时,匹配电路152可耦接在连接器150与RF功率源148之间。RF功率源148一般能够产生具有从约50kHz至约200MHz的频率以及在约0瓦特与约5000瓦特之间的功率的RF信号。RF功率源148可耦接到基座124中的导电板。来自RF功率源148的RF偏置功率可用于激发并维持由设置在腔室主体102的工艺区域109中的气体形成的等离子体放电。
基板支撑组件106的竖直移动由致动组件138提供。致动组件138可以包括耦接到腔室主体102和致动器142的支撑构件140。
盖组件104可用作远程等离子体源并且包括第一电极154,所述第一电极竖直地设置在第二电极156上方,从而在这两个电极之间限定等离子体容积或空腔160。第一电极154连接到电源158,诸如RF功率源,并且第二电极156连接到地面,从而在这两个电极154、156之间形成电容。第二电极156可以包括形成在等离子体空腔160下方以允许来自等离子体空腔160的气体通过其流动的多个气体通道或孔隙176。盖组件104还可包括将第一电极154与第二电极156电隔离的隔离环166。
盖组件104可以包括第一一个或多个气体入口162(仅示出了一个),所述第一组一个或多个气体入口至少部分地形成在第一电极154内。来自工艺气体源的一种或多种气体可以经由第一组一个或多个气体入口162进入盖组件104。第一组一个或多个气体入口162在其第一端与等离子体空腔160流体地连通,并且在其第二端耦接到一个或多个上游气源和/或其他气体递送部件(诸如气体混合器)。
盖组件104可进一步包括与第二电极156相邻的分配板168和阻挡板170。第二电极156、分配板168和阻挡板170可堆叠并设置在盖支撑板172上,所述盖支撑板172连接到腔室主体102。
阻挡板170可设置在第二电极156与分配板168之间。阻挡板170可与第二电极156良好地热接触和电接触。阻挡板170包括多个孔隙182以提供从第二电极156到分配板168的多个气体通道。孔隙182可被设定尺寸并且绕阻挡板170而定位以向分配板168提供受控的且均匀的流动分配。
分配板168可以是双通道喷淋头。分配板168可以包括多个孔隙178或通路以分配通过所述分配板168的气体的流动。分配板168可以包括第二组一个或多个气体入口192(仅示出了一个),所述第二组一个或多个气体入口至少部分地形成在气体分配板168内。第二组一个或多个气体入口192在其第一端与气体分配板168的多个孔隙178中的至少一些流体地连通,并在其第二端耦接到经选择成形成含硅和氧的膜的一个或多个前体气体源。孔隙178可被设定尺寸并且定位在分配板168周围以向待处理的基板所位于的腔室主体102提供受控的且均匀的流动分配。来自第一一个或多个气体入口162的气体和形成在等离子体空腔160中的自由基可以穿过孔隙178的第一部分,并且来自第二组一个或多个气体入口192的气体可以穿过孔隙178的第二部分。
形成初始层的方法包括可按任何顺序来执行的以下步骤:将硅氧烷前体引入工艺区域109中;以及将硅氧烷前体暴露于低能等离子体或远程地形成的非氧自由基。可选地,,可以将一种或多种惰性气体引入处理区域109中。
将硅氧烷前体引入处理腔室100的工艺区域109中以提供用于形成含硅和氧的初始层(诸如,二氧化硅初始层)的物种。可以从气体入口192将硅氧烷前体供应到气体分配板168,如参考图1所述,或者通过其他合适的手段。硅氧烷前体是具有Si-O-Si键合的分子。硅氧烷前体可以包括例如具有化学通式SixOx-1H2x+2的无环硅氧烷前体和具有通式SixOxH2x(环状)的环状化合物前体。代表性的前体包括二硅氧烷(SiH3OSiH3)、三硅氧烷(SiH3OSiH2OSiH3)、四硅氧烷(SiH3OSiH2OSiH2OSiH3)和环三硅氧烷(-SiH2OSiH2OSiH2O-)(以下示出)。
可选地,可以将次前体(secondary precursor)引入处理腔室100的工艺区域109中以便更改初始层的所得成分。也可将次前体从气体入口192供应到气体分配板168,如参考图1所述,或者通过其他合适的手段。次前体是除了硅氧烷前体以外的具有至少一个Si-H键的分子。次前体的使用可产生由硅和氧以及一种或多种不同元素构成的初始层,诸如SiON或SiOC。代表性的次前体包括三甲硅烷基胺、二甲硅烷基甲烷、三甲硅烷基甲烷和四甲硅烷基甲烷(以下示出)。
在替代性实施例中,可使用次前体中的一种或多种来沉积初始层而不使用硅氧烷前体,从而产生SiC、SiN、SiCN或其他初始层。例如,三甲硅烷基胺可以用于产生SiN初始层;二甲硅烷基甲烷、三甲硅烷基甲烷和四甲硅烷基甲烷中的一种或多种可以用于形成SiC初始层;并且三甲硅烷基胺与二甲硅烷基甲烷、三甲硅烷基甲烷和四甲硅烷基甲烷中的一种或多种的组合可以用于产生SiCN初始层。在又一实施例中,使用次前体来形成初始层的第一部分而无需硅氧烷前体,并且随后使用硅氧烷前体以及可选的次前体来形成初始层的第二部分。或者,可以使用硅氧烷前体来形成初始层的第一部分而无需次前体,并且可以使用次前体以及使用或不使用硅氧烷前体形成初始层的第二部分。
可选地,可以将一种或多种惰性气体引入处理腔室100的处理区域109中。一种或多种惰性气体可以是可产生并维持等离子体以形成初始层的等离子体形成气体。可将一种或多种惰性气体从气体入口192供应到气体分配板168,如参考图1所述,或者通过其他合适的手段。合适的惰性气体的示例包括氩、氦、氮和它们的组合。例如,可以使用氦和氮混合物。
为了使用低能等离子体来沉积膜,生成低能等离子体以选择性地使前体的Si-H键中的至少一些断裂来形成初始层。通过将来自RF功率源148的足够的RF偏置功率施加到基座124的RF电极而在处理腔室100中形成等离子体。可由小于约250W(诸如小于约100W,诸如在约10W与约50W之间)的偏置RF功率来生成等离子体。或者,可由小于10W的RF偏置功率来生成等离子体。
为了使用远程地形成的非氧自由基来沉积膜,可以将一种或多种非惰性的气体以及可选的一种或多种惰性气体引入远程自由基源中。例如,可从气体入口162将一种或多种非惰性的气体以及可选的一种或多种非惰性气体引入等离子体容积160中。可以将等离子体容积160中生成的自由基和其他中性物种引入处理腔室100的处理区域109中,但防止带电物种到达处理区域(诸如通过阻挡板170)。合适的非惰性的气体包括例如氢。合适的惰性气体包括例如氩、氦和氙。一旦将惰性气体与非惰性的气体的混合物(诸如包括氢和氩的混合物)引入等离子体容积160中,RF功率源158就将功率施加到第一电极154,以产生并维持含氢自由基的低能等离子体。可由小于约250W(诸如小于约100W,诸如在约10W与约50W之间)的RF源功率来生成等离子体。或者,可由小于约10W的RF源功率来生成等离子体。氢自由基行进通过第二电极156、阻挡板170和分配板168,并进入工艺区域109中,在所述工艺区域109中,氢自由基选择性地离解前体的Si-H键中的至少一些,从而导致初始层的沉积。在替代实施例中,远程地形成的自由基可由以下方式生成:HW-CVD腔室;微波等离子体辅助CVD(MPCVD);不同的远程等离子体源(诸如电感耦合的远程等离子体源);或者可离解氢并与工艺容积109隔离开的任何其他源或设备。
可以在范围从约10℃至约600℃(诸如在10℃与300℃之间,诸如在10℃与50℃之间)的温度下沉积初始层。在初始层沉积过程中的压力可以从约0.25Torr至约10Torr。沉积可以继续,直到初始层达到了约或更厚(诸如约)的厚度。或者,沉积可以继续,直到初始层达到了小于约的厚度。沉积的初始层包含至少一些Si-H键,如果需要,可以在之后的后处理步骤中去除所述至少一些Si-H键。
在替代实施例中,初始层形成在具有易氧化的表面的基板上。易氧化的表面可由金属(诸如,例如铜、银、金、铝、钛或钽)构成。在不存在氧自由基和氧离子的情况下形成初始层,这允许在不氧化易氧化的表面的情况下形成初始层。
在使用低能等离子体的初始层的沉积的代表性的示例中,将惰性气体氦和氩分别以2000sccm和500sccm的流率从气体入口192引入处理腔室100的工艺区域109中。处理腔室100的压力和温度为约1000mTorr和约15℃。通过将50W的RF偏置功率从RF功率源148施加到基座124内的RF电极来生成并维持等离子体。随后,以582sccm的流率将二硅氧烷引入腔室中。沉积进行90秒并且形成具有约的厚度的二氧化硅层。在替代实施例中,执行预调谐的等离子体匹配,并且在生成等离子体前,将二硅氧烷引入腔室中。
可选地,二氧化硅的块状层可以形成在初始层的顶部上。块状层可以具有大于初始层厚度的厚度。可以使用常规工艺(诸如通过将一种或多种硅氧烷和/或一种或多种其他含硅的前体(诸如硅烷)暴露于含氧等离子体)和/或使用更高的RF偏置功率(诸如250W以上的RF偏置功率)来形成块状层。在形成块状层的过程中,可以通过气体入口192将硅氧烷、其他含硅的前体和氧引入处理腔室100中,并且可以通过将足够的RF偏置功率从RF功率源148施加到基座124的RF电极来生成等离子体。初始层在块状二氧化硅层的沉积过程中保护易氧化的表面免受含氧等离子体的影响,从而允许在不氧化易氧化的表面的情况下,在易氧化的表面上形成具有期望的厚度的二氧化硅块状层。或者,可以使用公知的方法在初始层的顶部上形成其他成分的块状层。例如,SiOC、SiON和SiN块状层可以沉积在初始层的顶部上。
同样可选地,初始层可被后处理或被固化,以便减小初始层中的Si-H键的浓度。可在初始层被沉积之后或在初始层和块状层两者都被沉积之后执行固化步骤。代表性的固化工艺是在约1Torr与约100Torr之间、在约200℃下、在氮和氦气氛下并使用具有UVA、UVB和UVC信号和170nm的较低波长的宽带1200W UV灯泡来执行的紫外线固化工艺。然而,波长可以小于170nm,诸如小于150nm。或者,利用400W电源功率和高达5000W的偏置功率在20mTorr下执行具有氮的离子注入。在另一实施例中,利用处于约1000V至约15000V的电子束处理初始层,-100V的偏置功率被供应到中间的喷淋头,电流在1-20mA之间变化,并且压力在约1mTorr至约100mTorr的范围内。在另一实施例中,后处理工艺是伴随热干燥工艺的直接等离子体(诸如,高密度等离子体)。
在进一步的实施例中,可使用电子束固化来后处理或固化初始层。电子束固化或电子束处理涉及将所沉积的初始层暴露于电子束。在电子束处理过程中的基板温度一般可以是如上相对于处理所述那样。在所公开的实施例中,电子束能量可在从约0.5keV至约30keV,约1keV至约15keV,或约5keV至约10keV的范围内。在本文所述实施例中,曝光剂量可在从约1μθονα2至约400μθονα2,从约5μθονα2至约300μθονα2,或从约50μθονα2至约200μθονα2的范围内。最后,在实施例中,电子束电流可在从约1mA至约80mA或约5mA至约20mA的范围内,并且可在处理工艺期间跨基板扫描电子束电流。
使用本文所公开的方法来形成的含硅和氧的膜(诸如二氧化硅膜)允许在不氧化易氧化的表面的情况下将块状二氧化硅层以及其他成分的层形成在易氧化的表面(诸如金属)上。通过提供一种在不氧化下层易氧化的材料的情况下沉积含硅和氧的膜的方法,本文所公开的实施例允许集成电路几何形状的尺寸的持续减小。
尽管上述内容针对本发明的实施例,但可设计本发明的其他以及进一步的实施例而不背离本发明的基本范围,并且本发明的范围是由所附权利要求书来确定。
Claims (20)
1.一种用于沉积含硅和氧的膜的方法,所述方法包括以下步骤:
将包含有一种或多种硅氧烷前体的工艺气体引入处理腔室,所述处理腔室具有设置在其中的基板,其中所述一种或多种硅氧烷前体选自由具有化学式SixOx-1H2x+2的无环硅氧烷和具有化学式SixOxH2x的环状硅氧烷构成的组,所述硅氧烷前体具有一个或多个Si-H键和一个或多个Si-O键;以及
选择性地离解所述一种或多种硅氧烷前体的Si-H键中的至少一些,以将由硅和氧组成的初始层沉积在所述基板的第一表面上方,其中Si-O键基本上被维持并且所述初始层在不存在氧化剂的情况下被沉积;以及
在所述初始层上形成由硅和氧组成的块状层,包括:
将含氧等离子体或由大于250W的RF源或偏置功率形成的等离子体引入所述处理腔室中。
2.根据权利要求1所述的方法,其特征在于,选择性地离解所述Si-H键中的至少一些的步骤进一步包括以下步骤:将所述一种或多种硅氧烷前体暴露于以250W或更小的RF源或偏置功率生成的等离子体。
3.根据权利要求2所述的方法,其特征在于,所述工艺气体包含具有至少一个Si-H键的一种或多种次前体。
4.根据权利要求2所述的方法,其特征在于,所述一种或多种硅氧烷前体包括选自由以下各项构成的组中的至少一种硅氧烷前体:二硅氧烷(SiH3OSiH3)、三硅氧烷(SiH3OSiH2OSiH3)、四硅氧烷(SiH3OSiH2OSiH2OSiH3)和环三硅氧烷(-SiH2OSiH2OSiH2O-)。
5.根据权利要求3所述的方法,其特征在于,所述一种或多种次前体包括选自由以下各项构成的组中的至少一种前体:三甲硅烷基胺、二甲硅烷基甲烷、三甲硅烷基甲烷和四甲硅烷基甲烷。
7.根据权利要求4所述的方法,进一步包括以下步骤:后处理所述初始层以消除所述Si-H键的部分。
8.根据权利要求2所述的方法,其特征在于,所述基板的所述第一表面是易氧化的表面。
9.根据权利要求1所述的方法,其特征在于,选择性地离解所述Si-H键中的至少一些的步骤进一步包括将所述一种或多种硅氧烷前体暴露于远程地形成的氢自由基。
10.根据权利要求1所述的方法,其特征在于,所述一种或多种硅氧烷前体包括选自由以下各项构成的组中的至少一种硅氧烷前体:二硅氧烷(SiH3OSiH3)、三硅氧烷(SiH3OSiH2OSiH3)、四硅氧烷(SiH3OSiH2OSiH2OSiH3)和环三硅氧烷(-SiH2OSiH2OSiH2O-)。
11.一种用于沉积含硅和氧的膜的方法,所述方法包括以下步骤:
将具有可氧化的表面的基板定位在处理腔室中;
使用工艺气体将由硅和氧组成的初始层形成在所述可氧化的表面上,所述工艺气体包含:
一种或多种硅氧烷前体,所述一种或多种硅氧烷前体选自由具有化学式SixOx-1H2x+2的无环硅氧烷和具有化学式SixOxH2x的环状硅氧烷构成的组,所述硅氧烷前体具有一个或多个Si-H键和一个或多个Si-O键;以及
具有至少一个Si-H键的一种或多种次前体,使用以250W或更小的RF源或偏置功率生成的等离子体来激活所述工艺气体,其中所述初始层在不存在氧化剂的情况下被沉积;以及
在所述初始层上形成由硅和氧组成的块状层,包括:
将含氧等离子体或由大于250W的RF源或偏置功率形成的等离子体引入所述处理腔室中。
12.根据权利要求11所述的方法,其特征在于,形成所述初始层的步骤进一步包括将所述一种或多种硅氧烷前体或所述工艺气体暴露于低能等离子体。
13.根据权利要求11所述的方法,其特征在于,所述一种或多种硅氧烷前体包括选自由以下各项构成的组中的至少一种硅氧烷前体:二硅氧烷(SiH3OSiH3)、三硅氧烷(SiH3OSiH2OSiH3)、四硅氧烷(SiH3OSiH2OSiH2OSiH3)和环三硅氧烷(-SiH2OSiH2OSiH2O-)。
14.根据权利要求11所述的方法,其特征在于,所述一种或多种次前体包括选自由以下各项构成的组中的至少一种前体:三甲硅烷基胺、二甲硅烷基甲烷、三甲硅烷基甲烷和四甲硅烷基甲烷。
16.根据权利要求11所述的方法,进一步包括以下步骤:后处理所述含硅和氧的膜以消除在所述含硅和氧的膜中的所述Si-H键中的至少一些。
17.根据权利要求11所述的方法,进一步包括以下步骤:将所述一种或多种硅氧烷前体暴露于远程地形成的氢自由基。
18.根据权利要求11所述的方法,其特征在于,所述一种或多种硅氧烷前体包括二硅氧烷。
19.根据权利要求11所述的方法,其特征在于,所述等离子体离解所述Si-H键中的至少一些,同时维持所述Si-O键。
20.一种用于沉积含硅和氧的膜的方法,所述方法包括以下步骤:
将具有可氧化表面的基板引入处理腔室中;
在所述可氧化表面上形成由硅和氧组成的初始层,包括:
将一种或多种硅氧烷前体引入所述处理腔室中,其中所述一种或多种硅氧烷前体选自由以下各项构成的组:二硅氧烷(SiH3OSiH3)、三硅氧烷(SiH3OSiH2OSiH3)、四硅氧烷(SiH3OSiH2OSiH2OSiH3)和环三硅氧烷(-SiH2OSiH2OSiH2O-),所述一种或多种硅氧烷前体具有一个或多个Si-O键;
将一种或多种次前体引入所述处理腔室中,所述一种或多种次前体具有至少一个Si-H键,其中所述一种或多种次前体选自由以下各项构成的组:三甲硅烷基胺、二甲硅烷基甲烷、三甲硅烷基甲烷和四甲硅烷基甲烷;以及
选择性地离解所述一种或多种硅氧烷前体的所述Si-H键中的至少一些,其中所述Si-H键通过暴露于等离子体或通过暴露于远程地形成的氢自由基来离解,并且其中基本上维持所述Si-O键;以及
在所述初始层上形成由硅和氧组成的块状层,包括:
将含氧等离子体或由大于250W的RF源或偏置功率形成的等离子体引入所述处理腔室中,其中所述初始层在不存在氧化剂的情况下被沉积。
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