公开(公告)号：US08945414B1

公开(公告)日：2015-02-03

申请号：US14079442

申请日：2013-11-13

Applicant: Intermolecular Inc.

Inventor： Jingang Su ,  Ashish Bodke ,  Abhijit Pethe ,  J Watanabe

IPC: B44C1/22 ,  C03C15/00 ,  C03C25/68 ,  C23F1/00 ,  H01L21/3065 ,  H01L21/02

CPC classification number: H01L21/31116 ,  H01J37/32357 ,  H01J2237/334 ,  H01L21/02046 ,  H01L22/12 ,  H01L22/26

Abstract: Oxides (e.g., native or thermal silicon oxide) are etched from underlying silicon with a mixture of fluorine and oxygen radicals generated by a remote plasma. The oxygen radicals rapidly oxidize any uncovered bare silicon areas, preventing the pitting that can result from fluorine etching bare silicon more rapidly than it etches the surrounding oxide. A very thin (few Å), highly uniform passivation layer remaining on the silicon after the process may be left in place or removed. An oxygen-impermeable layer may be formed in-situ immediately afterward to prevent further oxidation. A pre-treatment with oxygen radicals alone fills pores and gaps in the oxide before etching begins.

Abstract translation: 通过由远程等离子体产生的氟和氧自由基的混合物从下面的硅蚀刻氧化物（例如天然或热氧化硅）。 氧自由基快速氧化任何未覆盖的裸硅区域，防止氟蚀刻裸硅的点蚀比其蚀刻周围氧化物更快。 在该过程之后残留在硅上的非常薄（几埃）的高度均匀的钝化层可能留在原位或去除。 可以立即就地形成不透氧层，以防止进一步的氧化。 单独的氧自由基的预处理在蚀刻开始之前填充氧化物中的孔隙和间隙。

公开(公告)号：US20150118828A1

公开(公告)日：2015-04-30

申请号：US14068906

申请日：2013-10-31

Applicant: Intermolecular Inc.

Inventor： Frank Greer ,  Amol Joshi ,  Kevin Kashefi ,  Albert Sanghyup Lee ,  Abhijit Pethe ,  J Watanabe

IPC: H01L21/28 ,  H01L21/02

CPC classification number: H01L21/28158 ,  C23C16/0218 ,  C23C16/45525 ,  H01L21/02175 ,  H01L21/0228 ,  H01L21/28194 ,  H01L21/28238

Abstract: Native oxide growth on germanium, silicon germanium, and InGaAs undesirably affects CET (capacitive equivalent thickness) and EOT (effective oxide thickness) of high-k and low-k metal-oxide layers formed on these semiconductors. Even if pre-existing native oxide is initially removed from the bare semiconductor surface, some metal oxide layers are oxygen-permeable in thicknesses below about 25 Å thick. Oxygen-containing species used in the metal-oxide deposition process may diffuse through these permeable layers, react with the underlying semiconductor, and re-grow the native oxide. To eliminate or mitigate this re-growth, the substrate is exposed to a gas or plasma reductant (e.g., containing hydrogen). The reductant diffuses through the permeable layers to react with the re-grown native oxide, detaching the oxygen and leaving the un-oxidized semiconductor. The reduction product(s) resulting from the reaction may then be removed from the substrate (e.g., driven off by heat).

Abstract translation: 在锗，硅锗和InGaAs上的天然氧化物生长不利地影响在这些半导体上形成的高k和低k金属氧化物层的CET（电容等效厚度）和EOT（有效氧化物厚度）。 即使预先存在的原生氧化物最初从裸露的半导体表面去除，一些金属氧化物层的厚度可以在大约25埃的厚度下透氧。 在金属氧化物沉积工艺中使用的含氧物质可以扩散通过这些可渗透层，与下面的半导体反应，并重新生长天然氧化物。 为了消除或减轻这种再生长，将基底暴露于气体或等离子体还原剂（例如含有氢气）中。 还原剂通过可渗透层扩散以与再生的天然氧化物反应，分离氧并留下未氧化的半导体。 然后可以从反应物中除去由反应产生的还原产物（例如，通过加热驱除）。

公开(公告)号：US09312137B2

公开(公告)日：2016-04-12

申请号：US14068906

申请日：2013-10-31

Applicant: Intermolecular Inc.

Inventor： Frank Greer ,  Amol Joshi ,  Kevin Kashefi ,  Albert Sanghyup Lee ,  Abhijit Pethe ,  J Watanabe

IPC: H01L21/00 ,  H01L21/28 ,  H01L21/02 ,  C23C16/02 ,  C23C16/455

CPC classification number: H01L21/28158 ,  C23C16/0218 ,  C23C16/45525 ,  H01L21/02175 ,  H01L21/0228 ,  H01L21/28194 ,  H01L21/28238

Abstract: Native oxide growth on germanium, silicon germanium, and InGaAs undesirably affects CET (capacitive equivalent thickness) and EOT (effective oxide thickness) of high-k and low-k metal-oxide layers formed on these semiconductors. Even if pre-existing native oxide is initially removed from the bare semiconductor surface, some metal oxide layers are oxygen-permeable in thicknesses below about 25 Å thick. Oxygen-containing species used in the metal-oxide deposition process may diffuse through these permeable layers, react with the underlying semiconductor, and re-grow the native oxide. To eliminate or mitigate this re-growth, the substrate is exposed to a gas or plasma reductant (e.g., containing hydrogen). The reductant diffuses through the permeable layers to react with the re-grown native oxide, detaching the oxygen and leaving the un-oxidized semiconductor. The reduction product(s) resulting from the reaction may then be removed from the substrate (e.g., driven off by heat).