JP6405958B2 - エッチング方法、記憶媒体及びエッチング装置 - Google Patents
エッチング方法、記憶媒体及びエッチング装置 Download PDFInfo
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- JP6405958B2 JP6405958B2 JP2014246894A JP2014246894A JP6405958B2 JP 6405958 B2 JP6405958 B2 JP 6405958B2 JP 2014246894 A JP2014246894 A JP 2014246894A JP 2014246894 A JP2014246894 A JP 2014246894A JP 6405958 B2 JP6405958 B2 JP 6405958B2
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- 238000005530 etching Methods 0.000 title claims description 101
- 238000000034 method Methods 0.000 title claims description 71
- 238000003860 storage Methods 0.000 title claims description 6
- 239000007789 gas Substances 0.000 claims description 335
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 102
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 102
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 65
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 65
- 239000000758 substrate Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 7
- 238000004590 computer program Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 53
- 238000009792 diffusion process Methods 0.000 description 14
- 238000011144 upstream manufacturing Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- 229940070337 ammonium silicofluoride Drugs 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Description
真空雰囲気中にて、フッ化水素ガスとアンモニアガスとを含む処理ガス、及び窒素、水素、フッ素を含む化合物を含む処理ガスのうち少なくとも一方の処理ガスに前記被処理基板を間欠的に複数回曝す工程を行うことを特徴とする。
前記コンピュータプログラムは、上述のエッチング方法を実施するためにステップ群が組まれていることを特徴とする。
被処理基板を載置する載置部を有する処理容器と、
前記載置部に載置された被処理基板に対して、フッ化水素ガスとアンモニアガスとを含む処理ガス、及び窒素、水素、フッ素を含む化合物を含む処理ガスのうち少なくとも一方の処理ガスを供給するためのガス供給部と、
前記処理容器内を真空排気するための真空排気部と、
前記被処理基板を前記処理ガスに間欠的に曝すように制御信号を出力する制御部と、を備えたことを特徴とする。
処理容器1の底面には排気口14が設けられている。排気口14には排気管15が接続されており、排気口14側から圧力調整バルブ16、開閉バルブ17が介設され、真空排気機構である真空排気ポンプ18に接続されている。これら排気管15等のパーツは真空排気部を構成している。
さらに前段パルス工程において十分なエッチングレートが得られる場合には、後段パルス工程は行わなくてもよい。
即ち、本発明は、被処理基板を、NH3ガス及びHFガスの混合ガスを含む処理ガスまたは窒素、水素、フッ素を含む化合物を含む処理ガスである、NH4FガスまたはNH4FHFを含む処理ガスに間欠的に複数回曝す手法である。なお、処理ガスがNH3ガス、HFガス及びNH4Fガス(または、NH4FHF)の混合ガスであってもよい。
本発明の実施の形態の効果を検証するために行った実施例について記載する。
(実施例1―1)
SiO2膜とSiN膜とを露出させた評価用のウエハを用い、図1に示す装置により第1の実施形態に記載した手法のうち図3に示すシーケンスを行った。即ち、HFガスを流しながら、NH3ガスを1秒間供給する工程と2秒間供給停止する工程とを5回繰り返し、その後、NH3ガスを3秒間供給する工程と5秒間供給停止する工程とを2回繰り返した。プロセス圧力は250Pa(1.88Torr)、プロセス温度は115℃である。
(実施例1−2)
図1に示したプリミックス型の装置に代えて、HFガスとNH3ガスとがシャワーヘッドのガス供給孔から別々に処理容器内に供給されるポストミックス型の装置を用いて、実施例1−1と同様のシーケンスで評価用のウエハに対してエッチングを行った。
(比較例1)
HFガスとNH3ガスとがシャワーヘッドのガス供給孔から別々に処理容器内に供給されるポストミックス型の装置を用いて、HFガスとNH3ガスとを11秒間供給してエッチングを行った。
実施例1−1では、SiN膜に対するSiO2膜のエッチング選択比は15.5と最も高くなっていた。図12は、実施例1−2と比較例1との各々について、SiO2膜のエッチング量、SiN膜のエッチング量、及びSiN膜に対するSiO2膜のエッチング選択比を示す。比較例では、SiN膜はSiO2膜と同程度エッチングされておりエッチング選択比は1.2と低かった。これに対して実施例1−2では、SiO2膜は比較例と同程度エッチングされたが、SiN膜はほとんどエッチングされずエッチング選択比も7.3と高かった。この結果によれば本発明のエッチング方法を用いることによりSiN膜に対するSiO2膜のエッチング選択比を高めることができるといえる。
NH3を流しながらHFガスを1秒間供給する工程と2秒間供給停止する工程とを5回繰り返し、その後、HFガスを3秒間供給する工程と5秒間供給停止する工程とを2回繰り返すシーケンスを用いたことを除いて、実施例1−1と同様な処理を行った。
この結果によれば実施例2ではSiN膜に対するSiO2膜のエッチング選択比は7.3であった。ウエハWをNH3とHFガスとを含む処理ガスに間欠的に曝すことによりSiN膜に対するSiO2膜のエッチング選択比を高めることができるが、HFガスを流しながらNH3ガスを間欠的に供給した場合には、より大きな効果があるといえる。
実施例1において、HFガスとNH3ガスとを含む処理ガスを250Paの圧力に調整した処理容器1内に供給する際に、各々の分圧が夫々(HFの分圧Pa:NH3の分圧Pa)=(12:105)、(20:73)、(22:55)、(58:115)、(38:19)となるようにHFガス及びNH3ガスの流量を調整した。そしてエッチング処理後において膜の表面におけるエッチングの仕上がり状態の良否について評価した。
図15は、HFガス及びNH3ガスの分圧を夫々の圧力に設定したときのエッチングの結果を示す特性図であり、処理ガスが狭い部位まで行き渡りSiN膜の近傍部までエッチングが揃いSiO2膜をすべて除去したときに表面が滑らかに仕上がった例は、◇で示し、SiN膜の近傍部のSiO2膜のエッチングが遅れ、SiO2膜をすべて除去したときに表面が滑らかに仕上がらなかった例を▲で示した。なお図中の直線は、HF:NH3の分圧比が1:1を示す。この結果によれば、HFガスの分圧を80Pa以下、NH3ガスの分圧を140Pa以下に設定した場合において、HFガスの分圧に対するNH3ガスの分圧の分圧比を1以上に設定した場合には、SiN膜の近傍部までエッチングが揃い、表面が滑らかにエッチングされていた。本発明によれば、狭い部位まで処理ガスを侵入させることができ、細部のSiO2膜まで効率よくエッチングできるといえる。
2 ステージ
9 制御部
10 処理容器
11 天板部
14 排気口
19 凹部
26 ヒータ
30 拡散板
31 ガス供給孔
32 ガス拡散部
35 分散室
36 外部流路
40 NH3ガス供給管
50 HFガス供給管
Claims (16)
- 表面部に窒化シリコン膜と酸化シリコン膜とを有する被処理基板に対して、酸化シリコン膜を選択的にエッチングする方法において、
真空雰囲気中にて、フッ化水素ガスとアンモニアガスとを含む処理ガス、及び窒素、水素、フッ素を含む化合物を含む処理ガスのうち少なくとも一方の処理ガスに前記被処理基板を間欠的に複数回曝す工程を行うことを特徴とするエッチング方法。 - 前記被処理基板に対する各回の処理ガスの供給時間の長さは0.1秒〜5秒であることを特徴とする請求項1記載のエッチング方法。
- 前記被処理基板に対する各回の処理ガスの供給停止時間の長さは1秒〜15秒であることを特徴とする請求項1または2記載のエッチング方法。
- 前記窒素、水素、フッ素を含む化合物は、NH4FまたはNH4FHFのいずれかであることを特徴とする請求項1ないし3のいずれか一項に記載のエッチング方法。
- 前記工程は、処理容器内を真空排気しながら、処理容器内の被処理基板に対して、フッ化水素ガスとアンモニアガスとを予め混合したガスを含む処理ガスをガス供給部から間欠的に供給する工程であることを特徴とする請求項1ないし3のいずれか一項に記載のエッチング方法。
- 前記工程は、フッ化水素ガスをガス供給部から連続的に供給し、フッ化水素ガスに間欠的にアンモニアガスを混合することを特徴とする請求項5記載のエッチング方法。
- 前記ガス供給部は、処理容器内に載置された被処理基板に対向する複数のガス供給孔を有することを特徴とする請求項5または6記載のエッチング方法。
- 前記工程は、前記被処理基板に対する処理ガスの各回の供給時間を第1の時間に設定した第1の工程と、この第1の工程の後に行われ、各回の処理ガスの供給時間を第1の時間よりも長い第2の時間に設定した第2の工程と、を含むことを特徴とする請求項1ないし7のいずれか一項に記載のエッチング方法。
- 前記第2の工程は、被処理基板に対する各回の処理ガスの供給停止時間が第1の工程における各回の処理ガスの供給停止時間よりも長いことを特徴とする請求項8に記載のエッチング方法。
- 真空雰囲気中におけるフッ化水素ガスの分圧が10Pa〜80Pa、アンモニアガスの分圧が10Pa〜140Paであって、
フッ化水素ガスの分圧に対するアンモニアガスの分圧の分圧比が1以上であることを特徴とする請求項1ないし8のいずれか一項に記載のエッチング方法。 - 処理容器内に載置され、表面部に窒化シリコン膜と酸化シリコン膜とを有する被処理基板に対して、酸化シリコン膜を選択的にエッチングする方法に用いられるコンピュータプログラムを記憶した記憶媒体であって、
前記コンピュータプログラムは、請求項1ないし10のいずれか一項に記載のエッチング方法を実施するためにステップ群が組まれていることを特徴とする記憶媒体。 - 表面部に窒化シリコン膜と酸化シリコン膜とを有する被処理基板に対して、酸化シリコン膜を選択的にエッチングする装置において、
被処理基板を載置する載置部を有する処理容器と、
前記載置部に載置された被処理基板に対して、フッ化水素ガスとアンモニアガスとを含む処理ガス、及び窒素、水素、フッ素を含む化合物を含む処理ガスのうち少なくとも一方の処理ガスを供給するためのガス供給部と、
前記処理容器内を真空排気するための真空排気部と、
前記被処理基板を前記処理ガスに間欠的に曝すように制御信号を出力する制御部と、を備えたことを特徴とするエッチング装置。 - 前記窒素、水素、フッ素を含む化合物は、NH4FまたはNH4FHFのいずれかであることを特徴とする請求項12に記載のエッチング装置。
- 前記ガス供給部から処理容器内に処理ガスが供給される前に、フッ化水素ガスとアンモニアガスとを混合する混合部を備え、
前記処理ガスは、フッ化水素ガスとアンモニアガスとの混合ガスを含むことを特徴とする請求項12記載のエッチング装置。 - 前記制御部は、フッ化水素ガスをガス供給部から連続的に供給し、フッ化水素ガスに間欠的にアンモニアガスを混合するように制御信号を出力するものであることを特徴とする請求項14記載のエッチング装置。
- 前記ガス供給部は、処理容器内に載置された被処理基板に対向する複数のガス供給孔を有することを特徴とする請求項11ないし15のいずれか一項に記載のエッチング装置。
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