TWI808274B - 含有具有不飽和鍵之含硫氟碳化合物的乾式蝕刻氣體組成物及使用其之乾式蝕刻方法 - Google Patents
含有具有不飽和鍵之含硫氟碳化合物的乾式蝕刻氣體組成物及使用其之乾式蝕刻方法 Download PDFInfo
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- 238000001312 dry etching Methods 0.000 title claims abstract description 61
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 32
- 239000011593 sulfur Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 33
- -1 fluorocarbon compound Chemical class 0.000 title claims description 11
- 238000005530 etching Methods 0.000 claims abstract description 131
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims description 83
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 17
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 15
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 15
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 13
- 238000001020 plasma etching Methods 0.000 claims description 10
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 8
- HZFIOEDAPJNTCQ-UHFFFAOYSA-N 2,2,3,4,5,5-hexafluorothiophene Chemical compound FC1=C(F)C(F)(F)SC1(F)F HZFIOEDAPJNTCQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229920005591 polysilicon Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 4
- 229920002120 photoresistant polymer Polymers 0.000 claims description 4
- QLEDBYJNMXXMRY-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethylsulfanyl)ethene Chemical compound FC(F)=C(F)SC(F)(F)F QLEDBYJNMXXMRY-UHFFFAOYSA-N 0.000 claims description 3
- DBNMHLDZMPEZCX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane-2-thione Chemical compound FC(F)(F)C(=S)C(F)(F)F DBNMHLDZMPEZCX-UHFFFAOYSA-N 0.000 claims description 2
- VAYXDELKTUVICD-UHFFFAOYSA-N 2,2,3,3,4,5-hexafluorothiophene Chemical compound FC1=C(F)C(F)(F)C(F)(F)S1 VAYXDELKTUVICD-UHFFFAOYSA-N 0.000 claims description 2
- GQORANNOOLLPOS-UHFFFAOYSA-N 2,3,4,5-tetrafluorothiophene Chemical compound FC=1SC(F)=C(F)C=1F GQORANNOOLLPOS-UHFFFAOYSA-N 0.000 claims description 2
- IXCNXWOYJYTCCJ-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene-1-thione Chemical compound FC(F)(F)C(=C=S)C(F)(F)F IXCNXWOYJYTCCJ-UHFFFAOYSA-N 0.000 claims description 2
- AMTIZNAGVRLIAB-UHFFFAOYSA-N FC(F)(F)C(=S)C(F)(F)C(F)(F)F Chemical compound FC(F)(F)C(=S)C(F)(F)C(F)(F)F AMTIZNAGVRLIAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
- 239000013077 target material Substances 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 230000006399 behavior Effects 0.000 description 5
- QVHWOZCZUNPZPW-UHFFFAOYSA-N 1,2,3,3,4,4-hexafluorocyclobutene Chemical compound FC1=C(F)C(F)(F)C1(F)F QVHWOZCZUNPZPW-UHFFFAOYSA-N 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- UCYHFCTVZCAVRH-UHFFFAOYSA-N 2,2,3-trifluoro-3-(trifluoromethyl)thiirane Chemical compound FC1(SC1(C(F)(F)F)F)F UCYHFCTVZCAVRH-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
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- C09K13/00—Etching, surface-brightening or pickling compositions
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- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
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Abstract
本發明的課題為提供含有含硫不飽和化合物之有用於矽系膜之層合結構體的蝕刻用途之新穎的蝕刻氣體組成物。
其解決手段為,一種乾式蝕刻氣體組成物,其含有以通式(1):CxFySz(式中,x、y及z為2≦x≦5、y≦2x、1≦z≦2)表示,且具有不飽和鍵之含硫氟碳化合物。
Description
本發明係關於含有含硫氟碳化合物之乾式蝕刻氣體組成物及使用其之乾式蝕刻方法。
伴隨半導體裝置之微細化或3D化,對蝕刻步驟之要求年年變得嚴格。特別是以記憶體用途為代表之SiO2
蝕刻或SiO2
與SiN之層合結構體的集中蝕刻、SiO2
與多晶矽(poly-Si)之層合結構體的集中蝕刻中,要求以通量改善為對象之高速蝕刻、對遮罩高選擇比、良好之加工形狀(頸部縮口(necking)或擴孔(bowing)之抑制、垂直形狀等)等之蝕刻特性。
關於含有具有不飽和鍵之含硫氟碳化合物的乾式蝕刻氣體組成物,專利文獻1中記載使用含硫不飽和化合物(全氟丙烯硫醚(C3
F6
S))之乾式蝕刻方法,但專利文獻1,關於以氧化矽與氮化矽之蝕刻去除的比率為特徵之用途(SiO2
/SiN選擇蝕刻用途)、以將氧化矽及氮化矽相對於非晶質碳層(ACL)選擇性地蝕刻為特徵的用途,或以將氧化矽及多結晶矽相對於非晶質碳層(ACL)選擇性地蝕刻為特徵之用途,並無記載。專利文獻2中,雖記載使用特定含硫化合物之乾式蝕刻方法,但所有的含硫化合物均為飽和化合物。
[先前技術文獻]
[專利文獻]
[專利文獻1]韓國專利10-0574923號(韓國申請案公開10-2001-0010568號)
[專利文獻2]國際公開2015/0365381號
[發明所欲解決之課題]
因而本發明之課題,為提供含有含硫不飽和化合物之有用於矽系膜之層合結構體的蝕刻用途之新穎的蝕刻氣體組成物。
[用以解決課題之手段]
依照本發明,提供以下者。
[1]
一種乾式蝕刻氣體組成物,其含有以通式(1):CxFySz(式中,x、y及z為2≦x≦5、y≦2x、1≦z≦2)表示,且具有不飽和鍵之含硫氟碳化合物。
[2]
如[1]之乾式蝕刻氣體組成物,其中前述含硫氟碳化合物為由2,2,3,4,5,5-六氟-2,5-二氫噻吩(C4
F6
S)及三氟乙烯基三氟甲基硫醚(C3
F6
S)中選出的至少一種。
[3]
如[1]或[2]之乾式蝕刻氣體組成物,其含有1~100vol%之量的含硫氟碳化合物。
[4]
如[1]~[3]中任一項之乾式蝕刻氣體組成物,其中除前述含硫氟碳化合物以外,尚含有選自由O2
、O3
、CO、CO2
、NO、NO2
、SO2
及SO3
所成之群的至少1種含氧化合物。
[5]
如[1]~[4]中任一項之乾式蝕刻氣體組成物,其中除前述含硫氟碳化合物以外,尚含有選自由N2
、He、Ar、Ne及Xe所成之群的至少1種惰性氣體。
[6]
一種乾式蝕刻方法,其具有使用如[1]~[5]中任一項之乾式蝕刻氣體組成物進行電漿蝕刻,蝕刻含有矽之沈積物或膜之步驟。
[7]
如[6]之乾式蝕刻方法,其中前述含有矽之沈積物或膜,為含有氧及/或氮之沈積物或膜。
[8]
如[6]或[7]之乾式蝕刻方法,其具有相對於對遮罩材料,選擇性地蝕刻前述含有矽之沈積物或膜之步驟。
[9]
一種乾式蝕刻方法,其包含藉由使用如[1]~[5]中任一項之乾式蝕刻氣體組成物,將(a1)含碳之矽系膜、(a2)單結晶矽膜、(a3)非晶質矽膜、(a4)多結晶矽膜(多晶矽膜)、(a5)矽氧氮化膜、(a6)非晶質碳膜及/或(a7)光阻膜,與(b1)矽氧化膜及/或(b2)矽氮化膜之層合結構體進行電漿蝕刻,來選擇性地蝕刻前述層合結構體中之(b1)矽氧化膜及/或(b2)矽氮化膜之步驟。
[10]
如[9]之乾式蝕刻方法,其中前述層合結構體包含(b1)矽氧化膜及(b2)矽氮化膜,且相對於(b2)矽氮化膜,選擇性地進行(b1)矽氧化膜之蝕刻。
[11]
一種乾式蝕刻方法,其包含藉由使用如[1]~[5]中任一項之乾式蝕刻氣體組成物,將(a1)含碳之矽系膜、(a2)單結晶矽膜、(a3)非晶質矽膜、(a4)矽氮化膜、(a5)矽氧氮化膜、(a6)非晶質碳膜及/或(a7)光阻膜,與(b1)矽氧化膜及/或(b2)多結晶矽膜(多晶矽膜)之層合結構體進行電漿蝕刻,來選擇性地蝕刻前述層合結構體中之(b1)矽氧化膜及/或(b2)多結晶矽膜(多晶矽膜)之步驟。
[12]
如[6]~[11]中任一項之乾式蝕刻方法,其係將如[1]~[5]中任一項之蝕刻氣體組成物電漿化來進行蝕刻,使包含S之離子或活性物種生成。
[13]
如[6]~[11]中任一項之乾式蝕刻方法,其係於可同時蝕刻(b1)矽氧化膜及(b2)矽氮化膜之電漿條件下,以如[1]~[5]中任一項之乾式蝕刻氣體組成物來進行蝕刻。
[發明之效果]
依照本發明,提供含有氧化矽及氮化矽之材料與非晶質碳層(ACL)的蝕刻去除之比率高的蝕刻氣體組成物。因此,藉由使用本發明之蝕刻氣體組成物,提供以非晶質碳層為遮罩,將含有氧化矽及氮化矽之材料正確地蝕刻之方法。
以下,詳細說明本發明中之乾式蝕刻氣體組成物及使用其之乾式蝕刻方法。本發明之範圍不拘束於以下所說明之範圍,可在不損及本發明之要旨的範圍進行變更。
本發明中之乾式蝕刻氣體組成物中,包含含有下述通式(1)所示之具有不飽和鍵之含硫氟碳化合物的混合氣體,或氣體單質。
通式(1):CxFySz
(式中,x、y及z為2≦x≦5、y≦2x、1≦z≦2)
通式(1)中,就乾式蝕刻氣體之操作容易性的觀點,較佳使用滿足x=2~4 、y=4~8、z=1者。適合的化合物,例如可列舉
2,2,3,4,5,5-六氟-2,5-二氫噻吩(C4
F6
S)、
三氟乙烯基三氟甲基硫醚(C3
F6
S)、
1,1,2,3,4,5-六氟-1,1-二氫噻吩(C4
F6
S)、
2,3-雙(三氟甲基)硫環丙烯(C4
F6
S)、
3,3,3-三氟-2-(三氟甲基)-1-丙烯-1-硫酮(C4
F6
S)、
2,2,3,3,4,5-六氟-2,3-二氫噻吩(C4
F6
S)、
2,2,3,4,4-五氟-3-丁烯硫酮基氟化物(C4
F6
S)、
2,2,3,3,3-五氟-丙烷硫酮基氟化物(C3
F6
S)、
1,1,1,3,3,3-六氟-2-丙烷硫酮(C3
F6
S)、
1,3,3,3-四氟-2-(三氟甲基)-1-丙烯-1-硫基氟(C4
F8
S)、
1,1,1,3,3,4,4,4-八氟-2-丁烷硫酮(C4
F8
S)、
2,3,4,5-四氟噻吩(C4
F4
S)等。
本發明中之乾式蝕刻氣體組成物中,通式(1)所示之含硫氟碳化合物之純度較佳使用95.0vol%~100.0vol%者。更佳使用純度99vol%以上者、又更佳使用99.9vol%以上者。所含有的雜質成分可列舉N2
、O2
、CO2
、H2
O、HF、HCl、SO2
、CH4
等,此等雜質成分之中,H2
O、HF、HCl、SO2
等係腐蝕氣體流通之路徑的可能性高,因此較佳為藉由精製而儘可能去除。
本發明中之乾式蝕刻氣體組成物中,藉由將通式(1)所示之含硫氟碳化合物與其他之氟碳(FC)氣體或氫氟碳(HFC)氣體混合來使用,相較於未混合通式(1)所示之化合物的情況,可更加提高蝕刻對象材料相對於非蝕刻對象材料之選擇比。又,蝕刻經非蝕刻對象材料而圖型化之結構的情況時,亦會提高垂直加工精度。
於經如上述之非蝕刻對象材料而圖型化之結構中,蝕刻對象材料為SiO2
等之含氧的Si系材料時,對選擇性的蝕刻、垂直加工精度良好的蝕刻而言,較佳為將通式(1)所示之化合物,與CF4
、CHF3
、C2
F6
、C3
F8
、C4
F8
、C4
F6
、C5
F8
等之蝕刻氣體混合來使用。特別是如要求選擇性高時,較佳與C數目多的C4
F8
、C4
F6
、C5
F8
混合。
於經非蝕刻對象材料而圖型化之結構中,蝕刻對象材料為SiN等之含氮的Si系材料時,對選擇性的蝕刻、垂直加工精度良好的蝕刻而言,較佳為將通式(1)所示之氣體化合物,與CHF3
、CH2
F2
、CH3
F等之HFC氣體混合而用於電漿蝕刻。特別是如要求選擇性高時,使用C的數目2以上之HFC氣體亦為有效。
本發明中之乾式蝕刻氣體組成物中,藉由對含有通式(1)所示之化合物的組成物,添加選自由O2
、O3
、CO、CO2
、NO、NO2
、SO2
及SO3
所成之群的至少1種含氧化合物,可得到抑制過剩之沈積(沈積物)、提高蝕刻對象物之蝕刻速率、提高蝕刻對象物相對於非蝕刻對象材料之選擇性等效果。
本發明中之乾式蝕刻氣體組成物中,可對含有通式(1)所示之化合物的組成物,添加選自由N2
、He、Ar、Ne及Xe所成之群的至少1種惰性氣體。其中較佳使用He、Ar、Xe。
本發明之方法所使用的蝕刻氣體組成物之例子,可列舉以下者。
(a)通式(1)所示之化合物,能夠以純度90vol%以上來實施,較佳以純度99vol%以上來實施、特佳以純度99.999vol%以上來實施。
(b)蝕刻所用之乾式蝕刻組成物中,通式(1)所示之化合物,較佳為1~100vol%。
(c)蝕刻所用之乾式蝕刻組成物中,於通式(1)所示之化合物以外,較佳含有選自由O2
、O3
、CO、CO2
、NO、NO2
、SO2
及SO3
所成之包含氧原子的化合物群之至少一者,特佳使用O2
。包含氧原子的化合物之比例,相對於通式(1)所示之化合物與包含氧原子的化合物之總量而言,較佳為5~80%、特佳為10~65%。
(d)蝕刻所用之乾式蝕刻組成物中,較佳含有通式(1)所示之化合物,與除了上述包含氧原子的化合物群以外/或取代該化合物群地,含有選自由稀有氣體或N2
所成之惰性氣體群的至少一者;特佳使用Ar。蝕刻氣體組成物中所包含的惰性氣體之比例,較佳為1~80vol%、特佳為50~75vol%。
本發明中之乾式蝕刻所用的乾式蝕刻裝置,可無特別限制地利用該技術領域所用者。例如,可使用螺旋波方式、高頻感應方式、平行平板型方式、磁控管方式及微波方式等之裝置等。
本發明中之乾式蝕刻方法,為進行微細之Si系材料的圖型晶圓之垂直加工者,因此蝕刻裝置,必需為適於離子輔助蝕刻之具備可再現低氣體壓力條件之真空容器的裝置。於低壓力條件下,電漿中之粒子的直進性提高,對基板所照射之離子亦不被其他粒子阻礙地到達基板,因此對基板垂直入射之離子增加,有利於垂直加工。本發明中之乾式蝕刻方法中,蝕刻時之真空容器內的壓力,較佳調節為100Torr~0.1mTorr、更佳調節為100mTorr~0.1mTorr。
本發明中之乾式蝕刻方法中,較佳將通式(1)所示之化合物以氣體的形態導入於蝕刻裝置之真空容器。因此,較佳為對本發明中之乾式蝕刻方法所用之蝕刻裝置以氣體的形態導入通式(1)所示之化合物,且進一步具備用以調節其導入量之機構。又,關於該機構,本發明中之電漿蝕刻方法,於通式(1)所示之氣體化合物以外,依目的亦使用複數種之例如O2
、Ar等的前述別的氣體化合物係為有效,因此較佳為亦具備4個以上之調節氣體導入、導入量之機構。
[實施例]
本實施例(蝕刻試驗(1)及(2)、沈積膜評估試驗)中,係使用SAMCO公司製平行平板型之電容耦合電漿蝕刻裝置,作為電漿蝕刻裝置。沈積膜之組成,係藉由SEM-EDX(掃描型電子顯微鏡/能量分散型X射線分光法)來決定。
作為矽氧化膜(SiOm)(m表示自然數),係使用藉由電漿CVD而於矽晶圓上沈積有SiO2
膜1000nm者。作為矽氮化膜(SiN),係使用藉由熱CVD而於矽晶圓上沈積有SiN膜300nm者。作為非晶質碳膜(ACL),係使用藉由電漿CVD而於矽晶圓上沈積有ACL 400nm者。
氣體之流量,係由以溫度(0℃)、壓力(1atm)為標準狀態之sccm(standard cc/min)來表現。
蝕刻時之樣品膜厚係以光干涉式膜厚測定器測定。蝕刻條件示於下述表1與表3。氣體之蝕刻速率,係由下式算出。
A/B選擇比,係由下式算出。
A/B選擇比=A膜之蝕刻速率(nm/min)÷B膜之蝕刻速率(nm/min)
堆積膜(以下稱為「沈積膜」)之形成係於裸矽晶圓(bare silicon wafer)上進行。沈積膜之膜厚係以掃描型電子顯微鏡測定。沈積膜形成及濺鍍之條件示於下述表2。沈積膜形成速度與濺鍍速度,係由下式算出。
[蝕刻試驗(1)]
使用於矽晶圓上分別沈積有SiO2
、SiN或ACL之不同3個樣品,以表1所示條件進行蝕刻試驗。蝕刻氣體係使用不含硫之全氟環丁烯(1,2,3,3,4,4-六氟-1-環丁烯(C4
F6
)作為比較例,與含硫之2,2,3,4,5,5-六氟-2,5-二氫噻吩(C4
F6
S)作為本發明之實施例。
表1. 蝕刻試驗條件(裝置:SAMCO RIE-10NR)
SAMCO RIE-10NR | |
總氣體流量 | 80 [sccm] |
Ar / 蝕刻氣體 / O2 | 40 / x / y [sccm] |
壓力 | 3.0 [Pa] |
RF 功率 | 300 [W] |
試驗結果示於圖1。Ar係恆定地流通40sccm(50%),使蝕刻氣體之量及氧(O2
)之量變化。蝕刻氣體之量為20sccm、氧之量為20sccm時,圖1之圖的O2
比成為50%,由該成分比開始測定,增加至蝕刻氣體之量為14sccm、氧之量為26sccm之圖1的圖之O2
比成為65%的蝕刻氣體之濃度。
ACL係由碳所構成,因此實施例及比較例中,均隨著O2
之濃度增加,蝕刻速率增大。另一方面,可知實施例之蝕刻氣體(C4
F6
S),隨著O2
比之增加,SiO2
之蝕刻速率急遽增加,於O2
比為55%(蝕刻氣體之量為18sccm、氧之量為22sccm)的時間點,SiO2
之蝕刻速率成為最大(大致為70nm/min),但比較例中,隨著O2
比增加,蝕刻速率係緩慢地增加,於O2
比為65%(蝕刻氣體之量為14sccm、氧之量為26sccm)大致成為最大(大致為70nm/min)。又,可知實施例之蝕刻氣體(C4
F6
S),隨著O2
比之增加,SiN之蝕刻速率係緩慢地增加,於O2
比為65%大致成為最大(大致為55nm/min),但比較例中,隨著O2
比之增加,SiN之蝕刻速率係更緩慢地增加,於比較例中,O2
比即使為65%,SiN之蝕刻速率亦未達40nm/min。
對於實施例與比較例所得之結果,以ACL之蝕刻速率為基準,評估SiO2
與SiN之蝕刻速率。其結果示於圖2。由圖2可知,比較例中,O2
比為55%之較低氧濃度時(蝕刻氣體之量為18sccm、氧之量為22sccm),僅SiO2
之蝕刻速率高,相對於SiN及ACL可選擇性地蝕刻SiO2
,另一方面,本發明之實施例中,O2
比為55%之較低氧濃度時(蝕刻氣體之量為18sccm、氧之量為22sccm),SiO2
之蝕刻速率更高,且SiN之蝕刻速率亦高,因此可將SiO2
與SiN兩方以高於ACL之蝕刻速率蝕刻。又,亦可知O2
比超過65%時,實施例與比較例之間蝕刻速率的差異消失。
由以上結果,可知使用含硫之蝕刻氣體的本發明之實施例,與使用不含硫之蝕刻氣體的比較例之間,蝕刻的行為有顯著不同。可知藉由利用本發明之新穎的蝕刻行為,可進行高速蝕刻與對遮罩材料高選擇性之兼顧。本實施例能夠以對於比較例而言統計上顯著的差異,相對於ACL,將SiO2
及/或SiN選擇性地蝕刻。又,藉由合併使用本發明之蝕刻氣體與以往之蝕刻氣體,可變動SiO2
與SiN之蝕刻速率的差分,可進行更精密之蝕刻。
[沈積膜評估試驗]
以蝕刻氣體蝕刻對象,與蝕刻氣體之分解物沈積,係存在競爭關係,蝕刻之時,另一方面會形成如此的沈積物。使用作為比較例之不含硫之全氟環丁烯(1,2,3,3,4,4-六氟-1-環丁烯(C4
F6
),與作為本發明之實施例之含硫之2,2,3,4,5,5-六氟-2,5-二氫噻吩(C4
F6
S),由以下表2所示之條件形成蝕刻氣體之沈積物,藉由Ar濺鍍評估沈積物之去除處理的容易性。
表2. 沈積膜評估試驗條件(裝置:SAMCO RIE-200NL)
SAMCO RIE-200NL | ||
沈積速率 | 濺鍍速率 | |
Ar /蝕刻氣體 | 10 / 20 [sccm] | 50 / 0 [sccm] |
壓力 | 5.0 [Pa] | 5.0 [Pa] |
RF 功率 | 100 [W] | 100 [W] |
時間 | 120 [sec] | 30 [sec] |
沈積膜評估試驗之結果示於圖3及圖4。不管沈積速率及濺鍍速率,本發明之實施例均較比較例為低,濺鍍速率(SR)與沈積速率(DR)之比(SR/DR),係本發明之實施例較低,因此可知本發明之實施例較容易沈積,不易被濺鍍。由於圖4所示之堆積膜的組成中檢測到硫,故可認為如此的本發明之特徵係起因於含硫膜。由該試驗結果,可知本發明之蝕刻氣體,係蝕刻SiO2
、SiN等之矽晶圓上之沈積層,另一方面,可形成不易被去除之堆積膜。如此的本發明之新穎的行為,例如係有用於蝕刻時之側壁保護或遮罩材料之保護等。
[蝕刻試驗(2)]
使用於矽晶圓上分別沈積有SiO2
、SiN或ACL之不同的3個樣品,以表3所示之條件進行蝕刻試驗。蝕刻氣體係使用不含硫之全氟丙烯(1,1,2,3,3,3-六氟-1-丙烯(C3
F6
)作為比較例,與含硫之三氟乙烯基三氟甲基硫醚(C3
F6
S)作為本發明之實施例。
表3. 蝕刻試驗條件(2) (裝置:SAMCO RIE-10NR)
SAMCO RIE-10NR | |
Ar /蝕刻氣體/ O2 | 50 / 20(x) / **(y) [sccm] |
壓力 | 10.0 [Pa] |
RF功率 | 300 [W] |
試驗結果示於圖5。Ar係恆定地以50sccm之量流通,蝕刻氣體係恆定地以20sccm之量流通,使氧(O2
)之量(sccm)變化。氧之量相對於蝕刻氣體(x)與氧(y)之合計(x+y)而言,超過20%時,即開始ACL之蝕刻。
實施例之蝕刻氣體(C3
F6
S),隨著O2
比之增加,SiO2
之蝕刻速率急遽增加,於O2
比為25%附近,SiO2
之蝕刻速率成為最大(大致為70nm/min),但比較例(C3
F6
)中,即使O2
比增加,SiO2
之蝕刻速率亦幾乎不增加,O2
比自超過20%時起即急遽地增加。又,實施例之蝕刻氣體(C3
F6
S),隨著O2
比之增加,SiN之蝕刻速率係緩慢地增加,於O2
比超過30%時大致成為最大(大致為55nm/min),但比較例中,即使O2
比增加,SiN之蝕刻速率亦幾乎不增加,O2
比自超過20%時起即急遽地增加。
對於實施例與比較例所得之結果,以ACL之蝕刻速率為基準,評估SiO2
與SiN之蝕刻速率。其結果示於圖6。由圖6可知,比較例中,O2
比為20%以下之較低氧濃度時,SiO2
、SiN、ACL之蝕刻速率均為低,相對於此,本發明之實施例中,O2
比為20%以下之較低氧濃度時,SiO2
、SiN之蝕刻速率均非常高,因此可知可將SiO2
與SiN兩方,以高於ACL之蝕刻速率蝕刻。又,亦可知O2
比超過30%時,實施例與比較例之間蝕刻速率的差異消失。
由以上結果,可知蝕刻試驗(2)中,亦與蝕刻試驗(1)同樣地,使用含硫之蝕刻氣體的本發明之實施例,與使用不含硫之蝕刻氣體的比較例之間,蝕刻的行為有顯著不同。亦即,可知藉由利用本發明之新穎的蝕刻行為,可進行高速蝕刻與對遮罩材料高選擇性之兼顧。本實施例能夠以對於比較例而言統計上顯著的差異,相對於ACL,將SiO2
及/或SiN選擇性地蝕刻。又,藉由合併使用本發明之蝕刻氣體與以往之蝕刻氣體,可變動SiO2
與SiN之蝕刻速率的差分,可進行更精密之蝕刻。
[圖1]顯示蝕刻試驗(1)之結果的圖。
[圖2]以ACL之蝕刻速率為基準,將蝕刻試驗(1)之結果以柱狀圖表示之圖。
[圖3]顯示沈積膜評估試驗之結果的圖。
[圖4]顯示於沈積膜評估試驗所形成之沈積膜的組成之圖。
[圖5]顯示蝕刻試驗(2)之結果的圖。
[圖6]以ACL之蝕刻速率為基準,將蝕刻試驗(2)之結果以柱狀圖表示之圖。
Claims (15)
- 一種乾式蝕刻氣體組成物,其含有以通式(1):CxFySz(式中,x、y及z為2≦x≦5、y≦2x、1≦z≦2)表示,且具有不飽和鍵之含硫氟碳化合物。
- 如請求項1之乾式蝕刻氣體組成物,其中前述含硫氟碳化合物為由
- 如請求項1或2之乾式蝕刻氣體組成物,其含有1~100vol%之量的含硫氟碳化合物。
- 如請求項1或2之乾式蝕刻氣體組成物,其中除前述含硫氟碳化合物以外,尚含有選自由O2、O3、CO、CO2、NO、NO2、SO2及SO3所成之群的至少1種含氧化合物。
- 如請求項1或2之乾式蝕刻氣體組成物,其中除前述含硫氟碳化合物以外,尚含有選自由N2、He、Ar、Ne及Xe所成之群的至少1種惰性氣體。
- 一種乾式蝕刻方法,其具有使用如請求項1~7中任一項之乾式蝕刻氣體組成物進行電漿蝕刻,蝕刻含有矽之沈積物或膜之步驟。
- 如請求項8之乾式蝕刻方法,其中前述含有矽之沈積物或膜,為含有氧及/或氮之沈積物或膜。
- 如請求項8或9之乾式蝕刻方法,其具有相對於對遮罩材料,選擇性地蝕刻前述含有矽之沈積物或膜之步驟。
- 一種乾式蝕刻方法,其包含藉由使用如請求項1~7中任一項之乾式蝕刻氣體組成物,將(a1)含碳之矽系膜、(a2)單結晶矽膜、(a3)非晶質矽膜、(a4)多結晶矽膜(多晶矽膜)、(a5)矽氧氮化膜、(a6)非晶質碳膜及/或(a7)光阻膜,與(b1)矽氧化膜及/或(b2)矽氮化膜之層合結構體進行電漿蝕刻,來選擇性地蝕刻前述層合結構體中之(b1)矽氧化膜及/或(b2)矽氮化膜之步驟。
- 如請求項11之乾式蝕刻方法,其中前述層合結構體包含(b1)矽氧化膜及(b2)矽氮化膜,且相對於(b2)矽氮化膜,選擇性地進行(b1)矽氧化膜之蝕刻。
- 一種乾式蝕刻方法,其包含藉由使用如請求項1~7中任一項之乾式蝕刻氣體組成物,將(a1)含碳之矽系膜、(a2)單結晶矽膜、(a3)非晶質矽膜、(a4)矽氮化膜、(a5)矽氧氮化膜、(a6)非晶質碳膜及/或(a7)光阻膜,與(b1)矽氧化膜及/或(b2)多結晶矽膜(多晶矽膜)之層合結構體進行電漿蝕刻,來選擇性地蝕刻前述層合結構體中之(b1)矽氧化膜及/或(b2)多結晶矽膜(多晶矽膜)之步驟。
- 如請求項8、9、11、12或13之乾式蝕刻方法,其係將如請求項1~7中任一項之蝕刻氣體組成物電漿化來進行蝕刻,使包含S之離子或活性物種生成。
- 如請求項8、9、11、12或13之乾式蝕刻 方法,其係於可同時蝕刻(b1)矽氧化膜及(b2)矽氮化膜之電漿條件下,以如請求項1~7中任一項之乾式蝕刻氣體組成物來進行蝕刻。
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