JP5346699B2 - Ge−Sb−Te膜の成膜方法および記憶媒体、ならびにPRAMの製造方法 - Google Patents
Ge−Sb−Te膜の成膜方法および記憶媒体、ならびにPRAMの製造方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 42
- 238000003860 storage Methods 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002994 raw material Substances 0.000 claims description 152
- 238000012545 processing Methods 0.000 claims description 72
- 230000015572 biosynthetic process Effects 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 25
- 239000011261 inert gas Substances 0.000 claims description 15
- 229910052714 tellurium Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 230000005587 bubbling Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- -1 diisopropyl tellurium Chemical compound 0.000 claims description 6
- RBEXEKTWBGMBDZ-UHFFFAOYSA-N tri(propan-2-yl)stibane Chemical compound CC(C)[Sb](C(C)C)C(C)C RBEXEKTWBGMBDZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 description 145
- 238000002474 experimental method Methods 0.000 description 21
- 238000000151 deposition Methods 0.000 description 14
- 230000008021 deposition Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 230000002093 peripheral effect Effects 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 239000012159 carrier gas Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910005872 GeSb Inorganic materials 0.000 description 5
- 229910000618 GeSbTe Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000004876 x-ray fluorescence Methods 0.000 description 5
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- AUCLTMBZNXIUKP-UHFFFAOYSA-N butylgermanium Chemical group CCCC[Ge] AUCLTMBZNXIUKP-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000003028 elevating effect Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910018321 SbTe Inorganic materials 0.000 description 1
- 229910004356 Ti Raw Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ILXWFJOFKUNZJA-UHFFFAOYSA-N ethyltellanylethane Chemical compound CC[Te]CC ILXWFJOFKUNZJA-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- LCTMIXFKOJXTHA-UHFFFAOYSA-N methylgermanium Chemical compound [Ge]C LCTMIXFKOJXTHA-UHFFFAOYSA-N 0.000 description 1
- ZUSRFDBQZSPBDV-UHFFFAOYSA-N n-[bis(dimethylamino)stibanyl]-n-methylmethanamine Chemical compound CN(C)[Sb](N(C)C)N(C)C ZUSRFDBQZSPBDV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QQXSEZVCKAEYQJ-UHFFFAOYSA-N tetraethylgermanium Chemical compound CC[Ge](CC)(CC)CC QQXSEZVCKAEYQJ-UHFFFAOYSA-N 0.000 description 1
- ZRLCXMPFXYVHGS-UHFFFAOYSA-N tetramethylgermane Chemical compound C[Ge](C)(C)C ZRLCXMPFXYVHGS-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PORFVJURJXKREL-UHFFFAOYSA-N trimethylstibine Chemical compound C[Sb](C)C PORFVJURJXKREL-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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Description
また、上記Ge−Sb−Te膜の成膜方法を実行させるプログラムが記憶された記憶媒体を提供することを目的とする。
さらに、上記Ge−Sb−Te膜の成膜方法を用いたPRAMの製造方法を提供することを目的とする。
Ge−Sb−Te膜を10K倍以上の拡大率で観察した際に表面平滑であることを確認することが好ましい。
また、前記Ge原料は、前記処理容器への供給量がマスフローコントローラによりGe原料流量で制御され、前記Sb原料および前記Te原料は、それぞれSb原料容器およびTe原料容器から不活性ガスによるバブリング法で供給され、これらの前記処理容器内への供給量は該不活性ガスの流量で制御されるようにすることができる。この場合に、前記Sb原料はトリイソプロピルアンチモンであり、前記Sb原料容器は50℃に温度コントロールされ、前記Te原料はジイソプロピルテルルであり、前記Te原料容器は35℃に温度コントロールされることが例示される。さらに、前記マスフローコントローラから前記処理容器までの配管、ならびに前記Sb原料容器および前記Te原料容器から前記処理容器までの配管は、マントルヒータにより160℃に保持されていることが好ましい。
本発明は、さらに、上記成膜方法を用いてPRAMを製造することを特徴とするPRAMの製造方法を提供する。
ここでは、Ge−Sb−Te膜を、半導体ウエハ上にPRAMの相変化層として成膜する場合について説明する。
<実験1>
上記図1の成膜装置において、カートリッジヒータにより処理容器壁の温度を160℃に設定し、ランプパワーを調節して、載置台の温度を360℃に設定し、搬送ロボットのアームを用いて処理容器内に直径200mmの円板状をなすウエハを搬入し、Ge−Sb−Te膜を成膜した。なお、Ge原料、Sb原料、Te原料として、ターシャリブチルゲルマニウム、トリイソプロピルアンチモン、ジイソプロピルテルルを用いた。ターシャリブチルゲルマニウムは、常温の原料容器の後段に設置したマスフローコントローラにて蒸気流量を直接制御して処理容器に供給し、トリイソプロピルアンチモンは、50℃に温度コントロールした原料容器にキャリアガスとして流量制御されたArガスを容器内に通じたバブリング法にて処理容器に供給し、ジイソプロピルテルルは、35℃に温度コントロールした原料容器にキャリアガスとして流量制御されたArガスを容器内に通じたバブリング法にて処理容器に供給した。この際、トリイソプロピルアンチモンの飽和蒸気圧は266Paであり、ジイソプロピルテルルの飽和蒸気圧は905Paであった。また、マスフローコントローラおよび原料容器から処理容器までの配管は、マントルヒータにより160℃に保持した。
載置台温度:360℃
処理容器内圧力:665Pa
Ge原料ガス流量:550mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:20mL/min(sccm)
TeキャリアArガス流量:50mL/min(sccm)
希釈Arガス流量:100mL/min(sccm)
バックサイドArガス流量:200mL/min(sccm)
成膜時間:90sec
次に、実験1と同様の装置条件で同様の原料を用い、以下の条件でGeSb膜を成膜した。
載置台温度:360℃
処理容器内圧力:1213Pa
Ge原料ガス流量:550mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:20mL/min(sccm)
TeキャリアArガス流量:0mL/min(sccm)
希釈Arガス流量:500mL/min(sccm)
バックサイドArガス流量:200mL/min(sccm)
成膜時間:240sec
実験2と同様の条件で第1段階の成膜を行った後、引き続き以下の条件でTe原料のみを供給する第2段階の成膜を行ってGe−Sb−Te膜を形成した。
載置台温度:360℃
処理容器内圧力:1213Pa
Ge原料ガス流量:0mL/min(sccm)
SbキャリアArガス流量:0mL/min(sccm)
TeキャリアArガス流量:50mL/min(sccm)
希釈Arガス流量:0mL/min(sccm)
バックサイドArガス流量:200mL/min(sccm)
成膜時間:120sec
処理容器内圧力を1173Paとした以外は実験2と同様の条件で第1段階の成膜を行った後、引き続き以下の条件でSb原料ガスおよびTe原料ガスを供給する第2段階の成膜を行ってGe−Sb−Te膜を形成した。
載置台温度:360℃
処理容器内圧力:1173Pa
Ge原料ガス流量:0mL/min(sccm)
SbキャリアArガス流量:20mL/min(sccm)
TeキャリアArガス流量:50mL/min(sccm)
希釈Arガス流量:500mL/min(sccm)
バックサイドArガス流量:200mL/min(sccm)
成膜時間:30sec
ここでは、第1段階の成膜におけるGe原料ガスとSb原料ガスの供給比率を変化させ、膜の組成と表面性状を把握した。載置台温度:360℃、処理容器内圧力:1213〜1293Pa、 希釈Arガス流量:500mL/min(sccm)、バックサイドArガス流量:200mL/min(sccm)とし、Ge原料ガス流量およびSbキャリアArガス流量を以下のNo.1〜7のように変化させた。
Ge原料ガス流量:800mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:20mL/min(sccm)
(SbキャリアArガス流量/Ge原料ガス流量)=0.025
成膜時間:120sec
No.2(実験2と同じ):
Ge原料ガス流量:550mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:20mL/min(sccm)
(SbキャリアArガス流量/Ge原料ガス流量)=0.036
成膜時間:240sec
No.3:
Ge原料ガス流量:550mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:30mL/min(sccm)
(SbキャリアArガス流量/Ge原料ガス流量)=0.055
成膜時間:180sec
No.4:
Ge原料ガス流量:550mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:40mL/min(sccm)
(SbキャリアArガス流量/Ge原料ガス流量)=0.072
成膜時間:120sec
No.5:
Ge原料ガス流量:550mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:100mL/min(sccm)
(SbキャリアArガス流量/Ge原料ガス流量)=0.18
成膜時間:240sec
No.6:
Ge原料ガス流量:200mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:50mL/min(sccm)
(SbキャリアArガス流量/Ge原料ガス流量)=0.25
成膜時間:240sec
No.7:
Ge原料ガス流量:200mL/min(sccm):ただしN2換算にて
SbキャリアArガス流量:100mL/min(sccm)
(SbキャリアArガス流量/Ge原料ガス流量)=0.50
成膜時間:240sec
No.1:Ge/Sb/Te=62/38/0(at%)
No.2:Ge/Sb/Te=61/39/0(at%)
No.3:Ge/Sb/Te=55/40/5(at%)
No.4:Ge/Sb/Te=57/43/0(at%)
No.5:Ge/Sb/Te=48/45/7(at%)
No.6:Ge/Sb/Te=34.8/55.9/9.3(at%)
No.7:Ge/Sb/Te=27.7/62.0/10.3(at%)
3;載置台
32;加熱ランプ
40;シャワーヘッド
50;処理ガス供給機構
52;Te原料貯留部
53;Sb原料貯留部
54;Ge原料貯留部
90;プロセスコントローラ
92;記憶部
100;成膜装置
W;半導体ウエハ
Claims (10)
- 処理容器内に基板を配置し、気体状のGe原料と、気体状のSb原料と、気体状のTe原料とを前記処理容器内に導入してCVDにより基板上にGe2Sb2Te5となるGe−Sb−Te膜を成膜するGe−Sb−Te膜の成膜方法であって、
気体状のGe原料および気体状のSb原料、または、それらに加えてGe2Sb2Te5が形成されない程度の少量の気体状のTe原料を前記処理容器内に導入して基板上に第1段階の成膜を行う第1工程と、
気体状のSb原料および気体状のTe原料、または、それらに加えてGe2Sb2Te5が形成されない程度の少量の気体状のGe原料を前記処理容器内に導入して前記第1工程で成膜された膜の上に第2段階の成膜を行う第2工程と
を有し、
前記第1工程により得られた膜と、前記第2工程により得られた膜とを一体化させて、表面平滑な前記Ge−Sb−Te膜を得ることを特徴とするGe−Sb−Te膜の成膜方法。 - 前記第1工程において、気体状のTe原料を導入する場合に、得られた膜のTeの含有量が10at%未満になる程度の流量とすることを特徴とする請求項1に記載のGe−Sb−Te膜の成膜方法。
- 前記第1工程において、得られた膜の組成比Ge/Sbが原子数比で50/50〜70/30となるか、またはGe原料の流量をx(mL/min(sccm))、Sb原料のキャリアArの流量をy(mL/min(sccm))とするとき、y/xが0.01〜0.1となるように気体状のGe原料および気体状のSb原料を導入することを特徴とする請求項1または請求項2に記載のGe−Sb−Te膜の成膜方法。
- 前記第2工程は、前記第1段階の成膜と前記第2段階の成膜とで安定してGe2Sb2Te5が得られる組成となる流量比で気体状のSb原料および気体状のTe原料を供給することを特徴とする請求項1から請求項3のいずれか1項に記載のGe−Sb−Te膜の成膜方法。
- Ge−Sb−Te膜を10K倍以上の拡大率で観察した際に表面平滑であることを特徴とする請求項1から請求項4のいずれか1項に記載のGe−Sb−Te膜の成膜方法。
- 前記Ge原料は、前記処理容器への供給量がマスフローコントローラによりGe原料流量で制御され、前記Sb原料および前記Te原料は、それぞれSb原料容器およびTe原料容器から不活性ガスによるバブリング法で供給され、これらの前記処理容器内への供給量は該不活性ガスの流量で制御されることを特徴とする請求項1から請求項5のいずれか1項に記載のGe−Sb−Te膜の成膜方法。
- 前記Sb原料はトリイソプロピルアンチモンであり、前記Sb原料容器は50℃に温度コントロールされ、前記Te原料はジイソプロピルテルルであり、前記Te原料容器は35℃に温度コントロールされることを特徴とする請求項6に記載のGe−Sb−Te膜の成膜方法。
- 前記マスフローコントローラから前記処理容器までの配管、ならびに前記Sb原料容器および前記Te原料容器から前記処理容器までの配管は、マントルヒータにより160℃に保持されていることを特徴とする請求項6または請求項7に記載のGe−Sb−Te膜の成膜方法。
- コンピュータ上で動作し、成膜装置を制御するプログラムが記憶された記憶媒体であって、前記プログラムは、実行時に、請求項1から請求項8のいずれかの成膜方法が行われるように、コンピュータに前記成膜装置を制御させることを特徴とする記憶媒体。
- 請求項1から請求項8のいずれかの成膜方法を用いてPRAMを製造することを特徴とするPRAMの製造方法。
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