JP5397464B2 - 成膜方法 - Google Patents
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- JP5397464B2 JP5397464B2 JP2011502513A JP2011502513A JP5397464B2 JP 5397464 B2 JP5397464 B2 JP 5397464B2 JP 2011502513 A JP2011502513 A JP 2011502513A JP 2011502513 A JP2011502513 A JP 2011502513A JP 5397464 B2 JP5397464 B2 JP 5397464B2
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- 238000000151 deposition Methods 0.000 title claims description 11
- 239000010408 film Substances 0.000 claims description 176
- 238000000034 method Methods 0.000 claims description 84
- 239000000758 substrate Substances 0.000 claims description 73
- 238000005259 measurement Methods 0.000 claims description 45
- 230000015572 biosynthetic process Effects 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 17
- 239000004065 semiconductor Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 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
- 239000011521 glass Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- -1 polyimideamide Polymers 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000005513 bias potential Methods 0.000 claims 2
- 239000012789 electroconductive film Substances 0.000 claims 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 19
- 239000010409 thin film Substances 0.000 description 18
- 238000010849 ion bombardment Methods 0.000 description 14
- 230000007423 decrease Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Description
Vc(t)=V0p×sin(2πf×t)+Vdc ・・・・・(1)
一方、プラズマの電位の時間変化vp(t)は、以下の(2)式のように示される。
Vp(t)=(V0p+Vdc)/2×{1+sin(2πf×t)} ・・・・・(2)
なお、(2)式は、例えば「プラズマ半導体プロセス工学」、内田労鶴圃、2003年、38-39ページに記載されている。
イオンは電子に比べて質量が非常に大きく、プラズマ電位の変化のうち高周波成分には追従できない。このため、イオンの挙動に影響を与えるプラズマ電位Vpは、(2)式から高周波成分を除去した値、すなわち(V0p+Vdc)/2となる。
本実施形態によっても、第1の実施形態と同様の効果を得ることができる。
第2電極120の電位を測定する方法として、整合器220の出口(整合器220の第2電極120側)で測定した場合と、測定用配線412を用いて測定した場合について比較実験を行った。
第2電極120へ直流電圧を重畳するにあたり、高周波電源210より直流電源310へ高周波が流れるのを阻止する高周波数カットフィルタ320を挿入している。この効果を確認するために、高周波数カットフィルタ320の後段にオシロスコープを接続して高周波の漏れを測定したが、検出範囲外であった。
第2電極120へ直流電圧を重畳することによって、プラズマ電位を下げることができるかを、第5の実施形態と同様の装置を用いて確かめた。
実施例3において、基板10として、金属膜を被覆していないガラスを用いた。ガラスは絶縁性であるため、直流バイアスの電流が流れにくくなった。この結果、基板10として導電性基板を用いた場合、Vb=−100Vでバイアス電流が0.29Aであったのに対して、基板10としてガラスを用いると同条件でバイアス電流が0.11Aに減少した。ここで流れた電流は、第1電極110のうち基板10に被覆されていない領域に流れたものと考えられる。このため、本発明において、基板10は成膜面が第1電極110と導通しているのが好ましいことがわかった。
微結晶シリコン薄膜太陽電池を対象に、イオン衝撃の低減による特性の向上について検証した。裏面電極としてのAg膜をコーティングしたポリイミドフィルム状の基板10に、n型の微結晶シリコン層(約30nm)、i型の微結晶シリコン層(約2μm)、p型の微結晶シリコン層(約30nm)、ITOからなる透明電極膜、及びAgからなる櫛状の電極を順次形成した。各微結晶シリコン層はプラズマCVD法を用いて成膜した。製膜装置は図9に示す装置を3台連結した装置であり、微結晶シリコン層の各層をn層、i層、p層の順に堆積した。バイアス電圧はi型の微結晶シリコン層を成膜するときのみに印加した。原料ガスとしては、i型の微結晶シリコン層を成膜するときにはSiH4及び水素ガスを使用し、n型の微結晶シリコン層とp型の微結晶シリコン層を成膜するときには、SiH4及び水素ガスに、それぞれホスフィンガスとジボランガスを添加した。裏面電極としてのAg膜及びITO透明電極膜はスパッタリング法で形成し、櫛状の電極は蒸着法で形成した。
実施例5の実験において、i型微結晶シリコン層の製膜条件の内、SiH4ガス流量を変えて微結晶シリコン薄膜太陽電池を作製した。そして作製した試料に対して、実施例6と同様の測定を行った。これらの測定結果および成膜速度を表2に示す。
100 成膜室
110 第1電極
120 第2電極
210 高周波電源
220 整合器
230 ハイパスフィルタ
310 直流電源
312 交流電源
320 高周波数カットフィルタ
410 電極電位測定部
412 測定用配線
414 電極電位測定部
416 測定用配線
420 制御部
Claims (32)
- 成膜室内に配置された第1電極を接地し、
前記第1電極に基板を設置し、
前記成膜室内に配置されていて前記第1電極に対向している第2電極に、高周波電力及びバイアス電圧を供給してプラズマCVDを行うことにより、前記基板に成膜処理を行い、
前記高周波電力及び前記バイアス電圧を供給したときの前記第2電極の平均電位を、前記高周波電力が供給されていて前記バイアス電圧が供給されていないときの前記第2電極の平均電位より低くし、
前記バイアス電圧を制御することにより、前記第1電極に対する前記プラズマの電位であるプラズマ電位を、前記高周波電力が供給されていて前記バイアス電圧が供給されていないときの前記プラズマ電位より小さく、かつ0より大きくし、
前記第1電極に対する前記第2電極の平均電位をVdcとして、前記第1電極に対する前記第2電極の電圧振幅をV0pとした場合、前記プラズマ電位を(Vdc+V0p)/2とする成膜方法。 - 成膜室内に配置された第1電極を接地し、
前記第1電極に基板を設置し、
前記成膜室内に配置されていて前記第1電極に対向している第2電極に、高周波電力及びバイアス電圧を供給してプラズマCVDを行うことにより、前記基板に成膜処理を行い、
前記高周波電力及び前記バイアス電圧を供給したときの前記第2電極の平均電位を、前記高周波電力が供給されていて前記バイアス電圧が供給されていないときの前記第2電極の平均電位より低くし、
前記成膜処理を行っているとき、プラズマ電位が特定の値より大きくなるように前記バイアス電位を制御し、
前記特定の値は、前記プラズマ電位を0に近づけていったときに前記第1電極と前記第2電極の間を流れる直流電流が急激に増加するときの前記プラズマ電位である成膜方法。 - 請求項1又は2に記載の成膜方法において、
前記基板に成膜される膜が、太陽電池の光電変換層である成膜方法。 - 請求項3に記載の成膜方法において、
前記光電変換層が結晶半導体又はアモルファス半導体である成膜方法。 - 請求項1又は2に記載の成膜方法において、
前記バイアス電圧は、直流電圧、又は平均電圧が0ではない交流電圧である成膜方法。 - 請求項1に記載の成膜方法において、
前記バイアス電圧を制御することにより、前記プラズマ電位を100V未満にする成膜方法。 - 請求項1に記載の成膜方法において、
前記第2電極に、前記高周波電力の電力導入線とは別の測定用配線を接続し、前記測定用配線を用いて前記第2電極の平均電位Vdc及び電圧振幅V0pを測定する成膜方法。 - 請求項1又は2に記載の成膜方法において、
前記バイアス電圧は、前記高周波電力の周波数成分を含む高周波電力を除去する高周波数カットフィルタを介して前記第2電極に供給される成膜方法。 - 成膜室内に配置された第1電極に基板を設置し、
前記成膜室内に配置されていて前記第1電極に対向している第2電極に、高周波電力を供給してプラズマを発生させ、かつ前記第1電極又は前記第2電極にバイアス電圧を供給し、
前記第1電極に対する前記第2電極の平均電位をVdcとして、前記第1電極に対する前記第2電極の電圧振幅をV0pとした場合、プラズマ電位を(Vdc+V0p)/2として、前記バイアス電圧を前記プラズマ電位に基づいて制御してプラズマCVDを行い、
前記プラズマ電位を、前記高周波電力が供給されていて前記バイアス電圧が供給されていないときの前記プラズマ電位より小さくなるように前記バイアス電圧を制御してプラズマCVDを行う成膜方法。 - 請求項9に記載の成膜方法において、
前記第1電極に対する前記プラズマの電位であるプラズマ電位が、0より大きくなるように前記バイアス電圧を制御してプラズマCVDを行うことにより、前記基板に成膜処理を行う成膜方法。 - 成膜室内に配置された第1電極に基板を設置し、
前記成膜室内に配置されていて前記第1電極に対向している第2電極に、高周波電力を供給してプラズマを発生させ、かつ前記第1電極又は前記第2電極にバイアス電圧を供給し、
前記第1電極に対する前記第2電極の平均電位をVdcとして、前記第1電極に対する前記第2電極の電圧振幅をV0pとした場合、プラズマ電位を(Vdc+V0p)/2として、前記バイアス電圧を前記プラズマ電位に基づいて制御してプラズマCVDを行い、
前記プラズマ電位が100V未満となるように前記バイアス電圧を制御してプラズマCVDを行う成膜方法。 - 請求項9〜11のいずれか一項に記載の成膜方法において、
前記基板に成膜される膜が、太陽電池の光電変換層である成膜方法。 - 請求項12に記載の成膜方法において、
前記光電変換層が結晶半導体又はアモルファス半導体である成膜方法。 - 請求項9〜13のいずれか一項に記載の成膜方法において、
前記バイアス電圧は、直流電圧、又は平均電圧が0ではない交流電圧である成膜方法。 - 請求項14に記載の成膜方法において、
前記バイアス電圧は交流電圧であり、かつ周波数が前記高周波電力より小さい成膜方法。 - 請求項9〜15のいずれか一項に記載の成膜方法において、
前記バイアス電圧は前記第2電極に供給され、
前記第1電極は接地されている成膜方法。 - 請求項16に記載の成膜方法において、
前記第2電極に前記バイアス電圧を供給するバイアス電圧供給線に、前記高周波電力の周波数成分を含む高周波電力を除去する高周波数カットフィルタを設ける成膜方法。 - 請求項16に記載の成膜方法において、
前記第2電極に、前記高周波電力の電力導入線とは別の測定用配線を接続し、前記測定用配線を用いて前記第2電極の平均電位Vdc及び電圧振幅V0pを測定する成膜方法。 - 請求項9〜15のいずれか一項に記載の成膜方法において、
前記バイアス電圧は前記第1電極に供給され、
前記第1電極は接地されていない成膜方法。 - 成膜室内に配置された第1電極に基板を設置し、
前記成膜室内に配置されていて前記第1電極に対向している第2電極に、高周波電力を供給してプラズマを発生させ、かつ前記第1電極又は前記第2電極にバイアス電圧を供給し、
前記第1電極に対する前記第2電極の平均電位をVdcとして、前記第1電極に対する前記第2電極の電圧振幅をV0pとした場合、プラズマ電位を(Vdc+V0p)/2として、前記バイアス電圧を前記プラズマ電位に基づいて制御してプラズマCVDを行い、
前記成膜処理を行っているとき、前記プラズマ電位が特定の値より大きくなるように前記バイアス電位を制御し、
前記特定の値は、前記プラズマ電位を0に近づけていったときに前記第1電極と前記第2電極の間を流れる直流電流が急激に増加するときの前記プラズマ電位である成膜方法。 - 請求項1、2、9、11、又は20に記載の成膜方法において、
前記プラズマCVDの材料ガスが、シリコン含有ガス、炭素含有ガス、ゲルマニウム含有ガスからなる群から選ばれた少なくとも一つを有する成膜方法。 - 請求項21に記載の成膜方法において、
前記材料ガスが、水素及び希ガスの少なくとも一つを含む希釈ガス、並びに不純物ガスを有する成膜方法。 - 請求項1、2、9、11、又は20に記載の成膜方法において、
前記基板に成膜される膜が半導体膜である成膜方法。 - 請求項23に記載の成膜方法において、
前記半導体膜がシリコン、ゲルマニウム、又は炭素を含有する成膜方法。 - 請求項1、2、9、11、又は20に記載の成膜方法において、
前記基板が可撓性を有する成膜方法。 - 請求項25に記載の成膜方法において、
前記基板を連続成膜する成膜方法。 - 請求項25に記載の成膜方法において、
前記基板は、ポリイミド、ポリアミド、ポリイミドアミド、ポリエチレンナフタレート、ポリエチレンテレフタレート、ポリエーテルイミド、ポリエーテルエーテルケトン、及びポリエーテルスルホン、からなる群から選ばれた少なくとも一つから形成されている成膜方法。 - 請求項25に記載の成膜方法において、
前記基板は、金属フィルムから形成されている成膜方法。 - 請求項1、2、9、11、又は20に記載の成膜方法において、
前記基板が、絶縁性の基材と、前記基材の表面に形成された導電性膜とを有する成膜方法。 - 請求項1、2、9、11、又は20に記載の成膜方法において、
前記基板の成膜面は前記第1電極と導通している成膜方法。 - 請求項1、2、9、11、又は20に記載の成膜方法において、
前記基板はガラス又は金属で形成されている成膜方法。 - 請求項1、2、9、11、又は20に記載の成膜方法において、
前記高周波電力の周波数は13MHz以上である成膜方法。
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Also Published As
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TW201100584A (en) | 2011-01-01 |
CN102341891A (zh) | 2012-02-01 |
WO2010100702A1 (ja) | 2010-09-10 |
US20120115257A1 (en) | 2012-05-10 |
US8586484B2 (en) | 2013-11-19 |
DE112009004581T5 (de) | 2012-09-06 |
JPWO2010100702A1 (ja) | 2012-09-06 |
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