JPS625230B2 - - Google Patents

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Publication number
JPS625230B2
JPS625230B2 JP55108164A JP10816480A JPS625230B2 JP S625230 B2 JPS625230 B2 JP S625230B2 JP 55108164 A JP55108164 A JP 55108164A JP 10816480 A JP10816480 A JP 10816480A JP S625230 B2 JPS625230 B2 JP S625230B2
Authority
JP
Japan
Prior art keywords
sih
film
grown
vapor deposition
chemical vapor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
JP55108164A
Other languages
English (en)
Other versions
JPS5747711A (en
Inventor
Yoshimi Shiotani
Mamoru Maeda
Kanetake Takasaki
Mikio Takagi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujitsu Ltd
Original Assignee
Fujitsu Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujitsu Ltd filed Critical Fujitsu Ltd
Priority to JP55108164A priority Critical patent/JPS5747711A/ja
Priority to EP81303589A priority patent/EP0046059B1/en
Priority to DE8181303589T priority patent/DE3172827D1/de
Priority to US06/290,978 priority patent/US4394401A/en
Publication of JPS5747711A publication Critical patent/JPS5747711A/ja
Publication of JPS625230B2 publication Critical patent/JPS625230B2/ja
Granted legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/02129Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being boron or phosphorus doped silicon oxides, e.g. BPSG, BSG or PSG
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/401Oxides containing silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/505Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
    • C23C16/509Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges using internal electrodes
    • C23C16/5096Flat-bed apparatus
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604Deposition from a gas or vapour
    • H01L21/31625Deposition of boron or phosphorus doped silicon oxide, e.g. BSG, PSG, BPSG

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Surface Treatment Of Glass (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)

Description

【発明の詳細な説明】
本発明は化学気相成長(CVD)により基板上
に酸化膜を形成させる方法に関し、更に詳しく
は、プラズマ化学気相成長によりリンシリケート
ガラス(PSG)膜をSi又はSi上のAl配線などの基
板上に成長させる方法に関する。 PSGなどの酸化膜はICの保護膜(カバー膜)
や配線の層間絶縁膜として使用されている。かか
る膜を基板等の上に化学成長させる方法として、
常圧法と呼ばれる、350℃〜450℃において
SiH4,O2及びPH3の反応ガスから常圧下(760ト
ル)に基板上に酸化膜を形成する方法と、減圧法
と呼ばれる、350℃〜450℃においてSiH4,O2
びPH3の反応ガスから減圧下(例えば、1トル)
に基板上に酸化膜を形成する方法などが知られて
おり、更に窒化膜やアモルフアスシリコンなどに
ついてプラズマ化学気相成長法と呼ばれる、平行
平板の電極に高周波をかけてガスをプラズマ化さ
せて低温下(例えば、20℃〜450℃)において化
学成長させる方法が知られている。 しかしながら、このような従来方法によつて化
学成長させた酸化膜は600℃位において熱処理す
ると成長した酸化膜にクラツクが入りやすく、ま
た成長後常温に戻すと歪んでしまいクラツクが入
りやすいという問題があつた。 従つて、本発明者等はかかる従来の酸化膜……
の成長方法の問題を解決すべく、鋭意研究を進め
た結果、SiH4、N2O及びPH3を含む反応ガスから
基板上にリンシリケートガラス膜を化学気相成長
させるに当り、反応ガス中のN2OとSiH4のモル比
(N2O/SiH4)を50以上とすることにより、高温熱
処理によるクラツク発生が防止でき、成長膜を常
温に戻したときに歪んでクラツクが発生しない
PSGの酸化膜をプラズマ化学気相成長できること
を見出し、本発明をするに至つた。 すなわち、本発明に従つたプラズマ化学気相成
長方法は、反応ガス中のN2OとSiH4のモル比
(N2O/SiH4)を50以上とすることによつて基板上
に酸化膜(SiO2又はPSG)を成長させることから
成る。 以下、図面に従つて本発明を更に詳しく説明す
る。 第1図に示したベルジヤー型プラズマ化学気相
成長装置10において、基板11上にPSG膜を化
学気相成長させる方法について説明する。なお、
SixOy膜(典型的にはSiO2膜)を化学気相成長さ
せる場合には反応ガスをSiH4―N2O―Arにする
だけで、他は以下に説明する方法で実施すること
ができ、更に以下のPH3ガスをB2H6又はAsH3
スに代えることによつて、それぞれ、ボロンシリ
ケートガラス又はヒ素シリケートガラスを成長さ
せることができる。 プラズマ化学気相成長は例えば石英製のベルジ
ヤー10内にPSG膜を成長させる基板11を配置
したのち、系内をライン12より排気して、例え
ば0.1〜2トルの真空に保ち乍らヒーター13で
系内の温度を20〜400℃、好ましくは300℃〜400
℃に保持してライン14よりSiH4,N2O,PH3
Arの反応ガス(例えば、1%SiH4/Ar,1%
PH3/Ar及びN2Oの混合ガス)をベルジヤー10
内に供給し、発振機15で50KHz〜2.45GHz(通
常は13.56MHz)として基板11上にPSG膜を気
相成長させる。この際反応混合ガス中のN2O/
SiH4(モル比)を50以上にすることが肝要で、
このモル比が50未満では高温で熱処理した場合に
成長したPSG膜などの酸化膜にクラツクが入り好
ましくない。 例1(参考例) 第1図に示したプラズマ化学気相成長装置を用
いてシリコン基板上に酸化ケイ素膜(厚さ1μ)
を成長させた。プラズマ成長は、周波数13.56M
Hz(40W)、温度300℃及び圧力1トルでSiH4
N2O及びAの反応ガスをN2O/SiH4(モル比)=
5,10,20,50,100及び200と変化させて実施し
た。 各N2O/SiH4比で成長させた酸化ケイ素膜の歪
を測定し、応力σ(108dyne/cm2)とN2O/SiH4
比との関係を第2図に示した。なお応力の測定
は、ニユートンリング法によつて行なつた。 次にN2O/SiH4比が5,50及び100で1μ厚に
プラズマ気相成長させた試料につき600℃、800℃
及び1000℃の温度でN2熱処理してクラツクの発
生状況を観察した。結果は下表の通りであつた。
【表】 上表の結果から明らかなようにN2O/SiH4比を
50以上にすることによつて、プラズマ気相成長膜
中のH2含量が少なくなりかつ密度も大きくなる
ためか、クラツクの発生が起らなくなる。また第
2図に示したようにN2O/SiH4比が50及び100の
場合には成長膜の応力がコンプレツシヨン側とな
る。これに対しN2O/SiH4比が5の場合には成長
膜の応力は、テンシヨン側となる。このことは、
熱処理を行なつた場合、酸化膜よりもSi基板の熱
膨張係数が大のためN2O/SiH4=5の場合に応力
はテンシヨン側により増大し膜中のHの量が多く
膜がもろいため破壊に到り、一方N2O/SiH4
50,100の場合には応力は夫々コンプレツシヨン
と熱膨張によるテンシヨンと相殺し、より小さな
値となり破壊しないことを示している。 Si上で成長させた酸化ケイ素膜のRI(屈析率)
及び密度とN2O/SiH4比との関係を第3図のグラ
フ図に示す。第3図において曲線AはRIとN2O/
SiH4比との関係を示し、曲線Bは密度とN2O/
SiH4比との関係を示す。また酸化ケイ素膜の赤
外吸収スペクトルの吸収係数αとN2O/SiH4比と
の関係を第4図のグラフ図に示す。第4図におい
て曲線AはSiHの吸収係数(2240cm-1)、曲線B
は(SiH2oの吸収係数(880cm-1)、曲線CはSiO
の吸収係数(810cm-1)、そして曲線DはSiO(伸
縮)の吸収係数(1070〜1090cm-1)を示す。 第3図及び第4図の結果からN2O/SiH4比を50
以上としてプラズマ化学気相成長させた酸化ケイ
素膜は、N2O/SiH4比が50未満の場合に比較して
膜中のHの含有量が少く十分SiH4がO2と反応し
た良質の膜になつていることがわかる。 例2(実施例) 第1図のプラズマ化学気相成長装置を用いてSi
基板上にPSG膜(厚さ1μ)を成長させた。プラ
ズマ成長は周波数13.56MHz(40W)、温度300℃
及び圧力1トルで実施し、反応ガスはSiH4,PH
,N2O及びArの混合ガスを用い、N2O/SiH4
を100とし、PH/SiH4比を0(この場合には酸
化ケイ素膜が成長)、0.05,0.1,0.15,0.2及び
0.3と変化させた。各反応ガスで成長させた酸化
膜の応力を例1と同様にして測定し、この歪とPH
/SiH4比との関係を第5図曲線Aに示した。 一方、従来の常圧化学気相成長法に従つて温度
425℃及び圧力760トルで上記反応ガス組成と全く
同一条件でSi基板上に酸化膜(厚さ1μ)を成長
させた。この酸化膜の応力を測定し、歪とPH
SiH4比との関係を第5図曲線Bに示した。 第5図の曲線AおよびBを比較すれば明らかな
ように、本発明に従つたプラズマ化学気相成長方
法によれば、P濃度が小さいPSG膜を成長させる
場合でさえ、0.08又はそれ以下のPH/SiH4モル
比を用いることによつて応力がコンプレツシヨン
側のPSG膜を基板上に成長させることができる。
このように、成長膜がコンプレツシヨン応力側な
ので、クラツキングが発生し難いPSG膜を成長さ
せることができる。それに対して常圧法によるP
濃度の小さい膜は応力がテンシヨン側に大となり
クラツクが生じやすい。すなわち、カバー膜、層
間絶縁膜等としての利用に最適な膜であるP濃度
が小さく耐湿性の優れた膜(P濃度が大だと外部
よりH2Oを吸収してリン酸を形成してしまい耐湿
性は低下する)を形成する場合、本発明は非常に
有効な方法である。
【図面の簡単な説明】
第1図は本発明のプラズマ化学気相成長方法を
実施するための装置の一例を示す概略説明図であ
り、10はベルジヤー型化学気相成長装置、11
は基板、12は排気ライン、13はヒーター、1
4は反応ガス供給ライン、15は発振機を示す。 第2図は例1においてプラズマ化学気相成長さ
せた酸化ケイ素膜の応力とN2O/SiH4比との関係
を示すグラフ図である。第3図は例1においてプ
ラズマ化学気相成長させた酸化ケイ素膜のRI
(曲線A)とN2O/SiH4比並びに密度(曲線B)
とN2O/SiH4比との関係を示すグラフ図であり、
第4図は例1の酸化ケイ素膜の赤外吸収スペクト
ルの吸収係数αとN2O/SiH4比との関係を示すグ
ラフ図である。第5図は例2において化学気相成
長させたPSG膜の応力とPH/SiH4との関係を示
すグラフ図であり、曲線Aが本発明のプラズマ化
学気相成長法によつたものであり、曲線Bが従来
の常圧法によつたものである。

Claims (1)

    【特許請求の範囲】
  1. 1 SiH4,N2OおよびPH3を含む反応ガスからリ
    ンシリケートガラス膜を基板上にプラズマ化学気
    相成長させるにあたり、反応ガス中のN2OとSiH4
    のモル比(N2O/SiH4)を50以上とすることを特
    徴とするプラズマ化学気相成長方法。
JP55108164A 1980-08-08 1980-08-08 Chemical plasma growing method in vapor phase Granted JPS5747711A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP55108164A JPS5747711A (en) 1980-08-08 1980-08-08 Chemical plasma growing method in vapor phase
EP81303589A EP0046059B1 (en) 1980-08-08 1981-08-05 Method of plasma enhanced chemical vapour deposition of films
DE8181303589T DE3172827D1 (en) 1980-08-08 1981-08-05 Method of plasma enhanced chemical vapour deposition of films
US06/290,978 US4394401A (en) 1980-08-08 1981-08-07 Method of plasma enhanced chemical vapor deposition of phosphosilicate glass film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP55108164A JPS5747711A (en) 1980-08-08 1980-08-08 Chemical plasma growing method in vapor phase

Publications (2)

Publication Number Publication Date
JPS5747711A JPS5747711A (en) 1982-03-18
JPS625230B2 true JPS625230B2 (ja) 1987-02-03

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JP55108164A Granted JPS5747711A (en) 1980-08-08 1980-08-08 Chemical plasma growing method in vapor phase

Country Status (4)

Country Link
US (1) US4394401A (ja)
EP (1) EP0046059B1 (ja)
JP (1) JPS5747711A (ja)
DE (1) DE3172827D1 (ja)

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Also Published As

Publication number Publication date
EP0046059B1 (en) 1985-11-06
DE3172827D1 (en) 1985-12-12
EP0046059A3 (en) 1983-01-05
EP0046059A2 (en) 1982-02-17
JPS5747711A (en) 1982-03-18
US4394401A (en) 1983-07-19

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