JPH0657405A - Method for reforming surface material and device therefor - Google Patents
Method for reforming surface material and device thereforInfo
- Publication number
- JPH0657405A JPH0657405A JP23897392A JP23897392A JPH0657405A JP H0657405 A JPH0657405 A JP H0657405A JP 23897392 A JP23897392 A JP 23897392A JP 23897392 A JP23897392 A JP 23897392A JP H0657405 A JPH0657405 A JP H0657405A
- Authority
- JP
- Japan
- Prior art keywords
- ultrapure water
- fluoride
- inert gas
- modifying
- surface substance
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title abstract description 13
- 238000002407 reforming Methods 0.000 title abstract description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 72
- 239000012498 ultrapure water Substances 0.000 claims abstract description 72
- 239000000126 substance Substances 0.000 claims abstract description 39
- 239000011261 inert gas Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 239000007769 metal material Substances 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003682 fluorination reaction Methods 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 229910021563 chromium fluoride Inorganic materials 0.000 claims description 3
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 3
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 3
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001512 metal fluoride Inorganic materials 0.000 claims 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 2
- 239000007789 gas Substances 0.000 description 19
- 238000010586 diagram Methods 0.000 description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910015475 FeF 2 Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は超純水を用いた表面物質
の改質方法及びそのための装置に係わる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying a surface material using ultrapure water and an apparatus therefor.
【０００２】[0002]
【従来の技術】従来、超純水は、薬品の希釈すること
（例えば９８％硫酸を目的の濃度まで希釈すること）に
使用したり、薬品を調合すること（例えば固体の水酸化
ナトリウムを超純水に溶解させ１規定の水酸化ナトリウ
ム溶液を調合すること）に使用したり、洗浄水として、
例えばビーカー、タンク等の容器を洗浄したり、薬液に
浸したシリコンウエハの表面から薬液及び薬液残査を除
去することに使用される。また、電気分解によって水
素、酸素を得る為の原料として使用される。この様に超
純水の使用範囲は狭い。2. Description of the Related Art Conventionally, ultrapure water has been used for diluting chemicals (for example, diluting 98% sulfuric acid to a desired concentration) or for preparing chemicals (for example, solid sodium hydroxide over Dissolve it in pure water to prepare 1N sodium hydroxide solution) or use it as washing water.
For example, it is used for cleaning containers such as beakers and tanks, and for removing chemical liquid and chemical liquid residue from the surface of a silicon wafer immersed in the chemical liquid. It is also used as a raw material for obtaining hydrogen and oxygen by electrolysis. Thus, the range of use of ultrapure water is narrow.
【０００３】一方、金属材料表面に形成された表面物質
の特性の改質（例えば、表面物質の組成の制御）は表面
物質の形成時にガス成分、反応温度を制御したり、生成
反応後、再度、他のガスと反応させることにより行われ
ている。On the other hand, the modification of the characteristics of the surface substance formed on the surface of the metal material (for example, the control of the composition of the surface substance) controls the gas component and the reaction temperature during the formation of the surface substance, and again after the formation reaction. , By reacting with other gas.
【０００４】図１３に、生成反応後、ガスを変えて組成
制御を行った場合の表面物質のＸＰＳ解析図を示す。図
１３中（ａ）は、ＳＵＳ３１６Ｌをフッ素ガスと２２０
℃で８０分間反応させた場合のＸＰＳ解析図であり、図
１３中（ｂ）は図１３（ａ）の処理後４００℃で２４時
間窒素雰囲気下で熱処理させたものである。図１３
（ａ）に示す表面はＦｅ：Ｆの比が１：２．２７と非化
学量論構造を有するのに対して、図１３（ｂ）に示す表
面はＦｅ：Ｆの比が１：２．００となりＦｅＦ2の化学
量論構造を有している。FIG. 13 shows an XPS analysis diagram of the surface substance when the composition is controlled by changing the gas after the production reaction. In FIG. 13, (a) shows SUS316L and fluorine gas 220
FIG. 14 is an XPS analysis diagram in the case of reacting at 80 ° C. for 80 minutes, and FIG. 13B shows a heat treatment performed at 400 ° C. for 24 hours in a nitrogen atmosphere after the treatment of FIG. 13A. FIG.
The surface shown in (a) has a non-stoichiometric structure with an Fe: F ratio of 1: 2.27, while the surface shown in FIG. 13 (b) has an Fe: F ratio of 1: 2. And has a stoichiometric structure of FeF 2 .
【０００５】図１４に化学量論構造を有しているものと
有していないものとをフッ素ガスに曝し、フッ素ガスに
対するバリヤ効果をフッ素ガスの消費圧で比較した結果
を示す。図１４から明らかな様に、白丸で示す化学量論
構造を有する表面の場合はフッ素ガスの圧力は一定であ
り、フッ素ガスの消費がみられないのに対して、黒丸で
示す非化学量論構造を有する表面の場合は、フッ素ガス
の圧力は時間とともに減少し、フッ素ガスの消費がみら
る。すなわち、化学量論構造を有しない表面はフッ素ガ
スに対するバリヤ効果がないことがわかる。この様に、
化学量論構造を有する表面は安定である。しかし、従来
法では高温下で長時間処理する必要がある。FIG. 14 shows the results of comparing the barrier effect for fluorine gas with the fluorine gas consumption pressure by exposing one having a stoichiometric structure and one not having a stoichiometric structure to the fluorine gas. As is clear from FIG. 14, in the case of the surface having the stoichiometric structure shown by white circles, the pressure of the fluorine gas is constant, and the consumption of fluorine gas is not observed, whereas the non-stoichiometry shown by the black circles. In the case of a structured surface, the pressure of fluorine gas decreases with time, and consumption of fluorine gas is observed. That is, it can be seen that the surface having no stoichiometric structure has no barrier effect against fluorine gas. Like this
Surfaces with a stoichiometric structure are stable. However, in the conventional method, it is necessary to perform the treatment at a high temperature for a long time.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、表面物質の
特性の改質（例えば、表面物質の化学組成の制御）を容
易に行うことができると共に超純水の新しい利用分野
（用途）を開発した表面物質の改質方法及びそのための
装置を提供することを目的とする。The present invention makes it possible to easily modify the characteristics of the surface substance (for example, control of the chemical composition of the surface substance) and to open a new application field (use) of ultrapure water. It is an object of the present invention to provide a developed method for modifying a surface substance and an apparatus therefor.
【０００７】[0007]
【課題を解決するための手段】本発明の表面物質の改質
方法は、金属材料上に形成された表面物質を、酸素を含
まない雰囲気下において超純水に接触させることを特徴
とする。A method of modifying a surface substance according to the present invention is characterized in that a surface substance formed on a metal material is brought into contact with ultrapure water in an atmosphere containing no oxygen.
【０００８】本発明の表面物質の改質装置は、内部に不
活性ガスを導入するための不活性ガス導入手段と、外部
へ該不活性ガスを排出するための不活性ガス排出手段と
を有するチャンバーと、該チャンバーの内部に配置され
た超純水を保持するための超純水用容器と、該チャンバ
ーの内部に配置された該超純水用容器内に保持された超
純水を加熱するための手段と、を少なくとも有すること
を特徴とするここで、金属材料としては、例えば、ニッ
ケル、クロム、鉄、アルミニウム、銅あるいはこれらの
１種以上を主成分とする合金があげられる。The surface substance reforming apparatus of the present invention has an inert gas introducing means for introducing an inert gas into the inside, and an inert gas discharging means for discharging the inert gas to the outside. Heating chamber, ultrapure water container for holding ultrapure water placed inside the chamber, and ultrapure water held in container for ultrapure water placed inside the chamber Here, the metal material includes, for example, nickel, chromium, iron, aluminum, copper, or an alloy containing at least one of these as a main component.
【０００９】また、表面物質としては、例えば、ニッケ
ルのフッ化物、クロムのフッ化物、鉄のフッ化物、アル
ミニウムのフッ化物または銅のフッ化物等があげられ
る。Examples of the surface substance include nickel fluoride, chromium fluoride, iron fluoride, aluminum fluoride, copper fluoride and the like.
【００１０】酸素を含まない雰囲気は、例えば、超純水
を配置したチャンバー内に不活性ガス（窒素、アルゴ
ン、ヘリウム等のガス）を導入することによって実現さ
れる。また、また、雰囲気中超純水を配置してもよい
し、また、密閉容器に超純水を流す様な方法で大気に触
れなければ不活性ガス雰囲気下でなくても良い。The oxygen-free atmosphere is realized, for example, by introducing an inert gas (a gas such as nitrogen, argon or helium) into a chamber in which ultrapure water is placed. In addition, ultrapure water may be placed in the atmosphere, and the atmosphere may not be in an inert gas atmosphere unless the atmosphere is exposed to the ultrapure water in a closed container.
【００１１】超純水としては、比抵抗が１８（ＭΩ・ｃ
ｍ ａｔ２５℃）以上のものが好ましい。また、０．２
μｍ以上の微粒子の含有量が２０個／ｍｌ以下のものが
好ましく、０．１μｍ以上の微粒子の含有量が３０個／
ｍｌ以下のものがより好ましい。また、ＴＯＣは１００
（μｇｃ／ｌ）以下が好ましく、５０（μｇｃ／ｌ）以
下がより好ましい。生菌数は１０（個／１００ｍｌ）以
下が好ましく、１（個／１００ｍｌ）以下がより好まし
い。As ultrapure water, the specific resistance is 18 (MΩ · c
mat at 25 ° C.) or higher is preferable. Also, 0.2
It is preferable that the content of fine particles of μm or more is 20 / ml or less, and the content of fine particles of 0.1 μm or more is 30 / ml
It is more preferably less than or equal to ml. Also, TOC is 100
(Μgc / l) or less is preferable, and 50 (μgc / l) or less is more preferable. The viable cell count is preferably 10 (cells / 100 ml) or less, more preferably 1 (cells / 100 ml) or less.
【００１２】本発明では、酸化雰囲気を制御した超純水
に金属材料を浸すことにより、化学的に安定な構造を有
する表面物質を容易に得ることができ、また、超純水の
新しい利用分野を提供できる。In the present invention, a surface material having a chemically stable structure can be easily obtained by immersing a metal material in ultrapure water in which an oxidizing atmosphere is controlled, and a new application field of ultrapure water is provided. Can be provided.
【００１３】改善の一例として、金属材料を不活性ガス
雰囲気下で、溶存酸素濃度を制御した超純水に浸す方法
である。この方法における超純水中の溶存酸素濃度は８
ｐｐｍ以下とする。超純水の温度は０℃以上好ましくは
５０℃以上である。また、処理時間は数分〜数時間で良
い。この方法により金属材料表面の物質の組成を制御で
きる。As an example of the improvement, there is a method of immersing a metallic material in ultrapure water whose dissolved oxygen concentration is controlled in an inert gas atmosphere. The dissolved oxygen concentration in ultrapure water in this method is 8
It should be below ppm. The temperature of the ultrapure water is 0 ° C or higher, preferably 50 ° C or higher. The processing time may be several minutes to several hours. By this method, the composition of the substance on the surface of the metal material can be controlled.
【００１４】[0014]
【実施例】以下に実施例を示して本発明を更に詳しく説
明する。The present invention will be described in more detail with reference to the following examples.
【００１５】まず、本発明装置の実施例を図１に示す。First, an embodiment of the device of the present invention is shown in FIG.
【００１６】本例の装置は、内部３に不活性ガスを導入
するための不活性ガス導入口（不活性ガス導入手段）５
と、外部へ該不活性ガスを排出するための不活性ガス排
出口（不活性ガス排出手段）６とを有するチャンバー１
と、チャンバー１の内部３に配置された超純水４を保持
するための超純水用容器２と、チャンバー１の内部３に
配置された超純水用容器２内に保持された超純水４を加
熱するための手段７と、を少なくとも有している。The apparatus of this embodiment is provided with an inert gas inlet (inert gas introducing means) 5 for introducing an inert gas into the interior 3.
And a chamber 1 having an inert gas discharge port (inert gas discharge means) 6 for discharging the inert gas to the outside.
An ultrapure water container 2 for holding the ultrapure water 4 placed inside the chamber 1; and an ultrapure water container 2 placed in the chamber 3 inside the ultrapure water container 2. At least means 7 for heating the water 4.
【００１７】不活性ガス導入口５から窒素、アルゴン等
の不活性ガスを二部３に導入することにより超純水４を
大気に触れない状態とする。その状態で、表面物質が形
成された金属材料を超純水４に浸漬する。その際加熱す
るための手段７により超純水４を加熱し、超純水中の酸
素を超純粋から追い出す。なお、超純水から追い出され
た酸素は、不活性ガスにより不活性ガス排出口６からチ
ャンバー１の外部に排出される。By introducing an inert gas such as nitrogen or argon into the second portion 3 through the inert gas inlet 5, the ultrapure water 4 is kept out of contact with the atmosphere. In that state, the metal material on which the surface substance is formed is immersed in the ultrapure water 4. At that time, the ultrapure water 4 is heated by the heating means 7 to expel oxygen in the ultrapure water from the ultrapure water. The oxygen expelled from the ultrapure water is discharged from the inert gas discharge port 6 to the outside of the chamber 1 by the inert gas.
【００１８】本発明方法の実施例を比較例とともに説明
する。Examples of the method of the present invention will be described together with comparative examples.
【００１９】（比較例１）アルミニウムの上にＮｉ−Ｗ
−Ｐメッキを施し、さらにフッ化処理を行った。(Comparative Example 1) Ni-W on aluminum
-P plating was performed, and further fluorination treatment was performed.
【００２０】フッ化処理は次の条件で行った。The fluorination treatment was performed under the following conditions.
【００２１】メッキ表面の酸化膜を０．５％希フッ酸溶
液に１分間侵入後、水洗、窒素ガス中で２５０℃におい
て乾燥を行った。次いで、１００％フッ素ガスを用い３
５０℃×８時間」のフッ化処理を行った。フッ化処理後
３５０℃×１２時間の熱処理を行った。The oxide film on the plating surface was immersed in a 0.5% dilute hydrofluoric acid solution for 1 minute, washed with water, and dried at 250 ° C. in nitrogen gas. Then, using 100% fluorine gas, 3
The fluorination treatment was performed at 50 ° C. for 8 hours. After the fluorination treatment, heat treatment was performed at 350 ° C. for 12 hours.
【００２２】その表面にはＮｉＦ2が形成されていた。
このサンプルを大気中で、超純水に浸漬し、５時間煮沸
した。図２に前記条件で形成された表面物質のＸＰＳ解
析図を示す。図２中（ａ）は超純水煮沸前、（ｂ）は超
純水煮沸後である。図から明らかな様に膜厚が減少した
ばかりでなく、酸素を含んだ膜となっていた。なお、図
２におけるスパッタリング時のスパッタ速度は１２０Å
／ｍｉｎであり、他の図におけるスパッタリング速度も
同じである。NiF 2 was formed on the surface.
This sample was immersed in ultrapure water in the air and boiled for 5 hours. FIG. 2 shows an XPS analysis diagram of the surface substance formed under the above conditions. In FIG. 2, (a) shows before boiling ultrapure water, and (b) shows after boiling ultrapure water. As is clear from the figure, not only was the film thickness reduced, but it was a film containing oxygen. The sputtering rate during sputtering in FIG. 2 is 120Å
/ Min, and the sputtering rates in other figures are also the same.
【００２３】（実施例１）アルミニウムの上にＮｉ−Ｗ
−Ｐメッキを施し、さらにフッ化処理を行って表面にＮ
ｉＦ2を形成させたサンプルを窒素雰囲気下で、溶存酸
素１ｐｐｍの超純水に浸漬し、溶存酸素１ｐｐｍの超純
水を流しながら、１時間煮沸した。図３に前記条件で形
成された表面物質のＸＰＳ解析図を示す。図３中（ａ）
は超純水煮沸前、図３中（ｂ）は超純水煮沸後である。
図から明らかな様に窒素雰囲気下、溶存酸素１ｐｐｍの
超純水で煮沸処理することによりＮｉ：Ｆの比が１：２
となり、ＮｉＦ2の化学量論構造ヘと組成変化してい
た。(Example 1) Ni-W on aluminum
-P plating is applied, and further fluorination treatment is applied to make N
The sample on which iF 2 was formed was immersed in ultrapure water with 1 ppm of dissolved oxygen in a nitrogen atmosphere, and boiled for 1 hour while flowing ultrapure water with 1 ppm of dissolved oxygen. FIG. 3 shows an XPS analysis diagram of the surface substance formed under the above conditions. Figure 3 (a)
Shows before boiling ultrapure water, and FIG. 3B shows after boiling ultrapure water.
As is clear from the figure, the Ni: F ratio was 1: 2 by boiling in ultrapure water containing 1 ppm of dissolved oxygen in a nitrogen atmosphere.
Therefore, the composition changed to the stoichiometric structure of NiF 2 .
【００２４】（実施例２）アルミニウムの上にＮｉ−Ｗ
−Ｐメッキを施し、さらにフッ化処理を行って表面にＮ
ｉＦ2を形成させたサンプルを大気に触れない雰囲気下
（密閉容器中）で、溶存酸素１ｐｐｂの超純水に浸漬
し、溶存酸素１ｐｐｂの超純水を流しながら、１時間煮
沸した。図４に前記条件で形成された表面物質のＸＰＳ
解析図を示す。図中（ａ）は超純水煮沸前、（ｂ）は超
純水煮沸後である。図から明らかな様に窒素雰囲気下、
溶存酸素１ｐｐｂの超純水で煮沸処理することによりＮ
ｉ：Ｆの比が１：２となり、ＮｉＦ2の化学量論構造へ
と組成変化していた。(Example 2) Ni-W on aluminum
-P plating is applied, and further fluorination treatment is applied to make N
The sample on which iF 2 was formed was immersed in ultrapure water of 1 ppb dissolved oxygen in an atmosphere not exposed to the air (in a closed container), and boiled for 1 hour while flowing ultrapure water of 1 ppb dissolved oxygen. FIG. 4 shows the XPS of the surface material formed under the above conditions.
An analysis figure is shown. In the figure, (a) shows before boiling ultrapure water, and (b) shows after boiling ultrapure water. As is clear from the figure, under a nitrogen atmosphere,
By boiling in ultrapure water with dissolved oxygen of 1 ppb, N
The i: F ratio became 1: 2, and the composition was changed to the stoichiometric structure of NiF 2 .
【００２５】実施例１で形成された表面と超純水処理前
の表面を１規定のＡｌＣｌ3溶液中に浸し、腐食電流を
測定し、耐食性能を比較した。分極曲線を図５に示す。
図から明らかな様に実施例１で形成された化学量論構造
をもつ表面は−６００ｍＶ〜２００ｍＶの間において腐
食電流が流れず、優れた耐食性能が認められた。The surface formed in Example 1 and the surface before ultrapure water treatment were immersed in a 1N AlCl 3 solution, the corrosion current was measured, and the corrosion resistance was compared. The polarization curve is shown in FIG.
As is clear from the figure, the surface having the stoichiometric structure formed in Example 1 did not pass a corrosion current between -600 mV and 200 mV, and excellent corrosion resistance was recognized.
【００２６】大気中煮沸で形成された表面と不活性ガス
雰囲気下で形成された表面を走査型顕微鏡（ＳＥＭ）で
観察した。図６に表面写真を示す。図中（ａ）は大気中
で煮沸した表面、（ｂ）は不活性ガス雰囲気下、溶存酸
素１ｐｐｍの超純水で煮沸した表面、（Ｃ）は不活性ガ
ス雰囲気下、溶存酸素１ｐｐｂの超純水で煮沸した表面
である。大気中で煮沸処理した表面は結晶粒が大きく、
ピットの様に隙間がみられるが、不活性ガス雰囲気下で
煮沸処理された表面は均一的な表面である。The surface formed by boiling in air and the surface formed under an inert gas atmosphere were observed with a scanning microscope (SEM). A surface photograph is shown in FIG. In the figure, (a) is a surface boiled in the atmosphere, (b) is a surface boiled with ultrapure water having a dissolved oxygen of 1 ppm in an inert gas atmosphere, and (C) is an inert gas atmosphere having a dissolved oxygen of more than 1 ppb. It is the surface boiled with pure water. The crystal grains are large on the surface boiled in the atmosphere,
Although there are gaps like pits, the surface boiled in an inert gas atmosphere is a uniform surface.
【００２７】（実施例３）ステンレス鋼（ＳＵＳ３１６
Ｌ）をフッ化処理することによりサンプルを得た。この
サンプルを室温で５時間、溶存酸素１ｐｐｍの超純水に
窒素雰囲気下で浸漬処理した。図７に超純水処理前後の
ＸＰＳ解析図、図８に超純水処理前後のＸＲＤ解析図を
示す。図７、図８中（ａ）は超純水処理前の表面、
（ｂ）は超純水処理後の表面である。酸化雰囲気を抑え
た超純水に浸漬することにより、ＦｅＦ2主体の膜から
ＣｒＦ3を主体とした不動態膜となった。(Example 3) Stainless steel (SUS316)
A sample was obtained by fluorinating L). This sample was immersed in ultrapure water having a dissolved oxygen concentration of 1 ppm for 5 hours at room temperature under a nitrogen atmosphere. FIG. 7 shows an XPS analysis diagram before and after the ultrapure water treatment, and FIG. 8 shows an XRD analysis diagram before and after the ultrapure water treatment. 7 and 8 (a) shows the surface before the ultrapure water treatment,
(B) is the surface after the ultrapure water treatment. By dipping in ultrapure water in which the oxidizing atmosphere was suppressed, a film containing FeF 2 as the main component was changed to a passive film containing CrF 3 as the main component.
【００２８】本例で形成された不動態膜を５％ＨＦ水溶
液中に２５℃、５時間浸漬し、耐食性を調査した。図９
に耐食性テスト後のＸＰＳ解析図を示す。図１０に同サ
ンプルのＸＲＤ解析図を示す。耐食性テスト前の解析図
（図７（ｂ）及びに図８（ｂ））に対して耐食性テスト
後の図９及び図１０は何ら変化は認められない。腐食性
の強い５％ＨＦ水溶液に対し優れた耐食性が認められ
た。The passivation film formed in this example was immersed in a 5% HF aqueous solution at 25 ° C. for 5 hours, and the corrosion resistance was investigated. Figure 9
The XPS analysis diagram after the corrosion resistance test is shown in FIG. The XRD analysis figure of the same sample is shown in FIG. 9 and 10 after the corrosion resistance test, no change is observed in comparison with the analysis diagrams before the corrosion resistance test (FIGS. 7B and 8B). Excellent corrosion resistance was observed in a 5% HF aqueous solution having strong corrosiveness.
【００２９】（比較例２）ステンレス鋼（ＳＵＳ３１６
Ｌ）及びＳｉウエハー上にスパッタで形成された純クロ
ムをフッ素化した場合の結果を図１１及び図１２に示
す。但し、図１１はスパッタにより形成されるクロムの
スパッタ膜を示し、また図１２はこれをフッ素化した場
合を示す。尚、これら図において、１１はステンレス鋼
またはＳｉウエハーを、１２はクロムのスパッタ膜を示
し、１３はフッ素化した場合を示す。純クロムをフッ素
化するとＣｒＦ4、ＣｒＦ5等の低沸点高次フッ化物が形
成されるために、フッ化不動態膜は形成し得ない。(Comparative Example 2) Stainless steel (SUS316
L) and the results of fluorinating pure chromium sputtered on the Si wafer are shown in FIGS. However, FIG. 11 shows a chromium sputtered film formed by sputtering, and FIG. 12 shows a case where this is fluorinated. In these figures, 11 is a stainless steel or Si wafer, 12 is a chromium sputtered film, and 13 is a fluorinated case. If pure chromium is fluorinated, low-boiling high-order fluorides such as CrF 4 and CrF 5 are formed, so that a fluorinated passivation film cannot be formed.
【００３０】[0030]
【発明の効果】本発明の超純水を用いて金属材料の表面
物質の組成を制御することにより、低温度、短時間で容
易に化学的に安定な化学量論構造の組成にすることがで
きる。また、超純水の新しい利用分野を見いだした。即
ち、超純水の工業的応用技術としての効果が期待でき
る。By controlling the composition of the surface substance of the metal material using the ultrapure water of the present invention, a composition having a stoichiometric structure that is chemically stable can be easily obtained at low temperature and in a short time. it can. We also found a new field of application for ultrapure water. That is, the effect of industrial application technology of ultrapure water can be expected.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の実施例に係る表面物質の改質装置を示
す概念図である。FIG. 1 is a conceptual diagram showing a surface material modifying apparatus according to an embodiment of the present invention.
【図２】比較例１において形成された表面物質のＸＰＳ
解析図である。2 is an XPS of a surface material formed in Comparative Example 1. FIG.
It is an analysis chart.
【図３】実施例１において形成された表面物質のＸＰＳ
解析図である。FIG. 3 is an XPS of the surface material formed in Example 1.
It is an analysis chart.
【図４】実施例２において形成された表面物質のＸＰＳ
解析図である。FIG. 4 is an XPS of the surface material formed in Example 2.
It is an analysis chart.
【図５】実施例２において形成された表面物質の分極曲
線図である。5 is a polarization curve diagram of the surface substance formed in Example 2. FIG.
【図６】実施例２において形成された表面物質のＳＥＭ
表面写真である。FIG. 6 is an SEM of the surface material formed in Example 2.
It is a surface photograph.
【図７】実施例３において形成された表面物質の超純水
処理前後のＸＰＳ解析図である。FIG. 7 is an XPS analysis diagram of the surface substance formed in Example 3 before and after the ultrapure water treatment.
【図８】実施例３において形成された表面物質の超純水
処理前後のＸＲＤ解析図である。FIG. 8 is an XRD analysis diagram of the surface substance formed in Example 3 before and after the treatment with ultrapure water.
【図９】実施例３において形成された表面物質の耐食性
テスト後のＸＰＳ解析図FIG. 9 is an XPS analysis diagram after a corrosion resistance test of the surface substance formed in Example 3
【図１０】実施例３において形成された表面物質の耐食
性テスト後のＸＲＤ解析図である。10 is an XRD analysis diagram after a corrosion resistance test of a surface substance formed in Example 3. FIG.
【図１１】スパッタにより形成されるクロムのスパッタ
膜を示す概念図である。FIG. 11 is a conceptual diagram showing a chromium sputtered film formed by sputtering.
【図１２】スパッタにより形成されるクロムのスパッタ
膜をフッ素化した場合を示す概念図である。FIG. 12 is a conceptual diagram showing a case where a chromium sputtered film formed by sputtering is fluorinated.
【図１３】生成反応後、ガスを変えて組成制御を行った
場合の表面物質のＸＰＳ解析図である。FIG. 13 is an XPS analysis diagram of the surface substance when the composition is controlled by changing the gas after the production reaction.
【図１４】化学量論構造を有しているものと有していな
いものとをフッ素ガスに曝し、フッ素ガスに対するバリ
ヤ効果をフッ素ガスの消費圧で比較した結果を示すグラ
フである。FIG. 14 is a graph showing the results of exposure of fluorine gas having a stoichiometric structure and those having no stoichiometric structure to fluorine gas, and comparing the barrier effect against the fluorine gas with the consumption pressure of the fluorine gas.
１ チャンバー、 ２ 超純水用容器、 ３ 内部、 ４ 超純水、 ５ 不活性ガス導入口（不活性ガス導入手段）、 ６ 不活性ガス排出口（不活性ガス排出手段）、 ７ 超純水を加熱するための手段。 1 chamber, 2 container for ultrapure water, 3 inside, 4 ultrapure water, 5 inert gas inlet (inert gas inlet), 6 inert gas outlet (inert gas outlet), 7 ultrapure water Means for heating the.
Claims (9)
素を含まない雰囲気下において超純水に接触させること
を特徴とする表面物質の改質方法。1. A method for modifying a surface substance, which comprises contacting a surface substance formed on a metal material with ultrapure water in an atmosphere containing no oxygen.
下とすることを特徴とする請求項１記載の表面物質の改
質方法。2. The method for modifying a surface substance according to claim 1, wherein the amount of dissolved oxygen in the ultrapure water is 1 ppm or less.
請求項１または２に記載の表面物質の改質方法。3. The method for modifying a surface substance according to claim 1, wherein the ultrapure water is heated.
とする請求項３に記載の組成制御法。4. The composition control method according to claim 3, wherein the ultrapure water is brought to a boiling state.
を特徴とする請求項１ないし４のいずれか１項に記載の
表面物質の改質方法。5. The method for modifying a surface substance according to claim 1, wherein the surface substance is a metal fluoride.
物、クロムのフッ化物、鉄のフッ化物、アルミニウムの
フッ化物または銅のフッ化物のいずれか１種以上を主成
分とするフッ化物であることを特徴とする請求項５に記
載の表面物質の改質方法。6. The metal fluoride is a fluoride containing, as a main component, one or more of nickel fluoride, chromium fluoride, iron fluoride, aluminum fluoride and copper fluoride. The method for modifying a surface substance according to claim 5, wherein:
つ前記金属フッ化物がクロムのフッ化物または鉄のフッ
化物を主成分とするフッ化物であることを特徴とする請
求項５に記載の表面物質の改質方法。7. The surface according to claim 5, wherein the metal material is stainless steel, and the metal fluoride is a fluoride containing chromium fluoride or iron fluoride as a main component. Method of modifying substances.
ッキにより形成された第２の金属材料をフッ化処理する
ことにより形成されたニッケルのフッ化物であることを
特徴とする請求項４に記載の表面物質の改質方法。8. The metal fluoride is nickel fluoride formed by subjecting a second metal material formed by plating on the metal material to fluorination. A method for modifying the surface substance described.
性ガス導入手段と、外部へ該不活性ガスを排出するため
の不活性ガス排出手段とを有するチャンバーと、該チャ
ンバーの内部に配置された超純水を保持するための超純
水用容器と、該チャンバーの内部に配置された該超純水
用容器内に保持された超純水を加熱するための手段と、
を少なくとも有することを特徴とする表面物質の改質装
置。9. A chamber having an inert gas introducing means for introducing an inert gas into the inside and an inert gas discharging means for discharging the inert gas to the outside, and a chamber disposed inside the chamber. A container for ultrapure water for holding the ultrapure water stored therein, and means for heating the ultrapure water held in the container for ultrapure water arranged inside the chamber,
An apparatus for modifying a surface substance, comprising at least:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23897392A JP3173164B2 (en) | 1992-08-14 | 1992-08-14 | Method for modifying surface material and apparatus therefor |
| PCT/JP1993/001138 WO1994004717A1 (en) | 1992-08-14 | 1993-08-12 | Method and apparatus for modifying surface material |
| EP94908102A EP0655517A1 (en) | 1992-08-14 | 1993-08-12 | Method and apparatus for modifying surface material |
| US08/901,341 US6110534A (en) | 1992-08-01 | 1997-07-28 | Method and apparatus for modifying surface material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23897392A JP3173164B2 (en) | 1992-08-14 | 1992-08-14 | Method for modifying surface material and apparatus therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0657405A true JPH0657405A (en) | 1994-03-01 |
| JP3173164B2 JP3173164B2 (en) | 2001-06-04 |
Family
ID=17038051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23897392A Expired - Lifetime JP3173164B2 (en) | 1992-08-01 | 1992-08-14 | Method for modifying surface material and apparatus therefor |
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| Country | Link |
|---|---|
| EP (1) | EP0655517A1 (en) |
| JP (1) | JP3173164B2 (en) |
| WO (1) | WO1994004717A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991001519A1 (en) * | 1989-07-21 | 1991-02-07 | Fanuc Ltd | System for resuming program for automatic operation |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19548740A1 (en) * | 1995-12-23 | 1997-06-26 | Abb Research Ltd | Process for surface treatment of aluminum and aluminum alloys |
| DE10314700A1 (en) | 2003-03-31 | 2004-10-14 | Behr Gmbh & Co. Kg | Method for producing surface-modified workpieces |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6445130A (en) * | 1987-08-14 | 1989-02-17 | Hitachi Ltd | Underwater oxidation of semiconductor wafer |
| JPH04234122A (en) * | 1990-12-28 | 1992-08-21 | Mitsubishi Electric Corp | Manufacture of semiconductor device |
-
1992
- 1992-08-14 JP JP23897392A patent/JP3173164B2/en not_active Expired - Lifetime
-
1993
- 1993-08-12 EP EP94908102A patent/EP0655517A1/en not_active Withdrawn
- 1993-08-12 WO PCT/JP1993/001138 patent/WO1994004717A1/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991001519A1 (en) * | 1989-07-21 | 1991-02-07 | Fanuc Ltd | System for resuming program for automatic operation |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0655517A1 (en) | 1995-05-31 |
| WO1994004717A1 (en) | 1994-03-03 |
| JP3173164B2 (en) | 2001-06-04 |
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